Study of H-Zeolite Addition in The Esterification Step of ... - ITS

The First International Seminar on Science and Technology 

January 24, 2009 

ISBN : 978 – 979 – 19201 – 0 – 0 

Study of H-Zeolite Addition in The Esterification Step of Biodiesel Synthesis 

from used Cooking Palm Oil 

Introduction 

Karna Wijaya, Triyono and Risqi Andini 

Laboratory of Physical Chemistry, 

Department of Chemistry, Gadjah Mada University 

Jl.Kaliurang, Km 5.5, Sekip Utara, Yogyakarta 55218 

Telp./Fax.: 0274-545188 

Correspondence author: karna_ugm@yahoo.com, Mobile phone: 08122692493 

Abstract 

It has been studied the effect of H-zeolite addition in esterifiction step of biodiesel synthesis from used 

cooking palm oil using a steinlessteel biodiesel reactor with capacity of 10 L and equipped with an automatic 

temperature control, a timer, and a stirrer. 

The study was initiated with natural zeolite activation using technical sulfuric acid. After activation the 

zeolite was characterized its acidity by gravimetric method, its structure by X-ray diffractometry, and FT-IR. 

The H-zeolite then was used as solid acid catalyst in esterification step of biodiesel synthesis to decrease the 

free fatty acid concentration in used palm oil. The H-zeolite which was used in the process was varied its 

weight towards (oil + methanol) weight i.e. 1.50%; 3.50%; 5.50% and 6.50%. As a comparison, pretreatment 

of used cooking palm oil also has been done over 1.50 % sulfuric acid. After pretreatment, the oil was 

separated from methanol and H-zeolite, the reaction was continued by transesterifying the oil with methanol 

using NaOH as catalyst. The transesterification product then was labeled as biodiesel. Both esterification and 

transesterification process were carried out in a steinlessteel biodiesel reactor at temperature of 70 o C for 2 

hours. The composition of the biodiesel was analyzed using Gas chromatography–Mass Spectroscopy (GC- 

MS), 1 H-NMR and their physical properties were analyzed using ASTM analysis methods. 

The research results showed that activation resulted in no destruction of zeolite structure and increased its 

acidity. Biodiesel reactor can used for biodiesel synthesis from used cooking palm oil. Addition of H-zeolite 

in esterfication could decrease its free fatty acid content. Increasing of H-zeolite would increase the biodiesel 

conversion. The highest conversion of biodiesel was 98,41% achieved by addition of H-zeolite of 5.5% 

(w/w). The result of GC-MS analysis showed that main components of biodiesel were mixture of methyl 

esters with methyl oleic as the major compound (40.66%). Based on the ASTM analysis data, the obtained 

biodiesel specification was in agreement with diesel fuel specification for automotive. 

Key words: esterification,transesterifiction, biodiesel, used palm oil, H-zeolite, 

The international demand for biodiesel and 

the promotion of the oil as sources of renewable 

energy which can decrease the greenhouse effect are 

increasing year after year. Biodiesel can be used in 

almost diesel engine when mixed with fossil diesel 

oil. Biodiesel can provide benefits including: 

reduction of greenhouse gas emissions and fossil fuel 

use, increase rural development and a sustainable fuel 

supply. However, biodiesel have some limitations 

such as the feedstocks for biofuel production must be 

replaced rapidly [1-10] 

Biodiesel is consisting of fatty-acid alkyl 

esters, known as FAME (fatty-acid methyl ester). 

Fatty-acid alkyl esters are long chains of carbon 

molecules with an alcohol molecule attached to one 

end of the chain. In a process called 

transesterification, vegetable oils, animal fats or 

restaurant greases are combined with alcohol and 

chemically altered to form fatty esters such as methyl 

ester [8-14] 

Beside fresh vegetables oil, used cooking oil 

may be used as raw material for biodiesel syntheses. 

However, used cooking oil which has been heated in 

high temperature usually contain high concentration 

of free fatty acids. Free fatty acids will create soap 

and hinder the formation of biodiesel in 

transesterification reaction step. One of the method to 

deal with this is by giving a preliminary treatment on 

used cooking oil in the form of an acid catalyst 

adding before transesterification is conducted. The 

Proceeding Book 433



purpose of the treatment is to reduce free fatty acids 

concentration in used palm cooking oil through 

esterification reaction. In the esterification reaction 

step,usually a catalyst homogen such as sulfuric acid 

was used. The use of sulfuric acid as catalyst in 

industry is not considered economical because 

sulfuric acid used is mixed with alcohol, so that it is 

difficult to separate them, moreover sulfuric acid 

which is containing sulfur can decrease the quality of 

the biodiesel as fuel. As an alternative, a solid acid 

catalyst such as acidified zeolite is used [13-19]. 

Materials And Methods 

Materials 

The natural zeolite was supplied by 

PT.Anindya Divisi Pertambangan, Yogyakarta. 

Technical grade Sodium hydroxide, methanol and 

sulfuric acid were used as received. Aquabidest as a 

dispersion media was purchased from Lab.of Physical 

Chemistry, Gadjah Mada University. Used cooking 

palm oil was purchased from CV.Kembang 

Nusantara,Yogyakarta. 

Instrumentations 

The X-Ray diffraction (XRD) patterns were 

obtained on Shimadzu PW3710 BASED 

diffractometer equipped with Shimadzu X-ray 

generator, using CuKα radiation. The scanning (2θ) 

range was from 2 to 40 o and the scanning rate was 

5 o /min. FTIR spectra was obtained from Shimadzu 

FTIR-8201 PC. Concentration of biodiesel was 

determined using 1 H-NMR (60 MHz) and Gas 

Chromatography (HP 5890 Shimadzu), meanwhile 

components of biodiesel were determined using Gas 

Chromatography–Mass Spectrometer (Shimadzu). 

Synthesis and Characterization of H-Zeolite 

The study was initiated with natural zeolite 

activation using technical sulfuric acid. One hundered 

gram natural zeolite with dimension of 250 mesh was 

dispersed into 1,6M technical grade sulfuric acid. The 

dispersion was stirred and then filtered. The solid 

phase was heated at 120 o C for 5 hours. The product 

was labeled as H-zeolite. After activation the Hzeolite 

was characterized its acidity by gravimetric 

method, its structure by X-ray diffractometry, and 

FT-IR. To calculate methyl esters content we used 

proton-NMR data and equation 1. 

C 

ME 

= 100% 

× 

5× 

I 

ME 

( 5× 

I ME ) + ( 9× 

ITAG 

) 

(1) 

Where 

CME 

IME 

ITAG 

ISBN : 978 – 979 – 19201 – 0 – 0 

=conversion of methyl ester (%) 

=integrtion value of methyl ester peaks (%) 

=integration value of triasylglicerol (%) 

Synthesis of Biodiesel 

The H-zeolite which was used in the process 

was varied its weight towards (oil + methanol) weight 

i.e. 1.50%; 3.50%; 5.50% and 6.50%. As a 

comparison, pretreatment of used cooking palm oil 

also has been done over 1.50 % sulfuric acid. After 

pretreatment, the oil was separated from methanol 

and H-zeolite, the reaction was continued by 

transesterifying the oil with methanol using NaOH as 

catalyst. The transesterification product then was 

labeled as biodiesel. Both esterification and 

transesterification process were carried out in a 

steinlessteel biodiesel reactor at temperature of 70 o C 

for 2 hours (Fig.1). The composition of the biodiesel 

was analyzed using Gas chromatography–Mass 

Spectroscopy (GC-MS), 1 H-NMR and their physical 

properties were analyzed using ASTM analysis 

methods. 

Figure.1 Biodiesel reactor with capacity of 10 L to 

prepare biodiesel from used cooking plm oil 

Results And Discuccion 

Preparation of H-Zeolite 




The study was initiated with natural zeolite 

activation using technical sulfuric acid. After 

activation the zeolite was characterized its acidity by 

gravimetric method, its structure by X-ray 

diffractometry, and FT-IR. From X-ray analysis result 

ISBN : 978 – 979 – 19201 – 0 – 0 

could be concluded that the acid activation resulted in 

no destruction of the natural zeolite structure 

significantly. It can be seen clearly from the reflexes 

of H-zeolite in its difractogram which almost all of 

the reflexes still exist after acid activation (Fig.2) 

Figure. 2 Difractogram of natural zeolite (above) and H-zeolit (below) 




ISBN : 978 – 979 – 19201 – 0 – 0 

Figure 3. FT-IR Spectra of H-zeolite (above) and natural zeolite (below) 

Infra red analysis result also supported the 

X-ray analysis data. There was no indication that acid 

activation caused a significant distruction of zeolite 

structure. After activation all importance vibrationts 

of the zeolite still appeared in H-zeolite spectra 

(Fig.3). 

Gravimetry analysis indicated that acid 

activation can cause the increasing of total acidity of 

the clay in some extent (from 0.02980 mmol 

NH3/gram to be 0.03125 mmol NH3/gram) . The 

increase of the acid uptake indicated that the surface 

area and adsorption sites of the H-zeolite was higher 

than natural unmodified zeolite, Therefore, it is 

expected that H-zeolite has catalytic properties higher 

than natural unmodified zeolite. 

Synthesis of Biodiesel 

Biodiesel reactor with capacity of 10 L can 

used for biodiesel synthesis from used cooking palm 

oil. The product and the used cooking palm oil are 

displayed in Fig.4. The color of obtained biodiesel 

was bright yellow meanwhile used cooking palm oil 

was dark brown. The characterization result indicated 

that addition of H-zeolite in esterfication could 

decrease its free fatty acid content from 4.166% to 

1.58% . 

Figure 4. Used cooking palm oil (left) and biodiesel 

(right) 

To determine the methyl esters concentration 

in product we used proton-NMR analysis method. 

Analysis results (Fig.3, Fig.4.and Fig.5) exhibited that 

esterification and transesterification resulted in the 

formation of biodiesel which indicated by appearing a 

sharp peak around 3,7 ppm at its spectrogram (Fig. 

7). Calculation using equation 1 showed that the 

increasing of H-zeolite would increase the biodiesel 

conversion. The highest conversion of biodiesel was 

98,41% achieved by addition of H-zeolite of 5.5% 

(w/w). 




Figure. 5. Proton-NMR spectra of used cooking palm oil 

Fig. 6. Proton-NMR spectra of esterification product 

ISBN : 978 – 979 – 19201 – 0 – 0 




The result of GC and GC-MS analysis 

showed that main components of biodiesel were 

mixture of methyl esters with methyl oleic as the 

The existence of methyl palmitic was indicated by the 

appearance of fragment with m/z= 270, 239 and 74 

(Fig.9). The appearance of fragments with m/z = 294, 

263, 81,55 and 41 was considered due to methyl 

linoleaic (Fig. 10). Fragments with m/z = 296, 266, 

Fig. 7. Proton-NMR spectra of biodiesel 

Figure.8 Chromatogram of mixed methyl esters 

ISBN : 978 – 979 – 19201 – 0 – 0 

major compound ca. 40.66% (Fig. 8-12). Other 

componets were methyl palmitic (34,37%), linoleic 

(13,12%) and stearic (6,84%) (Fig. 9-12). 

264, 74, 69, 55 and 41 was caused by methyl oleic 

(Fig.11). Finally, the methyl stearic appeared with 

m/z = 87, 101, 115, 129, 143, 157, 171, 185, 199, 

213, 227, 241, and 225 (Fig.12). 




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C 3H 6O 2 

m/z = 74 O 

C 16H 31O 

m/z = 239 

Figure 9. Mass spectra and structure of methyl palmitic 

C 18H 30O 

m/z = 262 

Figure 10. Mass spectra and structure of methyl linoleic 

C 18H 32O 

m/z = 264 

Figure 11. Mass spectra and structure of methyl oleic 

OCH 3 

OCH 3 

Proceeding Book 439 

O 

O 

OCH 3



Biodiesel produced from the above metioned 

process are further tested their physicochemical 

properties using ASTM method and are compared 

with the specification of ASTM biodiesel (Table 1). 

Biodiesel resulted from esterification with H-zeolite 

and transesterification proved to fulfil 8 criteria 

stipulated for diesel oil, which include viscosity, 

density, flash point, water content, Conradson carbon 

residue, fuel value and specific density. Viscosity of 

biodisel is related to specific density in which the 

higher the viscosity was, the greater the specific 

density would be. Biodiesel with high specific density 

will be difficult to flow so that it will slow down the 

ignition process. Biodiesel viscosity from used 

cooking palm oil had lower viscosity than used oil, 

and if it is used as fuel for diesel engine, the result of 

injection in ignition chamber will easily form nebula 

which facilitate ignition. 

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C 3H 6O 2 

m/z = 74 O 

C 18H 35O 

m/z = 267 

Figure 12. Mass spectra and structure of methyl stearic 

OCH 3 

Flash point of biodiesel from used cooking 

palm oil is relatively very high. The high flash point 

make biodiesel easy for storing. The biodiesel can be 

saved easily and safely in tropical areas. If flash point 

of the biodiesel was lower, the biodiesel will be easily 

flammable in storing. Biodiesel from used cooking 

palm oil is considered to have high pour point. The 

high pour point cause the diesel engine to stuck in 

lower temperature so that it is not suitable for use in 

sub tropical areas. 

The comparison between specification of 

biodiesel produced in the research with specification 

of diesel oil for industry and automotive was shown 

in Table 1. Of the five criteria presented, our 

biodiesel fulfil the requirements for being alternative 

fuel for diesel oil for industry and auttomotive. 

Table 1. Comparison between physical characteristic of biodiesel with diesel oil for industry 

and automotive diesel oil. 

Parameter 

Used cooking 

palm oil 

Automotive diesel 

oil *) 

Industry 

diesel oil *) 

Specific density 60/60 o F 0,9124 0,820-0,870 0,840-0,920 

Brutto fuel value (GHV), 

BTU/lb **) 19173,25 19031-19220 18842-19145 

Netto fuel value (NHV),BTU/lb **) 

17423,52 17856-17977 17735-17929 

Kinematic viscosity 40 o C 40,37 2,0-5,0 7,000 

Pour point, o F 

39,2 65,000 65,000 

Flash point, o F 

341,6 Min 150 Min 150 

Conradson carbon residue % 0,391 Max 0,100 Max 1,000 

Water content, % vol. 0,12 Max 0,05 Max 0,05 




Conclusions 

The research results showed that activation 

resulted in no destruction of zeolite structure and 

increased its acidity. Biodiesel reactor can used for 

biodiesel synthesis from used cooking palm oil. 

Addition of H-zeolite in esterfication could decrease 

its free fatty acid content. Increasing of H-zeolite 

would increase the biodiesel conversion. The highest 

conversion of biodiesel was 98,41% achieved by 

addition of H-zeolite of 5.5% (w/w). The result of 

GC-MS analysis showed that main components of 

biodiesel were mixture of methyl esters with methyl 

oleic as the major compound (40.66%). Based on the 

ASTM analysis data, the obtained biodiesel 

specification was in agreement with diesel fuel 

specification for automotive. 

References 

1. Arrowsmith, C.J., J. Ross, 1945, Treating 

Fatty Materials, US Patent , 2,383,580. 

2. Canakei, M., dan Van Gerpen, J., 2003, A 

Pilot Plant to Produce Biodiesel from High 

Free Fatty Acids Feedstocks, Am. Soc. 

Agric, Eng., 46, 945-954. 

3. Demirbas, A., 2003, Biodiesel Fuels from 

Vegetable Oils via Catalytic and Non- 

Catalytic Supercritical Alcohol 

Transesterifications and Other Methods: A 

Survey, J. Tur. Chem. Educ., 44, 2093-2109. 

4. Freedman, B., 1984, Variables Affecting the 

Yield of Fatty Aster from Transesterified 

Vegetables Oil, J: Am. Oil Chem, 10,61. 

5. Hamdan, H., 1992, Introduction to Zeolites: 

Synthesis, Characterization, and 

Modification, Universiti Teknologi 

Malaysia, Kuala Lumpur. 

6. Hanna, A.M., dan Ma, F., 1999, Biodiesel 

Production Areview, J., Agric & Natural, 70, 

1-15. 

7. Hardjono, A., 2001, Teknologi Minyak Bumi, 

Edisi pertama, Gadjah Mada University 

Press, Jogjakarta. 

8. Hidayat, D, 2008, Pengaruh katalis H-Zeolit 

pada Proses Pembuatan Biodiesel dari 

Minyak Jelantah kelapa Sawit Bekas 

Menggunakan Reaktor Biodiesel 

berkapasitas 10 L, Skripsi, Universitas 

Gadjah Mada, Jogjakarta. 

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9. Houas, A. Lachleb, H., Puzenut, E., Ksibi, 

M., Elaleui, E., Gullard, G., and Hermann, 

J.M., 2001, Photocatalytic Degradation 

Pathway of Methylene Blue in Water, Appl. 

Catal. B: Environmental 30. 145-157. 

10. Keim, G.I., 1945, Treating Fats and Fatty 

Oils U.S., Patent, 383. 

11. Knothe, G., 2000, Monitoring a Progressing 

Transesterification Reaction by Fiber-Optic 

Near Infrared Spectroscopy with correlation 

to H Nuclear Magnetic Resonance 

Spectroscopy, Jpn. Am. Oil. Chem. Soc., 77, 

J 9483, 489-493. 

12. Mastutik, D., 2006, Transesterifikasi Minyak 

Jelantah Kelapa Sawit menjadi Biodiesel 

Menggunakan Zeolit-Y Melalui Proses 

Esterifikasi, Tesis, Universitas Gadjah 

Mada, Jogjakarta. 

13. Nye, M.J., dan southwell, P.H., 1983, Esters 

from Repeseed Oil as Diesel Fuel In: Proc. 

Vegetable Oil as Fuel Seminar III, Pcoria: 

Northern Agricultural Energy Center, 78-83. 

14. Oudejans, J.C., 1984, Zeolite Catalysis in 

Some Organic Reactions, Chemical 

Research (SON), Holland. 

15. Patzer, R., dan Norris, M., 2002, Evaluated 

Biodiesel Made from Waste Fats and Oils, 

Final report, Agriculture Utilization 

Research Institute, University of Minnesota, 

Minnesota. 

16. Saefudin, A., 2005, Sintesis Biodiesel 

Melalui reaksi esterifikasi Minyak Jelantah 

Dengan Katalis Montmorillonit Teraktivasi 

Asam Sulfat Yang Dilanjutkan Dengan 

Reaksi Transesterifikasi Terkatalisis NaOH, 

Skripsi, Universitas Gadjah Mada, 

Jogjakarta. 

17. Setyawan, D.A., 2001, Pengaruh Waktu dan 

temperatur Hidrotermal terhadap 

Dealuminasi dan Keasaman Zeolit Alam 

Aktif, Skripsi, FMIPA UGM, Yogyakarta. 

18. Van, Gerpen, J., Shanks, B., Pruszko, R., 

2004, Biodiesel Production Technology, 

National Renewable Energy Laboratory, 

Collorado. 

19. Zappi, M., Hernandez, M., Spark, D., Horne, 

J., Brough, M., 2003, A Review of the 

Engineering Aspects of the Biodiesel 

Industry, MSU Environmental Technology 

Research and Applications Laboratory Dave 

C. Swalm School of Chemical Engineering 

Mississippi State University, Mississippi. 




ISBN : 978 – 979 – 19201 – 0 – 0 

Preparation of Solid Acid Catalysts from Bentonite and Their Catalytic 

Activities for The Esterification of Jatropha curcas Seed Oil 

Novizar Nazir 1,3 , Djumali Mangunwidjaja 2 , Mohd. Ambar Yarmo 3 Jumat Salimon 3 

and Nazaruddin Ramli 3 

1 Faculty of Agricultural Technology, University of Andalas Padang, Indonesia 

Kampus Limau Manis. Padang 25163, Indonesia 

Telp. +62 751 72772- E-mail address: nazir_novizar@yahoo.com 

2 Department of Agroindustrial Technology, Institut Pertanian Bogor 

Kampus IPB Darmaga, Bogor, Indonesia 

3 School of Chemical Science and Food Technology, FST UKM, Malaysia 

43600 UKM, Bangi, Selangor Darul Ehsan, Malaysia 

Abstract 

The esterification reaction of Jatropha curcas seed oil with methanol to remove free fatty acid (FFA) 

for biodiesel production was conducted using various bentonite catalysts. Solid acid catalysts from 

bentonite were prepared by aqueous impregnation technique. 5.3 M HCl and 40% by mass of H 2SO 4 

were supported on bentonite by aqueous impregnation, washed with deionized water till Cl -1 and SO 4 - 

2 ions were not detected, dried overnight and calcinated at 500 o C for three hours. Catalysts was 

characterized by XRD, nitrogen adsorption-desorption, and pyridine adsorption FTIR. Five catalysts 

used in esterification reactions of Jatropha curcas seed oil with methanol were compared: (A) nonactivated 

bentonite; (B) HCl 5.3 M-activated bentonite; (C) HCl 5.3 M-activated bentonite and 

calcinated at 500 o C (D) H 2SO 4 40%-activated bentonite; (E) H 2SO 4 40%-activated bentonite and 

calcinated at 500 o C. The effects structure properties of bentonite catalysts were discussed relating 

to the conversion of the FFA. 

Keywords: Jatropha curcas, solid acid catalyst, esterification, acid-activated bentonite, FFA, 

biodiesel 

Introduction 

With the increasing price of petroleum and 

environmental concerns over pollution caused by the 

internal combustion gases, alternative fuels have been 

developed [1, 2]. Biodiesel is considered as one of the 

alternative fuels for diesel engines become 

increasingly important [3]. 

Biodiesel is defined as the mono alkyl esters of 

long chain fatty acids derived from renewable 

feedstocks, such as vegetable oil or animal fats, use in 

compression ignition engine [4]. It is a clean-burning 

fuel, biodegradable, nontoxic and has low emission 

profiles and so is environmentally beneficial. Use of 

biodiesel has the potential to reduce the level of 

pollutants and of potential carcinogens [5,6,7]. 

In biodiesel production, the use of edible oils will 

compete with the food product. Consequently, the 

use of non-edible oil as alternative source will be 

important. Among several non-edible oil seed species 

could be utilized as source for oil production, J. 

curcas which grows in tropical and sub-tropical 

climates accross developing world is a multipurpose 

species with many attributes and potentials [8,9] 

However, the relatively higher amounts of free fatty 

acids (FFA) and water in this feedstock results in the 

production of soap in the presence of alkali catalyst. 

During alkaline-catalyzed transesterification, high 

content FFA will react with alkali catalysts to produce 

soaps which will inhibit the transesterification for 

biodiesel production. Furthermore, the large amount 

of soap can gel and also prevent the separation of the 

glycerol from the ester [5]. Acid-catalyzed 

transesterification, despite its insensitivity to FFA in 

the feedstock, has been largely ignored mainly 

because of its relatively slower reaction rate [6]. 

Therefore a process combining pretreatment with 

alkaline-catalyzed transesterification for feedstocks 

having high FFA content was investigated by many 

authors [10,11,12,3]. 

Acid-catalyzed esterification of high FFA content 

vegetable oils is a typical method of biodiesel 

production due to high reaction speed and high yield 

[13]. Some raw feedstocks with high FFA such as 

yellow and brown grease [10], rubber seed oil [11] 

mahua oil [14], waste cooking oil [15] and jatropha 

oil [11] have been used to produce biodiesel with 

homogeneous acid-catalyzed esterification followed 

by transesterification using alkaline catalyst. 

Compared with conventional liquid acid catalysts, 




solid acid catalyst is more environmentally friendly 

[15]. 

The present work was undertaken to investigate 

the pretreatment process for reducing the FFA content 

of jatropha oil for biodiesel production using various 

bentonite as solid acid catalyst. This paper focuses on 

the reaction parameters that affect the conversion of 

FFA in crude jatropha oil by means of acid-catalyzed 

esterification with methanol. 

Materials and Methods 

Materials 

Jatropha curcas oil was hydrolic press extracted of 

jatropha seed from Lampung, South Sumatra, 

Indonesia. Anhydrous methanol (MeOH), 99.8%, 

potassium hydroxide (KOH), sulfuric acid (H2SO4), 

and Hydrochloric acid (HCl), 37-38% pure were 

purchased from ChemAR ® . 

A calcium-rich bentonite (CaB) sample was 

obtained as powder from PT. Superintending 

Company of Indonesia used in the experiments. The 

bulk chemical analysis of the bentonite (mass %) is 

SiO2, 64.15; TiO2, 0.47; CrO3, 0.003; Al2O3,.70; 

Fe2O3, 0.10; MgO, 0.70; CaO, 0.03; , Na2O, 0.20; 

K2O, 0.50 and loss on ignition (LOI), 22.61. 

Preparation of Catalyst [16,17] 

Acid-activated Bentonite were prepared by 

aqueous impregnation technique. 5.3 M HCl and 

40% by mass of H2SO4 were supported on bentonite 

by aqueous impregnation (at 80 o C and 4 h), washed 

with deionized water till Cl -1 and SO4 -2 ions were not 

detected, dried overnight and calcinated at 500 o C for 

three hours. Five catalysts for esterification of 

jatropha oil with methanol were compared: (A) 

“untreated” bentonite catalyst; (B) esterification with 

5.3 M HCl-activated bentonite catalyst; (C) 

esterification with 5.3 M HCl-activated bentonite and 

calcinated at 500 o C catalyst (E) esterification with 

40% H2SO4-activated bentonite catalyst; (F) 

esterification with 40% H2SO4-activated bentonite 

and calcinated at 500 o C catalyst. 

Characterization of Catalyst 

The X-ray diffraction (XRD) patterns of natural 

and acid activated samples were recorded from 

random mounts prepared by glass slide method using 

a Rikagu D-Max 2200 Powder Diffractometer, 

operating at 40 kV and 30 mA, using Ni-filtered 

CuKa radiation having 0.15418 nm wavelength, at a 

scanning speed of 2 o 2θ min _1 . Surface area of 

bentonite was measured with multipoint Brunauer, 

Emmett and Teller (BET) method from the 

ISBN : 978 – 979 – 19201 – 0 – 0 

Quantachrome Surface Analysis Instrument 

(Autosorb 1-C, Boynton Beach, Florida, USA). This 

was done using nitrogen adsorption/desorption 

isotherms at liquid nitrogen temperature and relative 

pressures (P/Po) ranging from 0.04- 0.4 where a 

linear relationship was maintained. For acidity study, 

about 10 mg of the sample was pressed at 2-5 tonnes 

for a minute to obtain a 13 mm disk. The sample was 

introduced in infrared cell with calcium flourite. 

Each sample was degases for 16 hours under vacuum 

at 400 °C. The infrared spectra were collected at 

room temperature using Simadzu 2000 FTIR 

spectrometer at 2 cm- 1 resolution. The type of acid 

sites were examined using pyridine as probe 

molecule. Then pyridine was absorbed for 30 

seconds at room temperature, continued by desorption 

at 150 °C for 1 hour. Finally, the sample was 

desorpted at 400 °C for 1 hour. 

Esterification process catalyzed by sulfuric acid 

Esterification was conducted in a 250 ml threeneck 

flask. The flask was equipped with a 

mechanical agitator and a reflux condenser, and 

heated with a water bath to control the reaction 

temperature (60 o C). In the experiments, flasks loaded 

with Jatropha oil samples were firstly heated to the 

designated temperature. This was followed by the 

addition of the methanol (methanol : oil ratio, 0.28 

v/v) and sulfuric acid (1.34%) mixture before turning 

on the agitator, marking the start of the esterification 

reaction. 

The application solid acid catalyst in esterification 

process 

Esterification was conducted in a 250 ml threeneck 

flask. In the experiments, flasks loaded with 

Jatropha oil samples were firstly heated to the 

designated temperature (60 o C). This was followed by 

the addition of the methanol (methanol : oil ratio, 0.30 

v/v) and solid acid catalyst (5% w/v oil) mixture 

before turning on the agitator, marking the start of the 

esterification reaction. The esterification products 

were separated in a tap funnel to obtain the upper oil 

layer. After methanol recovery under vacuum at 

50 o C, oil layer was then washed with water several 

times until the pH of washing water was close to 7.0. 

The resultant esterified oil was dried by anhydrous 

magnesium sulfate before acid value analysis.The 

convertion of FFA was defined as the fraction of the 

FFA removed. The convertion of FFA (xFFA) was 

determined from acid number ration using below 

equation [15]: 




Where ai is the initial acid number of the reactant 

and at is the acid number of product at ‘t’ time. 

Alkali catalysed transesterification of jatropha oil 

The collected oil layer was transferred to 250 ml 

round bottom, 0.1g v/v methanol and 3.5 w/v +acid 

number of KOH were added. The mixture was 

reacted for 24 minutes at 65 o C. The mixture was left 

to settle to separate into two layers. The upper layer 

was the FAME (crude biodiesel). 

Results and Discussion 

Characterization of Catalyst 

Fig. 1 shows changes in intensity and width of 

the 001 peak, which indicate that the crystallinity of 

the bentonite is considerably affected by acid 

activation an calcination. The variation of relative 

intensity (I / I0) and full width at half-maximum 

(FWHM) peak height of the XRD peak for bentonites 

represent the intensities for the natural and acidactivated 

bentonite samples, respectively. The 

decrease in I / I0 and increase in FWHM on the 001 

XRD peak show that the crystallinity of bentonite 

decreases by increasing in acid [17]. 

2500 

2000 

1500 

1000 

500 

0 

ISBN : 978 – 979 – 19201 – 0 – 0 

HCl 5.3. M non-calicinated 

0 

0 5 10 15 20 25 30 35 

o2θ Fig. 1. The XRD patterns of the natural and some of 

the acid-activated bentonite (S: smectite, I: 

illite, FWHM: full width at half maximum 

peak height). 

The total pore volume of samples is measured by 

condensation of N2 adsorbate at P/Po 0.95 in the pores 

of diameter



ISBN : 978 – 979 – 19201 – 0 – 0 

[a] [b] 

Fig. 2. FTIR spectra of samples (a) after pyridine adsorption at room temperature for 30 seconds, (b) after 

pyridine adsorption and desorption at 150 o C for 1 h. 

Effect of esterification reaction time and type of 

bentonite to acid value 

The effect of esterification reaction time and 

type of bentonite to acid value is shown in Fig.3. 

The results show that the acid value decrease 

significantly after 6 hours esterification. The best 

catalyst is HCl-activated bentonite without 

calcination with 67.70% FFA convertion after six 

hours reaction time. This result is lower than 

heterogeneous catalyzed reaction of H2SO4 

(91.70% FFA convertion). 

Fig.3. Effect of esterification reaction time and type of bentonite to acid value of esterified oil 




Effect of esterification reaction time to convertion 

of FFA and acid value 

According to Lu et al [18], FFA convertion 

will increase with the increasing of time, 

temperature and ratio methanol to oil. In this 

experiment we increase the reaction temperature 

ISBN : 978 – 979 – 19201 – 0 – 0 

from 60 o C to 65 o C and methanol to oil ratio from 

0.30 (v/v) to 0.40 (v/v) using catalyst B. The 

convertion of FFA and acid value of esterified oil is 

shown in Fig.4. The result shows that the 

convertion of FFA increase from 67.70% to 81.7% 

Fig. 4. Effect of esterification reaction time to convertion of FFA and acid value of esterified oil 

Alkali catalysed transesterification of jatropha oil 

In this work, the lowest acid value of esterified 

jatropha oil was 2.32 mg KOH/g. In fact, the alkali 

catalyzed transesterification of jatropha oil could 

work, even if the FFA content was over 1% [19]. 

The reaction of jatropha oil with methanol was easy 

to perform. The bottom layer of glycerol was 

obvious after 24 minutes reaction time [12]. 

Chemical properties of jatropha biodiesel obtained 

from the FFA removal by esterefication of FFA in 

jatropha oil with H2SO4 (at 60 o C and 88 minutes 

reaction time) and HCl-activated bentonite (at 70 

o C and 6 hours reaction time) is shown in Table 2. 

Table 2. Chemical properties of jatropha biodiesel obtained from the FFA removal by esterefication of FFA in 

jatropha oil with H2SO4 (at 60 o C and 88 minutes reaction time) and HCl-activated bentonite (at 70 

o C and 6 hours reaction time) 

Conclusion 

Property Product after the 

reaction on H2SO4 

Product after the 

reaction on HClactivated 

bentonite 

Density (kg/m 2 ) 0,87 0,87 

Kinematic viscosity (mm/s 2 ) 1,73 1,74 

Free Fatty Acid (mg KOH/g oil) 0,24 0,47 

Based on the result of this study, it can concluded 

that: 

1. Acid activation and calcination on bentonite 

affect the cristalinity, surface area, pore 

volume and acidity properties of bentonite. 

2. HCl-activated bentonite without calcination has 

potential to be solid acid catalyst for 

esterification of jatropha oil. Convertion of 

FFA reached 81.7% when parameters are as 




follows: reaction time 6 h, amount of catalyst 

5%, ratio methanol oil 0.4 v/v and reaction 

time 65 o C. 

3. HCl-activated bentonite as acting as 

heteregeneous acid catalyst shows good 

activity to catalyze the esterification of 

jatropha oil and methanol. Compared with 

sulfuric acid, this catalyst is environmentally 

friendly, easy to separate from the system, 

reusable and does not need high cost 

equipment for anti-corrosion 

Acknowledgements 

The authors thank University Kebangsaan Malaysia 

for all facilities and supporting this study by the 

Research University Grant UKM-oup-nbt-29- 

151/2008. 

References 

[1] M. Fangrui, A.H. Milford (1999): 

Biodiesel production: a review. Bioresour. 

Technol. 70, 1–15. 

[2] J.M. Marchetti, V.U. Miguel, A.F. Errazu 

(2007). Possible methods for biodiesel 

production, J. Renew. Sustain. Energy Rev. , 

11, 1300–1311. 

[3] H.J. Berchmans,., and S. Hirata (2008). 

Biodiesel production from Jatropha curcas 

L. Seed oil with a high content of free fatty 

acids. Bioresour. Technol. 99, 1716-1721. 

[4] L.C Meher, V.D. Sagar, S.N. Naik (2006) 

Technical aspects of biodiesel production by 

transesterification—a review, J.Renew. 

Sustain. Energy Rev. 10, 248–268. 

[5] A.Demirbaş (2002). Biodiesel from 

vegetable oils via transesterification in 

supercritical methanol, Energy Conserv. 

Manage. 43, 2349–2356. 

[6] Y. Zhang, M.A. Dubè, D.D. McLean, M. 

Kates (2003). Biodiesel production from 

waste cooking oil: 1. Process design and 

technological assessment. Bioresour. Techn. 

, 89, 1-16. 

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Synthesis and Characterization of Al2O3/TS-1 

Rivone Septa Wijayanti, Didik Prasetyoko 

ISBN : 978 – 979 – 19201 – 0 – 0 

Laboratorium of Inorganic Chemistry, Department of Chemistry, Faculty of Mathematic and Sciences, Institut 

Teknologi Sepuluh Nopember (ITS), Surabaya, Indonesia. 

1) Corresponding author, Phone: +62-31-5943353 

email: didikp@chem.its.ac.id 

rivone_sw@yahoo.com 

Introduction 

Abstract 

TS-1 has good catalytic activity in reaction of selective oxidation of organic materials such as 

benzene and phenol using H 2O 2 as oxidizing agent. However, it has hydrophobic character that 

correlate with the slow rate of the reaction. Modification of catalyst using metal oxide result in 

decreased of hydrophobic property, and as a sonsequence the rate of the reaction will be 

increased. In this paper, TS-1 was modified by Al2O 3 using impregnation method. The solid 

were characterized by X-ray diffraction, infrared spectroscopy, and hydrophilicity techniques. 

Hydrophilicity test of Al2O 3/TS-1 was carried out using the mixture of xylene and water. The 

impregnated catalysts Al 2O 3/TS-1 show partially hydrophilic property. Al 2O 3/TS-1 catalyst with 

4%wt loading demonstrated fastest submerged time at water as compare to other samples. The 

addition of Al2O 3 increased hydrophilicity of TS-1 which is indicated by the results of 

hydrophilicity test. 

Key words: catalyst, Al2O 3/TS-1, hydrophilic 

The synthesis of titanium silicalite (TS- 

1) was first reported by Taramasso et al. [1] in 

1983. Titanium silicalite-1 (TS-1), a MFI-type 

titanosilicate, has been used as a highly-efficient, 

heterogeneous catalyst for selective oxidation of 

organic compounds using hydrogen peroxide as an 

oxidant. TS-1 can lessens tar product and side 

products which have potential as pollutant [2]. Over 

the last decade, the literature has reflected a high 

activity and selectivity of H2O2 on TS-1 as catalysts 

for mild oxidation reactions with H2O2 used as the 

oxidant, such as phenol hydroxylation, olefins 

epoxidation, cyclohexanone ammoximation, 

alkane oxidation, oxidation of ammonia to 

hydroxylamine, secondary amines to 

dialkylhydroxylamines [3]. 

TS-1 has been commercialize in 

hydroxylation reaction of phenol with high 

hydroquinone selectivity and high H2O2 efficiency 

[4]. Hydroxylation reaction of phenol to produce 

diphenol had draws many attention since 1970s, 

and some catalysts either homogen and also 

heterogeneous have been applied in this reaction 

[5]. 

Reaction mechanism of phenol 

hydroxylation is as follows (1) TS-1 will 

decompose H2O2 (oxidation agent) which has 

hydrophilic character to form titanium-peroxo 

radical (initiation step), then (2) propagation step in 

solution [2]. This mechanism can be explained via 

titanium-peroxo complex formation mechanism as 

intermediate from reaction between H2O2 and TS-1 

catalyst [6-10]. The rate of the forming of titaniumperoxo 

depended on the rate of H2O2 reach to active 

site in TS-1. H2O2 is hydrophilic, that is quiet 

different from hydrophobic character of TS-1. [11], 

consequently the reaction rate of phenol 

hydroxylation reaction is tends to be slow [7]. 

One of the way to increase phenol 

hydroxylation reaction rate by modifieng of catalyst 

TS-1. Hence the existence of modified catalyst will 

influence its the character of chatalytic. The 

property of TS-1 modified properties made become 

more hydrophilic character by increasing acidity. 

The addition of metal oxide is the way to increase 

acidity, so the reaction rate of H2O2 with TS-1 to 

forms Ti-peroxo becomes more quicker. The 

addition of acidity character may come from Lewis 

acidity site or Brønsted acidity site. In this research 

applied Al2O3/TS-1 having acidity side of Lewis 

which is high as metal oxide added at TS-1. So that 

also can increase reaction rate of H2O2 with TS-1 to 

forms Ti-Peroxo which in the end will yield 

product briefer. Finally the reaction rate of phenol 

hydroxylation at Al2O3/TS-1 will be much faster 

and shows increasing of catalytic activity and 

selectivity higher than TS-1. 




Material and Methods 

For TS-1 (1 mol% of Ti), tetraethyl 

orthosilicates, TEOS (Merck, 98%) was placed into 

a Teflon beaker and vigorously stirred, tetraethyl 

orthotitanate, TEOT (Merck, 95%) was carefully 

added dropwise into this TEOS. The beaker was 

covered with parafilm to avoid hydrolysis. The 

temperature of the mixture was raised to 35 o C and 

the reactants were mixed homogeneously for half 

an hour. Then the mixture was cooled to about 0 o C. 

The solution of TPAOH (Merck, 20% TPAOH in 

water), which was used as template, was also 

cooled to 0 o C. 

After a few minutes, TPAOH was added 

drop-wise slowly into the mixture of TEOS and 

TEOT. At first, one should wait a few minutes after 

addition of a few drops of TPAOH solution before 

more TPAOH solution is added, to avoid 

precipitation. Stirring and cooling were continued 

during this process. After the addition of about 10 

mL the addition rate of TPAOH solution was 

increased. When the addition of TPAOH was 

completed, the mixture was heated in the 

temperature range of 80-90 o C for about 4 h in order 

for the hydrolysis of TEOS and TEOT to take 

place. Distilled water was added to increase the 

volume of the mixture, after which a clear gel was 

obtained. The gel was transferred into autoclave 

and heated at 175 o C under static condition. The 

material was recovered after 4 days of 

hydrothermal crystallization by centrifugation and 

washing with excess distilled water. A white 

powder was obtained after drying in air at 100 o C 

overnight. The calcination of the sample to remove 

the template was carried out under static air at 

550 o C for 5 h with temperature rate at 1 o /min. 

Samples of Al2O3/TS-1 catalyst 

containing 0,5%; 1%; 2%; and 4% were prepared 

by impregnation method, titanium silicalit (TS-1) 

was added to alumunium (III) nitrate solution 

which obtained by dissolving alumunium (III) 

nitrat. This mixture stirred at 80ºC for 3 h, dried at 

80-90ºC to eliminate water, and calcined at 550ºC 

for 5 h. Catalyst TS-1 and Al2O3/TS-1 were 

characterized by X-ray diffraction (XRD) and 

infrared spectrum is recorded with Fourier- 

Transform Infrared (FT-IR) spectrophotometer, 

with KBr palette method. Hidrophilicity properties 

of samples was analyzed by catalyst sample powder 

ISBN : 978 – 979 – 19201 – 0 – 0 

dispersion method at water phase and organic phase 

mixture (water and xylene). The movement of 

catalyst sample at each phase was observed. 

Result and Discussion 

Structural and phase of samples were 

determined by X-ray diffraction. The XRD patterns 

were showed in figure 1. Characteristic diffraction 

line of TS-1 is observed at 2θ = 7.88; 8.78; 23.14; 

23.9; 24.39; 2478°. The peak at 2θ around 24º is 

observed for the change of crystal symmetry from 

monoclinic symmetry, which is symmetry of 

silicalit-1, becomes orthorombic symmetry which is 

symmetry of TS-1. This Phenomenon indicates that 

titanium atom is in the framework structure of TS-1 

[12]. 

X-ray diffraktogram pattern of 

Al2O3/TS-1 with various Al2O3 loading variation at 

TS-1, showed similar pattern. XRD pattern of 

Al2O3/TS-1 with various of Al2O3 loading showed 

similar pattern with parent sample TS-1 shown in 

figure 1. Main top of crystal TS-1 emerges at 2θ = 

7.88; 8.78; 23.14; 23.9; 24.39; 24.78°. The similar 

pattern of XRD Al2O3/TS-1 indicates that Al2O3 

dispersed at surface of titanium silikalit-1. 

Therefore, the low content of Fe2O3 (up to 4 %wt) 

on TS-1 catalyst surface doesn't change the initial 

structure framework of TS-1. 

This finding indicated that the MFI 

structure of TS-1 is not collapsed after 

impregnation of Al2O3. 

Catalyst samples of TS-1 and Al2O3/TS- 

1 showed absorption band at around 1100, 800, and 

450 cm -1 , which is vibration mode of SiO4 or AlO4 

tetrahedral [13]. Absorption band at around 1100 

cm-1 is unsimmetrical vibration mode of Si-O-Si, 

and absorption band at around 800 cm-1 is its 

symmetrical vibration mode. Absorption band 

appeared at around 1230 and 547 cm -1 . It is 

characteristic of tetrahedral structure in framework 

zeolite MFI [14]. Absorption band appeared at 

around 970 cm-1 is characteristic of TS-1 which is 

vibration mode of stretching Si-O from unit [SiO4] 

which tied at atom Ti IV with tetrahedral 

coordination in TS-1 framework. Absorption band 

appear at this wavenumber is evidence that titanium 

atom has stayed in framework catalyst [15]. 




ISBN : 978 – 979 – 19201 – 0 – 0 

4 Al2O3/TS-1 

2 Al2O3/TS-1 

1 Al2O3/TS-1 

0,5 Al2O3/TS- 

TS-1 

Figure 1 X-ray powder patterns of samples TS-1 and Al2O3/TS-1 with various loading 




1230 cm -1 

1100 cm -1 

970 cm -1 

800 cm -1 

ISBN : 978 – 979 – 19201 – 0 – 0 

547 cm -1 

4Al2O3/TS-1 

2Al2O3/TS-1 

1Al2O3/TS-1 

450 cm -1 

0.5Al2O3/TS-1 

TS-1 

Figure 2 Framework IR Spectra of samples TS-1 and Al2O3/TS-1 with various loading 




Hydrophilic 

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Table 1. Hydrophilicity Character Definition 

Sample pass submerged the interfacial phase into water as a whole and 

quickly 

Hydrophilic Sample pass submerged interfacial phase into water not fairly quickly 

but in the end all sample is submerged sample 

Hydrophilic Initially sample tantalum at interfacial phase and then immerses in 

water slowly and as a whole 

Initially sample tantalum at interfacial phase, then some particle will 

Partially Hydrophilic submerged into water slowly and some tantalum particles at interfacial 

phase, after squealer, all sample is immerses in water 

Initially sample tantalum at interfacial phase, after squealer, some 

Partially Hydrophobic particles there are still tantalum at interfacial phase 

Sample will be tantalum permanently at interfacial phase though after 

Perfect Hydrophobic squealer is done 

Tabel 2. Hydrophilicity Character of TS-1 dan Fe2O3/TS-1 

Sample Index Character Water sumerged time 

(seconds) 

TS-1 5 Partially Hydrophobic 1 minutes 10 second 

0,5Al2O3/TS-1 5 Partially Hydrophilic 42 second 

1Al2O3/TS-1 5 Partially Hydrophilic 38 second 



Hydrophilic test of sample was carrying 

out using mixture xylen and water [16]. The result 

of hydrophilic characterization test of sample is 

given at tables 2. 

Table 2 gives an information about 

hydrophilicity properties of catalyst samples. Ts-1 

sample has hydrophobic character. This result is 

similar with the research that had been carried out 

by Drago [14]. This phenomena is caused by the 

structure of TS-1 which active site Ti tetrahedral is 

isolated 

Presence metal oxide at TS-1, character 

of hydrophilic increased. This thing proves that 

with presence Al2O3 increased hydrophilicity side 

of TS-1 which is indicated from increases Lewis 

side acid. 

Conclusion 

1. Catalyst TS-1, 0,5% Al2O3/TS-1, 1% 

Al2O3/TS-1, 2% Al2O3/TS-1, and 4% 

Al2O3/TS-1 has successfully synthesized. 

2. The addition of Al2O3 at TS-1 doesn't change 

crystal structure TS-1 with zeolite type MFI. 

3. Catalyst sample TS-1 and Al2O3/TS-1 shows 

absorption band at around 1100, 800, and 450 

cm -1 , which is vibration mode of SiO4 or AlO4 

tetrahedral. This spectra is characterization of 

MFI. 

4. With existence of addition of Al2O3 at TS-1, 

character of hydrophilic increased. Al2O3/TS- 

1 4% loading gives submerged time at fastest 

water compare to other sample. 


References 

[1] Taramasso, M., Perego, G. and Notari, B. 

(1983), “Preparation of Porous Crystalline 

Synthetic Material Comprised of Silicon and 

Titanium Oxides”. (U. S. Patents No. 

4,410,501). 

[2] Kurian, M., Sugunan, S. (2006), “Wet Peroxide 

Oxidation of Phenol Over Mixed Pillared 

Montmorillonites”, Chemical Engineering 

Journal, Vol. 115, pp. 39-146. 

[3] Liu, X., Wang, X., Guo, X., Li, G. (2004), 

“Effect of Solvent on the Propylene 

Epoxidation over TS-1 Catalyst”, Catalysis 

Today, Vol. 93-95, pp. 505-509. 

[4] Choi, J., Yoon, S., Jang, S., Ahn, W. (2006), 

“Phenol Hydroxylation Using Fe-MCM-41 

Catalysts”, Catalysis Today, Vol. 111, pp. 280- 

287. 

[5] Tang, H., Ren, Y., Yue, B., Yan, S., He, H. 

(2006), “Cu-incorporated Mesoporous 

Materials : Synthesis, Characterization and 

Catalytic Activity in Phenol Hydroxylation”, 




Journal of Molecular Catalysis A : Chemical, 

Vol. 260, pp. 121-127. 

[6] Vayssilov, G. N. dan van Santeny, R. A. 

(1998), “Catalytic Activity of Titanium 

Silicalites—a DFT Study”, Journal of 

Catalysis, Vol. 175, pp. 170–174. 

[7] Sun, J., Meng, X., Shi, Y., Wang, R., Feng, S., 

Jiang, D., Xu, R., Xiao (2000), “A Novel 

Catalyst of Cu–Bi–V–O Complex in Phenol 

Hydroxylation with Hydrogen Peroxide”, 

Journal of Catalysis, Vol. 193, pp. 199–206. 

[8] Wilkenhöner, U., Langhendries, G., van Laar, 

F., Baron, G. V., Gammon, D. W., Jacobs, P. 

A., dan van Steen, E. (2001), “Influence of 

Pore and Crystalline Titanosilicates on Phenol 

Hydroxylation in Different Solvents”, Journal 

of Catalysis, Vol. 203, pp. 201-212. 

[9] Bonino, F., Damin, A., Ricchiardi, G., Ricci, 

M., Spano`, G., D’Aloisio, R., Zecchina, A., 

Lamberti, C., Prestipino, C., dan Bordiga, S. 

(2004), “Ti-Peroxo Species in The TS- 

1/H2O2/H2O System”, Journal of Physical 

Chemistry B, Vol. 108, pp. 3573-3583. 

[10] Liu, H., Lu, G., Yanglong Guo, Yun Guo, dan 

Wang, J. (2006), “Chemical Kinetics of 

Hydroxylation of Phenol Catalyzed by TS- 

1/Diatomite in Fixed-Bed Reactor”, Chemical 

Engineering Journal, Vol. 116, pp. 179–186. 

[11] Armaroli, T., Bevilacqua, M., Trombetta, M., 

Milella, F., Alejandre, A. G., Ramirez, J., 

Notari, B., Willey, R. J., dan Busca, G. (2001), 

“A Study of The External and Internal Sites of 

MFI-Type Zeolitic Materials through The 

FTIR Investigation of The Adsorption of 

Nitriles”, Applied Catalysis A : General, Vol. 

216, pp. 59–71. 

[12] Li, Y.G., Lee, Y.M., Porter, J.F. (2002), “The 

Synthesis and Caracterization of Titanium 

Silicalite-1”, Kluwer Academic Publishers, pp. 

0022-2461. 

[13] Flanigen. E. M. (1976). Structural analysis by 

infrared spectroscopy. In: Rabo, J. A. ed. 

Zeolite chemistry and catalysis. ACS 

Monograph Vol. 171; pp. 80-117. 

[14] Drago, R., Dias, S. C., McGilvray, J. M., 

Mateus, A. L. M. L., 1997, “Acidity and 

Hidrophobicity of TS-1”, Journal Physic 

Chemistry B, vol. 102, pp. 1508-1514. 

[15] Li, G., Wang, X., Guo, X.,Liu, S., Zhao, Q., 

Bao, X., Lin, L. (2001), “Titanium Species in 

Titanium Silicalite TS-1 Prepared By 

Hydrothermal Method”, Materials Chemistry 

and Physics, Vol. 71, pp. 195-201. 

[16] Wang, Z., Wang, T., Wang, Z., Jin, Y. (2004), 

“Organic Modification of Ultrafine Particles 

using Carbon-dioxide as the Solvent”, Journal 

of Powder Technology, Vol. 139, pp. 148-155. 

ISBN : 978 – 979 – 19201 – 0 – 0 




ISBN : 978 – 979 – 19201 – 0 – 0 

Synthesis and Characterization of Fe2O3/TS-1 Catalyst 

Cholifah Endahroyani, Didik Prasetyoko 


Teknologi Sepuluh Nopember (ITS), Surabaya, Indonesia 

Corresponding author, Phone: +62-31-5943353 

email: didikp@chem.its.ac.id 

Introduction 

Abstract 

Hydroxylation reaction of phenol into diphenol, such as hydroquinone and cathecol, has a great role 

in many industrial applications. Phenol hydroxylation reaction has been carried out by using Titanium 

Silicalite (TS-1) as catalyst and H2O 2 as an oxidant. TS-1 catalyst has high activity and selectivity for 

phenol hydroxylation reaction. However, its hydrophobic sites lead to slow H2O 2 adsorption toward 

the active site of TS-1. Consequently, the reaction rate of phenol hydroxylation reaction is tends to be 

low. Addition of metal oxide can enhanced hydrophilicity character of TS-1 catalyst. In this research, 

TS-1 catalyst was modified by addition of metal oxide Fe 2O 3 by impregnation method. Fe 2O 3/TS-1 

catalyst were characterized by X-ray diffraction, FT-IR spectroscopy and hydrophilicity analysis 

techniques. The new catalyst, Fe2O 3/ TS-1 showed higher hydrophilicity compared to TS-1, and it can 

be predicted that the reaction rate of phenol hydroxylation will be much faster and will be showed 

increasing of catalytic activity and selectivity than that of parent catalyst, TS-1. 

Key words: catalyst, TS-1, Fe2O 3/ TS-1, hydrophilic site, phenol hydroxylation 

Hydroxylation reaction of phenol to 

produce diphenol (catechol and hydroquinone) and its 

isomers is one of important reaction because phenol 

has various important functions such as antioxidant, 

polymerization inhibitor, photography, rubber 

production, antiseptic, reducing agent, intermediate in 

pharmacy, and many others. Hydroxylation reaction 

of phenol to produce diphenol had draws many 

attentions since 1970s and some catalysts, both 

homogeneous and heterogeneous have been applied 

in this reaction. Hydroxylation reaction of phenol 

becomes environmentally friendly reaction when TS- 

1 (Titanium Silicalite-1) is applied as catalyst and 

aqueous H2O2 as oxidant [1]. TS-1 had draws many 

attention since last decade because its unique catalytic 

characters to selective oxidation reaction of organic 

compounds like aromatic hydroxylation, epoxidation 

alkenes, ammoximation cyclohexanone and oxidation 

of alkene and alcohol with hydrogen peroxide as 

oxidant [2]. TS-1 has been commercialize in 

hydroxylation reaction of phenol with high 

hydroquinone selectivity (hydroquinone/cathecol 

ratio = 1) and high H2O2 efficiency [3]. 

Hydroxylation reaction of phenol with TS-1 catalyst 

shows high activity and selectivity, become clean 

reaction with low H2O2 non-productive 

decomposition, and high catalyst stability [4]. 

TS-1 can lessens tar product and side 

products which have potential as pollutant. Reaction 

mechanism of phenol hydroxylation is as follows: (1) 

TS-1 will decompose H2O2 (oxidation agent) which 

has hydrophilic character to form titanium-peroxo 

radical (initiation step), then (2) propagation step in 

solution [5]. This mechanism can be explained via 

titanium-peroxo complex formation mechanism as 

intermediate from reaction between H2O2 and TS-1 

catalyst [2, 6-9]. The rate of the formation of 

titanium-peroxo depended on the rate of H2O2 reach 

to active site in TS-1. H2O2 is hydrophilic, that is 

quite different from hydrophobic character of TS-1 

[10], consequently the reaction rate of phenol 

hydroxylation reaction is tends to be low [7]. One of 

the way to increase phenol hydroxylation reaction 

rate with TS-1 catalyst is by making TS-1 become 

more hydrophilic character, and the reaction rate of 

phenol hydroxylation will be much faster and shows 

increasing of catalytic activity and selectivity higher 

than TS-1. Hydrophilic improvement of catalyst can 

be carried out by addition of metal oxide which leads 

to increasing of acidity properties. The existence of 

metal oxide in TS-1 catalyst can gives acid site which 

capable to increase catalyst hydrophilicity, so that 




reactant adsorption in catalyst becomes faster [11,12]. 

Heterogeneous catalytic process in phenol 

hydroxylation reaction can be carried out with pure 

metals oxide or supported oxide such as MoO3, 

CuO/SiO2, Fe2O3, Fe2O3/Al2O3, Co3O4, V2O5 and 

colloid particle of TiO2. However, this metal oxides 

show very low catalytic activity and selectivity [13]. 

In previous research by Indrayani [14], 

synthesis and catalytic activity were carried out with 

low-loading of MoO3/TS-1 catalyst in phenol 

hydroxylation reaction. MoO3/TS-1 catalysts have 

showed improvement of hydrophilicity along with the 

increasing of MoO3 content in MoO3/TS-1 catalyst. 

The improvement of hydrophilic character of 

MoO3/TS-1 catalyst is also accompanied with the 

improvement of its catalytic activity in phenol 

hydroxylation reaction. In this research, TS-1 catalyst 

was modified by addition of metal oxide Fe2O3 on the 

surface of TS-1. The existence of Fe2O3 on the TS-1 

surface, is expected to bring this new catalyst 

(Fe2O3/TS-1) become higher hydrophilic character 

compared to TS-1, and the rate of phenol 

hydroxylation reaction becomes faster than TS-1. 

Experimental 

Samples TS-1 were prepared according to a 

procedure described earlier by Taramasso et al. 

(1983). Tetraethyl orthosilicates, TEOS (Merck, 

98%) containing 0.3145 mol of silicon was placed 

into a Teflon beaker and vigorously stirred, tetraethyl 

orthotitanate, TEOT (Merck, 95%) containing 0.0032 

mol of titanium in isopropyl alcohol was carefully 

added dropwise into this TEOS. The beaker was 

covered with parafilm to avoid hydrolysis. The 

temperature of the mixture was raised to 35 o C and the 

reactants were mixed homogeneously for half an hour 

to obtain depolymerisation of the titanate oligomers 

that may be present in TEOT. Then the mixture was 

cooled to about 0 o C. The solution of 

tetrapropylammonium hydroxide, TPAOH (Merck, 

20% TPAOH in water), which was used as template, 

was also cooled to 0 o C. After a few minutes, TPAOH 

containing 0.1287 mol of TPAOH was added dropwise 

slowly into the mixture of TEOS and TEOT. At 

first, one should wait a few minutes after addition of a 

few drops of TPAOH solution before more TPAOH 

solution is added, to avoid precipitation. Stirring and 

cooling were continued during this process. After the 

addition of about 10 mL the addition rate of TPAOH 

solution was increased. When the addition of TPAOH 

was completed, the mixture was heated in the 

temperature range of 80-90 o C for about 4 h in order 

ISBN : 978 – 979 – 19201 – 0 – 0 

for the hydrolysis of TEOS and TEOT to take place. 

Distilled water was added to increase the volume of 

the mixture to about 127 mL, after which a clear gel 

was obtained. The gel was transferred into a 150 mL 

autoclave and heated at 175 o C under static condition. 

The material was recovered after 4 days of 

hydrothermal crystallization by centrifugation and 

washing with excess distilled water. A white powder 

was obtained after drying in air at 100 o C overnight. 

Silicalite was synthesized by using the same 

procedure without the addition of TEOT. The 

calcination of the sample to remove the template was 

carried out under static air at 550 o C for 5 h with 

temperature rate at 1 o /min [15]. 

Catalyst TS-1 and Fe2O3/TS-1 is 

characterized with X-ray diffraction (XRD) 

technique, X-ray powder diffraction (XRD) patterns 

were collected using the Ni-filtered Cu-Kα radiation 

(λ = 1.5406 Å), the infrared spectrum is used for IR 

absorption spectra analysis with KBr palette method. 

The infrared spectrum is recorded from wavenumber 

1400–400 cm −1 . Catalysts hydrophilicity is analyzed 

by catalyst sample powder dispersion method at water 

phase and organic phase mixture (water and xylene). 

A mixture of xylene and water, which do not mix 

with each other, is employed to test the hydrophobic 

characteristics of the samples. Xylene and water of 

the same volume are added into a test tube to form a 

stable phase interface Unmodified and modified 

particles are, respectively, dispersed in the xylene– 

water system and stirred. After the mixture has 

stabilized, the hydrophobic characteristics can be 

qualitatively evaluated by inspecting the state of the 

floating/sinking of samples at the interface. The 

criterion of hydrophobic index is shown in table 2. 


Fe2O3/TS-1 catalysts were characterized by 

X-ray diffraction technique. The XRD patterns were 

showed in Figure 1. Characteristic diffraction lines of 

TS-1 is observed at 2θ = 7,94; 8; 23.08; 23.62; 23.88; 

23.92°. The peak at 2θ around 24º is observed for the 

change of crystal symmetry from monoclinic 

symmetry, which is symmetry of silicalite-1, becomes 

orthorombic symmetry which is symmetry of TS-1. 

This Phenomenon indicates that titanium atom is 

already in the framework structure of TS-1 [18]. Xray 

diffraction pattern of Fe2O3/TS-1 with various of 

Fe2O3 loading showed similar pattern with parent TS- 

1 sample. This finding indicated that the MFI 

structure of TS-1 is not collapsed after impregnation 

of Fe2O3. Therefore, the low content of Fe2O3 (up to 




ISBN : 978 – 979 – 19201 – 0 – 0 

4% wt) on TS-1 catalyst surface doesn't change the initial structure framework of TS-1. 

Figure 1. X-ray Diffractogram Pattern of TS-1 dan Fe2O3/TS-1 

The XRD peak intensity of the samples at 2θ around 

23.00 o is decrease along with the increasing of Fe2O3 

loading in TS-1 (table 1). This result indicates that 

Fe2O3 were already located on the TS-1 surface. 

Table 1. Crystallinity of Fe2O3/TS-1 and TS-1 

Intensity at 

Samples Code 

2θ = 23.00 o , 

Cps 

TS-1 (2θ = 23.060 o ) 

0,5Fe2O3/TS-1 (2θ = 23.167 o ) 

1Fe2O3/TS-1 (2θ = 23.183 o ) 

2Fe2O3/TS-1 (2θ = 23.138 o ) 

4Fe2O3/TS-1 (2θ = 23.302 o 3288 

3030 

2964 

2349 

) 2332 

Infrared spectra of the samples are shown in 

fig 2. Catalyst samples of TS-1 and Fe2O3/TS-1 

shows absorption band at wavenumber around 1100, 

800, and 450 cm -1 , which is vibration mode of SiO4 or 

AlO4 tetrahedral. Absorption band at wavenumber 

around 1100 cm -1 is unsymmetrical vibration mode of 

Si-O-Si, and absorption band at wavenumber around 

800 cm -1 is its symmetrical vibration mode. 

Absorption band at wavenumber around 1230 and 

547 cm -1 is characteristic for tetrahedral structure in 

framework zeolite MFI [19]. Absorption band at 

wavenumber around 970 cm -1 is characteristic of TS- 

1 which is vibration mode of stretching Si-O from 

unit [SiO4] which tied at atom Ti 4+ with tetrahedral 

coordination in TS-1 framework. Absorption band at 

this wavenumber is evidence that titanium atom has 

already stayed inside the structure of catalyst 

framework [20]. 




%T 

1230 cm -1 

1100 cm -1 

970 cm -1 

800 cm -1 

547 cm -1 

Figure 2. IR Spectra of TS-1 and Fe2O3/TS-1 samples with various loading 

wavenumber, cm -1 

ISBN : 978 – 979 – 19201 – 0 – 0 

450 cm -1 

1400 1300 1200 1100 1000 900 800 700 600 500 400 

4 Fe 2O3/TS-1 

2 Fe2O3/TS-1 

1 Fe 2O3/TS-1 

0.5 Fe2O3/TS-1 

TS1 

silicalite 




Hydrophilic 

Table 2. Hydrophilicity Character Definition [21] 

Samples sink into water quickly and completely 

Hydrophilic Samples sink into water not so quickly, but completely 

ISBN : 978 – 979 – 19201 – 0 – 0 

Hydrophilic Samples float at first and then sink into water slowly and completely 

Partially Hydrophilic Samples float at first and then sink into water slowly. Part of the powder 

floats on surface of water and, after agitation, sinks into water 

completely 

Partially Hydrophobic Samples float on the surface of water. After a long time agitation, part of 

the powder still floats on the surface of water 

Completely Hydrophobic Samples float on the surface of water even with strong agitation for a 

long time 

Table 3. Hydrophobicity Character of TS-1 and Fe2O3/TS-1 Samples 

Sample Index Character Water sinks time 

(seconds) 

TS-1 5 Partially Hydrophobic 

1 : 08.4 

0,5Fe2O3/TS-1 

1Fe2O3/TS-1 

2Fe2O3/TS-1 

4Fe2O3/TS-1 

Catalyst hydrophilicity character analysis is 

carried out by catalyst samples dispersion method in 

the mixture of water and organic phase (xylene). 

The results of hydrophobic tests are shown 

in Table 3. All samples seem to show similar 

behavior during the hydrophilicity test, this indicates 

that the addition of metal oxide on TS-1 surface 

didn’t give too much effect in TS-1 catalyst 

properties, which is partially hydrophobic. 

Nevertheless, the addition of metal oxide on TS-1 

surface makes Fe2O3/TS-1 catalyst become much 

more hydrophilic than TS-1 catalyst. It can be seen in 

table 3 that the higher Fe2O3 loading in TS-1 catalyst 

resulted in the faster sinks into water. From Table 3, 

it can be concluded that there is the increasing of the 

catalyst hydrophilicity character along with the 

increasing of metal oxide Fe2O3 content at TS-1 

catalyst surface. 

5 Partially Hydrophobic 

5 Partially Hydrophobic 

1 : 02.4 

0 : 47.2 

5 Partially Hydrophobic 0 : 36.9 

5 Partially Hydrophobic 0 : 34.1 

Conclusion 

1. Catalyst TS-1, 0,5Fe2O3/TS-1, 1Fe2O3/TS- 

1, 2Fe2O3/TS-1, and 4Fe2O3/TS-1 has been 

successfully synthesized 

2. Catalyst 0,5Fe2O3/TS-1, 1Fe2O3/TS-1, 

2Fe2O3/TS-1, and 4Fe2O3/TS-1 still have 

orthorombic structure MFI type which is 

characteristic of TS-1 catalyst. 

3. Catalyst hydrophilicity character increases 

successively from TS-1, 0.5Fe2O3/TS-1, 

1%Fe2O3/TS-1, 2Fe2O3/TS-1, and 

4Fe2O3/TS-1. 

Acknowledgement 

We gratefully acknowledge funding from the 

Directorate General of Higher Education, Indonesia, 




References 

[1] Tang, H., Ren, Y., Yue, B., Yan, S., He, H. 

(2006), “Cu-incorporated Mesoporous 

Materials : Synthesis, Characterization and 

Catalytic Activity in Phenol Hydroxylation”, 

Journal of Molecular Catalysis A : 

Chemical, Vol. 260, hal. 121-127. 

[2] Liu, H., Lu, G., Yanglong Guo, Yun Guo, dan 

Wang, J. (2006), “Chemical Kinetics of 

Hydroxylation of Phenol Catalyzed by TS- 

1/Diatomite in Fixed-Bed Reactor”, 

Chemical Engineering Journal, Vol. 116, 

hal. 179–186. 

[3] Choi, J., Yoon, S., Jang, S., Ahn, W. (2006), 

“Phenol Hydroxylation Using Fe-MCM-41 

Catalysts”, Catalysis Today, Vol. 111, hal. 

280-287. 

[4] Liu, X., Wang, X., Guo, X., Li, G. (2004), “Effect 

of Solvent on the Propylene Epoxidation 

over TS-1 Catalyst”, Catalysis Today, Vol. 

93-95, hal. 505-509. 

[5] Kurian, M., Sugunan, S. (2006), “Wet Peroxide 

Oxidation of Phenol Over Mixed Pillared 

Montmorillonites”, Chemical Engineering 

Journal, Vol. 115, hal. 39-146. 

[6] Vayssilov, G. N. dan van Santeny, R. A. (1998), 

“Catalytic Activity of Titanium Silicalites— 

a DFT Study”, Journal of Catalysis, Vol. 

175, hal. 170–174. 

[7] Sun, J., Meng, X., Shi, Y., Wang, R., Feng, S., 

Jiang, D., Xu, R., Xiao (2000), “A Novel 

Catalyst of Cu–Bi–V–O Complex in Phenol 

Hydroxylation with Hydrogen Peroxide”, 

Journal of Catalysis, Vol. 193, hal. 199–206. 

[8] Wilkenhöner, U., Langhendries, G., van Laar, F., 

Baron, G. V., Gammon, D. W., Jacobs, P. 

A., dan van Steen, E. (2001), “Influence of 

Pore and Crystalline Titanosilicates on 

Phenol Hydroxylation in Different 

Solvents”, Journal of Catalysis, Vol. 203, 

hal. 201-212. 

[9] Bonino, F., Damin, A., Ricchiardi, G., Ricci, M., 

Spano`, G., D’Aloisio, R., Zecchina, A., 

Lamberti, C., Prestipino, C., dan Bordiga, S. 

(2004), “Ti-Peroxo Species in The TS- 

1/H2O2/H2O System”, Journal of Physical 

Chemistry B, Vol. 108, hal. 3573-3583. 

[10] Armaroli, T., Bevilacqua, M., Trombetta, M., 

Milella, F., Alejandre, A. G., Ramirez, J., 

Notari, B., Willey, R. J., dan Busca, G. 

(2001), “A Study of The External and 

Internal Sites of MFI-Type Zeolitic 

Materials through The FTIR Investigation of 

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The Adsorption of Nitriles”, Applied 

Catalysis A : General, Vol. 216, hal. 59–71. 

[11] Nur, H., Prasetyoko, D., Ramli, Z., Endud, S. 

(2004), “Sulfation: A simple Method to 

enhance the Catalytic Activity of TS-1 in 

Epoxidation of 1-octene with Aqueous 

Hydrogen Peroxide”, Catalysis 

Communications . Vol.5, hal. 725–728. 

[12] Prasetyoko, D., Ramli, Z., Endud, S., Nur, H. 

(2005), “Enhancement of Catalytic Activity 

of Titanosilicalite-1–Sulfated Zirconia 

Combination Towards Epoxidation of 1- 

Octene With Aqueous Hydrogen Peroxide”, 

Reaction Kinetics Catalysis Letter, Vol. 86, 

hal. 83-89. 

[13] Ray, S., Mapolie, S. F., Darkwa, J. (2007), 

“Catalytic Hydroxylation of Phenol using 

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Salicylaldimine Complexes”, Journal of 

Molecular Catalysis A : Chemical, Vol. 267, 

hal. 143-148. 

[14] Indrayani Suci, (2008), Aktivitas Katalitik 

MoO3/TS-1 pada Reaksi Hidroksilasi Fenol 

menggunakan H2O2, Tesis M.Si, Jurusan 

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Nopember, Surabaya. 

[15] Taramasso, M., Perego, G. and Notari, B. 

(1983), “Preparation of Porous Crystalline 

Synthetic Material Comprised of Silicon and 

Titanium Oxides”. (U. S. Patents No. 

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[16] Choudhary, V. R., Jana, S. K., Mamman, A. S. 

(2002), “Benzylation of Benzene by Benzyl 

Chloride over Fe-modified ZSM-5 and H-β 

Zeolites and Fe2O3 or FeCl3 deposited on 

Micro-, Meso-, and Macro-porous 

Supports”, Microporous and Mesoporous 

Materials, Vol. 56, hal. 65-71. 

[17] Hattori, H., Ogawa, T., Jones, F., Knudson, C., 

Willson, W., Rindt, J., Mitchell, M., 

Stenberg, V., Radonovich, L., Janikowski, S. 

(1985), “Reduction Activities of Fe2O3/SiO2 

Catalysts with Hydrogen Sulphide and 

Hydrogen”, Fuel, Vol. 65, hal. 780-785. 

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Synthesis and Caracterization of Titanium 

Silicalite-1”, Kluwer Academic Publishers, 

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[19] Drago, R. S., Dias, S. C., McGilvray, J. M., 

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Hydrophobicity of TS-1”, Journal of 

Physical Chemistry, Vol. 102, hal. 1508- 

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201. 


“Organic Modification of Ultrafine Particles 

using Carbon-dioxide as the Solvent”, 

Journal of Powder Technology, Vol. 139, 

hal. 148-155. 

ISBN : 978 – 979 – 19201 – 0 – 0 




ISBN : 978 – 979 – 19201 – 0 – 0 

New Mixed Ligands Complexes of Zinc(II), Cadmium(II) and Bismuth(III) 

With Dithiocarbamates and 2,2’-Bipyridyl 

Normah Awang 1 , Ibrahim Baba 2 and Bohari Mohd Yamin 2 

1 Environmental Health Programme, Faculty of Allied Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja 

Muda Abdul Aziz, 50300 Kuala Lumpur 

normahawang1969@yahoo.com 

+60326878034 

2 School of Chemical Sciences and Food Technology, Faculty Science and Technology, Universiti Kebangsaan 

Malaysia, 43600 Bangi, Selangor 

Abstract 

A new series of zinc(II), cadmium(II) and bismuth(III) complexes with mixed ligands, dithiocarbamate and 2,2’bipyridyl 

were successfully synthesized using “in situ” method. Microelemental analysis data of the complexes are 

in agreement with the general formula, M[S CNR’R”] 2 nbipy (M = Zn, Cd & Bi; R = s-butyl, R’ = propyl; R = 

benzyl, i-propyl; bipy = 2,2’-bipyridyl). Infrared spectra of the complexes showed that the thioureide ν(C N) 

band is in the regions 1438 – 1453 cm -1 

-1 

bidentate nature of the chelated dithiocarbamate ligands. The 

. The unsplitting band of ν(C-S) in the region 930 – 1000 cm 

indicates the 

13 

C NMR chemical shift of the carbon atom of the N- 

CS 2 group appeared in the range of 201.67 – 208.27 ppm. The crystal structure of zinc(II) 

benzylisopropyldithiocarbamate(2,2’-bipyridyl) supports the elemental and spectroscopic data in which two 

dithiocarbamates and one bipy ligands chelated to the central Zn atom in bidentate manner in a distorted 

octahedron environment. 

Keywords: dithiocarbamate; chloroform; IR spectra; biological activity 

Introduction 

For several years considerable attention has been paid 

to dithiocarbamate compounds. Firstly, their 

biological effects have been researched, including 

antialkylation, anti-HIV properties [1] and antitumor 

activity against leucemic cells [2]. Some 

dithiocarbamate complexes also have some practical 

applications. For example, they are used in 

agriculture as fungiside and pesticide [3]. 

The 1:1 adducts of zinc and cadmium 

dialkyldithiocarbamates with 2,2’-bipyridyl have 

been reported and some of these complexes are very 

active accelerators for the vulcanization of rubber and 

low temperature vulcanization of latex [4]. The 

crystal structure of Zn[S2CN(C2H5)2]2(2,2’-bipy) has 

been reported [5]. 

In spite of the fact that many 

dithiocarbamate compounds with different transition 

metals are described in the chemical literature, we 

have only considered Zn(II), Cd(II) and Bi(III) 

coordination compounds with non-symmetrical 

dithiocarbamates with the general formula 

M[S 2 CNR’R”] nbipy. (M = Zn, Cd & Bi; R = s-butyl, 

R’ = propyl; R’ = benzyl, R”i-propyl; bipy = 2,2’bipyridyl). 

So far, no information on complexes of 

this type with the sec-butylpropyl and 

benzylisopropyldithiocarbamate ligands were found 

in the literature. 


Reagents 

All the reagents and solvents employed were 

commercially available analytical grade materials and 

were used as supplied, without further purification. Nbenzylisopropylamine, 

2,2’-bipyridyl and ethanol 

(95%) were obtained from Fluka Chemicals. Carbon 

disulphide and methanol (99.5%) from Ajax 

Chemical Ltd. Bismuth(III) chloride was obtained 

from Hayashi Pure Chemical Indsutries Ltd. 

Cadmium(II) dichloride monohydrate, chloroform 

and zinc(II) chloride were purchased from Merck. 

Physical and spectroscopic measurement 




Elemental analyses were performed on a Fision EA 

1108 CHN Elemental Analyser. Melting points were 

determind on a Electrothermal IA 9100 apparatus. 1 

H 

and 13 

C NMR spectra were recorded in CDCl3 

solution on a Joel JNM – LA400 spectrometer with 

chemical shifts relative to tetrametylsilane. IR spectra 

were obtained as KBr pellets on a Perkin Elmer 

FTIR Model GX spectrophotometer in the frequency 

range 4000 – 500 cm -1 

and 500 cm -1 

- 200 cm -1 . 

Synthesis of dithiocarbamate complexes 

The mixed-ligand complexes were prepared by 

adding equimolar of metal dithiocarbamate 

compound (zinc(II), cadmium(II) and bismuth(III)) 

and 2,2’-bipyridyl in the mixture of ethanol and 

chloroform solutions. The method used to prepare the 

metal dithiocarbamate compounds were synthesized 

by a method reported earlier [6]. The resulting 

mixture was stirred for one hour and the solvent was 

allowed to evaporate at room temperature. After two 

ISBN : 978 – 979 – 19201 – 0 – 0 

days, the crystals separated out and washed with cold 

ethanol. 

Results And Discussion 

The M n+ [S2CNR’R”]m(bipy) complexes (n = 2, m = 2; 

n = 3, m = 3; R’ = s-C4H9, R” = CH3; R’ = C7H7, i- 

C3H7; bipy = 2,2’-bipyridyl) were prepared via a 

straightforward process involving only two steps. All 

the compounds were non-hgroscopic and stable in air. 

They were insoluble or sparingly soluble in most 

common organic solvents and very soluble in 

chloroform. The results of elemental analyses (Table 

1) are in good agreement with those required by the 

proposed formulae. The formation of these complexes 

may proceed according to the following equation 

given below. 

M[S2CNR’R”]n + C10H8N2 → 

M[S2CNR’R”]n(C10H8N2) 

M = Bi(III), Cd(II), Zn(II); n = 2 or 3; R’ = C7H7, R” 

= i-C3H7; R’ = s-C4H9, R” = C3H7 

Table 1. Physical and elemental analysis data of mixed-ligand complexes 

Compound Colour Melting 

point 

(°C) 

Zn[S2CN(C7H7)(iC3H7)]2bipy Yellow 165.9- 

(compound 1) 

166.5 

Cd[S2CN(C7H7)(iC3H7)]2bipy Yellow 223.2- 

(compound 2) 

224.4 

Zn[S2CN(sC4H9)(C3H7)]2bipy Yellow 133.8- 

(compound 3) 

134.3 

Cd[S2CN(sC4H9)(C3H7)]2bipy Yellow 194.8- 

(compound 4) 

Bi[S2CN(sC4H9)(C3H7)]3bipy 

(compound 5) 

195.3 

Orange 115.8- 

116.5 

The infrared spectra of the title compounds 

and important characteristic absorption bands, along 

with their proposed assignments are summarized in 

Table 2. The IR spectra of the compounds are very 

similat to each other, except some slight shifts and 

intensity change of a few vibration bands caused by 

different metal ions, which indicate that the 

compounds have similar structures. Coordination in 

the mixed-ligand mainly affected the C-N and C-S 

stretching bands [7]. 

% Found (calcd) 

C H N S M 

55.80 

(57.37) 

52.30 

(53.60) 

52.83 

(51.88) 

47.68 

(48.12) 

43.84 

(43.64) 

5.03 

(5.38) 

4.65 

(5.02) 

7.27 

(6.65) 

6.65 

(6.17) 

6.76 

(5.99) 

8.36 

(8.37) 

7.51 

(7.82) 

9.55 

(9.31) 

9.71 

(8.64) 

8.57 

(7.49) 

20.23 

(19.12) 

17.34 

(17.87) 

22.18 

(21.28) 

19.09 

(19.74) 

21.80 

(20.54) 

11.32 

(9.77) 

14.07 

(15.69) 

8.73 

(10.87) 

16.00 

(17.33) 

20.87 

(22.35) 

Table 2. The important infrared absorption bands of 

compound 1-5 (cm -1 ) 

Compound ν(C N) ν(N- ν(C S) ν(M- 

1 1440 1174 967 386 

2 1438 1171 970 387 

3 1441 1196 967 376 

4 1439 1194 957 386 

5 1453 1189 951 358 




The selected 1 H NMR peaks for compounds 

1-5 are showned in Table 3. The aromatic proton 

signals for 2,2’-bipyridyl in compounds 1-5 were 

observed in the range 7.33 – 9.01 ppm. This signal 

was not observed in the 1 H NMR spectra for metal 

dithiocarbamate compounds. Two proton signals 

from 2,2’-bipyridyl in compounds 1-4 have shifted 

Table 3. The selected 1 H and 13 C NMR data (δ, ppm) for compounds 1-5 

ISBN : 978 – 979 – 19201 – 0 – 0 

which one signal to downfield and the other one 

signal to upfield. These shifts indicate that 2,2’bipyridyl 

has been coordinated to the metal atom. The 

IR spectra data combined with these data showed that 

the 2,2’-bipyridyl has coordinated to the metal atom 

in all of these compounds. 

Compound Formula 

1 

H NMR 

(bipy) 

2,2’-bipyridyl (C10H8N2) 8.70 (d), 8.41 (d), 7.83 (t), 

7.33 (t) 

1 Zn[S2CN(C7H7)(iC3H7)]2bipy 

8.95 (d), 8.26 (d), 7.86 (t), 

7.33 (t) 

2 Cd[S2CN(C7H7)(iC3H7)]2bipy 

9.01 (d), 8.19 (d), 7.95 (t), 

7.48(t) 

3 Zn[S2CN(sC4H9)(C3H7)]2bipy 

8.82 (d), 8.35 (d), 7.85 (t), 

7.35 (t) 

4 Cd[S2CN(sC4H9)(C3H7)]2bipy 

8.95 (d), 8.26 (d), 7.86 (t), 

7.33 (t) 

5 Bi[S2CN(sC4H9)(C3H7)]3bipy 

8.70 (d), 8.40 (d), 7.84 (t), 

7.33 (t) 

The most important signal in the 13 C NMR 

spectra was the chemical shift for N 13 CS2 carbon. The 

N 13 CS2 chemical shifts for compounds 1-5 were 

observed in the range 201.67-208.27 ppm which not 

observed in the 13 C NMR spectra for 2,2’-bipyridyl 

compund. The N 13 CS2 chemical shift for compounds 

1 and 2 dropped slightly to downfield compared to 

the parent compounds (205.08 and 205.77 ppm 

respectively). The high values of N 13 CS2 chemical 

shifts could be explainded by an increase of π bond 

order in the whole NCS2 moiety [8] which means that 

the chelation of 2,2’-bipyridyl to the metal atoms has 

promoted the delocalization of the unshared electron 

pair in the nitrogen atoms in the dithiocarbamate 

groups. 

Suitable crystal for X-ray crystallographic 

studies of compound 2 were obtained by slow 

evaporation of a chloroform:ethanol mixture at room 

temperature. The dithiocarbamate ligands and 2,2’bipyridyl 

are bidentically chelated to the zinc atom 

and the coordination geometry around zinc was 

distorted octahedral. 

Conclusion 

The elemental, spectroscopic and crystallographic 

data showed that the new mixed-ligand complexes 

have been successfully synthesized. The 

13 

C NMR 

(N 13 CS2) 

- 

206.62 

208.27 

203.88 

205.93 

201.67 

dithiocarbamate ligands and 2,2’-bipyridyl were 

chelated to the metal atom to form the 

hexacoordinated mixed-ligand complexes. The 

crystallographic study of compound 2 showed that 

both of the dithocarbamate ligands and 2,2’-bipyridyl 

were bidentically chelated to the zinc atom. 


The authors gratefully acknowledge the research 

grant provided by The Malaysian Government (IRPA 

09-02-02-0048-EA144) and Universiti Kebangsaan 

Malaysia for financial support. Technical support 

from laboratory assistants of Faculty Science and 

Technology, Universiti Kebangsaan Malaysia is 

gratefully acknowledged. 

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ISBN : 978 – 979 – 19201 – 0 – 0 

bipyridyl and 4, 4’-bipyridyl: synthesis, structure 

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Polyhedron 8(15): 1891-1896. 




ISBN : 978 – 979 – 19201 – 0 – 0 

Titanium Dioxide Thin Film as Solar Photocatalyst for A Chlorinated 

Degradation of Organics Contaminate 

Muneer. M.Baabbad 1 ,Abdul Amir H.Kadhum 1 ,Abu Bakar Mohamad 1 , 

Mohd S.Takriff 1 ,Kamaruzzaman. Sopian 2 . 

1 Faculty of Engineering and Built Engineering, Universiti Kebangsaan Malaysia 

43600 UKM, Bangi, Selangor Darul Ehsan, Malaysia. 

2 Solar Energy Research Institute (SERI) Universiti Kebangsaan Malaysia 

43600 UKM, Bangi, Selangor Darul Ehsan, Malaysia. 

Abstract 

This paper is reviewing a Titanium dioxide thin film used in solar photocatalytic process. Solar photocatalytic 

technology is one of the major applications in the degradation of organic pollutants in water. The 

heterogeneous photocatalytic distractions of organic contaminates on thin film fixed bed reactor (TFFBR) is 

investigated. The degradation is studied using TiO 2 and also with different doped such as Pd and Fe 3+ 

photocatalysts under solar light illumination. The thin films were prepared with the dip-coating technique 

(Sol-Gel) using titanium tetra-iospropoxide as a raw material for synthesis of thin film, followed by thermal 

treatment at 400C o . The sample characterized by X-ray diffraction, UV-vis spectroscopy, scanning electron 

microscopy and atomic force microscopy. The photoactivity of various films were tested using different 

organic pollutants such as phenol and 4-chlorophenol (one of the most common water pollutants).The 

photoeffcinency obtained is approximately similar to that obtained using suspension. This was done for 

avoiding many operational complications such as separation of the catalyst and continuous of process. 

Keywords: Titanium dioxide thin film (TiO 2), solar photocatalysis, organics contaminates. 

Introduction 

Photocatalysis is the generally accepted term for a 

process in which light and a catalyst bring about or 

accelerate a chemical reaction. The IUPAC 

definition states photocatalysis as ‘a catalytic 

reaction involving light absorption by a catalyst or 

by a substrate’. In semiconducting photocatalysis, 

no energy is stored; instead there is an acceleration 

of a reaction by a photon-assisted process. Titanium 

dioxide has been the practical photocatalyst [1] of 

choice for a variety of reactions due to its high 

stability and oxidising power. It functions by 

absorbing sub band-gap radiation, this generates an 

electron and positive hole that can migrate to the 

surface of the titania and promote oxidation and 

reduction reactions. Powders and thin films of 

titania will photodegrade a wide range of organic 

chemicals in water [2-3]. During the last decades 

several efforts have been focused on improving 

decontamination of water [4] one of the most 

attractive options is the treatment by oxidation 

using a semiconductor, typically titanium dioxide, 

in combination with solar irradiation. This process 

can destroy organic matter, transforming organic 

carbon to CO2 and H2O employing just solar energy 

and a low cost non-toxic catalyst. 

Thin films of TiO2 on glass can be doing by a 

number of different methods. It has been often 

prepared by expensive methods as pulsed laser 

deposition [5], reactive evaporation [6] and 

chemical vapour deposition [7-9]. The simplest and 

Low cost preparation methods are the sol-gel 

processes [10-14] including dip or spin-coating [14] 

as the final step of preparation. The latter, along 

with the source of titania, also determines the grain 

size, structure, phase and density of sol-gel derived 

films [15-17]. Although titania thin-films have been 

proven to be effective in photo-oxidising organic 

substances, they can only do so under sub 

approximately 350 nm radiation. Its band-gap of 

3.2 eV means that titania can use less than 

approximately 1% of the solar spectrum. Gerischer 

and Heller [18] have proposed that the activity of a 

photocatalyst is limited by the rate of electron 

transfer to oxygen on the surface of the catalyst. 

There has been some research that suggests the 

modification of the TiO2 surface by Noble metals 

increases the efficiency of electron transfer to 

oxygen, which in turn increases the photooxidation 

efficiency. Some metals such as Pd and Fe +3 have 

also been doped into titania in order to improve its 

physical and optical properties. 


Sol-Gel synthesis process 

The TiO2 film was prepared using water; alcohol as 

solvent and different salts of metal oxide. In this 




case, used titanium tetra-isopropoxide (TTIP) as a 

titanium dioxide precursor became easily TiO2 type 

due to rapid hydrolysis, and then, the acquired final 

products were divided in two parts, powder and 

solution, which are necessary as centrifugation for 

the separation of these to get a colloidal solution for 

TiO2 film [19] and procedure indicated in Fig 1 (a) 

[20] .An aqueous solution molar ratio different 

according of the type material films, show in the 

Table 1. 

Dip-coating 

The glass substrates were dipped in the solution by 

a locally constructed clipping machine. The 

withdrawal rate used for the single coated films was 

different speed show in the Table 1 .After each 

coat, the film was allowed to dry at room 

temperature for 10 min. The procedure was 

repeated to obtain multiple coatings, Samples were 

annealed in a furnace at 400-500 C o for 1-3 h in air 

to fully decompose the precursor and obtain 

crystalline samples. The rate of heating and cooling 

was 5 C o / min [21-22]. 

TTIP H2O Acid 

Alchol 

(a) 

Mixing and Stirring 

Titania Sol 

Dip Coating 

Drying 

Baking 

TiO2 Thin Film 

ISBN : 978 – 979 – 19201 – 0 – 0 

Characterization of TiO2 films using the sol–gel 

process 

The use of sol–gel multistep process led to the 

production of transparent nanocrystalline TiO2 thin 

films with excellent reproducibility, scratch 

resistance and adherence on the glass substrates. 

Also the low cost one technique produced opaque 

and thicker films with good uniformity, and with 

properties closely related to the starting powder 

material. [23]. Right now, the research for 

improving the photocatalytic activity of TiO2 

mainly focus on the aspects as follows: doping of 

metal ions, surface depositing of noble metal, 

recombination of semiconductor, surface 

photosensitization and so on. Doping of metal ions 

has been largely employed with the aim to enhance 

the photocatalytic activity of TiO2 [24].Scanning 

electron microscopy was employed to perform at 

first the surface characterization of the 

manufactured films. Crystallinity of the TiO2 thin 

film was anatase determined by X-ray diffraction 

(XRD) using a diffract-meter with Cu K radiation, 

consisted with the literature [25]. The transmittance 

and absorbency of thin film were measured by UV– 

visible spectrophotometer. 

Figure 1: (a) preparation of TiO2 film by sol-gel, (b) Stages of the dip coating process. 

(b) 




Degradation of pollutants (4- chlorophenols as 

example ) 

The photodegradation of chlorophenols in aqueous 

solution has received considerable attention 

because these compounds are important xenobiotic 

micropollutants of the aquatic environment 

originating, for example, from industrial chemical 

synthesis. More specifically, 4-chlorophenol (4-CP) 

is used for the production of quinizarin (a dye), 

clofibrate (a drug), chlorphenesin and dichlorophen 

(fungicides) [26]. Therefore, several investigations 

of the photocatalytic decomposition of 

chlorophenols using metal oxide semiconductors 

either in aqueous heterogeneous suspensions [27- 

31] or in an immobilized form [32-34] have been 

published. The kinetics of the photocatalytic 4-CP 

The generation of the observed reaction 

intermediates can be readily explained though 

reaction schemes which involve OH . radical attack 

of 4-CP, initially to give the 4-chlorodihydroxycyclodienyl 

radical, leading on to the 

generation of 4-CC, HQ and BQ as intermediates to 

the eventual mineralisation of 4-CP. The primary 

oxidant appears to be surface absorbed OH radicals 

generated through the reaction between a 

ISBN : 978 – 979 – 19201 – 0 – 0 

degradation have commonly been interpreted as 

being indicative of a Langmuir–Hinshelwood- type 

mechanism in which the limitation of the 4-CP 

decomposition rate at higher pollutant 

concentrations is related to the extent of adsorption 

of the pollutant molecule on the TiO2 surface 

[30,35]. However, Cunningham et al. showed [31] 

that the observed adsorption constants of 

chlorophenols on TiO2 in the dark differ from 

equivalent data obtained from the kinetic analysis 

of their photocatalytic degradation employing the 

same TiO2 particles under UVirradiation. 

The photo-oxidative mineralisation of 4chloropheno 

4-CP) by oxygen and sensitised by 

TiO2, can be summarised as follows [36]: 

photogenerated valence-band hole and a surfacebound 

OH - or H2O group. Other sources of oxidant, 

which may also make a significant contribution, 

include OH . radicals derived from the oxygen 

reduction side of the photomineralisation process 

and direct attack of the substrate by the 

photogenerated hole [37]. Fig. 2 illustrates a typical 

degradation reaction scheme for Degussa P25 TiO2 

power dispersions in acidic solution. 

Figure.2. Reaction scheme illustrating the likely mechanistic pathways to the formation of the major 

intermediates, 4-chlorocatechol (4-CC), hydroquinone (HQ) and benzoquinone (BQ), generated during 

the photomineralisation of 4-CP. 


Synthesis -TiO2 films 




The films were formed on the glass substrate by 

dipping into the aged sol and then with- drawing at 

a constant rate to obtain a uniform coating. The 

solution remained clear with no white TiO2 micro- 

particles precipitating out. Hydrochloric acid acts as 

a catalyst to complete the hydrolysis. The probable 

mechanism for the process is shown in Scheme 1. 

The titanium alkoxide is protonated in a rapid first 

step. This makes the Ti atom more electro- philic 

and susceptible to attack form the water [39]. 

Withdraw of the glass-slide from the fluid-sol 

Mechanism of degradation process on thin film 

The photocatalytic oxidation driven by a large band 

gap semiconductor starts with the promotion of 

electrons from the valence to the conduction band, 

creating an electron-hole couple. The electrons are 

removed by reaction with oxygen dissolved in 

water and the cationic holes react either with OH - 

and/or H2O adsorbed at the semiconductor surface 

to form OH . radicals. Greater amounts of adsorbed 

OH - and/or H2O generate a concomitant increase in 

the amount of hydroxyl radicals favoring thus the 

photodegradation process. Taking into account the 

heterogeneous photocatalytic mechanism of a thin 

film TiO2 catalyst, the following steps typically 

take place [38]: (i) light absorption on the 

photocatalytic surface (ii) chemical transformation 

of the molecule while several reaction surface sites 

are visited (iii) desorption to the liquid phase. 

Degradation of chlorinated of organics 

contaminate 

The use of sol–gel multistep process led to the 

production of transparent nanocrystalline TiO2 thin 

films with excellent reproducibility, scratch 

Scheme 1: illustrate the steps of Synthesis -TiO2 film 

ISBN : 978 – 979 – 19201 – 0 – 0 

produces a transparent film due to the evaporation 

of the solvent and hydrolysis of [Ti-(Oi Pr)4]. 

During dipping, aggregation, gelation and drying 

occurs in seconds to minutes, rather than days as in 

bulk sol-gel systems [40]. Annealing of the film 

removed any remaining solvent and the structure is 

stiffened i.e. a Ti-O-Ti network formed by removal 

of the alkoxy and hydroxyl groups to produce an 

anatase thin film. It was noted that the most 

photocatalyically active films were formed by dip- 

coating 24 h after the initial hydrolysis. 

resistance and adherence on the glass substrates. 

The photocatalytic activities of all of the films were 

determined by photodegradation of thin dip-coated 

film of chlorinated of organics contaminates. The 

most outstanding feature with dip-cotaing method 

is that photocatalytic activity is higher when glass 

is used as support. Some typical results are reported 

in the Table 1. 




ISBN : 978 – 979 – 19201 – 0 – 0 

Table 1 Illustrate Material of Sol-Gel method and Degradation of some Chlorinated Organics contaminate photocatalytic degradation of the 4-chlorophenol concentration as a 

function of exposure time to the solar irradiation and using TiO2 thin films as catalysts 

No Type of 

Thin 

TTIP* 

Mol 

Catalyst 

Mol 

Solvent 

Mol 

H2O 

Mol 

Acid 

Mol 

Film 

thickne 

Dipcoating 

Organic 

degradation 

Time of 

degradation 

Organic 

degradation 

C/C0 

% 

Ref 

. 

Film 

ss speed 

min 

% 

nm cm/min 

1 TiO2 0.1 0.4 0.1 Hcl 

0.008 

600 10 4-chlorophenol 180 - 24 41 

2 TiO2 titanium 

inn- 

sulfonicacid 500- 2 3,5-dichlorophenol 1600 100 - 42 

butoxide 

1.72gm 

butanol 

600 

3 

4 

5- 

Fe +3 / 1 Fecl EtOH 

TiO2 

1 20 

Pd/ TiO2 1 Pd ethyl 

(NO3)2 alcohol 

0.15 7.6 

TiO2 0.1 isopropyl 

alcohol 

0.4 

20 acetic acid 4, 

0.1 

HNO3 

0.5 

HCl 1000- 

1600 


490 6.9 Dichloroacetic acid 150 80 - 43 

180 2.4 Phenol 1440 83 - 44 

4 1,1_-dimethyl- 

4,4_-bipyidium 

dichloride 

900 95 - 46



After 3 h of concentrated solar irradiation, the final 

dissolved concentration of 4-chlorophenol is 24% 

of its initial for the TiO2 immobilized catalysts. This 

means that TiO2 immobilized catalysts high 

photoefficiency [41]. A.Mills & J.Wang [36] 

reported the temporal variations in: [4-CP], [4-CC], 

[HQ], [CO2] and it appears likely that the reaction 

scheme illustrated in Fig. 3 is also applicable to 

TiO2 films of Degussa P25, that is, there is no 

major difference in the overall degradation reaction 

mechanism for films or dispersions of the same 

TiO2 source material (Degussa P25 in this case). 

Photocatalytic experiments took place to evaluate 

the films as a possible material for 3,5dichlorophenol 

(3,5-DCP) pollutant purification 

from water. Each experiment included complete 

decomposition (100%) of the b 3, 5-DCP but at 

long time due to films are endowed with a higher 

real surface extension, which readily favors the 

photodecomposition process .In fact, such a surface 

not only permits the adsorption of a greater number 

of pollutant molecules, but also creates a rough 

environment where multiple light reflection can 

occur, thus considerable increasing the amount of 

the adsorbed photons [42] .The titania films 

functionalized with iron cations used model of 

Dichloroacetic acid (DCA) degradation. Fe/TiO2 

film in presence of DCA and oxygen lead to proton 

release due to degradation of the organic molecules 

[43]. The Fe/Ti films are more effective 

photocatalysts with single coated and it give 

degradation efficiency 80 %. The photodegradation 

of phenol using the film modified with palladium 

was superior to that achieved with the pure titanium 

film [44]. However, in the case of a film, the 

particles are attached to the surface of a solid 

substrate, without the occurrence of aggregates, as 

in the case of a suspension. Probably, in the case of 

thin films, the substrate–catalyst repulsion due to 

the dissociation of the −OH groups present on the 

titania surface is negligible, considering that the 

catalyst mass is small. Thus, the dominant factor in 

the photocatalytic process involving thin films is 

mass transport [45]. The photodegradations of 1,1dimethyl-4,4-bipyidium 

dichloride (Paraquat) with 

coating time are compared. First, in case of the film 

attained from the sol–gel method the Paraquat 

decomposition slowly increased with an increase of 

coating time. In particular, the conversion of 

Paraquat was above 90% with four-time coating 

after 25 h[46]. 

Conclusions 

The use of a sol–gel multistep process allowed 

producing thin TiO2 films with an excellent 

adherence onto glass substrates obtained by using 

ISBN : 978 – 979 – 19201 – 0 – 0 

commercial titanium tetra-isopropoxide (TTIP). 

The results showed that the films possessed good 

photocatalytic activity for the degradation of 

organics contaminate as a typical photocatalytic 

reaction in liquid–solid systems. The modified 

films (Pd and Fe 3+ / TiO2) prepared by the sol–gel 

route and deposited in film form on the surface of 

glass exhibited high photocatalytic activity and also 

TiO2 film. Since the use of the fixed catalyst avoids 

many operational complications for separation of 

the powder catalyst, this represents a great 

advantage towards the application of this 

technology. 


The authors greatly a acknowledge to Solar Energy 

Research Institute (SERI) Universiti Kebangsaan 

Malaysia for its financial support (UKM-RS-02- 

FRGS0004-20007). 

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ISBN : 978 – 979 – 19201 – 0 – 0 

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ISBN : 978 – 979 – 19201 – 0 – 0 

Biological Activity of New Schiff Bases Derived From Thiophene and Their 

Transition Metal Complexes 

Md. Uwaisulqarni Osman 1* , M. Ibrahim M. Tahir 2 , Karen A. Crouse 2 , A.M. Ali 3 

1 Department of Chemical Sciences, Faculty of Science and Techology, Universiti Malaysia Terengganu, 21030 

Kuala Terengganu, Terengganu Darul Iman, Malaysia. 

2 Department of Chemistry, Faculty of Science,Universiti Putra Malaysia, 

43400 UPM Serdang, Malaysia 

3 Laboratory of Molecular and Cell Biology, Institute of Bioscience, Universiti Putra Malaysia, 43400 Serdang, 

Selangor, Malaysia 

*uwais@umt.edu.my 

Introduction 

Abstract 

A new Schiff base formed from S-benzyldithiocarbazate (SBDTC) with selected aldehyde containing a 

thiophene ring namely, thiophene-2-carbaldehyde (NS’) in 95 % of ethanol have been synthesized. 

Complexes of Cobalt(III), Nickel(II), Copper(II), Zinc(II) and Cadmium(II) with this Schiff base was 

prepared. The Schiff base and their metal complexes were evaluated for their cytotoxic and 

antimicrobial activities. Cytotoxic screening was carried out against Human ovarian cancer cells 

(CaOV-3), Human breast carcinoma cells with negative estrogen receptor (MDA-MB-231) and Human 

liver carcinoma cells (HEP-G2). Antimicrobial screening was carried out against four bacteria and three 

fungi. 

Keywords: Schiff Base, metal complexes, S-benzyldithiocarbazate (SBDTC), Cytotoxic, Antimicrobial, 

thiophene-2-carbaldehyde 

Many researchers had been carried on Schiff 

bases and their complexes [1, 2, 3, 4, 5] where, Schiff 

bases are compounds with structure of –C=N- 

(azomethine group) which can be synthesized 

through condensation reaction between primary 

amines and active carbonyl groups. Usually, 

bidentate Schiff base can coordinate with various 

transition metals through –C=N- (azomethine group) 

and –C=S (mercaptide group) [6] and gives solid 

metal complexes together with various geometry 

depends on the nature of the metals. Their flexibility 

in chelating with transition metals had emerged the 

knowledge on relationship between coordination 

chemistry and their interesting and important 

properties e.g antimicrobial, antifungal and 

anticancer [6,7, 8, 9, 10]. 

The present study was under taken to 

investigate more on biological activity of the Schiff 

base derived from the S-benzyldithiocarbazate 

(SBDTC) with thiophene-2-carbaldehyde (NS’). 

However, all physico-chemical analyses to confirm 

the structures had been done using IR, magnetic, 1 H 

and 12 C NMR measurements, thermogravimetric 

analysis, CHNS analyses and X-Ray Crystallography. 

Furthermore, all the results are not included in the 

present study. 


Cytotoxic Assay 

All the Schiff base and metal complexes were tested 

to determine their cytotoxicity against CaOV-3 

(Human Ovarian Cancer cells), MDA-MB-231 

(Human breast carcinoma cells with negative 

estrogen receptor) and HEP-G2 (Human Liver 

carcinoma cells) cell lines at Faculty of Medicine and 

Health Science, Universiti Putra Malaysia. The cell 

lines were obtained from the National Cancer 

Institute, U.S.A. The cells were cultured in RPMI- 

1640 (Sigma) medium supplemented with 10% fetal 

calf serum. Generally, cells are separated into singlecell 

suspensions by a gentle pipetting action, then 

counted using trypan-blue exclusion on a 

hemacytometer, After counting, dilutions are made to 

give the appropriate cell densities for inoculation 




onto the microtiter plates. A 100 µL aliquot of 

complete medium is added to cell-free wells. Cells 

from all cell lines are counted, diluted and inoculated 

onto microculture plates. The microtiter plates 

containing the cells are preincubated for 

approximately 24 hours at 37°C to allow stabilization 

prior to addition of drug. After that, for initial 

screening of pure compounds, each agent is routinely 

tested at five 10 fold dilution, starting from a 

maximum concentration of 10 -4 M and immediately 

100 µL aluquots of each dilution are added to the 

appropriate microtiter plates wells. During 

development of these procedures, drug incubation 

time was 4 days at 37°C in an atmosphere of 5% CO2 

and 100% relative humidity. The plates were then 

assayed for cytotoxicity using the microtitration of 3- 

(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium 

bromide (MTT) assay (Sigma,) [11]. Controls that 

contained only cells were included for each sample. 

Cytotoxicity (CD50) was expressed as the 

concentration that reduced the absorbance of treated 

cells by 50% with reference to the control, untreated 

cells. Tamoxifen were used as the standard control. 

Qualitative Antimicrobial Assay 

Eight pathogenic microbials were used to test the 

biological properties of the Schiff bases and their 

complexes at Laboratory of Molecular and Cell 

Biology, Institute of Bioscience, Universiti Putra 

Malaysia. They were Methicillin resistant 

staphylococcus (MRSA), Bacillus subtilis wild type 

(B29), Subtilis mutant (mutant defective DNA repair, 

B28), Pseudomonas aeruginosa (60690), Candida 

albicans (C.A.), Aspergillus ochraceous (398), 

Saccharomyces cerevisiae ( 20341) and Candida 

lypolytica (2075). Antimicrobial activity of each 

sample was qualitatively determined by a modified 

disc diffusion method [12]. A lawn of 

microorganisms was prepared by pipetting and 

evenly spreading inoculum (10 -4 cm 3 , adjusted 

turbidometrically to 10 5 – 10 6 cfu/cm 3 (cfu: colony 

forming units) on to agar set in Petri dishes, using 

Nutrient agar (NA) for the bacteria and potato 

dextrose agar (PDA) for fungi. Whatman No. 1 filter 

paper discs of 6mm diameter were impregnated with 

stock solution of the compound (100mg/cm 3 ) and 

dried under sterile conditions. The dried discs were 

then placed on the previously inoculated agar surface. 

The plates were inverted and incubated for 24 hours 

at 30°C for bacteria and 37°C for fungi. 

Antimicrobial activity was indicated by the presence 

of clear inhibition zones around the discs. 

Commercially available Streptomycin (Sigma) was 

ISBN : 978 – 979 – 19201 – 0 – 0 

used for the antibacterial control while Nystatin 

(Sigma) was used as the antifungal control. 

Quantitative Antimicrobial Assay 

Compounds that showed positive (diameter >15 mm) 

anti-microbial inhibition with the disc diffusion assay 

were subjected to the broth dilution method for the 

quantitative measurement of microbiostatic 

(inhibitory) activity as described previously [13]. The 

lowest concentration that completely inhibited visible 

microbial growth was recorded as the minimum 

inhibitory concentration (MIC, µg/cm 3 ). 

Streptomycin and Nystatin were used as controls 

standard 


Cytotoxic Assay 

All the Schiff bases and complexes were evaluated 

in-vitro using CaOV-3 (Human ovarian cancer cells 

), MDA-MB-231 (Human breast carcinoma cells with 

negative estrogen receptor) and HEP-G2 (Human 

liver carcinoma cells) to see if they had potential use 

as anticancer agents. Measurement for cytotoxicity 

was in CD50, where CD50 refers to “cytotoxic dose at 

50%” i.e. the concentration required to reduce growth 

of cancer cells by 50%. Compounds having CD50 

values of less than 5 µg cm -3 are considered highly 

active and 5-10 µg cm -3 are moderately active. 

Compounds with CD50 from 10-20 µg cm -3 are 

classified as having weak cytotoxic activity while 

those compounds having CD50 values of more than 

20 µg cm -3 are considered as inactive. The results 

show that all screening results against selected cancer 

cells are shown in Table 1. All the Schiff bases and 

complexes were not active against all the cancer cell 

lines tested. 

The cytotoxic potential of the compounds 

containing thiophene is well supported by other 

researchers [14-17]. An earlier study with the related 

compounds [18], SB2ATP, SB3ATP, Co(SB2ATP)2, 

Cu(SB2ATP)2, Cu(SB3ATP)2, Zn(SB2ATP)2 and 

Cd(SB2ATP)2 showed high activity toward human 

breast carcinoma with positive estrogen receptor 

(MCF-7). Unfortunately, comparison with human 

breast carcinoma with positive estrogen receptor 

(MCF-7) was unable to be done as cells were 

unavailable. 

The results showed that the Schiff bases 

synthesized by condensation of SBDTC with furyl 

groups (5-methyl-2-furyldehyde and 2-furyl- 




methylketone) [6] were highly active against CEM- 

SS (Human cell T-lymphoblastic leukemia) with a 

CD50 value of 2.0 mg cm -3 when chelated to Zn(II) 

[Zn(NS)2]. Furthermore, [Cd(NS)2] was moderately 

active with a CD50 value of 4.95 mg cm -3 but none of 

the compounds were found to be active against HT- 

29 (Human colon adenocarcinoma cells). 

Unfortunately, comparison with CEM-SS (Human 

cell T-lymphoblastic leukemia) and HT-29 (Human 

ISBN : 978 – 979 – 19201 – 0 – 0 

colon adenocarcinoma cells) was unable to be done 

as those cells were unavailable also. 

It is clear that small changes in the backbone 

of the structure of a ligand, with benzyl ring, were 

unable to bring about great changes in the ability of 

the complex to act as an anticancer agent against 

different cell lines. However, it is hoped that some 

series of complexes would show activity with cancer 

cell lines that were not tested, i.e MCF-7, CEM-SS 

and HT-29. 

Table 1 Screening test against CaOV-3 (Human Ovarian Cancer cells ), MDA-MB-231 (Human breast carcinoma 

cells with negative estrogen receptor) and HEP-G2 (Human Liver carcinoma cells) 

Antimicrobial Assay 

CD50 (µg/ml) 

Compounds 

MDA- 

CaOV-3 MB-231 HEP-G2 

NS' - - - 

Co(NS')3 - - - 

Ni(NS')2 - - - 

Cu(NS')2. H2O - - - 

Zn(NS')2 - - - 

Cd(NS')2 

Standard 

- - - 

Tamoxifen 1.0 2.3 3.5 

- inactive 

The qualitative results are shown in Table 2. it was 

clearly seen that after chelation, the antimicrobial 

activity decreased for NS’ against B29, where the 

activity was similar. Among all the metal complexes, 

only [Cu(NS’)2.H2O] complexes showed weak 

activities against more than two types of microbes. 

None of the compounds showed any antimicrobial 

activity towards S.T and 60690. Ni(NS’)2 showed 

Table 2 Qualitative antimicrobial assay results a (diameter in mm) 

weak activity against 398. Finally B29 was less 

resistant with NS’ complexes. It can be deduced that 

the presence of a bulky group can enhance the 

activity. The same pattern has also been observed for 

amoebicidal activity of palladium(II) complexes 

derived from thiophene-2-carboxaldehyde 

thiosemicarbazones [26]. However, a series of 

thiophene derived dithiocarbazate Schiff bases and its 

complexes can enhance the antimicrobial activity 

only after chelation with Cu 2+ . 

Bacterial strains Fungal Strains 

Sample MRSA B29 S.Typhimurium 60690 C.A 398 20341 

NS' - 9 

Co(NS')3 - - - - - - - 

Ni(NS')2 - - - - - 6 - 

Cu(NS')2. H2O 10 9 10 9 - - - 

Zn(NS')2 - - - - - - 6 

Cd(NS')2 - - - - - - 8 

Streptomycin 

(antimicrobial 

control) 25 15 17 20 

Nystatin 

(antifungal control) 23 24 28 




ISBN : 978 – 979 – 19201 – 0 – 0 

Methicillin resistant Staphylococcus (MRSA); Bacillus subtilis wild type (B29); S.typhimurium – Salmonella 

typhimurium; Pseudomonas aeruginosa (60690); Candida albicans (C.A); Aspergillus ochraceous (398); 

Saccharomyces cerivisiae (20341) 

a Diameter of 15 mm and above considered active; - inactive 

Conclusion 

The biological activity results showed that the 

thiophene derivatives were not promising undergo 

against the targeted pathogens/cell lines. Small 

changes in the backbone of the structure of a ligand 

(with phenyl ring) was unable to bring about great 

changes in the potential bioactivity of the ligands or 

their complexes. Furthermore, the presence of the 

thiophene ring in the compounds synthesized did not 

show any enhanced biological activity as compared 

to similar compounds with a furyl group. This was in 

contrast to results found for acetylthiophene isomers 

(2-acetylthiophene and 3-acetylthiophene). 


We thank the Department of Chemistry, Universiti 

Putra Malaysia for support and the provision of 

laboratory facilities. Also to Clinical Genetics Unit, 

Department of Human Growth and Development, 

Faculty of Medicine and Health Science and the 

Laboratory of Molecular and Cell Biology, Institute 

of BioSciences, Universiti Putra Malaysia for the 

Biological studies. This work has been carried out 

with the financial support from Ministry of Science 

and Environment, Malaysia, under the Intensification 

of Research in Priority Area (IRPA) program (Grant 

no 09-02-04-0755-EA001) 

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459-465. 

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thiophene-2-carboxaldehyde thiosemicarbazone 

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derivatives and Their cyclooctadiene Ru(II) 

complexes. Bioorganic & Medicinal Chemistry 

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[17] Chaviara, A. T., Cox, P. J., Repana, K. H., 

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Universiti Putra Malaysia, Malaysia. 




Introduction 

ISBN : 978 – 979 – 19201 – 0 – 0 

Selectivity and Cation Exchange Capacity Determination ff Zeolite 

from Fly Ash 

Nungki Puspita Sari, Hamzah Fansuri, Lukman Atmaja 

Chemistry Department, Faculty of Mathematics and Natural Sciences 

Institut Teknologi Sepuluh November (ITS) Surabaya 

Keputih Sukolilo Surabaya, East Java, Indonesia 

Corresponding Author: h.fansuri@chem.its.ac.id 

Abstract 

Cation exchange capacity of Zeolite A, synthesized from fly ash by using a two step process namely 

fusion and then followed by hydrothermal, was investigated by ammonium acetate and barium chloride 

methods. Ammonium acetate method is the common way to measure cation exchange capacity of 

zeolites. However the Barium chloride was reported as having an advantage than the ammonium acetate 

because the exchange process is not an equilibrium reaction since the exchange product is a non water 

soluble salt. The experimental results give quite different exchange capacity. The Barium method found 

that the capacity is 1.15 meq/g while the ammonium method found 3.52 meq/g. The result disparity is 

due to the pore opening of zeolite A which is not large enough to be accessed by large barium ions and 

therefore not all exchangeable cation can be exchanged by the barium ion. The selectivity, acquired 

from the ratio of selectivity coefficient of the cation, of single component system follows the order Ca 2+ 

> K + >NH 4 + > Mg 2+ . Meanwhile, in a multi-component exchanged cation is in the order of Ca 2+ > Mg 2+ 

> NH4 + >K + . It was found that higher valence cations are more selective than the lower one. 

Keyword: cation exchange capacity, fly ash, selectivity, zeolite 

Fly ashes are mainly produced from coal 

combustion. They contains silicates and aluminates, 

which are the main components of zeolite. Many 

zeolites were successfully synthesized from fly ash 

such as zeolite X [1, 2], Na-P1 [3], zeolite A [1], 

zeolit K-H [4], Analcime, Chabazite, Cancrinite, 

Gismodine, and Gmelinite [5]. 

Zeolites have capability to exchange their 

cation which is proportional to Al 3+ concentration in 

their framework. Structure with lower Si/Al ratio has 

higher exchangeable cation. Their framework stability 

increases by the increase of Si/Al ratio. Zeolite A is a 

synthetic zeolite that has high cation exchange 

capacity (CEC) due to its high Si/Al ratio. Cation 

exchange capacity is the most useful nature of 

zeolites. 

García-Sosa and Solache-Ríos [6] reported 

that zeolite A with Si/Al ratio = 1 has theoretical and 

experimental CEC 5,3 and 4,06 meq/g, respectively. 

The authors determined the CEC using ammonium 

acetate method. Lower CEC (3,5 meq/g) of zeolite A 

which was synthesized from fly ash was reported by 

Wang et al. [7]. 

Several experiments have been reported in 

relation to cation selectivity of zeolites. Langella et.al 

[8] found that NH4 + and Pb 2+ selectivities in 

clinoptilolite are better than Cu 2+ , Zn 2+ and Cd 2+ . The 

selectivity order is NH4 + > Pb 2+ > Na + > Cd 2+ > Cu 2+ ≈ 

Zn 2+ . Whereas Inglezakis et.al [9] reported the cation 

selectivity of clinoptilolite at total concentration of 

cation 0,01 N and acidity 2 in both single- and 

multicomponent solution follow the order Pb 2+ > 

Fe 3+ > Cr 3+ ≥ Cu 2+ . On the other hand selectivity in 

single metal solutions where acidity is not adjusted 

follow the order of Pb 2+ >Cr 3+ >Fe 3+ ≈Cu 2+ . When the 

zeolite was analchime, the cation exchange selectivity 

follows the order Pb 2+ > Cu 2+ > Zn 2+ > Ni 2+ [10]. Thus, 

it was shown that different zeolites will have different 

cation exchange selectivity. 

This paper reports the experimental cation 

exchange capacity and cation selectivity toward Ca 2+ , 

Mg 2+ , NH4 + , K + of the zeolites synthesized from fly 

ash. 

Materials And Methods 

Materials 

Chemicals that were used in this experimet are 

BaCl2.2H2O (Merck, pa), aqua DM, CH3COONH4 

(Merck, pa), KCl (Mallincrodt, pa), MgCl2.6H2O 

(pa), CaCl2.2H2O (pa), aquades, NaOH (Merck,pa), 




NaAlO2 (Riedel-de Haën, Al2O3 50-56 %; Na2O 40- 

45%; Fe2O3 maksimum 0,05 %), tecnical ethanol. 

Methods 

The synthesis of Zeolite A 

The zeolite A used was syntesized from fly 

ash according to a method which was reported by 

Sudarno [11]. Firstly, the fly ash was fused with 

NaOH at 2:3 mass ratio of fly ash to NaOH in a 

muffle furnace at 600 o C for 2 hours. Then, the fused 

mass was allowed to cooling down to room 

temperature in a desiccator. When the mass reach 

room temperature, it was dissolved in 127.5 mL of 

water and stirred for 12 hour. Un-dissolved solids 

were separated from the solution by filtration and the 

composition of the filtrate was adjusted so the molar 

ratios of SiO2/Al2O3, Na2O/SiO2, H2O/Na2O becomes 

1.64, 8.09 and 56.51, respectively. The adjusted 

solution then was crystallized in a hydrothermal 

reactor at 100 o C for 12 hours. The crystal products 

were filtered, washed with aqua DM until the pH of 

the filtrate was 10 and then dried at 100 o C for 24 

hours. X-ray diffraction technique was used to 

characterize the product. 

A similar product of zeolite A, which was 

synthesized from TEOS (Tetra Ethyl Ortho Silicate) 

and NaAlO2, was also prepared as a reference. 

Cation Exchange Capacity (CEC) determination 

The CEC of zeolites were determined using 

Barium chloride and Ammonium acetate methods. In 

barium acholired method, half gram (0.50 g) of 

zeolite sample were added into a 5 mL barium 

chloride solution 0,5 N in a conical flask. The mixture 

was shaken for 24 hours. Then, the solution was 

sentrifuged at 1000 rpm for 15 minutes to separate the 

supernatant from the zeolite. Then, 10 mL of barium 

chloride solution 1 N was added to the zeolite and 

shake for another 2 hours. The zeolite was separated 

and washed with 20 mL ethanol 96%. This procedure 

saturated the zeolite with Ba 2+ . The Ba 2+ saturated 

zeolite was then added into 22,5 mL of ammonium 

ISBN : 978 – 979 – 19201 – 0 – 0 

acetate 1 M and shaken for 24 hours. The supernatant 

was separated from the zeolite by centrifugation and 

then analyzed with ICP-AES [12] for Ba 2+ ion 

concentration. In the ammonium acetate procedure, 

the barium chloride was replaced by potassium 

chloride. 

The Cation Exchange Capacity (CEC) was 

determined by calculating the number of equivalents 

of Ba 2+ or K + replaced by ammonium ion (NH4 + ). 

Cation Selectivity Determination 

One and a half gram of zeolite was added to 

a conical flask containing 50 ml of single and mixedmetal 

solutions at total concentration of 1 N and 

shook for 24 hours. The following solutions were 

used in cation selectivity determination: 

(a) Solutions of single cation (KCl, CaCl2, MgCl2, 

NH4CH3COO) where the concentration of each 

cation was 1 N. 

(b) Four-component solution where the 

concentration of each cation was 0.25 N. 

Liquid samples were taken from the continuously 

shakes mixture at 1, 3, 6, 12, 24 hours where total 

volume of the samples were not exceeding 4% of the 

total volume of initial solution. The concentration of 

metal cations in the liquid samples was measured 

with ICP AES and ammonium was determined 

spectrophotometrically using Nessler reagent. 


Cation Exchange Capacity (CEC) 

CEC is a calculated value that is an estimate 

of materials ability to attract, retain, and exchange 

cation elements. In this experiment, CEC of zeolite 

products were determined by Barium Chloride 

method [12]. A few modifications were used in this 

method. Barium that enter framework were 

exchanged with ammonium. Ammonium acetate 

method is used for comparator of barium chloride 

method. The CEC was calculated by Equation (3.1). 

Table 1 shows the CEC values of zeolite A. 

− 1 V ( L) 

100g 

CEC( 

meq / 100g) 

= ( mgL cation) 

× × 

(3.1) 

MECation zeolite( 

g) 

Table 1 Cation Exchange Capacity of Zeolite from Fly Ash and TEOS 

Sample Zeolite 

CEC 

(meq/ 100 g) a 

CEC 

(meq/ 100 g) b 

CEC calculated 

(meq/100 g) c 

Zeolite from TEOS 189,72 320,94 

530 

Zeolit from fly ash 115,83 352,27 

a. barium chlorida method, b. ammonium acetate method, c. García-Sosa and Solache-Ríos (2001) 




Table 1 shows that CEC of zeolite from 

TEOS and fly ash using ammonium acetate method is 

higher than using barium chloride method. It 

happened because particle size of potassium ion is 

smaller (r(K + ) = 133 pm) than barium (r(Ba 2+ ) = 143 

pm) so the potassium ion can enter the cation site in 

the pore the zeolite easier than the barium ion. 

The Table also shows that the CEC of zeolite 

from TEOS is higher than those from fly ash while it 

is lower for the zeolites synthesized from fly ash. 

Zeolite from TEOS contains higher purity zeolite A 

Figure 1 The X-ray diffractograms of zeolite A from: a) fly ash and b) TEOS 

The main impurities in the zeolite A 

synthesized from fly ash are amorphous phases. 

The phases are clearly shown as the baseline of 

zeolite A from fly ash is more curvature than those 

ISBN : 978 – 979 – 19201 – 0 – 0 

while those from fly ash has lower zeolite A purity 

where the impurity might be other zeolites with 

smaller apertures to the site of exchangeable cation. 

Thus, only smaller cations have higher probability to 

enter the sites and replace the cations. The difference 

in zeolite A purity can be seen from the diffractogram 

of the zeolites in Figure 1. 

(a) 

(b) 

JCPDS-ICDD 

No PDF 39-0222 

from TEOS. These phases may contain very fine 

crystal of other types of zeolites which can 

exchange their cations and thus added to the total 

exchangeable cations in the zeolite product. 




The difference in the CEC might also been 

caused by the use of TEOS as a source material in 

the zeolite synthesis. The hydrolysis of TEOS 

which was occurred during the hydrothermal 

process produced ethanol that may be trapped in the 

cation exchange sites so that exchange cations 

cannot enter the site. 

Table 2 CEC Comparison using Ammonium Acetate and BaCl2 Method [12-14] 

KOH 

Reaction Condition 

Initial 

Hydrothermal 

time 

Initial 

Hydrothermal 

temperature 

CEC (a) 

(mek/100 g) 

ISBN : 978 – 979 – 19201 – 0 – 0 

The same results were also found when the 

two CEC determination methods were used for 

other zeolites from fly ash, prepared by Hidayati 

[13], Nafiah [14] and Muasyaroh [15]. All zeolite 

synthesized from fly ash shows higher CEC value 

when determined using ammonium acetate than 

using barium chloride method as shown in Table 2. 

CEC (b) 

(mek/100 g) 

3 M 1 Hours 180C 325,81 6,80 K-F 

Mineral Phases 

3 M 3,5 Hours 180C 309,11 9,40 M,Q, K-F,K-P 

3 M 5 Hours 180C 397,80 7,20 K-F 

3 M 3,5 Hours 100C 230,39 6,04 M,Q, K-F, K-G,K-P 

3 M 3,5 Hours 120C 250,94 5,52 M,Q, K-F, K-G,K-P 

1 M 3,5 Hours 180C 261,00 6,95 K-M, M 

5 M 3,5 Hours 180C 134,10 4,03 K-D 

(a) Ammonium acetate method; (b) BaCl2 method 

M: Mullite; Q: Quartz; K-F: zeolite K-F (LTF) ;K-P: K-Phillipsite; K-G: K- Chabasite; K-M: zeolite K-M; K-D: 

Kaliophilite 

Cation Selectivity 

Cation exchange reaction in zeolites can 

be written as Equation 3.2. Initially the sodium ions 

are in the cation site of the zeolites. When they are 

replaced by the exchange cation in a solution, the 

sodium ion will be exiled from the zeolite and 

available in the exchange solution. Therefore, the 

equilibrium state of the exchange reaction which 

shows the degree of exchange can be studied from 

the concentration of sodium ion in the exchange 

solution at the equilibrium state. Equation 3.3 and 

3.4 are examples of the reaction using cations with 

different oxidation states. They show that cation 

with higher oxidation number can exchange more 

sodium ion than the lower ones. 

(nNa)-Zeolite + A n+ = A-zeolite + nNa + ................................................... (3.2) 

Na-zeolite + KCl = K-zeolite + NaCl ................................................. (3.3) 

(2Na)-zeolite + CaCl2 = Ca-Zeolite + 2NaCl ............................................. (3.4) 

Figure 2 shows sodium extracted by Mg 2+ , 

Ca 2+ , K + , and NH4 + at the equilibrium state. The 

extraction depends on the selectivity of the 

exchange reaction toward the incoming cations and 

hence it means that the exchange selectivity follows 

the order Mg 2+ >NH4 + >K + ≈Ca 2+ . 

Interesting result is shown by Mg 2+ 

because the cation theoretically has higher 

capability to exchange the sodium ion than NH4 + 

and K + since it has higher oxidation number. By 

virtue of the valence, magnesium should be capable 

to exchange with sodium in the same manner with 

calcium. Hence it is concluded that it may be 

precipitated during the exchange reaction since the 

pH of the zeolite is high. As aforementioned, the 

zeolite was washed until the pH was 10. 




Sodium extracted (meq/L) 

180 

170 

160 

150 

140 

130 

0 5 10 15 20 25 

Time (hours) 

K + 

Ca 2+ 

+ 

NH4 Mg 2+ 

Figure 2 Sodium extracted in single component 

system 

Under alkali condition, magnesium 

precipitates to form Mg(OH)2. In comparison to 

calcium, the Mg(OH2) has smaller Ksp (7,1× 10 -12 ) 

than Ca(OH)2 (Ksp= 6,5× 10 -6 ). Therefore, 

although the condition of exchange is the same, 

Mg 2+ precipitates easier than Ca 2+ . 

Numerical value of cation selectivity dan 

be calculated using Equation 3.5. Table 3 shows the 

calculated selectivity based on experimental 

exchange data. 

[ ] [ ] 

A 

Z A ZC 

RC A 

K C / A = Z Z 

C RA 

(3.5) 

[ ] [ ] C 

Table 3 Selectivity coefficient in single component 

system 

KK/Na KMg/Na KNH4/Na KCa/Na 

0.77 0.30 0.55 15.68 

The cation exchange raction in multicomponent 

system gives better insight into the real 

cation selectivity where each cation compete with 

others in the same system. As in a single 

component system, the selectivity in multicomponent 

system was investigated based on the 

amount of extracted sodium from the zeolite as 

shown in Figure 3.3. The Figure shows that the 

equilibrium occurs at 3 hours 

Table 4 shows the selectivity coefficients 

of all cations used in this experiment. The 

selectivity follows the order Ca 2+ > Mg 2+ > 

NH4 + >K + . Hence the order follows the rule that the 

ion exchange prefer higher valence cation. 

Therefore, calcium and magnesium are more 

selective than ammonium and potassium as 

mentioned by Helferich [16]. 

ISBN : 978 – 979 – 19201 – 0 – 0 

Table 4 Selectivity Coefficient in multi-component 

system 

Sodium extracted (meq/L) 

210 

200 

190 

180 

170 

KK/Na KMg/Na KNH4/Na KCa/Na 

1.38 3.42 3.04 8.61 

0 5 10 15 20 25 

waktu (jam) 

Figure 3 Sodium extracted on multicomponent 

system 

Conclusions 

1. The CEC of zeolite from fly ash is 115,83 

meq/100g using barium chloride method and 

352,27 meq/100g using ammonium acetate 

method. The difference is due to different in 

cation size of B 2+ in barium method and K + 

used in ammonium acetate method. 

2. Cation selectivity in single component system is 

following the order Ca 2+ >K + > Mg 2+ >NH4 + . 

Magnesium is the lowest because the zeolite is 

alkaline that cause the formation of 

magnesium hydroxide precipitate. 

3. Cation selectivity in multi-component system is 

following the order Ca 2+ > Mg 2+ >K + > NH4 + . 

Cations with higher oxidation state have higher 

selectivity than the lower ones. 

Acknowledgment 

The authors acknowledge The Ministry of 

Research and Technology for research grant under 

the scheme of Insentif Riset Terapan in 2007. 




References 

1. Ojha, K., Pradhan, N.C. and Samanta, A.N. 

(2004), ”Zeolite from fly ash: synthesis 

and characterization”, Mater Sci B, Vol 

27, No 6, p. 555–64. 

2. Chang, H.L. and Shih, W.H. (2000), “Synthesis 

of Zeolites A and X from Fly Ashes and 

Their Ion-Exchange Behavior with Cobalt 

Ions”, Ind. Eng. Chem. Res., Vol 39, p. 

4185-4191 

3. Woolard, C.D., Petrus, K. and van der Horst, M. 

(2000), “The use of a modified fly ash as 

an adsorbent for lead”, Water SA , Vol 26 

(4), p. 531–536. 

4. Mimura, H.K, Yokota, K., Akiba, Y. and 

Onodera, Y. (2001), “Alkali hydrothermal 

synthesis of zeolites from coal fly ash and 

their uptake properties of cesium ion”, J 

Nucl Sci Technol; Vol 38(9), p. 766–772. 

5. Elliot, A.D and Zhang, D.K. (2005), “Controlled 

Release Zeolite Fertilizers: A Value Added 

Product Produced from Fly Ash”, 

www.flyash.info/2005, Perth. 

6. García-Sosa. I and Solache-Ríos. M. (2001), 

“Cation-exchange capacities of zeolites A, 

X, Y, ZSM-5 and Mexican erionite 

compared with the retention of cobalt and 

cadmium”, Journal of Radioanalytical and 

Nuclear Chemistry, Vol. 250, No. 1, p. 

205–206. 

7. Wang, C.F., Li, J.S., Wang, L.J. and Sun, X.Y. 

(2008), "Influences of NaOH 

Concentrations on Synthesis of Pure-Form 

Zeolite A from Fly Ash using Two-Stage 

Method", Journal of Hazardous Materials, 

Vol. 155, p. 58-64. 

8. Langella, A., Pansini, M., Cappelletti, P., de 

Gennaro, B. and de Gennaro, .M. (2000), 

”NH4 + , Cu 2+ , Zn 2+ , Cd 2+ and Pb 2+ exchange 

for Na + in sedimentary clinoptilolite, North 

Sardinia, Italy”, Microporous and 

Mesoporous Materials, Vol. 37, p. 337– 

343. 

ISBN : 978 – 979 – 19201 – 0 – 0 

9. Inglezakis, V.J, Loizidou, M.D. and 

Grigoropoulou, H.P. (2003), “Ion 

exchange of Pb 2+ , Cu 2+ , Fe 3+ , and Cr 3+ on 

natural clinoptilolite: selectivity 

determination and influence of acidity on 

metal uptake”, Journal of Colloid and 

Interface science, Vol. 261, p. 49-54. 

10. Tangkawanit, S., Rangsriwatananon, K. and 

Dyer, A. (2005), ”Ion exchange of Cu 2+ , 

Ni 2+ , Pb 2+ and Zn 2+ in analcime (ANA) 

synthesized from Thai perlite”, 

Microporous and Mesoporous Materials, 

Vol. 79, p. 171 –175. 

11. Sudarno (2008), Pengaruh Komposisi NaOH 

Pada Konversi Abu Layang Batubara 

Paiton Menjadi Zeolit A, Skripsi Sarjana 

Kimia, ITS, Surabaya. 

12. Gillman, G.P. (1979), “A Proposed Method for 

the Measurement of Exchange Properties 

of Highly Weathered Soils”, Aust. J. Soil 

Res., Vol. 17, p. 129-139. 

13. Hidayati, R.E, (2008), Sintesis zeolit dari abu 

layang batubara: kajian pengaruh waktu 

hidrotermal awal terhadap pembentukan 

zeolit, Tesis Magister Kimia, ITS, 

Surabaya. 

14. Nafiah, C. (2008), Pengaruh Komposisi KOH 

pada Sintesis Zeollit dari Abu Layang 

Batubara, Tesis Magister Kimia, ITS, 

Surabaya. 

15. Muasyaroh, D. (2008), Pengaruh Suhu 

Hidrotermal Awal terhadap Pembentukan 

Zeolit dari abu Layang Batubara, Tesis 

Magister Kimia, ITS, Surabaya. 

16. Helferich, F. (1962), Ion Exchange, McGraw- 

Hill Book Company, Inc., New York. 




ISBN : 978 – 979 – 19201 – 0 – 0 

Relationship Pattern Between SiO2/Na2O Ratio 

and Microstructure of Fly Ash Based Geopolymer 

Mochamad Zakki Fahmi, Lukman Atmaja*, Hamzah Fansuri 

MasterDegree StudyProgram, Chemistry Departemant, Faculty of Mathematics and Natural Sciences Sepuluh 

Nopember Institute of Technology Surabaya, Sukolilo – Surabaya 60111 

* Corresponding author 

Email address : lukman.at@gmail.com 

Introduction 

Abstract 

Converting fly ash to geopolymers is one of the most important scheme to reduce its dengerous effect to 

environment. The initial molar contents of SiO2, Na 2O and Al 2O 3 of geopolymer systems gave some 

influence to geopolymer matrices. This research studied that the Na 2O gave effect to physical properties 

of Cilacap and Asam-asam fly ash-based geopolymers, which increase SiO2/Na 2O ratio made positive 

effect to compressive strength and caused the microstructure of geopolymers more compact and 

homogen. Although NaOH (main source for variation SiO2/Na 2O ratio in this research) is needed for 

disolve fly ash particles, high content of sodium cation can discontinu geopolymersation process. The 

effect of sodium cation has been investigated by quantiative analysis FTIR as well as their 

microstructure by SEM 

Key word : fly ash, geopolymer, microstructur, SiO2/Na 2O ratio 

Geopolymers , a kind of inorganic 

polymer, are alumnosilicate materials which exhibit 

excellent physical and chemical properties. Since 

1979, when davidovits first introduced the term 

“geopolymers” to designate a new class of three 

dimensional alumino-silicate materials (Davidovits, 

1979), the interest toward the implementation of 

new technologies for manufacture of great 

potentialities geopolymers based products has 

steadily grown. Geopolymers also exihibit a diverse 

range of potential applications, including precast 

structures and non-structural elements, concrete 

pavements and products, containment and 

immobilisation of toxic, hazardous and radioactive 

wastes, advanced structural tooling and refractory 

ceramics, and fire resistant composites used in 

buildings, aeroplanes, shipbuilding, race cars and 

nuclear power industry (Komnitsas and Zaharaki, 

2007). 

The synthesis of geopolymers takes place 

by polycondensation and can start from a variety of 

raw materials. Davidovits (1994, 1995), Schmücker 

and Mackenzie (2005), Xu et al. (2001,2002), Van 

Jaarsveld and van Deventer (1999,2003) and 

Duxson et al. (2005) use metakaolinite to obtain 

geopolymers by reaction with alkaline (Na or K) 

solution. Meanwhile, Swanepoel and Strydom 

(2002), Fernández-Jiménez and Palomo 

(2003,2005), Andini et al.(2007), Álvarez-ayuso et 

al (2007) and Criado (2007) have proven that 

geopolymers could be obtained starting material 

from many raw alumino-silicates, including coal fly 

ash as starting material. Also in this case the 

polycondensation takes place by reaction with 

alkaline solution. 

In material contruction, fly ash based 

geopolymers is prefered over Portland cement 

because can reduce the emission of greenhouse 

gases into the atmosphere (essentially CO2 and NOx; 

the manufacture of one tonne of cement generates 

approximately one tonne of CO2) (Criado, 2007). 

Beside that, Rangan et al. (2005) was estimated that 

production of fly ash based geopolymer concrete 

may be 10-30% cheaper than that of Portland 

cement concrete. 

Fly ash based geopolymers products and its 

process depend on many aspects, the SiO2/Al2O3, 

SiO2/Na2O and H2O/ Na2O ratio was commonly 

chemical aspects to make geopolymers materials 

with excellent physical and chemical properties. 

Álvarez-ayuso (2007), Alfiyah (2008), Muslihah 

(2008) and Mulyanto (2008) explain that the 

SiO2/Na2O ratio in alkaline solution affects the 

degree of polymerisation of the dissolved species. 

The increase of NaOH contain lead to increasing the 

dissolution of alumino-silicate materials and, 




consequently, geopolymers product will have 

excellent mechanical strength. Fernández-Jiménez 

and Palomo (2005), Lodeiro dkk.(2006) and De 

Silva dkk.(2007) have shown that increasing 

SiO2/Na2O ratio affects the production of 

geopolimer because it increases porosity and 

heterogenity. 

The SiO2/Al2O3, SiO2/Na2O and H2O/ 

Na2O ratio and other chemical aspects can also 

influence other physical properties, such as 

microstructure and compressive strength. The 

present paper is studied the microstructures of fly 

ash based geopolymers derived from the activation 

of fly ash by concentrated alkaline solution (made 

from mixed sodium hydroxide and sodium silicate). 

Variation effect of SiO2/Na2O ratio is expected to 

show different geopolymer morphology and could 

be related to its compressive strength. 


Material 

Class C (according to ASTM C 618-03) fly 

ash from the Cilacap steam power plant and class F 

Table 1.Chemical analysis of the original fly ash in precentage 

Cilacap 

fly ash 

(%) 

Asamasam 

fly ash 

(%) 

ISBN : 978 – 979 – 19201 – 0 – 0 

fly ash from the Asam-asam steam power plant in 

Indonesia were used in the present study. The ashs 

chemical composition are given in table 1. 

The ash activated with a series of alkaline 

solution that consist of 98% NaOH pellet supplied 

by Merck and sodium silicate using following 

composition : 37.99% Na2O, 19.16% SiO2 and 

28.07% H2O. H2O that use in the present study was 

destilated water. Composition of the systems studied 

is shown in table 2. Sodium hidroxsida content in 

the solution was varied to have different SiO2/Na2O 

ratio. 

Method 

The properties of geopolymer matrices 

normally depend on the consistency of geopolymer 

materials and the consistency itself is influenced by 

the amount of enhanced water. Therefore, to make 

consistency factor can be disregarded, all 

geopolymer reactant should have similar 

consistency. In this study, method for consistency 

test was adopted from Cindaprasirt (2006). With 

same concistency, Solid/Liquid ratio is constant for 

whole geopolymer reactant. 

SiO2 Al2O3 CaO Fe2O3 K2O MgO Na2O P2O5 SO3 TiO2 MnO BaO SrO LOI Total 

31.5 12.4 21.4 22.5 0.75 7.87 0.27 0.12 1.06 0.76 0.27 0.24 0.09 0.49 99.72 

43.7 21 4.85 22.5 0.88 2.55 0.44 0.07 0.58 0.95 0.44 0.21 0.06 1.66 99.89 

LOI = loss on ignition 

Table 1.Composition of geopolymer systems were studied 

Sample * Fly ash 

(g) 

Na2SiO3 

(g) 

NaOH(g) H2O (g) 

As 1 40,38 10 20,96 10,37 

As 1,5 40,38 10 12,26 9,13 

As 2 40,38 10 7,92 8,46 

As 2,5 40,38 10 5,31 8,13 

As 3 40,38 10 3,57 7,88 

Ci 1 35,39 10 12,42 9,38 

Ci 1,5 35,39 10 6,60 8,38 

Ci 2 35,39 10 3,40 7,97 

Ci 2,5 35,39 10 1,95 7,64 

Ci 3 35,39 10 0,70 7,47 

* 

As refers to Asam-asam and Ci refers to Cilacap 




The water content of geopolymers system 

is the amount of water added to the mixture of fly 

ash, NaOH and Na2SiO3, so that, the paste has a 

flow rate of 33 seconds when the paste was 

inclinated at 6,13°. 

The pastes were made by mixing the fly 

ash with alkaline solution, then shaped in cylindrical 

container (1.5 cm and 3 cm diameter and long, 

respectively) and cured in an oven at 60°C for 24 

hours. Geopolymer pellets were then kept in room 

temperature for different curing times (7, 14, 21 and 

28). Mechanical test using universal testing machine 

and morphology analysis using scanning electron 

microscopy (SEM), which conducted with energy 

dispersive X-ray (EDX), were conducted to pellets 

geopolymer in each curing time. The highest and the 

lowest compressive strength of pellets from Cilacap 

(Ci) and Asam-asam (As) were analyzed with 

fourier transform infrared (FTIR) for 

geopolymerisation paste study 


Compressive Strength Analysis 

Compressive strength analysis was carried 

out to investigation in which composition system 

that having excellent performaces. Compressive 

strength results of varying geopolymer pellets were 

shown in Fig.1 and Fig.2 for Cilacap and Asamasam 

geopolymers, respectively. 

Compressive strength(MPa) 

90 

80 

70 

60 

50 

40 

30 

20 

10 

7 day 

14 day 

21 day 

28 day 

0 

0.5 1.0 1.5 2.0 2.5 3.0 

Rasio SiO 2 /Na 2 O 

Figure. 1. Compressive strength result for Cilacap 

geopolymers 

Both Cilacap and Asam-asam geoplymers 

show that the compressive strengths result increase 

Compressive strength (MPa) 

ISBN : 978 – 979 – 19201 – 0 – 0 

with the increase of curing times, facts, this is 

indicated that geopolymerisation process still 

happens during curing time and gives positive effect 

to the compressive strengths. 

Fig. 1. show that the increase on 

SiO2/Na2O ratio for Cilacap geopolymers will 

increase its comperssive strength and reach a max at 

SiO2/Na2O ratio = 3, ie. 81,53 MPa. Fig. 2 was 

Shown that the increase on SiO2/Na2O ratio not 

always increace the compressive strength. In Fig 2., 

the highest compressive strength is owned by 

geopolymers with SiO2/Na2O ratio about 2,5 (40.48 

MPa). Panias et al.(2006) explained that the 

increased sodium hidroxide (NaOH) concentration 

of the aqueous phase of geopolymeric system cause 

positive, as well as negative effects on the 

mechanical properties of the geopolymeric 

materials. In low concentration, NaOH is used to 

dissolve Si and Al species from fly ash particles that 

produce component for geopolymerisation process. 

Whereas in high concentration, sodium cation, 

which are normally presented at high concentrations 

in the geopolymeric systems, are specifically 

adsorbed ions on the surface of fly ash particles 

changing the surface speciation (silanol and 

aluminol). The sodium cation adsorption make 

chemical bonding between the insoluble solid 

particle and the geopolymeric framework takes 

place in the final stage of geopolymeric process. 

Thus, the resulted geopolymeric materials have low 

low mechanical strength. 

40 

35 

30 

25 

20 

15 

10 

5 

7 day 

14 day 

21 day 

28 day 

0 

0.5 1.0 1.5 2.0 2.5 3.0 

Rasio SiO 2 /Na 2 O 

Fig. 2. Compressive strength result for Asamasam 

geopolymers 

Comparing the compressive strengths 

between Cilacap and Asam-asam geopolymers, it 

can be seen thatt compressive strength from Cilacap 

geopolymers are normally higher than Asam-asam 




geopolymers. This fact is in line with previous 

reportthat the CaO content of fly ash can give 

positive effect to geopolymer products, cause Ca + 

cation will form amorphously structured Ca-Al-Si 

gel in geopolymeric process (Komnitsas and 

Zaharaki, 2007). 

The Setting time in Asam-asam 

geopolymers are longer than that of Cilacap 

geopolymers. It’s also should be reportedthat a 

pellets of Asam-asam geopolymers with SiO2/Na2O 

ratio about 1 at 7 day can not be analyzed because 

the result was too small and undetected. In general, 

compressive strength related to SiO2/Al2O3 ratio in 

Asam-asam geopolymers was higher than that of 

Cilacap geopolymers and this fact plays an 

important to the setting time of geopolymeric 

process (De Silva, 2007). 

Morphology Analysis 

Morphology analysis of Cilacap and 

Asam-asam geopolymers was shown at Fig. 3. it is 

clear that the increase of SiO2/Na2O ratio would 

. 

ISBN : 978 – 979 – 19201 – 0 – 0 

decrease heterogenous surface phase and increase 

compact region in its morphology. This region lies 

where dissolution of fly ash particle and the 

geopolymeric process perfectly take place. 

The figures. also show that at low 

SiO2/Na2O ratio most fly ash particles had been 

dissolved, but in high SiO2/Na2O ratio many fly ash 

particles apparently unreacted. This phenomenon 

could be due to low NaOH content at SiO2/Na2O 

ratio acting as dissolveing agent of fly ash particle . 

Beside unreacted ash, many internal crack 

was also found in high SiO2/Na2O ratio. Internal 

cracks were arising when the shorten setting time 

geopolymers loose waters at curing temperature of 

geopolymer pellets. Beside that, Na2SiO3 content 

have potential to rise internal cracks. Hermanus and 

Lapu’ (2001) have shown that Na2SiO3 activated 

geopolymers giver more crack than NaOH activated 

geopolymer. In present study, Na2SiO3 content in 

every geopolymer systems is constant but NaOH 

content is varied. Thus, morphology effect of 

Na2SiO3 content in high SiO2/Na2O ratio more 

apparent than in low SiO2/Na2O ratio 




Cilacap 

Ci 1 : SiO/Na2O 

Ci 1,5 : SiO/Na2O 

Ci 2,5 : SiO/Na2O = 

Asam-asam 

As 1 : SiO/Na2O = 

As 1,5 : SiO/Na2O = 

Ci 2 : SiO/Na2O = A s 2 : SiO/Na2O = 

As 2,5 : SiO/Na2O = 

Ci 3 : SiO/Na2O = As 3 : SiO/Na2O = 

ISBN : 978 – 979 – 19201 – 0 – 0 

Fig. 3 SEM micrograph of Cilacap (Ci) and Asam-asam (As) geopolymers at SiO2/Na2O ratio about 1-3. 




(a) (b 

(c) (d 

Fig. 4. Zeolite phase at As 1 (a), As 1,5 (b), Ci 2 (c) 

and Ci 3(d) 

( 

( 

Fig. 5. SEM micrograph and square EDX analysis of As 1 (a) and Ci 

ISBN : 978 – 979 – 19201 – 0 – 0 




The Effect of sodium cation on 

geopolymerisation process was shown at SEM-EDX 

of As 1 and Ci 1 geopolimer (Fig. 5). In line with 

previous explanation by Panias et al.(2006), square 

EDX graphic show that sodium cation cause 

ungeopolymerized region with uncompact and high 

heterogenicity. In the same picture, Al element that 

need to geopolimerisation was undetected. 

FTIR Analysis 

Fig. 6. shows the infrared spectroscopy 

results for Cilacap fly ash from previous study 

Transmitance (%) 

The band at 995 cm -1 (a) in Cilacap original ash is 

associated with T-O (T=Si,Al) asymmetric 

stretching vibrations. The intensity at 457 cm -1 (d) is 

associated in all cases with T-O bending vibrations. 

The band appering at 780-790 cm -1 (b) corresponds 

to the quartz present in the original fly ash. Finally, 

the band at 547 cm -1 (c) corresponds to the mullite 

present in the ash. After alkaline activated, many 

signal appearing at 1093 cm -1 (e) and 996 cm -1 (g) 

were attributed, respectively, to the vitreous phase 

of the quartz and unreacted phase; while the new 

component appearing at around 1025 cm -1 (see Fig. 

7). Criado (2007) was shown that peaks around 

1025-1006 cm -1 indicate the sodium alumino-silicate 

gel as result of activation. 

Investigation of sodium cation to 

geopolymer product can be seen on Fig. 8. in which 

ISBN : 978 – 979 – 19201 – 0 – 0 

(Tolah, 2008) and the reaction products after 

activation (Ci 3). Original ash consisted mostly in a 

vitreous phase comprising SiO2 and Al2O3. The 

presence of quartz in the fly ash rise the IR spectrum 

to a series of bands located at 1150, 1084, 796-778, 

697, 668, 522 and 460 cm -1 . The presence of mullite 

is responsible for series of band at around 1180- 

1130 cm -1 and 560-550 cm -1 . Thus, the bands 

generated by quartz and mullite of the ash show 

overlap in wavenumber between 1200 and 900 cm -1 ( 

Criado et al., 2007). 


a 

e 

f 

g 

4000 3500 3000 2500 2000 1500 1000 500 

Wavenumber (cm -1 ) 

Ci 3 

Cilacap Fly ash 

b 

c d 

Fig. 6. FTIR spectra of Cilacap fly ash and Cilacap geopolymer (Ci 3 ) 

spectra shown quantitative FTIR analysis of Cilacap 

geopolimer at SiO2/Na2O 1 and 3 is shown. 

Furthermore, the lower peak at 3500 cm -1 and the 

higher peak at 966 cm -1 of Ci 1 than Ci 3 

geopolymer indicate to a lot of silanol content (Si- 

OH that give peak 3500 cm -1 (h)and weak peak at 

882 cm -1 (j)) in Ci 3. The band at region 980-960 cm - 

1 , which was investigated by Lee and Deventer 

(2007), indicate Si-O - stretching vibration that 

bonding with alkaline (Na + or K + ). Thus, higher 

peak of Ci 1 geopolymer at 966 cm - 1(i) shown Si- 

ONa stretching as result higher Na2O. Si-ONa 

species gave bad effect, may discontinuing, for 

geopolymerisation prosess. This is make more 

heterogenicity of geopolymer and, consequently 

lower compressive strength.



Transmitance (%) 

e 

f 

1200 1150 1100 1050 1000 950 900 850 

g 


ISBN : 978 – 979 – 19201 – 0 – 0 

Fig. 7 FTIR Spectra of Cilacap geopolymers at wavenumber range 850 -1200 cm -1 

k 

l 

400 600 800 1000 1200 1400 


As 2.5 

Asam-asam fly ash 

Fig. 9 . FTIR spectra of Asam-asam fly ash and Asam-asam geopolymer (2.5) 

Asam-asam fly ash and geopolymer spectra 

can be seen at Fig.9. Asam-asam fly ash shown that 

wide peak in region 1400-827 cm -1 indicate 

overlapping peaks which generated by quartz, 

mullite and vitreous phase of fly ash. The weak 

peaks at 790 cm -1 (l) and 461 cm -1 (k) were indicate, 

respectively, T-O stretching of mullite and quartz 

(Panias et al.,2006). Fig.10. shows same 

phenomenon with Fig.8, where As 1 spectra have 

lower peak at 3500 cm -1 (m) and higher peak at 980 

cm -1 (n) than As 2,5 spectra. In this quantitative 

analysis of As 1 and As 2,5 were choosen as, 

respectively, the lowest and the highest 

compressive strength Asam-asam geopolymers, 

respectively. 




Conclusions 

Transmitance (cm -1 ) 

30 

25 

20 

15 

10 

5 

0 

n 

0 500 1000 3000 3500 4000 4500 5000 5500 

m 


ISBN : 978 – 979 – 19201 – 0 – 0 

As 1 

As 2.5 

Fig. 8 Quantitative analysis of FTIR to Asam-asam geopolymer at SiO2/Na2O 1 and 2.5. 

Following conclusions can be made from 

this study. 

1. The initial molar constants of Na2O, SiO2 and 

Al2O3 were given influence for geopolymers 

product. 

2. The Na2O content of geopolymer plays a key 

part in dissolving fly ash particle, but in 

inhigher content, it affects the compressive 

strength and its microstructure. 

3. Increase in SiO2/Na2O ratio for geopolymers 

system, relatively, will increase compressive 

strength and make geopolymer microstructure 

more compact and homogen. 

4. Sodium cation, at high content, can influence 

geopolymer process as detected by FTIR 

quantitative analysis. 


the authors thank to Directorate of high 

education republic of Indonesia for financial support 

HIBAH PASCASARJANA Program. 

Reference 

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Semen Gresik Ltd. Fly Ash-Based Geopolimer, 

Chemistry department Faculty of Mathematics 

and Natural Sciences Sepuluh Nopember Institut 

of Technology, Surabaya. 

Álvarez-ayuso, E., Querol, X., Plana, F., Vázquez, 

E. dan Barra, M., 2007, Enviromental, Physical, 

and structural characterization of Geopolymer 

Matrixes Synthesisd from coal (co)combustion 

fly ashes, Journal of Hazardous Material 154, 

175-183. 

Andini, S., Cioffi, R., Montagnaro, F. dan Santoro, 

L.,2007, Coal Fly Ash as Raw Mmaterial for 

the Manufacture of Geopolymer-based 

Products, Waste Management 28, 416-423. 

Criado, M., Fernández-Jiménez, A. dan Palomo, A., 

2007, Alkali Activation of Flyash: Effect Study 

of the SiO2/Na2O Ratio (FTIR study part I), 

Microporous and Mesoporous Materials 106, 

180-191. 

Davidovits, J., 1979, SPE PATEC ’79, Society of 

Plastic Engineering, Brookfield Center, USA. 

Davidovits, J., 1994, Gepolymers: Man-Made Rock 

Geosynthesis and the Resulting Development 

of Very Early High Strength Cement, 

Journals of Materials and Education 16, 91- 

137. 

Davidovits, J., 2005, Geopolymer Chemistry and 

Sustainable Development. the Poly(Sialate) 

Terminology: a very useful and simple model 

for the promote and understanding of 

greenchemistry, Proceeding of the World 




Congress Geopolymer, Saint Quentin, France, 

28 june-1 july, 111-121. 

De Silva, P., Sagoe-Crenstil, K. dan Sirivivatnanon, 

V., 2007, Kinetics of Geopolymerization: role 

of Al2O3 and SiO2, Cement and Concrete 

Research 37, 512-518. 

Duxson, P., Provis, J.L., Lukey, G.C., Kriven, M.W. 

dan van Deventer, J.S.J., 2005, Microstructural 

Characterisation of Metakaolin-Based 

Geopolymer. Ceramic Transactions 165, 71-85. 

Hermanus, P.A.Y., and lapu’, A.S., 2001, Behaviour 

of Bottom Ash for Aspalt Concrete Component, 

department of Civil Engineeing Christian Petra 

University, Surabaya. 

Fernández-Jiménez, A.M. dan Palomo, A., 2003, 

Characterisation of Fly Ash : potensial 

reactivityas alkaline cements, Fuel 82, 2259- 

2264. 

Fernández-Jiménez, A.M. dan Palomo, A., 2005, 

Composition and Microstructure of Alkali 

Activated Fly Ash Binder : effect of the 

activator, Cement and Concrete Research 35, 

1984-1992. 

Komnitsas, K. dan Zaharaki, D., 2007, 

Geopolymerisation: a review and prospect for 

the minerals industry, Minerals Engineering 20, 

1261-1277. 

Lee, W.K.W. dan van Deventer, J.S.J., 2007, 

Chemical Interactions between Siliceous 

Aggregatesan and Low-Ca Alkali-activated 

Cemant, Cement and Concrete Research 37, 

844-855. 

Lodeiro, G., Palomo, A. dan Fernández-Jiménez, A., 

2006, Alkali-Aggregat Reaction in Activated 

Fly Ash Systems, Cement and Concrete 

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Mulyanto, H., 2008, Mixed Geopolymer from Semen 

Gresik Ltd., Cilacap Power Plant and Asamasam 

Power Plant Fly Ash, Chemistry 

department Faculty of Mathematics and Natural 

Sciences Sepuluh Nopember Institut of 

Technology, Surabaya. 

Muslihah, 2008, Synthesis and Characterization of 

Mixed Geopolymers from Semen Gresik Ltd. and 

Asam-asam Power Plant Fly Ash, Chemistry 

department Faculty of Mathematics and Natural 

Sciences Sepuluh Nopember Institut of 

Technology, Surabaya. 

Panias, D., Giannopoulou, I.P. dan Perraki, Th., 

2006, Effect of Synthesis parameters on 

Mechanical Properties of Fly Ash-Based 

Geopolymers, Colloids and Surfaces Area : 

Physicochemistry Engineering Aspects. 

Accepted Manuscript. 

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Rangan, B.V., Hardjito, D., Wallah, S.E., 

Sumajouw, D.M.J., 2005, Studies on fly ashbased 

geopolymer concrete, Proceedings of the 

World Congress Geopolymer, Saint Quentin, 

France, 28 June – 1 July, pp. 133–137. 

Schmücker, M. dan Mackenzie, K.J.D., 2005, 

Microstructure of Sodium Polysialate Siloxo 

Geopolymer, Ceramic International 31, 433- 

437. 

Swanepoel, J.C dan Strydom, C.A., 2002, 

Utillisation of Fly Ash in a Geopolymeric 

Material, Applied Geochemistry 17, 1143- 

1148. 

Van Jaarsveld, J.G.S. dan van Deventer, J.S.J.,1999, 

Effect of Metal Alkali Activator on the 

Properties of Fly Ash-Based Polymers, 

Industrial Engineering Chemistry Research 38, 

3932-3941. 

Van Jaarsveld, J.G.S. dan van Deventer, J.S.J.,2003, 

The Characterization of Source Materials in 

Fly Ash-Based Geopolymer, Materials Latters 

57, 1272-1280. 

Xu, H. dan van Deventer, J.S.J., 2002. 

Microstructural Characteristion of 

Geopolymers Synthesised from 

Kaolinite/Stilbite Using XRD, MAS- 

NMR,SEM?EDX,TEM/EDX and HREM, 

Cement and Concrete Research 32, 1705-1716. 

Xu, H., van Deventer, J.S.J., Lukey, G.C., 2001. 

Effect of Alkali Metal on the Preferential 

Geopolymerisation of Stilbite/Kaolinite 

Mixtures. Industrial Engineering Chemistry 

Research 40, 3749-3756. 




Synthesis and Characterization NiO/TS-1 Catalyst 

Siti Qamariyah Khairunisa and Didik Prasetyoko 

ISBN : 978 – 979 – 19201 – 0 – 0 


Teknologi Sepuluh Nopember (ITS), Surabaya, Indonesia. 


email: skhairunisa@gmail.com and didikp@chem.its.ac.id 

Introduction 

Abstract 

Hydroxylation of phenol to hydroquinone and catechol is an important reaction for many industrial 

applications, such as: photographic film developer, antioxidant, polymerization inhibitor, medicines, 

perfumes, and etc. The production of hydroquinone and catechol from hydroxylation of phenol can be 

produced by using homogeneous catalyst. However, this process is not efficient because need separation 

between reactant, product, and catalyst. The alternative of this process is used Titanium Silicalite (TS-1) 

as heterogeneous catalyst . TS-1 has great properties, such as high activity and selectivity to oxidation 

reaction and green chemistry. Because TS-1 is hydrophobic, so the reaction rate of whole reaction is 

low. The presence of nickel oxide on TS-1 can be increased the hydrophilicity and acid sites. NiO/TS-1 

was prepared by impregnation method. The sample was characterized by XRD, FTIR, and 

hydrophobicity techniques. The XRD analysis of NiO/TS-1 revealed that the MFI structure of the TS-1 

support was found to be intact incorporation of nickel oxide. The infrared spectra showed that the 

tetrahedral titanium in the TS-1 is still remained after impregnation with nickel oxide. The 

hydrophilicity of the modified samples increased as a function of the amount of nickel oxide loading, on 

contrary with XRD peak intensity. 

Key words: Hydrophobicity, NiO/TS-1, Microporous material 

Hydroxylation of Phenol to hydroquinone and 

catechol is an important reaction for many industrial 

applications, such as: photographic film developer, 

antioxidant, polymerization inhibitor, medicines, 

perfumes, and etc [1]. Dihydroxybenzenes are 

largely used today as intermediate chemicals. They 

are produced by decomposition of diisopropyl 

benzenes hydroperoxides or by hydroxylation of 

phenol in strong acid. Hydroquinone (pdihydroxybenzene) 

was also produced by the 

oxidation of aniline using manganese dioxide and 

sulfuric acids. This was then followed by reduction 

using typically Fe/HCl [2]. This is homogenous 

catalytic process, the disadvantage found in case of 

homogeneous catalytic process is being highly 

expensive and hydroxylation of phenol gives very 

low para to ortho ratio [3]. But the use 

heterogeneous catalyst is a promising alternative to 

over come this problem. So many works have been 

done to enhance the production of hydroquinone and 

cathecol due to importance in industrial. Titanium 

silicalite molecular-sieves (TS-1) for hydroxylation 

of phenol with hydrogen peroxide as the oxidant was 

discovered in 1983 by Taramasso et al. and since 

then it has gradually been acknowledged as one 

milestone in heterogeneous catalysis. This reaction is 

environmentally friendly because only produce water 

as by-product. In addition, hydrogen peroxide is a 

stable reagent with high active oxygen [4]. One of 

the advantages of TS-1 is higher para selectivity, 

which is attributed to the shape selectivity of the 

catalyst. Another advantage of this catalyst is the 

higher phenol conversion and the low amount of tar 

formation [5]. The conversion of hydroxylation of 

phenol with hydrogen peroxide catalyzed by TS-1 

obtained 97% [6]. 

From the unique properties, TS-1 has 

hydrophobic nature. The hydrophobicity nature of 

TS-1 can be decreased by incorporation of metal 

oxide. It has been reported that the presence of metal 

oxide even in very small amount can be increased the 

catalytic activity due to hydrogen peroxide with TS- 

1 formed Ti-peroxo easily. Though hydrophilicity 

increases, acid sites also increases. Acid sites 

(Brønsted and Lewis) can be found in some 

transition metals such as metal oxide of V2O5, 

Nb2O5, MoO3, WO3, Re2O7, NiO, ZnO, Fe2O3, 

Cr2O3, dan Cr2O3/Al2O3 [7]. The use of 

heterogeneous catalysts is an alternative for 

oxidation reactions due to more effective than 

homogeneous catalysts. The other heterogeneous 

catalysts for hydroxylation phenol are CuO–MCM– 




48 [8], V2O5/Nd2O3 [9], Cu–VSB–5 [10], 

molibdovanadofosfor/ZrO2 [3], Fe–HMS [11]. 

The increased of loading nickel oxide ca be 

increased catalytic activity for dimerization and 

isomerization of olefins [12]. It has been reported 

that the impregnation of MoO3 on TS-1 can be 

increased hydrophilicity and acid sites, therefore, its 

catalytic activity for hydroxylation of phenol also 

increased [13]. The conversion of phenol on 

MoO3/TS-1 catalyst is higher than TS-1 catalyst was 

reported [14]. 

In this paper, nickel oxide has been loaded on 

the surface of TS-1 to introduce acidity. 

Commonly, in the TS-1 structure, titanium was 

initially assumed to occupy a substitute position in 

the zeolite framework, since XRD measurements 

indicated that unit cell volume increases linearly 

with the Ti content, in good agreement with the 

isomorphous substitution of Ti for Si at tetrahedral 

framework sites. However, the local environment 

of Ti in TS-1 can studied using several techniques 

such as FTIR. The hydrophobicity of TS-1 can 

studied using hydrophobicity tests using the 

mixture of xylene and water. 


Sample 

Titanium silicalite 

(TS-1) 

Table 1: The sample code and preparation method 

The code of 

sample 

ISBN : 978 – 979 – 19201 – 0 – 0 

TS-1 was prepared according to a procedure 

described in the literature [15] with slight 

modification, using tetraethyl orthosilicates TEOS 

(Merck 98%), tetraethyl orthotitanate TEOT 

(Merck 95%) in isopropyl alcohol, 

tetrapropylammonium hydroxide (Merck 20% 

TPAOH in water), and distilled water. The gel was 

charged into 300 ml autoclave and heated at 175 o C 

under static condition. The material was recovered 

after 4 days by centrifugation and washed with 

excess distilled water. A white powder was 

obtained after drying in air at 100 o C overnight. The 

calcinations of sample to remove the template was 

carried out in air at 550 o C for 5 hour with 

temperature rate 1 o min-1. 

Sample NiO/TS-1, TS-1 loaded with nickel 

oxide (0.5; 1; 2; 4) were prepared by impregnation 

technique using Ni(NO3)2 as a precursor. About 

0.0126 g of Ni(NO3)2 was dissolved in distilled 

water to obtain the desired metal loading and 

required quantity of pre-dried of TS-1 was 

immediately added to clear solution with stirring. 

The mixture was stirred at room temperature for 3 

hour. The solid was recovered by evaporating the 

distilled water at 80 o C. The solid was then dried at 

100 o C for 24 hour. Then solid was calcined at 500 

o C for 5 hour with temperature rate 1 o min -1 . The 

method and compositions of the samples are listed 

in Table 1. 

NiO/(NiO+TS-1),% Method 

TS-1 1 *(gel) hydrothermal 

0.5% NiO/TS-1 0.5NiO/TS-1 0.5 Impregnation- hydrothermal 

1% NiO/TS-1 1NiO/TS-1 1 Impregnation- hydrothermal 



NiO NiO 100 calcination 

* (%Ti) = Ti/(Ti+Si) 

All molecular sieves were characterized by 

powder X-ray diffraction (XRD) for identification 

of the crystalline phases in the catalysts using 

diffractometer with the Cu Kα (λ = 1.5405 Å) 

radiation as the diffracted monochromatic beam at 

40 kV dan 40 mA. Typically, powder sample were 

ground and spread into a sample holder and then 

analyzed. The pattern was scanned in the 2θ range 

of 5–50 o at step 0.020o and step time 1 second. 

Infrared (IR) spectra of samples were collected on a 

Perkin Elmer Fourier Transform Infrared (FTIR) 

spectrophotometer, with a spectral were recorded in 

the region of 1400 – 400 cm -1 . Hydrophobicity test 

were determined by the mixture of xylene and 

water, which do not mix each other. Xylene and 

water of the same volume are added into a test tube 

to form a stable phase interface, as shown in figure 

1. TS-1 and NiO/TS-1 samples were dispersed in 

the xylene-water system and stirred. After the 

mixture has stabilized, hydrophobic characteristics 

can be qualitatively evaluated by inspecting the 

state of the floating/sinking of samples pass the 

phase interface and sinking of samples at the 

interface. The criteria of hydrophobic index is as 




follows: (1) hydrophilic: samples pass the phase 

interface and sink into water quickly and 

completely; (2) hydrophilic: samples pass the phase 

interface and sink into water not so quickly; (3) 

hydrophilic: samples float at first on the phase 

interface and then sink into water slowly and 

completely; (4) partially hydrophilic: samples float 


X-ray Diffraction (XRD) 

Xylene 

Interface 

Water 

The XRD pattern of the samples are shown 

Figure 2, while the phase containing sample are 

tabulated in Table 2. The XRD pattern of TS-1 and 

NiO/TS-1 sample indicated that the sample 

contained framework structures of the MFI type 

zeolite. The XRD pattern showed the framework 

structures of the MFI at 2θ = 8.00; 8.88; 23.12; 

23.18; 23.44; 23.74°. The peak at 2θ = 24.45º 

indicated a changing of a monoclinic symmetry 

(silicalite) to an orthorhombic symmetry (titanium 

silicalite, TS-1) [17]. For sample NiO/TS-1, the 

structure of TS-1 is not strongly affected by the 

presence of impregnated nickel oxide. The XRD 

pattern showed that no diffraction line assigned for 

Figure 1. Testing of hydrophobic nature of sample 

ISBN : 978 – 979 – 19201 – 0 – 0 

at first on the phase interface and then some 

particles sink into water completely; (5) partially 

hydrophobic: samples float on the phase interface. 

After mixing a long time, some particles still float 

on the phase interface; and (6) completely 

hydrophobic: samples float on the phase interface 

even with vigorous mixing for along time [16]. 

crystalline phase of the nickel oxide were 

investigated. This indicated that nickel was well 

dispersed on the TS-1. The peak intensity of 

NiO/TS-1 with various loading is drastically 

decreased as addition of nickel oxide increased. It is 

suggested that nickel is either located on the surface 

of TS-1 or covering the surface of TS-1. 

Table 2 The crystallinity of TS-1 and NiO/TS-1 

samples 

Code sample 

Intensity at 

2θ = 23.18, a.u 

Phase 

TS-1 

3083 MFI 

0,5 NiO/TS-1 

3035 MFI 

1 NiO/TS-1 

2720 MFI 

2 NiO/TS-1 

2598 MFI 

4 NiO/TS-1 

2563 MFI 




Intensity, a.u. 

5.00 15.00 25.00 35.00 45.00 

2 theta, degree 

ISBN : 978 – 979 – 19201 – 0 – 0 

4NiO/TS-1 

2NiO/TS-1 

1NiO/TS-1 

0.5NiO/TS-1 

TS-1 

NiO 

Figure 2 XRD pattern of the NiO, TS-1, and XNiO/TS-1 samples 

Fourier Transform Infrared (FTIR) Spectroscopy 

The infrared spectra of the samples in the 

lattice vibration region between 1400 and 400 cm -1 

are depicted in figure 3. Sample TS-1 and 

XNiO/TS-1 showed similar bands. According to 

Flanigen [18], the absorption bands at around 1100, 

800, and 450 cm -1 were three lattice modes 

associated with internal linkages in tetrahedral SiO4 

and are insensitive to structure changes. The 

absorption bands at about 1225 and 547 cm -1 are 

characteristic of MFI type zeolite associated with 

the particular structural assembly of the tetrahedral 

and are sensitive to structure changes. It is already 

known that the infrared spectrum of titanium 

silicalite, TS-1 is characterized by an absorption 

band at around 960 cm -1 . However, the vibrational 

modes at around this frequency may be the result of 

several contributions i.e. the asymmetric stretching 

modes of Si-O-Ti linkages, terminal Si-O stretching 

of SiOH-(HO)Ti “defective sites” and titanyl 

[Ti=O] vibrations [19]. Our TS-1 sample shows a 

weak band at 970 cm -1 . This band can be attributed 

to the titanium in the framework and with addition 

NiO 

of nickel oxide onto TS-1 by impregnation still 

show band at 970 cm -1 . It included that TS-1 and 

NiO/TS-1 sample contains Si-O-Ti connections. 

In addition, a small band at around 970 

cm -1 assigned to the titanium ions in the tetrahedral 

structure is still present after impregnation of nickel 

(NiO/TS-1). No additional band after impregnation 

of nickel into the TS-1 can be observed. This 

finding shows that impregnation of nickel has not 

effected the MFI structure of TS-1 significantly. 

Meanwhile, infrared spectroscopy technique cannot 

detect the presence of nickel oxide in the sample 

NiO/TS-1, due to addition nickel oxide into TS-1 is 

low. However, the frequency of bands decreased as 

the amount of loading nickel oxide in the 

investigated samples increased. 




Transmittance, % 

1100 970 

Wave number cm -1 

1400 1200 1000 800 600 

400 

Hydrophobicity Tests 

The results of hydrophobic tests are shown in 

the Table 3. From Table 3, it can be seen that TS-1 

sample is strongly hydrophobic, while NiO/TS-1 

samples are more hydrophilic than TS-1. The result 

of hydrophobicity tests with the criterion of 

hydrophobic index are (1) until (6) [16]. The 

800 

550 

Figure 3. Spectra FTIR of the TS-1, XNiO/TS-1 samples 

ISBN : 978 – 979 – 19201 – 0 – 0 

459 

Table 3. The results of hydrophobicity tests of all samples 

4NiO/TS-1 

2NiO/TS-1 

1NiO/TS-1 

0 5NiO/TS-1 

TS-1 

NiO 

purpose of this observation of time is to compare 

hydrophilicity among the samples. The 

incorporation of nickel oxide can be increased the 

hydrophilic nature of TS-1. The hydrophilicity of 

NiO/TS-1 samples increased as a function of nickel 

oxide loading, as shown in Table 3. 




No. Sample Criterion of 

hydrophobic index 

Time 

1. TS-1 5 2 minutes 31 seconds 

2. 0.5NiO/TS-1 5 1 minutes 26 seconds 

3. 1NiO/TS-1 5 1 minutes 6 seconds 

4. 2NiO/TS-1 5 1 minutes 1 seconds 

5. 4NiO/TS-1 3 50 seconds 

Among all samples, 4NiO/TS-1 sample showed the 

faster drop than the other samples, while TS-1 is 

the lowest. It is indicated that TS-1 has 

hydrophobic character with hydrophobic index 5. 

While 4NiO/TS-1 sample showed strongly 

hydrophilic than other samples (Table 3). 4NiO/TS- 

1 has hydrophilic character with hydrophobic index 

3, when samples float at first on the phase interface 

and then sink into water slowly and completely, as 

shown in Figure 4e. It indicated the incorporation 

of nickel oxide can be increased the hydrophilicity 

of TS-1 and can effect of catalytic activity. Besides 

ISBN : 978 – 979 – 19201 – 0 – 0 

that, with the incorporation of nickel oxide can be 

increased Lewis acid site. Lewis acid site can be 

effect hydrophilicity of TS-1 because can be accept 

free electron pairs from water. This is will be 

studied further. All samples with hydrophobic 

index 5, before stirring float on the interface, after 

stirring and keep on overnight some particles still 

float on the interface, as shown in Figure 4 and 5. 

But sample with hydrophobic index 3, there is no 

particles float at the interface before and after 

stirring. 

Figure 4: Sample TS-1 (a) and XNiO/TS-1 (X = 0.5, 1, 2, and 4) (b-d) in the water-xylene before stirring. 

a b c d e 

0.5NiO/TS-1 

1NiO/TS-1 2NiO/TS-1 4NiO/TS-1 

a b c d e 

Figure 5: Sample TS-1 (a) and XNiO/TS-1 (X = 0.5, 1, 2, and 4) (b-d) in the water-xylene after stirring. 

Conclusion 

NiO/TS-1 catalysts were successfully 

synthesized by impregnation of nickel oxide on the 

surface of TS-1. X-ray diffraction indicated that all 




the samples had the MFI crystalline structure. The 

MFI crystalline structure was not changed with the 

loading of nickel oxide. Infrared spectroscopy 

showed band at around 960 cm -1 , attributed to the 

titanium in the framework and spectra was still 

remained with the loading of nickel oxide. The 

increasing of catalyst hydrophobicity depended on 

the loading amount of nickel oxide. 


We gratefully acknowledge funding from the 

Directorate General of Higher Education, 

Indonesia, under Hibah grant. 

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on Hydroxylation of Phenol”, Mater. Lett., 

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Their Relationship to Acidic Properties”, 

Catal. Today, 73:197-209. 

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”The Nature of Surface Acidity and 

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SiO2 for Transesterification of Dimethyl 

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Investigation”, Appl. Catal. B: 

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[14] Indrayani, Suci, (2008), Aktvitas Katalitik 


menggunakan H2O2, Tesis, Institut Sepuluh 

November, Surabaya. 

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“Preparation of Porous Crystalline Synthetic 

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ISBN : 978 – 979 – 19201 – 0 – 0 

Coal Fly Ash Geopolymer: 

Study of SiO2/Al2O3 Mol Ratios and the Resulted Geopolymer Properties 

Introduction 

Ella Kusumastuti 1 , Hamzah Fansuri 2 , Lukman Atmaja 3* , 

1 Chemistry Department, Sepuluh Nopember Institute of Technology, Surabaya 

2, 3 Chemistry Department, Sepuluh Nopember Institute of Technology, Surabaya 

* Corresponding author : lukman_at@chem.its.ac.id 

Abstract 

The effect of SiO 2/Al 2O 3 mol ratio with the contribution of each SiO 2 and Al 2O 3 in the reaction 

mixture to the chemical and mechanical properties of the geopolymer product has ben investigated. 

Type C of fly ash from Cilacap Power Plant was used as the based material which had initial mol ratio 

SiO 2/Al 2O 3=4.32. Two series of variation SiO 2/Al 2O 3 were made by varying the amount of soluble 

additives (Na2SiO 3 and Al(OH) 3) added to the initial reaction mixture (fly ash, Na 2SiO 3, NaOH, and 

H 2O). All conditions have been done at constant consistency. 

The results showed that the addition of aluminate species at constant silicate and the reduction of 

NaOH molarity increase the setting time due to more Al(OH)3(H 2O) complex species was available to 

inhibited polycondensation reaction. The optimum compressive strength was achieved at mol ratio of 

SiO2/Al 2O 3=3.0 for Al 2O 3 series and SiO 2/Al 2O 3=5.0 for of SiO 2 series. Phase development showed 

that the greater SiO2/Al 2O 3 mol ratio, the greater formation of amorf homogenous phase and lead to 

reach optimum SiO 2/Al 2O 3 mol ratio. FTIR study showed that the greater SiO 2/Al 2O 3 mol ratio, the 

greater the wave number of vibration meaning both the increasing of chain length Si-O-Al or Si-O-Si 

and the vibration energy. It also revealed that there were more formation of gel aluminosilicate in 

geopolimerisation and that the chemical bond of Si-O-Al or Si-O-Si getting strong at optimum 

SiO2/Al 2O 3 mol ratio. Grain structure appeared at low SiO 2/Al 2O 3 causing a lower strength, while 

homogenous geopolymer matrix appeared at optimum SiO 2/Al 2O 3 mol ratio cauisng to a higher 

strength. Unreacted fly ash and residual reactant appeared at high SiO2/Al 2O 3 mol ratio and lead to a 

lower strength. 

Keywords: geopolymer, coal fly ash, aluminosilicates, SiO 2/Al 2O 3 

Efforts for reducing the world cement consumption 

have been developed by synthesing material that 

has cementitious properties and potential to 

partially replaced conctrete. Davidovits, a scientist 

in polymer, in 1978 for the first time developed 

aluminosilicate inorganic polymer called 

geopolymer (Davidovits, 1994). Geopolymer which 

has general formula nM2O·Al2O3· xSiO2· yH2O was 

obtained from polycondensation reaction of 

pozzolanic materials or alumonosilicate minerals 

with alkali silicate solution (Davidovits, 1991). 

This relatively new material has a similar 

cementitious properties to concrete. 

Fly ash, by-product of coal-based industry, has 

pozzolanic properties as its major content are 

reactive silica and alumina. Thus, it is a good 

starting materials to synthesize geopolymer. 

Pozzolanic properties describes the reactivity of 

silica and alumina which took a part in the 

formation of Si-O-Al chains in geopolymer. 

One of major parameters in the initial mixture of 

the starting material, in the case of fly ash, is the 

quantity of the essential compounds involved in the 

formation of geopolymer chains. SiO2 and Al2O3 

are the major oxides besides the other oxides which 

have an important role in the formation of Si-O-Al 

chains in geopolymer. The dissolution of silica and 

alumina in the surface of fly ash was determined by 

the chemical composition of fly ash itself (Rizain, 

2008). In the high alkali condition, Al2O3 

solubilities were greater than that of SiO2 (Swaddle, 

2001). In the condition of more reactive 

SiO2/Al2O3, there would be a different contribution 

of silica and alumina, i.e., alumina is responsible 

for initial properties while silica is for final 

properties. 

This research was objected for studying the effect 

of SiO2/Al2O3 moles ratio having contribution of 

each SiO2 and Al2O3 in the starting material to the 

chemical and mechanical properties of the 

geopolymer product such as setting time, 

compressive strength, phase development, the 

changing of chemical bond and microstructure. 

Materials and Method 

Fly ash from Cilacap Power Plant was used as the 

based material, and NaOH, H2O, sodium silicate 




and aluminium hidroxide were used as additive 

(added aluminate species). Some standard 

laboratory tools were used to mix and mold the 

geopolimer matrixs. X-Ray Fluorescence (XRF) 

was used for the determination of fly ash 

composition, while the characterisations of 

geopolymer such as setting time, compressive 

srength and phase development used a Vicat Needle 

Apparatus, Universal Testing Machine and X-Ray 

Diffraction (XRD), respectively. Scanning Electron 

Microscopy (SEM) was used to investigate the 

morphology and Fourier Transform Infra Red 

(FTIR) to investigate chemical bond of the resulted 

geopolymer. 

At first, geopolymer synthesis has been carried out 

by mixing the fly ash with activator (NaOH 

solution). The initial mixing was done by hands for 

2 minutes then by mixer for 5 minutes so the 

mixture was really homogenous (van Deventer, 

2000 and van Jaarsveld, 2002). The mixture then 

poured into plastic cilinder mold with 1.5 cm in 

diametre and 3 cm in high (Bakharev, 2005 and 

Andini, 2008). Vibration has been done for about 

15 minutes to remove air bubble in paste so it was 

be more dense (Duxson, 2005). The result of 

moulding process was let in the room temperature 

for 2 hours until it could be released from its 

mould. It then was sealed/wrapped with plastics to 

avoid loosing water quickly which could the pellet 

cracked. Pellets then cured at 60°C for 24 hours in 

the oven (Chindaprasirt, 2007 and Aly, 2008) to 

maximise the reaction of geopolymerisation. 

The SiO2/Al2O3 mol ratios were made by varying 

the amount of soluble additives (Na2SiO3 and 

Al(OH)3, respectively) that added to the initial 

reaction mixture (fly ash, Na2SiO3, NaOH, and 

H2O). Two series of variations were used. The first 

was achieved by varying Al2O3 content at constant 

SiO2 and the other was achied by varying SiO2 

content at constant Al2O3. The amount of Na2O in 

all variations was kept constant. Water was added 

to achieve the same mixture consistency in all 

variations. 

The total moles in every composition were 

presented below : 

Table 1 The Total Moles in Variation of Al2O3 at 

Constant SiO2 

Total Moles 

SiO2 Al2O3 Na2O 

SiO2/Al2O3 

0.217 0.434 0.113 0.5 

0.217 0.217 0.113 1.0 

0.217 0.145 0.113 1.5 

0.217 0.109 0.113 2.0 

0.217 0.087 0.113 2.5 

0.217 0.072 0.113 3.0 

ISBN : 978 – 979 – 19201 – 0 – 0 

0.217 0.062 0.113 3.5 

0.217 0.054 0.113 4.0 

0.217 0.048 0.113 4.5 

0.217 0.043 0.113 5.0 

0.217 0.043 0.113 5.064 

Table 2 The Total Moles in Variation of SiO2 at 

Constant Al2O3 

Total Moles 

SiO2 Al2O3 Na2O 

SiO2/Al2O3 

0.021 0.043 0.113 0.5 

0.043 0.043 0.113 1.0 

0.064 0.043 0.113 1.5 

0.086 0.043 0.113 2.0 

0.107 0.043 0.113 2.5 

0.129 0.043 0.113 3.0 

0.150 0.043 0.113 3.5 

0.171 0.043 0.113 4.0 

0.193 0.043 0.113 4.5 

0.214 0.043 0.113 5.0 

0.217 0.043 0.113 5.064 

The gepolymer pellets then were characterized for 

studying the chemical properties after cured for 28 

days (Hardjito, 2004). The mechanical properties 

were determined after 1 and 28 days. 


Fly ash Characterization 

The composition of fly ash from Cilacap Power 

Plant is presented in Table 3. It can be seen that the 

major oxides of the fly ash were SiO2, Al2O3, CaO 

and Fe2O3. This fact lead to catagorising the fly ash 

as class C. 

Phase analysis by XRD showed that the phase 

majority was quartz (SiO2) and mullite (3Al2O3 

xSiO2) and albite (NaAlSi3O8)in minor amount. 

Most of them were amorf and it was signed by the 

present of hump at 2θ 20° up to 30°. Amorf phase 

in fly ash showed reactivity of silica and alumina in 

fly ah, because only amorf phase could dissolve in 

high alkali solution (Duxson et al, 2007). 

Table 3 The Composition of Fly Ash 

Oxide % Mass Oxide 

SiO2 31,50 

Al2O3 12,40 

CaO 21,40 

Fe2O3 22,50 

K2O 0,75 

MgO 7,87 




intensity 

200 

150 

100 

50 

0 

Na2O 0,27 

P2O5 0,12 

SO3 1,06 

TiO2 0,76 

MnO 0,27 

BaO 0,24 

SrO 0,09 

LOI 0,49 

Q 

Q 

M 

A 

A 

Q Q Q Q 

0 10 20 30 40 50 60 70 80 

M 

2 tetha 

Figure 1 X-Ray Diffraction Spectra of Fly Ash 

Setting Time and Strength Development 

ISBN : 978 – 979 – 19201 – 0 – 0 

Figure 2 Final Setting Time of SiO2/Al2O3 Mol 

Ratios 

The mol ratios of SiO2/Al2O3 increase as the 

addition of Al 3+ species from Al(OH)3 decrease 

from a sample to another (Table 1). Figure 2 shows 

that the greater SiO2/Al2O3 mol ratios, the shorter 

the setting time. This behaviour could be explained 

by the role of aluminium hydroxide. The Al(OH)3 

additions to the system of the geopolymerisation 

process would cause the setting time of geopolymer 

was stretched from a sample to another. Further 

explanation could arise from a fact that in this 

composition the NaOH molarities increased with 

increasing SiO2/Al2O3 mol ratios and that of the fly 

ash fraction did, too. Both NaOH molarities and the 

solid fraction had been reported to have significant 

effects to setting time (Kamhangrittirong et al, 

2006) due to the need of water to reach the same 

consistency was different. The greater SiO2/Al2O3 

mol ratios, the less needed water and this mean the 

greater NaOH molarity. 

In the strong alkaline solution with high pH where 

NaOH molarity is high, the formation of aluminates 

Al(OH)4 – is preferred to have [Al(OH)3(H2O)] 0 

form and [SiO2(OH)2] 2- is preferred to have 

[SiO(OH)3] - form (Weng, 2005) following the 

equations below : 

Al(OH) 3 + OH – → Al(OH) 4 – ........................ (4.1) 

Setting Time by Vicat Needle Apparatus Al(OH)3 + OH – + H 2O → [Al(OH) 3(H 2O)] 0 (4.2) 

Geopolimer paste setting time is defined as time 

needed for transport, placing and compaction 

process (Teixeira-Pinto, 2002). Terms transport 

and placing describe the transportation process of 

dissolved species (Si and Al) from particle surface 

of fly ash into interparticle spaces, while the term 

compaction describes the polycondensation process 

of the the species to form aluminosilicate three 

dimensional structure. 

Determination of geopolymer paste setting time by 

Vicat Needle Apparatus presented in Figure 2 

below : 

Final Setting Time (minutes) 

200 

180 

160 

140 

120 

100 

80 

60 

40 

20 

Final Setting Time of SiO 2 /Al 2 O 3 Mol Ratios 

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 

SiO /Al O Moles Ratio 

2 2 3 

Mol Variation of Al 2 O 3 at Constant SiO 2 

Mol Variation of SiO 2 at Constant Al 2 O 3 

SiO 2 + OH - → [SiO 2(H 2O)] 2– ....................... (4.3) 

SiO2 + OH – + H 2O → [SiO(OH) 3] – ............. (4.4) 

It could be understood that in very high alkaline 

condition, Al(OH)4 – and [SiO2(H2O)] 2– play more 

important role than [Al(OH)3(H2O)] 0 and 

[SiO(OH)3] – so that the policondensation reactions 

of the geopolymerisation process was also quicker 

that that of the low alkaline condition. The greater 

addition of Al(OH)3, the lower SiO2/Al2O3 mol 

ratios, the more [Al(OH)3(H2O)] 0 available, the 

more difficult polycondensation reaction to happen, 

and so the longer the setting time. 

Compressive Strength by Universal Testing 

Machine 

To study strength development of SiO2/Al2O3 mol 

ratios, measurements of compressive sterngth were 

carried out at different age, 1 day for initial strength 

and 28 days for final strength. Compressive 

strength development of geopolymer with variation 

of SiO2/Al2O3 mol ratios is presented in Table 4. 




ISBN : 978 – 979 – 19201 – 0 – 0 

Table 4 Compressive Strength Development of Geopolymer with Variation of SiO2/Al2O3 Mol Ratios 

Al2O3 Variation SiO2 Variation Strength Increase 

SiO2/Al2O3 

Mol Ratios 

Initial 

Strength 

(MPa) 

Final 

Strength 

(MPa) 

Initial 

Strength 

(MPa) 

Final 

Strength 

(MPa) 

Al2O3 

Variation 

SiO2 

Variation 

0.5 0.60 1.51 - - 2.50 - 

1.0 30.92 52.04 - - 1.68 - 

1.5 31.87 64.20 0.66 0.85 2.01 1.29 

2.0 35.64 66.75 1.51 11.13 1.87 7.38 

2.5 39.41 78.06 2.04 21.13 1.98 10.36 

3.0 58.92 91.07 11.32 31.70 1.55 2.80 

3.5 48.08 85.79 13.76 34.90 1.78 2.54 

4.0 40.73 68.08 27.72 44.69 1.67 1.61 

4.5 43.94 56.71 52.04 54.30 1.29 1.04 

5.0 54.49 74.67 47.18 70.90 1.37 1.50 

The Average of Strength Increase 1.77 3.56 

Compressive Strength (MPa) 

100.00 

90.00 

80.00 

70.00 

60.00 

50.00 

40.00 

30.00 

20.00 

Compressive Strength of SiO2/Al2O3 Mol Ratios 

10.00 

0.00 

0.00 1.00 2.00 3.00 4.00 5.00 6.00 

SiO2/Al2O3 Mol Ratios 

Initial Strength Initial of Al2O3 Strength Variation on Al2O3 Variation FFinal inal Strength on of Al2O3 Al2O3 Variatio Variationn 

Initial StrengthInitial of SiO Strength on SiO2 Variation Final Strength on of SiO2 Variation 

2 Variation 

Variation 

Figure 3 Compressive Strength Development of Geopolymer with Variation of SiO2/Al2O3 Mol Ratios 

In the variation of Al2O3 moles at constant SiO2, 

there were similar trends in both initial and final 

compressive strength. Figure 3 exhibited that the 

greater SiO2/Al2O3 mol ratios, the greater 

compressive strength and the optimum value was 

reached at SiO2/Al2O3 = 3.0, i.e., 58.92 Mpa and 

91.07 MPa for 1 and 28 days, respectively. The 

compressive strength decreased at SiO2/Al2O3 = 3.5 

and it decreased with increasing SiO2/Al2O3 mol 

ratios. The average final strength increase was 1.77 

times more than the initial strength. These 

important data could be correlated with the setting 

time data previously presented in Fig.2. Setting 

time at SiO2/Al2O3 ≥ 3 was low and it decreased 

with increasing SiO2/Al2O3 mol ratios. Setting time 

at SiO2/Al2O3 < 3 were increased significantly with 

decreasing SiO2/Al2O3 mol ratios. 

In the variation of SiO2 moles at constant Al2O3, the 

trend in both initial and final compressive strengths 

was different. The initial stength increased with 

increasing SiO2/Al2O3 mol ratios, and reached 

maximum value at SiO2/Al2O3 = 4.5, i.e., 52.04 

MPa, while final strength reached maximum valua 

at SiO2/Al2O3 = 5.0, i.e., 70.90 MPa. The average 

final strength increase was 3.56 times more than the 

initial. The addition of SiO2 moles clearly 

influences the development of the compressive 

strength. 

The average increasing final strength on SiO2 

variation was greater than that on Al2O3 variation. 

One then could concluded that the final strength 

development was influenced mainly by SiO2 mol 

addition. However, all of strengths in Al2O3 

variation was greater than all of strengths in SiO2 




variation. It could be explained that SiO2/Na2O 

mol ratio in Al2O3 variation was greater than in 

SiO2 variation. Na2O species could reduce the 

strength of geopolymer because it would form 

Na2CO3 if it reacted with CO2 in the air. Density of 

Na2CO3 was also low also and could reduce the 

strength of geopolymer. 

Phase Development by XRD 


0 10 20 30 40 50 60 70 80 

ISBN : 978 – 979 – 19201 – 0 – 0 

X-Ray Diffraction spectroscopy was used to 

determine the phase mineralogy of geopolymer 

with variation of SiO2/Al2O3 moles. It was 

conducted on geopolymer sample aged of 28 days 

to ensure that the geopolymerisation process was 

stable. 

For the variation of Al2O3 moles, the spectra is 

presented in Figure 4 below : 

MaMM 

Q 

MaM 

M 

Q 

G 

G 

Q 

M M M 

Q 

M MM 

GK 

Q G QQ 

G 

G 

G 

K G 

G G G 

M Q 

G 

Q 

G Q 

Q 

Q 

Q Q 

Q 

G 

Q 

Q 

Q 

Q 

Q 

Q 

SiO /Al O =5.06 

2 2 3 

Q 

G 

G 

SiO /Al O =5.0 

2 2 3 

Q Q 

Q Q Q 


2 2 3 

Q Q 

Q 


2 2 3 

G 

G 

G 

Q 

G Q Q Q 


2 2 3 

2tetha 

Figure 4 X-Ray Diffraction Spectra of Geopolymer with Variation of Al2O3 Moles 

Q=quartz (SiO2), M=mullite (3Al2O3.2SiO2), G=gibbsite (Al(OH)3), 

Ma=magnetite (FeFe2O4), K=kaolinite (Al2Si2O5(OH)4) 

The formation of geopolymer was signalled by the 

shift of 2θ=20-30° in fly ash into 2θ=25-35° in 

geopolymer. From spectra in Figure 4 it could be 

seen that at low SiO2/Al2O3 mol ratio, there was 

more crystaline phase than at high SiO2/Al2O3 mol 

ratio. It was very clear that at SiO2/Al2O3 = 0.5, 

most of all phase were crystaline with the main 

minerals are gybbsite and the minor minerals are 

quartz. It should be noted that SiO2/Al2O3 = 0.5 was 

the larges of Al(OH)3 addition. The phase of 

gibbsite then decreased with increasing SiO2/Al2O3 

mol ratio because the addition of Al2O3 mol was 

also decreased. On the other hand, quartz phase 

increased with increasing SiO2/Al2O3 mol ratio. 

Some minor minerals appeared because of the 

heterogenousity of fly ash component such as 

magnetite and kaolinite while the major minerals 

such as quartz and mullite came from both alumina 

and silika species. All spectra in Figure 4 showed 

that the most homogenous phase was found at 

SiO2/Al2O3=3.0 because it only contained quartz 

and mullite. This data could explain the sample 

with SiO2/Al2O3=3.0 had the highest strength. 

When a materials contain more amorphous phase, 

its strength would have a higher strength. However, 

SiO2/Al2O3=0.5 samples had the lowest value in 

strength because it contain very crystaline phase. 

Amorphous phase had more rigid structure than 

crystaline phase which had more brittle structure. 





S 

Q 

Q 

Q 

MaMM 

Q 

MaM 

M 

Q 

Q 

S 

S 

Q Q G MM 

Q 

Q G 

Ma 

Q Q 

M 

S Ma 

G 

Q Q 

Q 

Q 

M M 

Q 

Q 

Q G Q G 

Q QG 

0 10 20 30 40 50 60 70 80 

2tetha 

Q 

Q Q 

K Q 

SiO /Al O =5.06 

2 2 3 

Q 

Q 

Q 

Q 

Q 

Q 

K 

Q 

KQ 

K 

Q 

Q G G 

Q 

Q 

Q 

ISBN : 978 – 979 – 19201 – 0 – 0 

SiO 2 /Al 2 O 3 =5.0 

SiO 2 /Al 2 O 3 =3.5 

SiO 2 /Al 2 O 3 =2.5 

Q 


2 2 3 

Figure 5 X-Ray Diffraction Spectra of Geopolymer with Variation of SiO2 Moles 

Q=quartz (SiO2), M=mullite (3Al2O3.2SiO2), G=gibbsite (Al(OH)3), 

Ma=magnetite (FeFe2O4), K=kaolinite (Al2Si2O5(OH)4), 

S= sodalite (Al6Na8(SiO4).6Cl2) 

From spectra in Figure 5 shows the phase 

development of SiO2 variation. It can be seen that 

the minerals phase were more heterogenous than 

the samples coming from Al2O3 variation. The 

greater SiO2/Al2O3 mol ratios, the more 

homogenous and more amorf its mineral. Some 

minor minerals appeared because of the 

heterogenous of fly ash component such as 

magnetite and kaolinite while the major minerals 

such as quartz and mullite came from both alumina 

and silika species. Small zeolite phase such as 

sodalite appeared in low SiO2/Al2O3 mol ratios, that 

were SiO2/Al2O3=1.5; 2.5 and 3.5. From all spectra 

in Fig. 5, it could be seen that SiO2/Al2O3 = 5.0 was 

the most homogenous phase so it supported that 

final strength at SiO2/Al2O3 = 5.0 was the highest. 

SiO2/Al2O3 = 1.5 had heterogenous phase with the 

greatest gibbsite phase leading to the lowest final 

strength value. 

Chemical Bond Development by FTIR 

FTIR spectroscopy was used to investigate the 

chemical bond in geopolymer using the variation of 

SiO2/Al2O3 mol ratios. This study is based on the 

vibration of molecules as a result of its interaction 

with the infrared waves. The change of resulted 

vibration spectra was investigated. 

The main characteristic of vibration spectra 

appeared as a sign that Si-O-Al chain in 

geopolymer has been formed. Vibration spectra at 

wave number 1090-990 cm -1 signed asymetric 

stretching vibration of Si-O-Al or Si-O-Si while 

vibration at 750-550 cm -1 signed symetric 

stretching vibration of Si-O-Al or Si-O-Si. 

Vibration at 470-450 cm -1 signed the bending 

vibration of Si-O-Al or Si-O-Si and vibration at 

about 800cm -1 signed AlO4 vibration (Bakharev, 

2005). 

FTIR spectra of geopolymer with variation of 

Al2O3 moles and variation SiO2 moles were 

presented at Figure 6 and Figure 7 below. The 

investigation was conducted by comparing each of 

the spectra. It shows that the greater SiO2/Al2O3 

mol ratios, the higher its intensity. Increasing 

intensity meant increasing the chain length of Si-O- 

Al or Si-O-Si and it signed that there were more 

formation of gel aluminosilicate in 

geopolimerisation. It also showed that the greater 

SiO2/Al2O3 mol ratios, the greater the wave 

number. Increasing wave number meant increasing 

vibration energy, and it signed that the chemical 

bond of Si-O-Al or Si-O-Si got stronger. The 

increase of SiO2/Al2O3 mol ratios lead to the 

decrease of vibration and intensity in wave number 

of 3400 cm -1 . It signed the loosing of water as a 

result of polycondensation process in geopolymer. 

In this cases, H-O-H bond getting weak. 




%T 

3448.72 

3448.72 

3448.72 

3456.44 

3456.44 

1010.70 

4500 4000 3500 3000 2500 2000 1500 1000 500 0 

Wave Number (cm -1 ) 

ISBN : 978 – 979 – 19201 – 0 – 0 


972.12 

964.41 

956.69 

964.41 

SiO 2 /Al 2 O 3 =5.06 

SiO 2 /Al 2 O 3 =5.0 

SiO 2 /Al 2 O 3 =3.0 

SiO 2 /Al 2 O 3 =2.0 

SiO 2 /Al 2 O 3 =0.5 

Figure 6 FTIR Spectra of Geopolymer with Variation of Al2O3 Moles 

%T 

Microstructure Development by SEM 

3448.72 

3448.72 

3433.29 

3448.72 

3448.72 

972.12 

462.92 

972.12 455.20 

972.12 447.49 


2 2 3 

979.84 

455.20 


2 2 3 

972.12 

439.77 

4000 3000 2000 1000 0 

Wave Number (cm -1 ) 

SiO 2 /Al 2 O 3 =5.06 

SiO 2 /Al 2 O 3 =5.0 

SiO 2 /Al 2 O 3 =3.5 

Figure 7 FTIR Spectra of Geopolymer with Variation of SiO2 moles 

Geopolymer morphology in the micro scale has 

been investigated by Scanning Electron 

Microscopy. SEM images of polished samples with 

corresposnding SiO2/Al2O3 mol ratios are presented 

in Figure 8, 9 and 10. A significant change in 

microstructure, especially homogeneity, 

compactness, pores structure and some microcracks 

were associated with changing SiO2/Al2O3 mol 

ratios. 

As shown in Fig.8, microstucture of SiO2/Al2O3 = 

5.06 which was designed without any addition of 

Al(OH)3. It shows a homogeneity and compactness 

of geopolymer matrix, but some microcracks and 

pores caused its final strength was lower than that 

of SiO2/Al2O3 = 5.06 presented in Figure 8.(iii). 

The latter figure shows more homogenous, more 

compact, less porous and less fracture surfaces.



SEM images of geopolymer with variation of 

Al2O3 moles are presented in Fig. 9. Microstucture 

of SiO2/Al2O3 = 0.5 shows grain structures, which 

intergrains were not cemented. This exhibited less 

compact structure and made it has the lowest final 

strength. Microstucture of SiO2/Al2O3 = 2.0 was 

more compact, with grain structure began to be 

cemented, so it had final strength greater than 

SiO2/Al2O3 = 0.5. Microstucture of SiO2/Al2O3 = 

3.0 was the most wanted structure because its 

c 

ISBN : 978 – 979 – 19201 – 0 – 0 


a 

Figure 8 SEM Micrograph of Geopolymer with SiO2/Al2O3 = 5.06 

a. geopolymer matrix, b. microcrack and fracture surface, 

c. pores 

(i) SiO2/Al2O3 =0.5 (ii) SiO2/Al2O3 = 2.0 

c 

a 

d 

b 

matrix had homogenous and a good compactness, 

although there were some residual (unreacted) fly 

ash and some pores leading to the highest final 

strength. Microstucture of SiO2/Al2O3 = 5.0 

exhibited more unreacted fly ash and residual 

matter, so its final strength decreased. Improvement 

in microstructural homogheneity is conventionally 

a strong indication of higher strength (De Silva, 

2007). 

(iii) SiO2/Al2O3 = 3.0 (iv) SiO2/Al2O3 = 5.0 

Figure 9 SEM Micrograph of Geopolymer with Variation of Al2O3 Moles (a. grain structure, 

b. Cemented grain structure, c. Dense matrix geopolymer, d. Pore, e. Unreacted fly ash) 

b 

e



SEM images of geopolymer with variation of SiO2 

moles are presented in Fig. 10. Microstucture of 

SiO2/Al2O3 = 1.5 showed needle structure with 

some grains. This structure was caused by the ratio 

of SiO2/Na2O which was very lower than the other 

composition. There were no geopolymer matrix so 

it exhibited the lowest strength. Microstucture of 

SiO2/Al2O3 = 2.5 shows more cemented grain 

structure with unreacted fly ash, so it caused more 

Conclusions 

a 

ISBN : 978 – 979 – 19201 – 0 – 0 

strength than that of SiO2/Al2O3 = 1.5. 

Microstucture of SiO2/Al2O3 = 3.5 showed 

geopolymer matrix with some unreacted reactants 

and pores so it reached high enough strength. While 

microstucture of SiO2/Al2O3 = 5.0 showed dense 

geopolymer matrix with some cracks and unreacted 

fly ash. This matrix of SiO2/Al2O3 = 5.0 was so 

compact that it had the highest strength in variation 

of SiO2. 

c 

b d 

(i) SiO2/Al2O3 = 1.5 (ii) SiO2/Al2O3 = 2.5 

f 

d 

e g d 

(iii) SiO2/Al2O3 = 3.5 (iv) SiO2/Al2O3 = 5.0 

Figure 10 SEM Micrograph of Geopolymer with Variation of SiO2 Moles 

a. grain structure, b. needle structure, c. more cemented grain 

structure, d. unreacted fly ash, e. geopolymer matrix, 

f. Pores, g. cracks 

Addition of aluminate species at constant silicate 

and decrease of NaOH molarity made setting time 

increase as there were more Al(OH)3(H2O) 

complex species prohibited polycondensation 

reaction. The optimum compressive strength was 

acieved at mol ratio of SiO2/Al2O3=3.0 for variation 

of Al2O3 and SiO2/Al2O3=5.0 for variation of SiO2. 

The total moles of the starting materials of both 

variation were similar, but they were very different 

in compressive strength because of the effect of 

differences in SiO2/Na2O ratio. The phase 

e 

development shows that the greater SiO2/Al2O3 mol 

ratio, the greater formation of amorphous 

homogenous phase. It lead to reach optimum 

SiO2/Al2O3 mol ratio. FTIR study shows that the 

greater SiO2/Al2O3 mol ratio, the greater intensity 

wave number of vibration meaning increasing of 

the chain length Si-O-Al or Si-O-Si and increasing 

vibration energy. It revealed that there were more 

formation of gel aluminosilicate in 

geopolimerisation and that the chemical bond of Si- 

O-Al or Si-O-Si getting strong at optimum 

SiO2/Al2O3 mol ratio. Grain structure appeared at 

low SiO2/Al2O3 and it made lower strength, while 

homogenous geopolymer matrix appeared at 




optimum SiO2/Al2O3 mol ratio and it lead to higher 

strength. Unreacted fly ash and residual reactant 

appeared at high SiO2/Al2O3 mol ratio caused a 

lower strength geopolymer. In the SiO2-Al2O3- 

Na2O-H2O system, all component are 

interdependent relationship, so in this research there 

was significant effect of Na2O and H2O, too. 

References 

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Griffith, C. S., Davis, J., and Durce, D., 

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Prepared Using Class F Fly Ash and 

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1232. 

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Cement and Concrete Composites, Vol. 29, 

page 224-229. 

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Rock Geosynthesis and the Resulting 

Development of Very Early High Strength 

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Vol. 16 (2&3), page 91-139. 

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University, Kiev, Ukraine, page 131-149. 

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“Geopolymer : Ultra-High Temperature 

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ISBN : 978 – 979 – 19201 – 0 – 0 

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W., M., and van Deventer, J., S. J., (2007), 

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Relationship between Geopolymer 

Composition, Microstructure and 

Mechanical Properties”, Colloids and 

Surfaces, Vol. 269, page 47-58. 

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October 2008. 

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and Sanz, J., (2006), “The Role Played by 

Reactive Alumina Content in the Alkaline 

Activation of Fly Ashes”, Microporous and 

Mesoporous Materials, Vol. 91, page111- 

119. 

Fletcher, R.A., MacKenzie, K. D. J., Nicholson, C. 

L., and Shimada, S., (2005), “The 

Composition Range of Aluminosilicate 

Geopolymers”, Journal of The European 

Ceramic Society, Vol. 25, page. . 1471-1477. 

Hardjito, D., Wallah, S. E., Sumajouw, M. J., 

Rangan, B. V, (2004), “Factors Infuencing 

The Compressive Strength of Fly Ash-Based 

Geopolymer Concrete”, Dimensi Teknik 

Sipil, Vol. 6, No. 2, page 88-93. 

Kamhangrittirong, P. and Suwanvitaya, P., (2006), 

“The Effect of Fly Ash Content and Sodium 

Hydroxide Molarity on Geopolymer”, 

International Conference on Pozzolan, 

Concrete and Geopoymer, page 213-218. 

Komnitsas, K. and Zaharaki, D., (2007), 

“Geopolimerisation : A Review and 

Prospects for the Minerals Industry“, 

Minerals Engineering, Vol. 20, page 1261- 

1277. 

Lee, W. K. W. and van Deventer, J. S. J., (2002), 

“The Effect of Ionic Contaminants on the 

Early-Age of Alkali-Activated Fly Ash 

Cement“, Cement and Concrete Research, 

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Mishra, A., Choudhary, D., Jain, N., Kumar, M., 

Sharda, N., and Dutt, D., (2008). “Effect of 

Concentration of Alkaline Liquid and Curing 

Time on Strength and Water Absorption of 

Geopolymer Concrete”. Asian Research 

Publishing Network (ARPN) Journal of 

Engineering and Applied Sciences, Vol. 3, 

No. 1, page 14-18. 




Palomo, A., Grutzeck, M. W., and Blanco, M. T., 

(1999), “Alkali-Activated Fly Ashes, A 

Cement for the Future”, Cement and 

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1329. 

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(2003), “Characteristics of Aluminosilcate 

Hydrogels Related to Commercial 

Geopolymers”, Materials Letters, Vol. 57, 

page 4356-4367. 

Rizain, (2008), Pelarutan Aluminium and Silikon 

Berbagai Abu Layang Batubara dari Empat 

PLTU Menggunakan Variasi Konsentrasi 

NaOH and Temperatur, Tesis, Program 

Magister FMIPA Institut Teknologi Sepuluh 


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Aluminum(III) in Aqueous Systems”, 

Coordination Chemistry Reviews, Vol. 219- 

221, page 665-686. 

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(2002), “Geopolymer Manufacture and 

Application – Main Problems when Using 

Concrete Technology”, Proceeding of 

International Conference on Geopolymer, 

28-29 October, Melbourne, Australia. 

van Deventer, J. S. J., Provis, L. J., and Lukey, G. 

C., (2007), “Reaction Mechanisms in the 

Geopolymeric Conversion of Inorganic 

Waste to Useful Products”, Journal of 

Hazardous Materials, Vol. A139, page 506- 

513. 

van Jaarsveld, J. G. S., and van Deventer, J. S. J., 

(1996), “The Potential Use of Geopolymeric 

Materials to Immobilize Toxic Metals : Part 

I. Theory and Application”, Journal of 

Minerals Engineering, Vol. 10, No. 7, page 

659-669. 

van Jaarsveld, J. G. S., van Deventer, J. S. J., and 

Lukey, G. C., (2003), “The Characterization 

of Source Materials in Fly Ash-Based 

Geopolymers”, Materials Letters. Vol. 57, 

page 1272-1280. 

van Jaarsveld, J.G.S. and van Deventer, J. S. J., 

(1996), The Potential Use of Geopolimeric 

Materials to Immobilize Toxic Metals : Part 

I. Theory and Applications, Minerals 

Engineering, Vol. 10, No. 7, page 659-669. 

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S., (2005), “Effects of Aluminates on the 

Formation of Geopolimers”, Materials 

Science and Engineering B, Vol. 117, page 

163-168. 

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Geopolymerisation of Alumino-silicate 

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Processing, Vol. 59, page 247-266. 

ISBN : 978 – 979 – 19201 – 0 – 0 




ISBN : 978 – 979 – 19201 – 0 – 0 

Structural Shielding Design for Mobile X-Ray Units in Local Public Hospitals 

in Yogyakarta. 

Introduction 

Zaenal Abidin 

Sekolah Tinggi Teknologi Nuklir-Badan Tenaga Nuklir Nasional 

Jln Babarsari. P.O.BOX 6101 YKBB Yogyakarta 55281 

Telp : (0274) 48085, 489716; Fax : (0274) 489715 

E-mail : zaenala6@gmail.com 

Abstract 

A research has been conducted on the operation of mobile X-ray units in three local public hospitals in 

Yogyakarta in order to determine the minimum thickness for safe structural shielding. Data were taken by 

operating each machine 25 times, respectively, in 70 kV and 40 mAs. The level of radiation exposure was 

then measured with the tube positions of vertical, axial, horizontal to determine the safe distance and shield 

thickness. The result shows that the safe distance for the position beside the tube is 3.08 meters for the 

operators and 12.02 meters for others, while for the position behind the tube, the safe position is 1.41 

meters for both. The structural shielding needed is 1.5 mm lead (Pb) or 16 cm concrete. 

Keywords: X-ray Mobile Unit, tube position, safe distance, structural shielding. 

Mobile X-ray systems are moved around hospitals 

all the time to perform radiographic photography on 

patients who cannot easily get into an X-ray room. In 

operating the machine, we must be sure that it is safe 

for the staffs, personnel or operators of the X-ray unit, 

patients and other members of the public. 

International regulations demand that diagnostic 

and therapy departments are built to ensure that 

radiology and radiotherapy staffs, personnel working in 

the vicinity of a radiation source, patients and members 

of the public are exposed to the minimum amount of 

radiation [1] . 

Local public hospitals in Yogyakarta which possess 

the facility of x-ray mobile units rarely use them in the 

treatment room (in situ) due to the fact that the safe 

distance from the radiation shining is not yet known 

concerning the radiation exposure [2] . This research will 

reveal how much the radiation exposure is, what the 

safe distance is and how to design the required 

structural shielding. 

Theory 

The basic principles of external radiation 

protection are lengthening the distance, shortening the 

shining exposure, and using appropriate radiation 

shield. A mobile X-ray machine is a source of external 

radiation. Therefore, for protection from external 

radiation, make sure to use shortest time with 

the radiation, and farthest possible distance for 

radiation, and the necessary thickness of 

radiation shield. 

The formula in calculating radiation and 

distance is a reversed square: [3] 

1 

Dr = K × 2 

r 

or Dr . r 2 = K 

so Dr 1 . r1 2 = Dr 2 . r2 2 = Dr 3 . r3 2 = K 

[1] 

where: 

K is a constant which depends on the source, 

Dr 1 is dose rate at distance r1, 

Dr 2 is dose rate at distance r2, and 

Dr 3 is dose rate at distance r3. 

The purpose of radiation shielding is to 

limit radiation exposures to human beings (both 

workers and the public) to an acceptable level. 

Shielding of X-ray machines consists of two 

kinds: tube housing shielding and structural 

shielding. 

X-ray tube housing shielding of energies less 

than 500 KV, in accordance with NCRP 

(National Council on Radiological Protection 

and Measurement) shall have the maximum 

leakage dose of 1 R/hr [1] . 

Primary protective barrier is the wall of 

x-ray room designated to face primary rays or 




useful beam and the secondary protective barrier is 

intended to shield Leakage radiation from the tube 

housing and scattered radiation from the machine. 

Primary Protective barrier (Barrier against Useful 

Beam) 

The attenuation or the number of Roentgens per milli 

Ampere minutes in a week for the useful beam 

normalized at one meter, K [4] (see Fig.1) 

2 

P.( 

d pri) 

K = R / mA- 

min at 1 m [2] 

WUT 

ISBN : 978 – 979 – 19201 – 0 – 0 

P = permissible dose 0.1 R/week for 

Radiation Worker (Controlled Area) or 

0.01 R/week for Non Radiation Worker 

(Non Controlled Area) 

dpri = distance between focus and point of 

interest 

W = work load (mA-minutes)/week 

U = Use factor (U=1 for Floor, and U 

=0.25 for walls) 

T = Occupancy factor 

By calculating the K value, we can determine 

the thickness of Primary Protective barrier by 

plotting K value to the graph for certain kV of 

Fig.1 

Figure 1 Attenuation in lead of x-rays produced by potentials of 50 to 200 kV. [4] 

Secondary Protective Barrier (Barrier against Leaked 

Radiation) 

The transmission factor B [4] is 

2 

P.( 

dsec) 

. 60. 

I 

B = [3] 

W. 

T 

Where: 

P = permissible dose 0.1 R/week for 

Radiation Worker (Controlled Area) or 

0.01 R/week for non Radiation Worker 

(Non Controlled Area) 

dsec = distance between focus and point of 

interest 

W = work load (mA-minutes)/week 

T = Occupancy factor 




I = milli Ampere 

To determine the thickness of secondary protective 

barrier against leakage radiation transmission factor B 

is equal to 

n 

B = ( 1/ 

2) 

[4] 

n = X / HVL 

Where: 

X = thickness of Secondary protective barrier 

against leakage radiation 

HVL = Half Value Layer 

Secondary Protective Barrier (Barrier against 

Scattered Radiation) 

The attenuation or the number of Roentgens per milli- 

Ampere minutes in a week for the useful beam 

normalized at one meter, K (see Fig.1). We take Fig.1 

because of by assuming that the energy of the scattered 

radiation when the X-rays are generated at 500kV or 

less, is equal to the energy of the useful beam [4] 

2 2 

P.( 

dsec) 

.( dsca) 

. 400 

K = [5] 

a. 

W. 

T. 

F 

P =permissible dose 0.1 R/week for Radiation 

Worker (Controlled Area) or 0.01 R/week for 

Non Radiation Worker (Non Controlled Area) 

dsec =distance between focus and point of interest 

dsca = distance between focus and scattered 

W =work load (mA-minutes)/week 

T =Occupancy factor 

F =Area of scattered to incident exposure at 1 

meter from the scattered 

By calculating K value, we can determine the 

thickness of the Secondary Protective barrier against 

scattered radiation by plotting K value to the graph for 

certain KV of Fig. 1 above. 

If the thickness of required barrier for leakage 

and scattered radiations is found to be approximately 

the same, one HVL should be added to the larger one 

to obtain the required total secondary barrier thickness. 

If the two differ by at least one TVL, the thicker of the 

two will be adequate. 

Selecting the material and form used for the 

structural radiation shield is based on the number of 

radiation energy exposed to be attenuated, the barrier 

function, factors of practicality and efficiency in usage, 

storage, and economical, as well as the rules by 

Department of Health in 1999 [6] . The selected material 

is lead (Pb) plat of 2 mm thick with the U-form [7] . 


Device and material 

ISBN : 978 – 979 – 19201 – 0 – 0 

Survey meter was used in measuring the 

radiation secondary exposure, roll meter in 

measuring distance, and warning sign lamps, 

film badge (to record the individual radiation 

dose), mobile X-ray machines (Siemens DSA-7), 

and protective lead apron. 

Activity 

Data were taken by operating each machine 25 

times in three hospitals: Regional Public 

Hospital (RPH) Yogyakarta, RPH Sleman, and 

RPH Wonosari Gunung Kidul, by measuring 

the dose rate at the distances of 2.24 m and 1.41 

m from tube placed as high as the gonad, using 

the protection procedure taken with exposure at 

70kV/40mAs. The data were recorded and 

calculated using the formulation explained 

above. Shining was conducted to the object of a 

fat body by 70kV and 40mAs. Focus film 

distance (FFD) is 1 meter and then pulled aside 

2 meters with the farthest assumption distance 

of patient’s bed, so the distance r1 is 2.24 meters 

from the focusing tube, while for the behind 

position used FDD one meter, and distance of r1 

is 1.41 meter from the focusing tube; such a 

distance is assumed as the distance of the 

worker in standing position. 

The Calculation 

Calculation taken into consideration by using 

the formulations above concerning with the 

condition of: 

Orientation factor (U) [5] 

• If the radiation beam is oriented in 

some particular direction for more than 

50 per cent of the time when the device 

is in use, then a value of U = 1 is used 

for specifying the shielding in this 

direction. 

• If the radiation beam is oriented in 

some particular direction for less than 

50 per cent of the time when the device 

is in use, then a value of 0.25 

may be used for specifying the 

shielding. However, the orientation 

factor must always be no smaller than 

the proportion of time in use for which 

the beam is oriented in this direction. 




• A value of U = 1 is used in directions affected 

only by leakage and scattered radiations. 

Occupancy factor (T) 

• A value of T = 1 is used in working premises 

and, in the case of medical use of radiation, 

also in waiting rooms and patient rooms. 

• A value of 0.1 < T < 1 may be used in indoor 

or outdoor premises where human beings do 

not remain on a continual basis (e.g. WCs, 

corridors, storerooms or streets). However, the 

occupancy factor shall always be no smaller 

than the proportion of time during which 

human beings occupy the area concerned. 

Result and Discussions 

In the medical radiography, the technique of 

taking pictures, i.e. the tube position, is determined by 

patient condition. The position and function of the tube 

should be as follows: 

Table 1. Tube Position and Function [2] 

No Position Function 

1. Vertical Taking pictures of 

cranium, cervical, thorax, 

abdomen, pelvis, thoracic 

vertebrae, lumbosacral 

2. Axial 

vertebrae, for high and 

low extremities. 

35 o 

Taking pictures of thorax 

with the patient’s 

position half seated, 

abdomen with the 

patient’s position half 

seated, and cranium with 

towne’s position 

3. Horizont Taking pictures of 

al cranium lateral, cervical 

lateral, and abdomen 

with the patient’s 

position of LLD (Lateral 

Left Dicubitus) 

For RPH Yogyakarta, the pause time is assumed 

10 minutes, shining is conducted for 144 times each 

day, 7 days a week, at each exposure uses the current 

rate of 40 mAs,70 kV. So the total number of exposure 

is 1008 times per week. 

Workload W = 1008 exposure/week X 40mAs: 

60(min/s) 

= 672 mA.min/week 

ISBN : 978 – 979 – 19201 – 0 – 0 

Calculating the thickness of Shielding for 

Primary Radiation 

P (maximum exposure allowed) is 0.1 (for 

controlled area), and 0.01 (for uncontrolled 

area), the distance (d) = 2 m, W= 672 

mA.min/week, U (Use Factor) = for wall and 

1 for floor. 

T (Occupancy Factor) : 1 

(active room) 

a.Wall A = primary radiation = horizontal beam 

Kwall A = 0.002 R/mA-min = 2 x 10 -3 

R/mA-min. 

Based on reference 6, to obtain the required 

attenuation for the curve 125 kVp we need the 

lead (Pb) thickness of 1.5 mm while to get the 

same attenuation for concrete the thickness 

needed is 12.7 cm. 

b.Floor = primary radiation = Vertical Beam 

Kfloor = 0.000067 R/mA-men = 7 x 10 -3 R/mAmin. 

Based on reference 8, the thickness required is 

2.8 mm for lead or 21.895 cm for concrete. 

Calculating the thickness of Shielding for 

Secondary Radiation 

Wall B 

a. Wall B = scattered radiation = Vertical 

beam 

Given: 

P = 0.01 R (uncontrolled area) 

W = 672 mA-min/week 

dSCA = 1 m 

T = 1 

dSEC = 1.4 m 

F = 38.3087 cm 2 

a = 0.0015 (90 O ) 

f = 1 

= 0.2072 

KUX 

Based on reference 6, the thickness required for 

radiation shielding is 0.2 mm for lead or 0.5 cm 

for concrete. 

b.Wall B = scattered radiation = Horizontal 

beam 

Given: 



dSCA = 1.5 m 

T = 1 

dSEC = 1.803 m 

F = 86.1948 cm 2 




ISBN : 978 – 979 – 19201 – 0 – 0 

a = 0.0015 (45 O ) 

f = 1 

e. Wall B = leaked radiation = Vertical beam 

KUX = 0,3367 

Given: 


From the curve for 125 kVp the required thickness for W = 672 mA-min/week 

radiation shielding is 0.13 mm for lead or 0 cm for d = 1.414 m 

concrete. 

T = 1 

I = 125 mA 

c.Wall B = scattered radiation = Horizontal beam 

BLx = 2.2315 

BLx = ½ n 

Given: 

2.2315 = ½ n 



n = -0.2895 

dSCA = 1.5 m 

T = 1 Because the result of n is negative, then the 

dSEC = 1.803 m 

leaked radiation is not taken into account, so 

F = 86.1948 cm that there is not shielding required for leaked 

radiation. 

2 

a = 0.0015(90 O ) 

f = 1 

KUX = 0,3367 f. Wall B = leaked radiation = Horizontal beam 

Given : 

From the curve for 125 kVp the required thickness for P = 0.01 R 

radiation shielding is 0.13 mm for lead or 0 cm for W = 672 mA-min/week 

concrete. 

d = 1.803 m 

T = 1 

d. Wall B = scattered radiation = Horizontal beam 

I = 125 mA 

Given: 

BLx 

BLx 

= 3.628 

= ½ n 


3.628 = ½ n 


dSCA = 1.5 m n = -0.4648 

T = 1 

dSEC = 1.803 m Again, because the result of n is negative, then 

F = 86.1948 cm the leaked radiation is not taken into account, so 

that there is not shielding required for leaked 

radiation. 

2 

a = 0.0025 (135 O ) 

f = 1 

KUX = 0.2020 The safe distances for radiation exposure from 

the mobile X-ray machines in the three hospitals 

From the curve for 125 kVp the required thickness for 

radiation shielding is 0.2 mm for lead or 0.5 cm for 

concrete. 

can be seen in the tables below. 

No Tube 

position 

Table 2. Result of measurement mobile x-ray machine in RPH Senopati Bantul 

Patient’s 

bed 

position 

1 Vertical Beside 

tube 

2 Axial 

35 0 

Beside 

tube 

Distance 

patient’s 

bed 

r1(m) 

Average 

Dose 

scatter 

(mrem) 

D1 

(mre 

m/s) 

DVL (D2) 

Mrem/s 

2.24 0.018 0.009 694E-6(worker) 

208E-6(staff) 

694E-6(public) 

2.24 0.01 0.005 694E-6(worker) 

208E-6(staff) 


2 

D xr 

D 

2 

1 1 

Safe 

distance (m) 

8.06 

14.73 

25.51 

6.01 

10.98 

19.01 


r = 

2



3 Axial 

35 0 

4 horizon 

tal 

5 horizon 

tal 

No Tube 

position 

Behind 

tube 

Beside 

tube 


tube 

1.41 0.00 0.000 694E-6(worker) 

208E-6(staff) 

ISBN : 978 – 979 – 19201 – 0 – 0 


2.24 0.01 0.005 694E-6(worker) 

208E-6(staff) 


1.41 0.00 0.000 694E-6(worker) 

208E-6(staff) 


Table 3. Result of measurement mobile x-ray machine in RPH Sleman 

Patient’s 

bed 

position 


tube 

2 Axial 

35 0 

3 Axial 

35 0 

4 horizon 

tal 

5 horizon 

tal 

Beside 

tube 


tube 

Beside 

tube 


tube 

Distance 

patient’s 

bed 

r1(m) 

Average 

Dose 

scatter 

(mrem) 

D1 

(mre 

m/s) 

DVL (D2) 

Mrem/s 

2.24 0.018 0.009 694E-6(worker) 

208E-6(staff) 


2.24 0.014 0.007 694E-6(worker) 

208E-6(staff) 


1.41 0.00 0.000 694E-6(worker) 

208E-6(staff) 


2.24 0.04 0.002 694E-6(worker) 

208E-6(staff) 


1.41 0.00 0.000 694E-6(worker) 

208E-6(staff) 


Safe 

6.01 

10.98 

19.01 

Safe 

r = 

2 

Safe 

distance (m) 

8.07 

14.73 

25.51 

7.11 

12.99 

22.50 

Safe 

3.80 

6.94 

12.02 

Safe 

Table 4. Result of measurement mobile x-ray machine in RPH Wonosari Gunung Kidul 

No Tube 

position 

Patient’s 

bed 

position 


tube 

2 Axial 

35 0 

3 Axial 

35 0 

4 horizon 

tal 

Beside 

tube 


tube 

Beside 

tube 

Distance 

patient’s 

bed 

r1(m) 

Average 

Dose 

scatter 

(mrem) 

D1 

(mre 

m/s) 

DVL (D2) 

Mrem/s 

2.24 0.01 0.005 694E-6(worker) 

208E-6(staff) 


2.24 0.01 0.005 694E-6(worker) 

208E-6(staff) 


1.41 0.00 0.000 694E-6(worker) 

208E-6(staff) 


2.24 0.002 0.005 694E-6(worker) 

208E-6(staff) 


D xr 

D 

2 

1 1 

Safe 

distance (m) 

6.01 

10.98 

19.01 

6.01 

10.98 

19.01 

Safe 

3.80 

6.94 

12.02 


r = 

2 

2 

D xr 

D 

2 

1 1 

2



5 horizon 

tal 


tube 

1.41 0.00 0.000 694E-6(worker) 

208E-6(staff) 


Using the formulations above, the shielding can presented in the table below. 

Location K (R/ 

Table 5. Result of thick shielding calculation for structural shielding 

mA - minut 

week 

Floor / Primer 6 . 10 -5 

Wall A / Primer 2 . 10 -3 

Wall B/ scattering 2.07 . 10 -1 

3.37 . 10 

Wall B/ scattering 

-1 

3.37 . 10 -1 

2.02 . 10 -1 

Wall C/ scattering 1.295 . 10 -1 

5.18 . 10 

Wall C/ scattering 

-1 

5.18 . 10 -1 

3.11 . 10 -1 

Wall D/ scattering 3.367 . 10 -1 

4.656 . 10 

Wall D/ scattering 

-1 

4.656 . 10 -1 

2.793 . 10 -1 

Ceiling /scattering 3.7291 

Ceiling /scattering 7.3090 

) Direction 

Thickness(mm) 

Lead 

ISBN : 978 – 979 – 19201 – 0 – 0 

Safe 

Thickness 

(cm) 

concrete 

Vertical 2.,8 21.895 

Horizontal 1.5 12.7 

Vertical 0.2 0.5 

0.13 

0 

Horizontal 0.13 

0 

0.2 

0.5 

Vertical 0.33 0 

0.06 

0 

Horizontal 0.06 

0 

0.13 

0 

Vertical 0.13 

0.1 

0 

Horizontal 

0.1 

0.13 

0 

Vertical 0 0 

Horizontal 0 0 

Table 6. The calculation of Leak radiation 

Location Direction BLx = ½ n 

= P x (d)² x 600 x I 

N 

W x T 

Wall B Vertical 2.2315 -0.2895 

Horizontal 3.6280 -0.4648 

Wall C Vertical 1.3950 -0.1201 

Horizontal 5.5800 -0.6201 

Wall D Vertical 3.2810 -0.4649 

Horizontal 5.0161 -0.5817 

Ceiling Vertical 151.7882 -1.8117 

Horizontal 111.6071 -1.7007 

Discussion 

NCRP (National Council on Radiological 

Protection and Measurement) recommends that the 

maximum permissible dose is 25 µSv/hr (2.5 mrem/hr) 

for radiation workers, 7.5 µSv/hr for staff, and 2,5 

µS3v/hr.(0.25 mrem/hr) for public [6] . In this research, 

using the closest distance assumption among the 

patient’s beds 1,5 meters and FFD 1 meter, it 

was found that the distance of r2 was 1.80 

meters from the tube. After that, the results of 

calculating the dosage rate (D2) in each hospital 

can be seen in Table 7, 8 and 9. 




No Tube position 

1. 

2. 

3. 

4. 

5. 

Vertical 

Axial 35 0 

Axial 35 0 

Horizontal 

Horizontal 


1. 

2. 

3. 

4. 

5. 

Vertical 

Axial 35 0 

Axial 35 0 

Horizontal 

Horizontal 


1. 

2. 

3. 

4. 

5. 

Vertical 

Axial 35 0 

Axial 35 0 

Horizontal 

Horizontal 

D1 

(mrem/s) 

0.009 

0.005 

0.000 

0.005 

0.000 

Table 7. Dose rate in RPH Senopati Bantul 

r1 

(m) 

2.24 

2.24 

1.41 

2.24 

1.41 

Patient’s bed 

Beside tube 

Beside tube 

Behind tube 

Beside tube 


Table 8. Dose rate in RPH Sleman 

D1 

(mrem/s) 

0.009 

0.007 

0.000 

0.002 

0.000 

r1 

(m) 

2.24 

2.24 

1.41 

2.24 

1.41 


Beside tube 

Beside tube 


Beside tube 


ISBN : 978 – 979 – 19201 – 0 – 0 

r2 

(m) 

1.80 

1.80 

1.80 

1.80 

1.80 

Table 9. Dose rate in RPH Wonosari Gunung Kidul 

D1 

(mrem/s) 

0.005 

0.005 

0.000 

0.002 

0.000 

r1 

(m) 

2.24 

2.24 

1.41 

2.24 

1.41 

Based on the tables above, calculating the 

design of safe structural barrier in the U-form (see in 

Fig 3 & Table 5), the highest load is for RPH Sleman, 

which is then taken as the standard for the other two 

hospitals for more safety. The calculation result 

requires the structural barrier with the thickness of 1.5 

mm (rounded to 2 mm) for lead wall or 16 cm for 

concrete wall, and 2.8 mm for lead floor [6] . 

Conclusion 

1. The assumption that the closest distance among 

the patient beds is 1.5 meters beside the tube 

proved to be unsafe for the workers. The closest 

safe distance beside the tube is 3.80 meters for the 

workers and is 12.02 meters for public. While for 

the position behind the tube, the closest safe 

distance for both the workers and public is 1.41 

meters. 


Beside tube 

Beside tube 


Beside tube 


r2 

(m) 

1.80 

1.80 

1.80 

1.80 

1.80 

D2 

(mrem/s) 

0.0139 

0.0077 

0.0000 

0.0077 

0.0000 

r2 

(m) 

1.80 

1.80 

1.80 

1.80 

1.80 

D2 

(mrem/s) 

0.0077 

0.0077 

0.0000 

0.0031 

0.0000 

D2 

(mrem/s) 

0.0139 

0.0108 

0.0000 

0.0031 

0.0000 

2. Based on the calculation, the minimum 

thickness required for safety shield for the 

primer radiation is 1.5 mm for lead (Pb) 

wall or 16 cm for concrete wall, and 2.8 

mm for lead floor. 

References 

(1) NCRP, 2004, Structural Shielding 

Design for Medical X-ray Imaging 

Facilities, Report No. 147 (Revised 

March 2005), NCRP Bethesda, MD. 

(2) Abidin Z.,Toto K.& Taufiq Z.,2008, The 

Operation of X-ray Mobile Unit in Three 

Local Public Hospital in Yogyakarta, 

Proceeding Seminar NHI &GTN, ISSN 

No 1693-3346 page 119-125, Jakarta. 

(3) Taufiq Z, 2008, The Analysis of Safety in 

The Operation of X-Ray Mobile Unit in 

The Care Room of The Regional State 




Hospital in Yogyakarta, Final Report in POIN, 

Yogyakarta. 

(4) Cember H, Introduction to Health Physics, 

Second Edition, Pergamon Press, 1985. . 

(5) Simpkin DJ, Dixon RL. Secondary Shielding 

Barriers for Diagnostic X-Ray Facilities: 

Scatter and Leakage Revisited. Health Phys 

1998;74:350–65. 

Figure 2 Scheme of the existing shielding in most hospital 

ISBN : 978 – 979 – 19201 – 0 – 0 

(6) NCRP, 1976, Structural Shielding 

Design and Evaluation, Report No. 49 

(September 1976), NCRP 

(7) Bumiasih T, 2008, The Design of The 

Radiation Shielding of The X-Ray 

Generator in Distric General Hospital 

Yogyakarta City, Final Report in POIN, 

Yogyakarta. 




Wall D Wall B 

Peeping window 

Wall C 

Wall D. Side orientation 

Supporting frame made from steel plat of 3 mm thick and 

3,2 cm wide 

Figure 3 Design of Structural Shielding 

ISBN : 978 – 979 – 19201 – 0 – 0 




Introduction 

ISBN : 978 – 979 – 19201 – 0 – 0 

MgF2 as Catalyst and Support on Phenol Acylation 

Nisa Nurina Valerie and Irmina Kris Murwani * 

Chemistry Study Program, Faculty of Mathematics and Natural Sciences, 

Sepuluh Nopember Institute of Technology, 

Keputih ITS Campuss, Sukolilo, Surabaya, Indonesia, 60111. 

*e-mail : irmina@chem.its.ac.id 

Abstract 

The using of MgF 2 as catalyst and support for phenol acylation with acetic acid has been studied. The 

reaction is an alternative method to reduce the phenol concentration. Generally, the acylation reactions 

involve the use of Lewis acid catalysts. MgF 2 is one of the non toxic Lewis acid catalysts. MgF 2 in this 

research were prepared and characterized using X-ray diffraction (XRD), Fourier Transform infrared 

spectroscopy (FTIR) and measurement of specific surface area with N 2 adsorption. The catalytic activities 

were determined based on phenol conversion. Result of this research indicated that MgF 2 and CuO/MgF 2 

serve the purpose of supported catalyst with phenol conversion 95.23 and 90.53%, respectively. This 

conversion value showed a linear correlation with its specific surface area, that is 31.38 and 12.75 m 2 /g, 

respectively. Analysis of phenol acylation using HPLC showed that acetophenone was the main product 

with selectivity MgF 2 45.37% and CuO/MgF 2 52.32%. 

Keywords: Catalyst, MgF 2, phenol acylation, support. 

Phenol acylation is an important and frequently used 

organic transformation as it provides not only an 

efficient and inexpensive route for the protecting 

hydroxy group but also produced important organic 

intermediates in multi-step synthetic processes which 

are widely used in the synthesis of fine chemicals, 

pharmaceuticals, perfumes, plasticizers, cosmetics, 

chemical auxiliaries, etc. [6]. Hidroxyacetophenones 

(HAP) which are useful intermediates for the 

manufacture of pharmaceuticals can be obtained 

through catalytic rearrangement of phenyl acetate or 

direct acylation of phenol by acetic acid [9]. In 

particular, p-HAP is widely used for the synthesis of 

paracetamol and o-HAP is a key intermediate for 

producing 4-hydroxycoumarin and warfarin, which 

are both, used as anticoagulant drugs [8]. Acylation is 

normally achieved by treatment with acetic acid in the 

presence of suitable catalysts. Homogeneous catalysts 

such as AlCl3, CoCl2, CuCl2, FeCl3 and TiCl5 have 

been used for the acylation of phenol. However, one 

of the major problems in homogeneous reaction is the 

separation of the catalyst from the reaction mixture. 

Heterogeneous catalysts are found to be very good 

alternatives to the problems associated with proton 

acids (Lewis acids) or Friedel-Crafts type catalysts 

[2,8,12]. Phenol acylation with acetic acid over MgF2 

and copper oxide catalyst supported on MgF2 was 

investigated. The aim of this investigation is also to 

study the effect of copper oxides on MgF2 during 

acylation. The catalysts were characterized by various 

techniques like XRD, FTIR and BET surface area. 

MgF2 as Lewis acid is one candidate as support and 

catalyst. 


Catalyst preparation and characterization 

Magnesium fluoride was prepared according to the 

literature [14]. The copper oxides catalyst supported 

on MgF2 was prepared by wet impregnation method. 

The support was impregnated with Cu(ClO4)2 in 

water followed by drying. This precursor was 

activated by calcinations at 400°C for 4 h. Catalysts 

characterization was carried out by means of XRD, 

FTIR and BET. XRD characterization was performed 

using XRD JEOL JDX-3530 (Cu Kα). FTIR 

characterization was performed using Shimadzu 

FTIR-8400S with DRS-8000. Specific surface areas 

were determined by means of N2 adsorption measured 

with Quantachrome NovaWin2-Data Acquisition and 

Red for NOVA instruments version 2.1. 

Catalytic activity on phenol acylation 




The catalytic properties of the catalysts were 

determined using HPLC method. Phenol acylation 

were carried out in magnetically stirred glass reactor 

at the following reaction conditions: reaction mixture 

= catalyst + acetic acid + phenol, temperature = 25°C, 

reaction period = 15 minutes. The catalytic activity 

was observed based on concentration of phenol 

conversion. The catalytic selectivity was observed 

based on acetophenone product formed. 


MgF2 Catalyst 

This paper reports results on obtaining magnesium 

fluoride in the sol-gel reaction of magnesium nitrate 

hexahydrate and hydrofluoric acid, according to the 

equation below: 

Mg(NO3)2.6H2O + 2HF → MgF2 + 2HNO3 + 

6H2O 

Powder X-ray diffractogram of MgF2 is shown 

in Fig. 1. The sharp diffraction lines at d = 3.275 Å, 

2.231 Å and 1.711 Å (2θ values are 27.2°, 40.4° and 

53.5°, respectively) are due to the tetragonal form of 

magnesium fluoride (PDF No. 06-0290). No 

diffraction lines noticed corresponding to 

Mg(NO3)2·6H2O, MgO or other contaminants 

detected. 

Fig. 1. X-ray diffractogram of MgF2 

FTIR spectra of magnesium fluoride is shown in 

Fig. 2. A stretching vibration for the O–H bond 

appears at 3600-3200 cm -1 . A bending vibration of 

the H–O–H bond appears at 1648.2 cm -1 [5]. During 

the preparation of magnesium fluoride, or when it is 

contacted with water vapour, water dipoles interact 

with coordinatively unsaturated Mg ions and fill their 

coordination sphere. This leads to the formation of 

surface hydroxyls. The stretching vibration for the 

Mg–F bond appears at 1200 cm -1 , 1000 cm -1 , 730 cm - 

1 and 458 cm -1 [3,11,14]. 

CuO/MgF2 catalyst 

ISBN : 978 – 979 – 19201 – 0 – 0 

Fig. 2. FTIR spectra of MgF2 

The impregnated sample was dark gray in color, 

which suggests that copper oxide phase exists in the 

sample. The copper oxide phase was formed during 

calcinations [13]. The X-ray diffraction patterns of 

CuO/MgF2 and MgF2 are presented in Fig. 3 below. 

The XRD profile of CuO/MgF2 sample exhibits the 

characteristic features of copper oxide as monoclinic 

phase (PDF No. 72-0629) with the characteristic 

peaks at at d = 2.5226 Å, 2.3217 Å and 1.7113 Å (2θ 

values are 35.6°, 38.7° and 53.5°, respectively) and 

the characteristic features of magnesium fluoride as 

tetragonal phase (PDF No. 06-0290) with the 

characteristic peaks at 2θ = 27.2°, 40.4° and 53.5°. 

Fig. 3. X-ray diffractograms of CuO/MgF2 and 

MgF2 (, : CuO) 

The copper oxide phase giving strong reflections 

only at 2θ = 38.7° appeared in the sample prepared 

by impregnation with copper loading of 2.35 wt. %. 

Diffraction pattern of CuO/MgF2 show a strong 

characteristic features of MgF2. This indicated that 

the CuO species particles, which are amorphous or 

very small, are highly dispersed within the matrix [5]. 




The FTIR spectra of CuO/MgF2 reported in Fig. 

4. The spectra have a broad absorption band at 

approximately 3550-3200 cm -1 , which is assigned to 

the O–H stretching vibration of waters. Similarly, the 

band near 1630-1600 cm -1 is associated with the 

bending mode of O–H groups of adsorbed water [5]. 

The stretching vibration for Cu–O bond appears at 

1500 cm -1 and 500 cm -1 [4,13] and the stretching 

vibration of Mg–F appears at 1000 cm -1 , 730 cm -1 and 

458 cm -1 [3,11,14]. 

Fig. 4. FTIR spectra of CuO/MgF2 

Surface area measurement 

The specific surface areas of the catalysts is given in 

Table 1. The data indicate that the impregnation of 

magnesium fluoride with an aqueous solution of 

copper perchlorate reduces the surface area and the 

pore volume of the samples, while increasing the pore 

size. This is probably due to a certain contribution of 

the CuO to the total surface area: a microporous 

system is not well developed in CuO (surface area 

1,10 m 2 /g) [5]. CuO/MgF2 showed a clear decrease in 

surface areas and average pore diameters relative to 

their supports. This is expected because the pores in 

each support are partially filled by copper oxide 

particles. 

Table 1. BET characterization of MgF2 and 

CuO/MgF2 

Catalyst Surface Area (m 2 /g) 

MgF2 

31,38 

CuO/ MgF2 

12,75 

Catalytic activity on phenol acylation 

The catalytic activity of samples was examined in 

phenol acylation with acetic acid using HPLC 

method. Acetic acid can be employed as acylating 

agent because stable and its handling are easier than 

acetic anhydrides [9]. Phenol acylation under solvent 

free condition and the using of acetic acid as 

acylating agent, hence reaction can take place faster 

ISBN : 978 – 979 – 19201 – 0 – 0 

[6]. Phenol acylation done at optimum condition 

obtained maximum catalyst activity. Activity is 

ability of catalyst in conversion reactant to become 

product wanted. Catalyst activity was determined 

based on concentration of phenol conversion that 

measured based on concentration of remains phenol. 

Phenol detected on HPLC is phenol that was not 

reacted or remains phenol. Smaller concentration of 

remaining phenol, hence ever greater converted 

phenol yielded. Optimum conditions at phenol 

acylation as according to report from [6], at 

temperature 25°C for 15 minutes. Fig. 6 presents the 

activity and selectivity of MgF2 and CuO/MgF2 

catalysts. 

Fig. 6. The activity and selectivity of MgF2 and 

CuO/MgF2 at room temperature 

Higher conversion was obtained for catalyst MgF2 

reach 95.23%. The activity of copper oxide catalyst 

supported on MgF2 was lower with phenol 

conversion reach 90.53%. Introduction of copper 

oxide caused a decrease in catalytic activity. The 

degree of conversion depends on the surface area of 

catalysts, where MgF2 shows surface area was higher 

than CuO/MgF2. Phenol conversion also can yield 

acetophenone product [1]. The copper oxide catalyst 

supported on MgF2 have proved more selective in 

phenol acylation than those MgF2 itself. Highest 

product of acetophenone was obtained by CuO/MgF2 

and declines when applied by MgF2. From the above 

characterization of catalysts, we conclude that the 

differences of selectivity would not be related to the 

specific surface area data. The state and distribution 

of Cu species in the catalysts are the key factors to 

the reaction. Based on the above results, we can 

conclude that the catalytic activity was related to the 

surface area of catalysts. All catalysts showed good 

catalytic activity for phenol acylation, which can be 

ascribed to the highest activity of each catalyst. 




Conclusion 

MgF2 proved to be an interesting catalyst and 

support for copper oxide catalyst in phenol acylation. 

This result can be ascribed to the highest activity of 

each catalyst. The experiment results showed that 

percentage of phenol conversions using the MgF2 and 

CuO/MgF2 catalysts were 95.23 and 90.53%, 

respectively. This conversion showed a linear 

correlation with surface area of each catalyst, that is 

31.38 and 12.75 m 2 /g, for MgF2 and CuO/MgF2, 

respectively. Analysis of the acylation product 

showed that the acetophenone was the main product 

of the acylation with selectivity MgF2 45.37% and 

CuO/MgF2 52.32%. 


We gratefully the support from LPPM ITS for 

financial support 

References 

[1] Baltrok, I.M., Aliyan, H., Khosropuur, A.R. 

2001. Bismuth(III) salts as convenient and 

efficient catalysts for the selective acetylation 

and benzylation of alcohols and phenol. 

Tetrahedron Lett. 57: 5851-5854. 

[2] Chandrasekhar, S., Ramachander, T., Takhi, 

M. 1998. Acylation of alcohols with acetic 

anhydride catalyzed by TaCl5: Some 

implications in kinetic resolution. Tetrahedron 

Lett. 39: 3263-3266. 

[3] Cho, D.H., Yim, S.D., Cha, G.H., Lee, J.S., 

Kim, Y.G., Chung, J.S., Nam, I.S. 1998. 

Behavior of chromium oxide on MgO or 

MgF2. J. Phys. Chem. A. 102: 7913-7918. 

[4] El-Bahy. 2007, Oxidation of carbon monoxide 

over Cu- and Ag-NaY catalysts with aqueous 

hydrogen peroxide. Mater. Research Bull. 42: 

2170-2183. 

[5] Haber, J., Wojciechowska, M., Zielinski, M., 

Przystajko, W. 2007. Effect of MgF2 and 

Al2O3 supports on the structure and catalytic 

activity of copper-manganese oxide catalysts. 

Catal. Lett. 113: 46-53. 

[6] Jeyakumar, K., Chand, D.K. 2006. Copper 

perchlorate: Efficient acetylation catalyst 

under solvent free conditions. J. Mol. Catal. A: 

Chem. 255: 275-282. 

[7] Kadgaonkar, M.D., Laha, S.C., Pandey, R.K., 

Kumar, P., Mirajkar, S.P., Kumar, R. 2004. 

Cerium-containing MCM-41 materials as 

ISBN : 978 – 979 – 19201 – 0 – 0 

selective acylation and alkylation catalysts. 

Catal. Today. 97: 225-231. 

[8] Olah, G.A. 1973. Friedel-Crafts Chemistry. 

USA: John Wiley & Sons. 

[9] Padro, C.L., Apesteguia, C.R. 2005. Acylation 

of phenol on solids acids: Study of the 

deactivation mechanism. Catal. Today. 107- 

108: 258-265. 

[10] Rao, Y.V.S., Kulkarni, S.J., Subrahmanyam, 

M., Rao, A.V.R. 1995. An improved acylation 

of phenol over modified ZSM-5 catalysts. 

Appl. Catal. A: Gen. 133: L1-L6. 

[11] Rywak, A.A., Burlitch, J.M. 1996. Sol-gel 

synthesis of nanocrystalline magnesium 

fluoride: Its use in the preparation of MgF2 

films and MgF2-SiO2 composites. Chem. 

Mater. 8: 60-67. 

[12] Velusamy, S., Borpuzari, S., Punniyamurthy, 

T. 2005. Cobalt(II)-catalyzed direct 

acetylation of alcohols with acetic acid. 

Tetrahedron. 61: 2011-2015. 

[13] Wang, Z., Liu, Q., Yu, J., Wu, T., Wang, G. 

2003. Surface structure and catalytic behavior 

of silica-supported copper catalysts prepared 

by impregnation and sol-gel methods. Appl. 

Catal. A: Gen. 239: 87-94. 

[14] Wojciechowska, M., Zielinski, M., 

Malczewska, A., Przystajko, W., Pietrowski, 

M. 2006. Copper-cobalt oxide catalysts 

supported on MgF2 or Al2O3-their structure 

and catalytic performance. Appl. Catal. A: 

Gen. 298: 225-231. 




ISBN : 978 – 979 – 19201 – 0 – 0 

The Relation between The First Step Hydrothermal Temperature and Zeolites 

Distribution on Synthesis of Zeolite from Fly Ash 

Introduction 

Aulia Rochmah, Hamzah Fansuri 

Chemistry Department, Faculty of Mathematics and Natural Sciences 

Institut Teknologi Sepuluh November (ITS) Surabaya 

Keputih Sukolilo Surabaya, East Java, Indonesia 

Corresponding Author: h.fansuri@chem.its.ac.id 

Abstract 

This research investigates the relation between the first step hydrothermal temperature on the 

synthesis of zeolite from fly ash and the zeolite distribution. The zeolite quantities were 

calculated by Quantitative X-Ray Powder Diffractions (QXRPD) using Rietveld refinement 

method supported by XRF and Cation Exchange Capacity (CEC) data. Different compositions 

of three mixed zeolite phases, i.e K-Chabazite, K-Phillipsite, and K-F, were formed at different 

first step hydrothermal temperature, i.e 100, 120, 150 and 180 o C, and second hydrothermal 

reaction at 100 o C for 6 to 96 hrs on synthesis of zeolite from fly ash. The differences between 

calculated weight percentage of oxide of zeolites XRF data was due to the existences of oxides 

in unidentified phases and amorphous phases. The differences between calculated CEC and 

experiment were caused by exchangeable cations of other phases. It was found that zeolite 

crystallization time was shorter when the first step hydrothermal temperature was higher. 

Keywords: Zeolite synthesis, Zeolite from fly ash, Quantitative XRD 

Fly ash is one of the solid wastes generated in coal fired 

power stations which has harmful effect on 

environment. One of the environmental friendly efforts 

of fly ash utilizations is fly ash conversion into zeolite 

materials. Many methods of zeolite synthesis from fly 

ash hydrothermally has been explored, i. e direct 

conversion [14, 15, 16], fusion methods [2, 4, 17], and 

extraction methods [6, 8]. Direct zeolite synthesis 

procedures have shorter stages then indirect conversion 

such as fusion and extraction methods. Although the 

direct conversion produce lower purity then those two 

methods, the zeolite products have reasonably high 

cation exchange capacity (CEC) (175 meq/100 g 

zeolites [14]). Thus, for lower grade zeolite such as 

fertilizers, the zeolite synthesis from fly ash by direct 

conversion is still feasible. 

Zeolite synthesis from fly ash by direct 

conversion has been conducted before by Muasyaroh et 

al. [13] hydrothermally using potassium hydroxide as 

alkali sources. More than one type zeolites was 

obtained, i.e K-Chabazite, K-Phillipsite, and K-F [13]. 

However, the zeolite quantities have not been 

determined, then it is not known the relation between 

the reaction conditions and zeolite formed distributions. 

It was reported that step-change of synthesis 

temperature during hydrothermal treatment reduce by 

half of the total synthesis time [9]. Moreover, 

Muasyaroh et al. [13] also showed that higher first step 

hydrothermal temperature could improve dissolution of 

silica and alumina in fly ash and shorten the zeolite 

crystallization time. 

The aims of the present work were to explore 

the relation between the first step hydrothermal 

temperature and zeolite formed distributions, in order to 

provide another method for synthesis certain zeolite 

type from fly ash with specific properties. 


Experimental 

Zeolite materials was obtained from Muasyaroh, et al. 

[13] that were synthesized from fly ash using variation 

of first step hydrothermal temperature at 100, 120, 150, 

and 180 0 C for 3,5 hours then continued by second 

hydrothermal temperature at 100 o C for 6, 24, 48, and 96 

hours. 

The zeolites were characterized by XRD, XRF 

and CEC determinations. XRD analysis was carried out 

by adding 20% internal standard of Rutile to samples 

that contain zeolite phases. The diffractograms obtained 




was analyzed quantitatively by Rietveld refinements 

method using RIETICA software. The chemical 

composition was measured using XRF and the CEC was 

determined by ammonium acetate methods. 


ISBN : 978 – 979 – 19201 – 0 – 0 

Diffractogram of samples were analyzed qualitatively 

using X’Pert Grafic and Identify Software. Table 1 

shows the identified phases found as a result of 

variations on the first step hydrothermal temperature i.e 

Mullite (PDF 15-0776), Quartz (PDF 05-0490), 

Hercynite (PDF 34-0192), Magnetite (PDF 02-1035), 

Kaliophilite (PDF 11-0313), K-Chabazite (PDF 44- 

0250), K-Phillipsite (PDF 16-0715), K-F (PDF 25- 

0619), Kalsilite (PDF 33-0988). 

Table 1. Identified Phases of zeolite products 

No. Samples 

T First Step Hydrothermal 

( o C) 

t Second Step 

Hydrothermal (h) 

Phases 

1. M1a 100 6 Ml, Q, H, Mt 

2. M1b 100 24 Ml, Q, H, Mt 

3. M1c 100 48 Ml, Q, H, Mt 

4. M1d 100 96 K-Cha, K-F, K-Phi, Ml, Q, H, Mt 

5. M2a 120 6 Ml, Q, H, Mt 

6. M2b 120 24 Ml, Q, H, Mt 

7. M2c 120 48 K-Cha, K-F, K-Phi, Ml, Q, H, Mt 

8. M2d 120 96 K-Cha, K-F, K-Phi, Ml, Q, Mt 

9. M3a 150 6 Ml, Q, H, Mt 

10. M3b 150 24 Ml, Q, H, Mt 

11. M3c 150 48 K-Cha, K-F, K-Phi, Ml, Q, H, Mt 

12. M3d 150 96 K-Cha, K-F, K-Phi, Ml, Q, H, Mt 

13. M4a 180 6 Ml, Q, H, Mt 

14. M4b 180 24 K-Cha, K-F, K-Phi, Ml, Q, Mt 

15. M4c 180 48 K-Cha, K-F, K-Phi, Ml, Q,H, Mt 

16. M4d 180 96 K-Cha, K-F, K-Phi, Ml, Q, Mt 

Mul=Mullite, Q=Quartz, H=Hercynite, Mag=Magnetite, K-Cha=K-Chabazite, K-F= K-F, 

K-Phi=K-Phillipsite 

Figure 1 Zeolite distribution at variation of first 

step hydrothermal temperature 100, 120, 

150 and 180 o C: (a) K-Chabazite, (b) K- 

Phillipsite, and (c) K-F. ∆= 100 o C; □ = 

120 o C; ● = 150 o C; x = 180 o C. 

Types of zeolite from fly ash product similar 

to zeolite that produced by Juan et al. (2007) at 

variation of hydrothermal temperature. The 

distribution is shown in Fig. 1. K-Chabazite 

distribution can be seen at Fig. 1(a). At 100 o C, K- 

Chabazite formed after second hydrothermal time 48 

hs. At 120 o C and 150 o C, this type zeolite formed 

after 24 hs, but at 120 o C its compositions decreased 

after 48 hs, while at 150 o C, its increased. At 180 o C, 

K-Chabazite formed between 6 and 96 hs. The zeolite 

compositions changes as shown at Fig. 1 due to phase 

transformation of K-Chabazite phase into another 

phase such as, K-Phillipsite and K-F. Distribution of 

K-Phillipsite and K-F shown at Fig.1(a) and 1(c). 

K-Phillipsite not formed until second 

hydrothermal time 96 hs at 100 o C as shown at Fig. 

1(b). At 120 o C and 150 o C, K-Phillipsite formed after 

24 hs and its compositions increased until 96 hs. At 

180 o C, K-Phillipsite formed after 6 hs and its 

compositions increased until 48 hs, but after 48 hs its 

decreased. The K-Phillipsite compositions decline 

could be caused by redissolution of zeolite crystals 




and turn into another phase, such as K-F zeolite as 

shown at Fig. 1 (c). 

Fig. 1(c) described K-F zeolite distributions. 

At 100 o C, K-F formed after second hydrothermal 

temperature 48 hs. At 120 o C, 150 o C and 180 o C, K-F 

formed after 24 hs and until 96 hs their compositions 

increased, but after 48 hs K-F compositions at 180 o C 

was the highest then its compositions at 120 o C and 

150 o C. 

Variation of first step hydrothermal 

temperature as shown at Fig. 1 indicates a trend of 

higher first step hydrothermal temperature shorter 

zeolite crystallisation time. First step hydrothermal 

process was process of dissolution of silicate, 

aluminate and aluminosilicate species in fly ash. 

Temperature influence in dissolution process based 

on Kamali, et al. reports shows that Si concentration 

in filtrate increase as temperature increase. While 

Catalfamo, et al. (in Molina and Poole [12]) reported 

that dissolution rate of aluminum goes faster than 

Silicon dissolution at beginning of the process and its 

concentration tends to increase as the temperature 

increase. The higher silicate, aluminate, and 

aluminosilicate concentrations in solution, the shorter 

zeolite crystallisation rate. Bo and Hongzhu [3] 

reported that higher temperature can promote 

dissolution of the solid phase in the zeogel and 

increases the concentration of the solution, thus 

accelerating the formation of larger crystals and 

decreasing the crystallization time. The temperature 

was the main factor that affecting the type of 

synthesized zeolite with KOH [10]. By applying 

temperature in particular time intervals, one type of 

zeolite phase transformed into another phase that 

more stable, as the Ostwald_s rule; the first 

polymorph of a compound formed from solution is 

the least thermodynamically stable and is then 

replaced in succession by more thermodynamically 

stable polymorphs [1]. The changes of zeolite type at 

variation of first step hydrothermal temperature 

shown at Fig. 2. 

ISBN : 978 – 979 – 19201 – 0 – 0 

Figure 2 The Changes of Zeolite Type at 

Variation of First Step Hydrothermal 

Temperature: a) 100 o C, b) 120 o C, c) 

150 o C, and d) 180 o C. 

• = K-Chabazite; ○ = K-Phillipsite, and * 

= K-F. 

The formed zeolites at 100 o C were K- 

Chabazite, K-Phillipsite, and K-F that formed 

together after 48 hs. K-Chabazite at second 

hydrothermal time 96 hs have highest composition 

compared to K-Phillipsite and K-F compositions. At 

120 o C, K-Chabazite, K-Phillipsite, and K-F were 

formed together. Although those three zeolite types 

formed togheter, but after 24 hs K-Phillipsite and K-F 

compositions increased as second hydrothermal time 

increased. K-Chabazite compositions also increased 

after 24 hs but its compositions decreased after 48 hs. 

At 150 o C, K-Chabazite, K-Phillipsite, and K-F also 

formed together after 48 hs, but at 96 hs K-Chabazite 

compositions were the highest of all zeolites. At 180 

o C after 6 hs, the three zeolite types, i. e K-Chabazite, 

K-Phillipsite, and K-F formed together, but after 48 

hs K-Chabazite and K-Phillipsite compositions 

decreased while K-F compositions increased. 

The variation of first step hydrothermal 

temperature on zeolite synthesis from fly ash obtained 

mixed three zeolite types, which there were 

composition changes among formed zeolite phases. 

These due to the zeolites may undergo different kinds 

of structural changes including [5] : (i) cell volume 

contraction due to the removal of water and/or 

templating organic molecules (dehydration and 

calcination); (ii) displacive or reconstructive phase 

transformation(s) to more or less metastable phase(s); 

(iii) breaking (and new formation) of T–O–T bonds; 

(iv) negative thermal expansion (NTE); (v) structural 

collapse; (vi) structural breakdown (i.e. complete 

amorphization or recrystallization). Beside of 

structural changes, the formation of mixed several 

zeolite types due to the zeolites synthesized from fly 

ash by direct conversion methods. Zeolite that 

synthesized from fly ash by indirect conversion, such 

as fusion methods or extractions could obtain single 

phase zeolites [4,8]. 

Chemical compositions of zeolite from fly 

ash were obtained from XRF measurement on sample 

M4b and M4d as shown at Table 2. Chemical 

compositions of zeolite from XRF analysis were 

compared to calculated chemical composition from 

quantitative XRD analysis. 

Table 2 Chemical Compositions of Sample M4b and 

M4d from XRF Analysis 

% Weights 

Components 

M4b M4d 

Al2O3 29,20 26,70 




SiO2 36,00 32,50 

K2O 15,10 26,88 

Fe2O3 12,83 9,99 

Al2O3 could be found in Mullite, Hercynite, 

K-Chabazite, K-Phillipsite, and K-F. SiO2 could be 

found in Mullite, Quartz, Hercynite, K-Chabazite, K- 

Phillipsite, and K-F. K2O could be found in K- 

Table 3 Mineral Compositions of Sample M4b and M4d 

Mineral Phases Compositions (%) 

ISBN : 978 – 979 – 19201 – 0 – 0 

Chabazite, K-Phillipsite and K-F. Fe2O3 could be 

found in Hercynite and Magnetite. The weight 

percentage of those oxides was proportional to the 

weight percentage of phases that contain those oxides. 

Thus, the chemical compositions could explain the 

zeolite quantities. 

M4b M4d 

Quartz (SiO 2) 3,37 0,53 

Mullite (Al 6Si 2O 13) 10,02 3,72 

Magnetite (Fe 3O 4) 7,65 6,55 

Hercynite (FeAl 2O 4) 0,02 0,00 

K-Chabazite (K 12(Al 11Si 25O 72).40H 2O) 22,97 0,39 

K-Phillipsite (K10(Al 10Si 22O 64).20H 2O) 1,26 0,57 

K-F (K 10(Al 10Si 10O 40).8H 2O) 0,73 30,77 

Amorphous 53,98 57,47 

Based on Table 3, SiO2 contents in sample 

M4b were 17,39% and in sample M4d were 12,74 %. 

Al2O3 contents in sample M4b were 23,05 % and in 

sampel M4d were 23,89 %. K2O contents in sample 

M4b were 8,77 %, while in sample M4d were 20,50 

%. Fe2O3 contents in sample M4b were 15,29 % and 

in sample M4d were 13,08 %. 

SiO2, Al2O3, K2O, and Fe2O3 contents in 

sample M4b and M4d in Table 3 different from XRF 

results in Table 2. These due to the existence of SiO2, 

Samples 

Al2O3, K2O, and Fe2O3 that contained in unidentified 

phases by XRD methods. Besides, those oxides could 

be in amorphous phases that have high contents, i. e 

53,98 % in sample M4b and 57,47 % in sample M4d. 

CEC measurement of zeolite from fly ash 

was conducted only to sample M1d, M2d, and M4d 

because of sample availability. Zeolite phase 

compositions calculated and measured CEC results 

shown in Table 4. 

Table 4 Zeolite Phase Compositions, Calculated and Measured CEC Results. 

Zeolite Phase Compositions (%) 

K-Cha K-Phi K-F 

Calculated CEC (meq/g) Measured CEC (meq/g) 

M1d 47,40 0,03 1,24 1,778 2,304 

M2d 2,90 3,33 19,44 1,360 2,509 

M4d 0,39 0,57 30,77 1,819 3,091 

The differences between calculated and 

measured CEC might be caused by the existence of 

nonzeolitic phases that have ability to exchange 

cations. Those phases may be contained in 

unconverted phases of fly ash. Hidayati, et al.[7] 

reported that CEC measured of the fly ash were 4,46 

meq/100 g fly ashes. This result indicates that there 

are phases in fly ash that able to exchange cations. 

Conclusions 

From the discussions above, it is concluded that the 

higher the first step hydrothermal temperature on 

synthesis of zeolite from fly ash, the shorter the 

second hydrothermal reaction needed for zeolite 

crystallisation. Different compositions of three mixed 

zeolite phases, i.e K-Chabazite, K-Phillipsite, and K- 

F formed at variation of first hydrothermal 

temperature (100, 120, 150 and 180 o C) during second 

hydrothermal time 6-96 hs on synthesis of zeolite 

from fly ash. 

Calculated weight percentage of oxide of 

zeolites in this study different from XRF result due to 




the existences of oxides in unidentified phases and 

amorphous phases, then could not be quantified by 

Rietveld method. The differences between calculated 

CEC and experiment were caused by exchangeable 

cations of nonzeolitic and amorphous phases. 


The authors would like to thank Mr. Suminar Pratapa 

from Physics Department, ITS Surabaya for his help 

on part of the XRD data collection and analyses. 

Funding for this research was provided by grant from 

The Ministry of Research and Technology, Republic 

of Indonesia. 

References 

[1] Barrer, R. M. 1982. Hydrothermal chemsitry of 

zeolites. London: Academic Press. 

[2] Berkgaut, V.& Singer, A. 1996. High capacity 

cation exchanger by hydrothermal 

zeolitization of coal fly ash. Applied Clay 

Science 10: 369-378. 

[3] Bo, W. & Hongzhu, M. 1998. Factors affecting 

the synthesis of microsized NaY zeolite. 

Microporous and Mesoporous Materials 25: 

131–136. 

[4] Chang, H., & Shih, W. 1998. Conversion of fly 

ash into zeolites for ion-exchange 

applications. Materials Letters 28: 263-268. 

[5] Cruciani, G. 2006. Zeolites upon heating: factors 

governing their thermal stability and 

structural changes. Journal of Physics and 

Chemistry of Solids 67: 1973–1994. 

[6] El-Naggar, M.R., El-Kamash, A.M., El-Dessouky, 

M.I., Ghonaim A.K. 2008. Two-step method 

for preparation of Na-X zeolite blend from 

fly ash for removal of Cesium ions. Journal 

of Hazardous Materials 154: 963–972. 

[7] Hidayati, R.H. 2008. Sintesis zeolit dari abu 

layang batubara: kajian pengaruh waktu 

hidrotermal awal terhadap pembentukan 

zeolit. Tesis tidak diterbitkan Institut 

Teknologi Sepuluh November Surabaya. 

[8] Hollman, G.G., Steenbruggen, Janssen- 

Jurkovicvova M. 1999. A two-step process 

for the synthesis of zeolites from coal fly 

ash. Fuel 78: 1225–1230. 

[9] Hui, K.S. & Chao, C.Y.H. 2006. Effects of stepchange 

of synthesis temperature on synthesis 

of zeolite 4A from coal fly ash. Microporous 

and Mesoporous Materials 881: 45–151. 

[10] Juan, R., Hernandez, S., Andres, J. M., Ruiz, C. 

2007. Synthesis of granular zeolitic materials 

with high cation exchange capacity from 

ISBN : 978 – 979 – 19201 – 0 – 0 

agglomerated coal fly ash. Fuel 86:1811– 

1821. 

[11] Kamali, M., Vaezifar, S., Kolahduzan, H., 

Malekpour, A., Abdi, M. R. 2008. Synthesis 

of nanozeolite a from natural clinoptilolite 

and aluminum sulfate: optimization of the 

method. Powder Technology, Article in 

Press. 

[12] Molina, A. & Poole, C. 2004. A comparative 

study using two methods to produce zeolites 

from fly ash. Minerals Engineering 17: 167– 

173. 

[13] Muasyaroh, D., Prasetyoko, D., Fansuri, H. 

2007. Pengaruh waktu hidrotermal terhadap 

pembentukan zeolit dari fly ash batu bara. 

Prosiding, Seminar Nasional Kimia Jurusan 

Pendidikan Kimia FMIPA Universitas 

Negeri Yogyakarta, 17 November 2007. 

[14] Murayama, N., Takahashi, T., Shuku, K., Lee, 

H., Shibata, J. 2008. Effect of reaction 

temperature on hydrothermal syntheses of 

potassium type zeolites from coal fly ash. 

Int. J. Miner. Process., Article in Press. 

[15] Querol, X., Alastuey, A. S., Lopez-Soler, A., 

Plana, F. 1997. A fast method for recycling 

fly ash: microwave-assisted zeolite synthesis. 

Environ. Sci. Technol. 31: 2527-2533. 

[16] Querol, X., Uman’a, J.C., Plana F., Alastuey, A., 

Lopez-Soler, A., Medinaceli, A., Valero, A., 

Domingo, M. J., Garcia-Rojo, E. 2001. 

Synthesis of zeolites from fly ash at pilot 

plant scale. example of potential 

applications. Fuel 80: 857-865. 

[17] Shigemoto, N., Hayashi, H., Miyaura, K. 1993. 

Selective formation of Na-X, zeolite from 

coal fly ash by fusion with sodium hydroxide 

prior to hydrothermal reaction. J. Mater. Sci. 

28: 4781– 4786. 




ISBN : 978 – 979 – 19201 – 0 – 0 

NOx Adsorption with CuO Supported on NaY Zeolite from Rice Husk 

Introduction 

Chusnul Suraidah, Irmina Kris Murwani * 

Chemistry Departement, Faculty of Mathematics and Natural Sciences 

Institut Teknologi Sepuluh Nopember 

Kampus ITS Sukolilo, Surabaya, Indonesia 

* e-mail : irmina@chem.its.ac.id 

Abstract 

NO x adsorption has been studied on NaY zeolite and CuO (5, 10 and 15% wt) supported on NaY zeolite 

(CuO/NaY) from rice husk. NaY and CuO/NaY were characterized using XRD, FT-IR and spesific 

surface area were determined by methylene blue method. The spesific surface area of NaY, 5% CuO/NaY, 

10% CuO/NaY and 15% CuO/NaY are 8,130; 8,127; 8,124 and 8,121 m 2 /g respectively. After adsorption, 

the NO x concentration on adsorbent was determined by colorimetry method. Adsorptivity of NO x 

adsorbent from higher to lower are 5% CuO/NaY > 10% CuO/NaY > 15% CuO/NaY > NaY. This result 

are proportional with spesific surface area and reverse with adsorbent acidity for CuO/NaY zeolite. 

Adsorptivity was influenced by active adsorbent sites. 

Keywords: NaY and CuO/NaY synthesis, NO x adsorption, colorimetry. 

Experiment about nitrogen oxides (NOx) has been 

studied before because NOx are important family of 

air polluting chemical. NOx sources produced from 

chemistry reaction, combustion, automobiles and 

industrial. NOx are extremely toxic, it can made 

ozone in the air, lung diseases such asthma and acid 

rain [15]. Adsorption principle can used to solve this 

problem, adsorbent was used to NOx adsorption. NOx 

adsorption with zeolite and Al2O3 adsorbent has been 

studied before [1,2,12]. Zeolite synthesis has been 

done from rice husk as silica source [10]. 

Hydrothermal method was used to NaY zeolite 

synthesis with comparison specific composition [13]. 

High sillica content (94-96%) in rice husk to enable 

zeolite was synthezed from this material [6,17]. Ba, 

Pt and MnO2 supported on NaY zeolite was used as 

adsorbent, present metal loading in zeolite shown 

adsorptivity zeolite increase [1,5,9]. 

Indonesia as producer rice plant yield rice husk 

garbage, for that reason benefit of rice husk must be 

looking. High silica content in rice husk can used as 

silica precursor in zeolite synthesis that used as 

adsorbent. On the other hand, increasingly industrial 

and automobiles make NOx emission increase. Based 

on two problem above, experiment zeolite synthesis 

from rice husk must be done and than zeolite used as 

NOx adsorbent. Metal supported on zeolite can 

increase adsorptivity, so that CuO supported on 

zeolite NaY from rice husk must be studied too. 

Thus, rice husk garbage was hoped useful and NOx 

can reducible. 


Preparation Adsorbent 

In this research, SiO2 precursor for synthesis of NaY 

was taked from rice husk. NaY zeolite synthesis was 

performed according to composition of 10 Na2O : 

Al2O3 : 15 SiO2 : 300 H2O (molar ratio). The initial 

precursor was prepared by mixing aluminate gel and 

silicate gel. After that, the mixture was heated in an 

oven at 100ºC for 24 hour. Subsequenly, the solid 

product was separated by filtration, washed and dried 

for overnight. CuO/NaY zeolite synthesis was 

prepared by incipient wetness impregnation with CuO 

prosentage 5,10 and 15%. The mixture was dried at 

temperature 100ºC. The calcination of the prepared 

samples was performed in air at 400ºC for 4 hour. 

Characterization 

Adsorbent characterization was carried out by means 

of XRD and FTIR. XRD characterization was 

performed using XRD JEOL JDX – 3530 (Cu) 

equipment. FTIR characterisation was performed 

using FTIR Shimadzu – 8201 P equipment. The 

specific surface area of adsorbent was determined by 

methylene blue method. Adsorbent acidity was 

analysed by FT-IR after pyridine adsorption 

(pyridine-FTIR). 




NOx adsorption test 

The adsorptivity of solids product NaY and 

CuO/NaY were tested by adsorption of NOx onto 

adsorbent samples, extraction of NOx from the 

occluded samples using a solvent, reduction of 

nitrogen oxides to nitrite ions contained in the extract 

using hydrazine sulfate and detection and 

quantification of nitrogen oxides by colorization 

using a modified Griess reagent [8, 11]. 


The XRD pattern of NaY zeolite, shown in Fig. 1. 

The diffraction lines characteristic of NaY at 2θ : 6, 

10, 12, 15 dan 24 [PPIT FAU (Powder Pattern 

Identification Tabel Faujasite)]. The framework IR 

spectra of NaY zeolite, shown in Fig. 2. The bands at 

about 3450 cm -1 was caused by vibrations of O-H and 

HO-H which are the consequence of the adsorption of 

water. The presence of water was also evidenced by 

the H-O-H band at 1633 cm -1 . The bands at about 

1116 cm -1 , 955 cm -1 , 774 cm -1 , 714 cm -1 are due to 

symmetric and asymmetric stretching mode of 

(Si,Al)O4 tetrahedra. The bands at about 574 cm -1 , 

503 cm -1 are due to vibration related to external 

linkages of double ring polyhedra in the zeolite 

framework [7, 13, 16]. 

CuO/NaY zeolite was synthezed by the incipient 

wetness impregnation with 5, 10 and 15% of Cu 

loadings. The XRD pattern of NaY and CuO/NaY, 

shown in Fig. 3. The XRD pattern of CuO/NaY show 

evidence of CuO phase at 2θ : 35; 38 dan 48 that 

labeled with (*) [3]. The framework IR spectra of 

CuO/NaY zeolite, shown in Fig. 4. The bands at 

about 3450 cm -1 , 1633 cm -1 are caused by vibrations 

of O-H and HO-H, bending vibration of H-O-H, 

respectively. The bands at about 1116 cm -1 , 955 cm -1 , 

774 cm -1 , 714 cm -1 , 574 cm -1 , 503 cm -1 are typical for 

NaY [7 13, 16]. The bands at about 1396 cm -1 , 567 

cm -1 dan 458 cm -1 due to CuO [3]. 

Intensitas (cps) 

3000 

2000 

1000 

%T 

0 

90 

60 

30 

ISBN : 978 – 979 – 19201 – 0 – 0 

10 20 30 40 50 60 70 80 90 

2 θ(°) 

Figure 1. XRD pattern of NaY zeolite 

OH 

4000 3000 2000 1000 

1/cm 

Figure 2. FT-IR spectra of NaY zeolite 


∗ 

∗ 

∗ 

HOH 

TO 

TO 

TO 

TO 

574 

503 

10 20 30 40 50 60 70 80 90 

2θ(°) 

Figure 3. XRD pattern of NaY (a) and CuO/NaY(b) 


(b) 

(a)



HO 

(d) 

(c) 

(b) 

(a) 

4000 3000 2000 1000 

1/cm 

HOH 

CuO 

T-O 

T-O 

T-O 

T-O 

CuO 

CuO 

Figure 4. FT-IR spectra of NaY (a) and CuO/NaY 

(5% CuO/NaY (b), 10% CuO/NaY (c), 15% 

CuO/NaY (d)) 

Specific surface area measured by methylene blue 

method. Surface area of NaY, 15% CuO/NaY, 10% 

CuO/NaY and 5% CuO/NaY are 8,130; 8,121; 8,124 

and 8,127 m 2 /gram, respectively. 

FTIR spectra of pyridine adsorbed on NaY and (5, 

10 and 15%) CuO/NaY are shown in Fig. 5. The 

vibration bands at about 1450 cm -1 , 1490 cm -1 and 

1610 cm -1 correspond to pyridine coordinated on 

Lewis acid sites that labeled with (*) [14]. Adsorbent 

acidity from higher to lower are 15% CuO/NaY > 

10% CuO/NaY > 5% CuO/NaY > NaY. 

(a) 

(b) 

(c) 

(d) 

* 

* 

* 

1800 1700 1600 1500 1400 1300 

1/λ (cm -1 ) 

Figure 5. FT-IR spectra of NaY (a) and CuO/NaY 

(5% CuO/NaY (b), 10% CuO/NaY (c), 15% 

CuO/NaY (d)) after pyridine adsorbed. 

The result of NOx adsorption test on NaY and (5, 

10, 15%) CuO/NaY adsorbent shown in Fig. 6. 

Adsorptivity of CuO/NaY zeolite was higher than 

NaY zeolite, it caused presence CuO in NaY zeolite. 

Adsorptivity of 5% CuO loading was higher than 

15% CuO loading. Adsorptivity decrease with 

increasingly CuO loading on NaY zeolite, because 

CuO cover zeolite surface. This results are 

proportional with spesific surface area and reverse 

* 

* 

* 

* 

ISBN : 978 – 979 – 19201 – 0 – 0 

with adsorbent acidity for CuO/NaY zeolite. NOx was 

adsorpted on cation, oxygen atoms and hydroxyl 

groups, that are active zeolite sites [1,2,4,9,12]. NOx 

adsorption on CuO/NaY zeolite was not influenced 

presence Cu 2+ because this cation has been 

surrounded by oxygen atoms. This indicate that 

adsorptivity was influenced active adsorbent sites. 

NO x (mmol) 

0.4 

0.3 

0.2 

0.1 

0.0 

NaY 5% CuO/NaY 10% CuO/NaY 15% CuO/NaY 

Adsorbent 

Figure 6. NOx adsorption test on adsorbent NaY and 

CuO/NaY. 

Conclusion 

Adsorptivity of zeolite increase after CuO 

supported on NaY zeolite. Adsorptivity of NOx 

adsorbent from higher to lower are 5% CuO/NaY > 

10% CuO/NaY > 15% CuO/NaY > NaY. 

Adsorptivity was influenced by active adsorbent sites 

and surface area, but was not influenced adsorbent 

acidity. 


This reasearch was supported by Chemistry 

Departement, Faculty of Mathematics and Natural 

Sciences, Institut Teknologi Sepuluh Nopember 

Surabaya. The autors thanks LPPM ITS for their 

financial support. 

References 

[1] Bentrup, Ursula., Angelika Brückner, Manfred 

Richter, Rolf Fricke, Applied Catalysis B: 

Environmental 32, (2001), 229–241. 

[2] Brosius, Roald., Kalle Arve, Marijke H. 

Groothaert, Johan A. Martens, Journal of 

Catalysis 231, (2005), 344–353. 

[3] El-Bahy, Zeinhom Mohamed., Materials 

Research Bulletin, (2007). 

[4] Gil, Barbara., Karolina Mierzyn´ska, Monika 

Szczerbin´ska, Jerzy Datka, Applied Catalysis 

A: General 319, (2007), 64–71. 




[5] Goscianska, Joanna., Philippe Bazin, Olivier 

Marie, Marco Daturi, Izabela Sobczak, Maria 

Ziolek, Catalysis Today 119, (2007), 78–82. 

[6] Harsono, heru., Jurnal Ilmu Dasar vol. 3, No. 

2, (2002), 98-103. 

[7] Holmberg, Brett A., Huanting Wang, Yushan 

Yan, Microporous and Mesoporous Materials 

74, (2004), 189–198. 

[8] Kil, Jeong Ki., In Sik Nam, Joo-Hyoung Park, 

Sang Jun Park, United States Patent 

Application Publication, US 2006/0024836 

A1, (2006). 

[9] Li, Gonghu., Conrad A. Jones, Vicki H. 

Grassian, Sarah C. Larsen, Journal of Catalysis 

234,(2005), 401–413. 

[10] Malek, Nik Ahmad Nizam Nik., Alias Mohd 

Yusof, The Malaysian Journal of Analytical 

Sciences, Vol 11, No 1, (2007), 76-83. 

[11] Park, Joo-Hyoung., Min S. H., Sang J. P., Sang 

j. P., et all, Journal of Catalysis 241, (2006), 

470-474. 

[12] Perdana, Indra, , Derek Creasera,, I. Made 

Bendiyasab, Rochmadib, BomaWikan Tyosob, 

Chemical Engineering Science 62, (2007), 

3882 – 3893. 

[13] Sang, Shiyun., Zhongmin Liu, Peng Tian, Ziyu 

Liu, Lihong Qu, Yangyang Zhang, Materials 

letters 60, (2006), 1131-1133. 

[14] Salama, Tarek M., Ayman H. Ahmed, Zeinhom 

M. El-Bahy, Microporous and Mesoporous 

Materials 89, (2006), 251–259. 

[15] Velsen, Daniel Van., Sulphur Dioxide and 

NitroOxides in ndustrial Waste Gases: 

Emission, Legislation and Abatement, Kluwer 

Academic Publishers, Netherlands, (1991). 

[16] Weitkamp, J., L. Puppe, Catalysis and Zeolites 

Fundamental and Application, Springer, New 

York, (1999). 

[17] Yalcin, N., V. Sevinc, Ceramic International 27, 

(2001), 219-224. 

ISBN : 978 – 979 – 19201 – 0 – 0 




ISBN : 978 – 979 – 19201 – 0 – 0 

NOx Adsorption with Cr Supported on NaY Zeolite from Rice Husk 

Adhita Febriana and Irmina Kris Murwani 

Chemistry Study Program, Faculty of Mathematics and Natural Sciences 

Sepuluh Nopember Institute of Technology Surabaya, 

Keputih Sukolilo, Surabaya, Indonesia, 60111. 

*Email : irmina@chem.its.ac.id 

Abstract 

NO x adsorption with Cr supported on NaY zeolite from rice husk have been investigated. The 

adsorbent used in this studied were NaY zeolite and Cr 2O 3/NaY that made from rice husk. Rice husk 

was used for precursor NaY zeolite because its has high content SiO 2 about 94 – 96%. Cr 2O 3/NaY 

(2,97 and 3,84 wt%) were synthesized by impregnation method. The adsorbents were characterized 

by XRD, FTIR, the specific surface areas was determined by the methylene blue method and the 

acidity was carried out by pyridine – FTIR. The concentration of NO x gas was analyzed with 

colorimetric method. The adsorptivity for NO x gas decreased in the order Cr 2O 3/NaY 3,84% > 

Cr 2O 3/NaY 2,97% > zeolit NaY. The specific surface areas of NaY zeolite was 8,1301 m 2 /g, 

Cr 2O 3/NaY 2,97% was 8,1301 m 2 /g, and Cr 2O 3/NaY 3,84% was 8,1048 m 2 /g. 

Keywords: Adsorption NO x gas, NaY, Cr 2O 3/NaY, rice husk 

Introduction 

Generally, chemical reactions will produce side 

products that often become waste, where the waste 

will become a new problem because it will 

contaminate the surrounding environment. One of 

the side products of the chemical reaction is 

nitrogen oxide gas (NOx), which is one of the side 

products of the synthesis of picric acid. Generally, 

the NOx gas is a chemical compound derived from 

burning coal or petroleum, generated from the 

disposal automobile and machine. NOx gas is one 

of the air pollutant that is quite dangerous for the 

environment because the NOx gas can cause 

damage to people, such as emphysema and lung 

damage, and will also damage the ozone, which is a 

major cause of global warming and acid rain. 

Therefore, need to be a way to the NOx gas in the 

air can be reduce (Kil, 2006; Sakamoto, 2006). 

One way to reduce NOx gases in the air is 

adsorption the NOx gases with an adsorbent. 

Materials that can be used as adsorbent is Al2O3, 

MgF2, zeolite and many more other materials that 

can be used as adsorbent. Synthesis of zeolite has 

been done by many researchers on the previous 

investigation including Sang (2005), Malek (2007), 

and Gonghu Li (2005) by using several methods 

and comparison mol certain. One way to get zeolite 

is from rice husk because SiO2 content on rice husk 

is high (94 - 96%) allows zeolite can be synthesis 

from these raw materials. Zeolite containing metal 

such as Mn, Mo, Pt, Pd and Ba have also been 

made by previous researchers, where loading 

zeolite with metal shows the influence of increasing 

the capacity of adsorption. 

Rice is the main agricultural products in the 

agricultural countries, including Indonesia. This is 

because rice is one of the staple food in Indonesia. 

Rice husk is one of the side products of rice milling 

process, which until the current rice husk is waste 

that still has not been used optimally. During this 

rice husk is only used as a propellant brick or just 

casually discarded. Some research indicates that 

rice husk ash have the silica content is high enough, 

where silica is one of the basic materials for 

synthesis of zeolite (Harsono, 2002; Malek, 2007). 

During this research about adsorption of NOx 

gas is very low, which zeolite used as support for 

adsorption of NOx gas. In order for the utilization 

of waste rice husk as a producer of silica for 

synthesis zeolite and in order to overcome the air 

pollution in the NOx gas, so need research on the 

NOx gases adsorption on zeolite NaY and 

Cr2O3/NaY made from rice husk. This research 

started from preparation source of silica from rice 

husk and synthesis zeolite NaY. Then zeolite NaY 

will impregnation with CrCl3·6H2O that will be 

obtained Cr2O3/NaY, where zeolite NaY and 

Cr2O3/NaY is then tested with XRD, FT-IR, with a 

surface area of the measurement method methylene 

blue and test the acidity with pyridine-FTIR. In 

addition, the test adsorption of zeolite NaY and 

Cr2O3/NaY will be done by conducting NOx gas at 

adsorbent and analyzed by colorimetric method to 

know the concentration of NOx gases. 





Preparation of adsorbents 

In this research, SiO2 precursor for synthesis of 

NaY zeolite was taked from rice husk. Synthesis 

NaY zeolite was performed according to the 

composition of 10 Na2O : Al2O3 : 15 SiO2 : 300 

H2O (molar ratio) [12]. The initial precursor was 

prepared by mixing the required amounts of 

aluminat gel solution and silicate gel, stirred for 

two hours, and then heated at the temperatures of 

100°C for 12 hours. The results of synthesis then 

filtered, washed, and dried in an oven at the 

temperatures of 100°C for 24 hours so it will be 

acquired zeolite NaY. The adsorbents of 2,97 and 

3,84 wt% Cr2O3/NaY were prepared by 

impregnation method using CrCl3·6H2O solution. 

The adsorbents were dried at 100°C for 24 hours 

and calcined in air at 400°C for 4 hours [14]. 


Adsorbents characterization was carried out by 

means of XRD and FTIR. XRD characterization 

was performed using XRD JEOL JDX 3530 (Cu 

Kα) equipment. FTIR characterization was 

performed using Shimadzu FTIR 8400S equipment. 

Specific surface areas were determined by 

methylene blue method. Lewis acid sites and 

Brønsted acid were analyzed by pyridine – FTIR. 

Adsorption of NOx Gas on Zeolite NaY and 

Cr2O3/NaY from Rice Husk 

Adsorption involves the uptake NOx gas by the 

adsorbents. The tube contains about 20 mg of 

adsorbent were placed in the reactor adsorption. 

The sample were activated by heating to 100°C and 

then NOx gas was adsorbed for 1 hour at room 

temperature. All the adsorbents were extracted at 5 

times. About 15 mL aquades was added to each 

adsorbents, and then sentrifuge for 15 minutes. One 

mL CuSO4 solution, 1 mL hidrazine sulphate 

solution and 2 mL sodium hydroxide solution were 

added per 1 mL of eluted solvent. Reduction was 

performed at 40°C for 15 minutes, and then the 

chemical sensor was the Griess reagent, containing 

N-1-naphthylethylenediamine dihydrochloride 

(NED) dissolved in 85% phosphate solution 

containing 1 g of sulphanyl amide, then diluted to 

100 mL was added. The changes color then 

measured with spectrophotometer on the 

wavelength 540 nm [2,4,9]. 


Synthesis of zeolite NaY begins with preparation 

of SiO2 obtained from rice husk ash. Zeolite NaY 

is synthesized from silicate gel and aluminat with 

the comparison 10 Na2O : Al2O3 : 15 SiO2 : 300 

ISBN : 978 – 979 – 19201 – 0 – 0 

H2O (Sang, 2005). Synthesis of zeolite NaY will 

also be performed on hidrotermal assisted with the 

high temperatures with the water. 

The solvent of silicate gel and aluminat are 

mixed, and then inserted into the reactor and 

heated at the temperatures of 100°C for 12 hours. 

After cold, the mixture is filtered and washed with 

aquades up to its neutral pH (Prasetyoko, 2005; 

Sang, 2006). The solid that have been obtained, 

then dried in the oven for 24 hours at the 

temperature of 100°C so it will be obtained powder 

of zeolite NaY is creamy. Powder of zeolite NaY 

is then characterized with XRD, as seen in the 

Figure 2. 


Zeolit NaY 

PPIT 

20 40 60 80 

2θ (°) 

Figure 1. Pattern of Zeolit NaY 

Pattern of zeolite NaY showed the peak in the 

region 2θ about 6, 10, 12, 15 and 24º, which where 

area in the region 2θ about 6 º with the highest 

intensity shows typical peak of zeolite NaY. This is 

in accordance with the peaks on the standard PPIT 

(Powder Pattern Identification Table), so this shows 

that the synthesis of zeolite NaY has been 

successful. 

In addition analyzed with XRD, zeolite NaY 

also analyzed by FTIR. In the figure 3, there is a 

peaks in the region 3,450 cm -1 shows the region of 

O-H vibration stretching associated with water. At 

the peak of 1633 cm -1 shows the peak for H-O-H. 

Peak area in 1116 cm -1 shows the peak of TO4 

asimetri external linkages vibration stretching (T = 

Si or Al) (Prasetyoko, 2005). 

T (%) 

O - H 

4000 3500 3000 2500 

1/cm 

2000 1500 1000 500 

Figure 2. Spectra FTIR of Zeolit NaY 


H - O - H 

TO 4 eksternal 

TO 4 internal 

NaY 

T - O ulur 

Cincin ganda



At the peak of 955 cm -1 shows the region to 

TO4 tetrahedron asimetri internal vibration 

stretching (Liu, 2003) and can also indicate areas 

vibration stretching (alumino) of silicate and silica 

polimorfis. Peak in the 774 and 714 cm -1 is the 

peak symmetry vibration stretching T-O. Peak in 

the 578 and 503 cm -1 which does not show sharp 

regional for a double ring of the external linkages 

related to the structure of the framework Zeolite 

NaY (El - Bahy, 2007; Sang, 2006; Weitkamp, 

1999). 

After synthesis of zeolite NaY as supported 

have been successful, this research followed by 

metal loading CrCl3·6H2O on supported zeolite 

NaY through impregnation. The impregnation 

method used is the incipient wetness method. 

Impregnation will done by mixed the powder 

zeolite NaY in solution CrCl3·6H2O with a 

percentage loading are 2.97 and 3.84%. Mixed in 

the form of pulp is then dried at temperatures of 

100°C for 24 hours and calcined at the 

temperatures of 400°C for four hours for activation 

adsorbent with the purpose to remove the solvent 

(Weitkamp, 1999). The powder are obtained after 

calcinations are a bright yellow powder and then 

characterized with XRD. The pattern of the 

analysis as shown in figure 4. 


♦♦ 

♦ ♦ 

∗ 

♦ 

♦ 

∗ 

∗ 

Zeolit NaY 

Cr 2 O 3 /NaY 

20 40 60 80 

2θ (°) 

Cr 2 O 3 

Figure 3. Patterm of Zeolite NaY, Cr2O3/NaY and 

Cr2O3 

In the figure 4, the pattern of impregnation is 

not shows the significant changes of the pattern of 

zeolite NaY. There are differences in the intensity 

both of the pattern where the intensity of 

Cr2O3/NaY (♦) is lower than zeolite NaY. This 

shows that zeolite NaY has been impregnated with 

Cr2O3, but because the percentage of loading of 

ion Cr 3+ is small, the peak of Cr2O3 (*) does not 

appear, but will only reduce the intensity of the 

supported of zeolite NaY. From the pattern can 

also be known that impregnation is not damage the 

structure of supported zeolite NaY, although the 

intensity is reduced when compared with pattern of 

supported zeolite NaY. Cr2O3/NaY which has been 

obtained, besides characterized with XRD also 

analyzed by FTIR. 

ISBN : 978 – 979 – 19201 – 0 – 0 

In the figure 4 shows that peak intensity at 

3,492 cm -1 shows the region O-H vibration 

stretching associated with water. Peak at 1641 cm -1 

shows region of the H-O-H (Liu, 2003). Peak in 

2071 cm -1 (ξ) shows the intensity decreased from 

zeolite NaY > Cr2O3/NaY 2,97% > Cr2O3/NaY 

3,8%. This is because this area is a likely peak of 

the T-O-H (T = Al or Si), where the H atoms in the 

T-O-H will be replaced with ion Cr 3+ , which are 

absorbed into the Zeolite NaY when impregnation. 

Because not all H atoms can be replaced by ion 

Cr 3+ , the peak intensity in the region in 2071 cm-1 

will not lost all. 

T (%) 

O - H 

a 

b 

c 

4000 3500 3000 2500 2000 1500 1000 500 

1/cm 

⌧ 

⌧ 

⌧ 

H - O - H 

 

 

Figure 4. Spectra FTIR of (a) Zeolit NaY, 

(b) Cr2O3/NaY 2,97%, (c) Cr2O3/NaY 

3,84% 

Two peaks in 1478 and 1423 cm -1 on zeolite 

NaY ( ) after becoming lost when zeolite NaY 

impregnation with Cr 3+ , but this peak can not be 

characterized. Peak area in 1179 cm -1 shows the 

structure of chromium where this is related to Cr5 + 

= O (Wojciechowska, 1995). At the peak of 797cm - 

1 shows the region to TO4 tetrahedron external 

symmetry vibration stretching (Liu, 2003) and can 

also indicate areas vibration stretching of 

tetrahedral symmetry SiO4 (Prasetyoko, 2005). 

Peak 955 cm -1 shows vibration stretching that TO4 

tetrahedron asimetri internal (Liu, 2003) and 

vibration stretching (alumino) silicate and silica 

polimorfis. 

In this research, the specific surface area of the 

determination made by using the methylene blue 

method. This method begins with the determination 

of the maximum length of the wave and making the 

calibration curve to know the concentration of 

methylene blue absorbed by the sample so that the 

specific surface area of each sample can be 

calculated. The result as shown in table 1. 

Table 1. Surface Area Adsorbent 

Adsorbent 

Spesific Surface Area 

(m 2 /g) 

Zeolite NaY 8,1301 

Cr2O3/NaY 2,97% 8,1301 

Cr2O3/NaY 3,84% 8,1048 


 

 

Cr 5+ = O 

TO 4



Adsorbent which has been obtained in this 

research is then used to adsorption of NOx gas with 

the ability to see how the adsorptivity from each 

adsorbent. The results of adsorption test for each 

adsorbent as the following: 

NO x (mmol) 

0.40 

0.35 

0.30 

0.25 

0.20 

0.15 

0.10 

0.05 

0.00 

NaY 

Cr O /NaY 2,97% Cr O /NaY 3,8% 

2 3 2 3 

Figure 5. Relations between the adsorbent with the 

amount of gas absorbed NOx 

On the figure 6, adsorbent shows that most 

high adsorptivity is Cr2O3/NaY 3.84% at 0.39 

mmol. Adsorptivity adsorbent sequence from the 

largest to the smallest is Cr2O3/NaY 3.84% > 

Cr2O3/NaY 2.97% > zeolite NaY. Adsorbent with 

a specific surface area is large that is expected to 

have a high adsorptivity, but the adsorptivity from 

the adsorbent is not influenced by the specific 

surface area and acidity, but more influenced by 

the distribution of ion Cr 3+ . This can be seen from 

the surface area of the order of the adsorbent : 

zeolite NaY = Cr2O3/NaY 2.97% > Cr2O3/NaY 

3.84%. From the spesific surface area that zeolite 

NaY and Cr2O3/NaY 2.97% have large surface 

area but the adsorptivity smaller when compared 

with Cr2O3/NaY 3.84%, which has a surface area 

of the smallest but have the highest adsorptivity if 

compared with the other adsorbent. This indicates 

that the specific area of the adsorbent not affect 

adsorptivity. 

In terms of acidity, the nature acidity of 

Cr2O3/NaY 2,97% and 3,84% is Brønsted acid. On 

the other side, zeolite NaY is Lewis acid. From the 

data specific surface area and acidity of the each 

adsorbent, the adsorptivity from the adsorbent is 

not influenced by the specific surface area and the 

acidity, but more influenced by the distribution of 

ion Cr 3+ . The adsorbent Cr2O3/NaY 3.84% has ion 

Cr 3+ more on the surface if compared with other 

adsorbent, so the adsorptivity of Cr2O3/NaY 3.84% 

will have the highest if compared with the other 

adsorbent. This is in accordance with the results of 

the test adsorption of NOx gas that has been done, 

where the NOx gas will be attached to the surface 

Cr2O3 in the form of [-O-N = O +], where N atoms 

that has positive charge will be attached to the O 

atoms in the Cr2O3 so a lot of Cr2O3 that are 

absorbed and stick on zeolite NaY surface, the NOx 

gas that adsorp on the adsorbent will be higher. 

Conclusion 


ISBN : 978 – 979 – 19201 – 0 – 0 

The authors are grateful to the Chemistry 

Departement, all the participant that help make this 

research, and the financial support from The 

Ministry of National Education. 

. 

References 

[1] El - Bahy, Z. H., (2007), “Oxidation of Carbon 

Monoxide over Cu- and Ag-NaY Catalysts 

with Aqueous Hydrogen Peroxide”, Materials 

Research Bulletin. 

[2] Haris, Daniel C., (1997), Exploring Chemical 

Analysis, New York : W. H. Freeman and 

Company. 

[3] Harsono, Heru, (2002), “Pembuatan Silika 

Amorf dari Limbah Sekam Padi”, Jurnal Ilmu 

Dasar, Vol. 3, No. 2, hal. 98 – 103. 

[4] Kil, J. K., Nam, I. S., Park, J. H., Park, S. J., 

(2006), “Quantitative Analysis of Nitrogen 

Oxides Occluded in Heterogeneous Catalysis”, 

Patent Application Publication, Pub. No. US 

2006/0024836 A1. 

[5] Li, G., Jones, C. A., Grassian, V. H., Larsen, S. 

C., (2005), “Selective Catalytic Reduction of 

NO2 with Urea in Nanocrystalline NaY 

Zeolite”, Journal of Catalysis, 234, hal. 401– 

413. 

[6] Liu, X., Yan, Z., Wang, H., Luo, Y., (2003), “In 

– situ Synthesis of NaY Zeolite with Coal- 

Based Kaolin”, Journal of Natural Gas 

Chemistry, 12, hal. 63-70. 

[7] Malek, N. A. N. N., Yusof, A. M., (2007), 

“Removal of Cr(III) From Aqueous Solutions 

Using Zeolite NaY Prepared From Rice Husk 

Ash”, The Malaysian Journal of Analytical 

Sciences, Vol. 11, No. 1, hal. 76 – 83. 

[8] Nakamoto Kazuo. 1978. Infrared and Raman 

Spectra of Inorganic and Coordination 

Compounds. Third edition. America : John 

Wiley & Sons. 

[9] Park, Joo-Hyoung., Han, M. S., Park, S. J., 

Kim, D. H., Nam, In-Sik, Yeo, G. K., Kil, J. 

K., Youn, Y. K., (2006), “Colorimetric Assay 

for a Fast Parallel Screening of NOx Storage”, 

Journal of Catalysis, 241, hal. 470 – 474. 

[10] Prasetyoko, D., Ramli, Z., Endud, S., 

Hamdan, H., Silikowski, B. (2005), 




“Conversion of Rice Husk Ash to Zeolite 

Beta”, Waste Management. 

[11] Sakamoto, Y., Okumura, K., Kizaki, Y., 

Matsunaga, S., Takahashi, N., Shinjoh, H., 

(2006), “Adsorption and Desorption Analysis 

of NOx and SOx on a Pt/Ba Thin Film Model 

Catalyst”, Journal of Catalysis, 238, hal. 361 – 

368. 

[12] Sang, S., Liu, Z., Tian, P., Liu, Z., Qu, L., 

Zhang, Y., (2006), “Synthesis of Small 

Crystals Zeolite NaY”, Materials Letters, 60, 

hal. 1131 – 1133. 

[13] Weitkamp, J and Puppe, L. 1994. Catalysis and Zeolites 

Fundamentals an Aplications. Springer. 

[14] Wojciechowska, M., Zielinski, M., 

Przystajko, W., Pietrowski, M., (2007), “NO 

Decomposition and Reduction by C3H6 Over 

Transition Metal Oxides Supported on MgF2”, 

Catalysis Today, 119, hal. 44 – 47 

[15] Yalçin, N., Sevinç, V., (2001), “Studies on 

Silica obtained from Rice Husk”, Ceramics 

International, 27, hal. 219 – 224. 

ISBN : 978 – 979 – 19201 – 0 – 0 




ISBN : 978 – 979 – 19201 – 0 – 0 

Synthesis of Calcium Phosphate Carbonate-Polyglycolide Composite using 

Precipitation Method 

Introduction 

Kiagus Dahlan, Arif Rahmadi, Yessie Widya Sari 

Department of Physics, Faculty of Mathematics and Natural Sciences, Institut Pertanian Bogor, 

Jalan Meranti, Kampus IPB Dramaga, Bogor, Indonesia 

Abstract 

Composite of calcium phosphate carbonate-polyglycolide has been synthesized using 

precipitation method. Calcium phosphate carbonate was resulted by pouring CaCl2.2H2O into 

NaHCO3 and Na2HPO4.2H2O solutions using precipitation method at temperature of 70 o C 

and N2 atmosphere to eliminate foreign ions. Porous polyglycolide was resulted from solid 

state polymerization of sodium chloroacetate at temperature of 212 o C. The composite was 

synthesized by adding polyglycolide into NaHCO3 and Na2HPO4.2H2O using precipitation 

method. The precipitate was dried at 110 o C for 10 hours after which the precipitate mass was 

then measured. AAS analysis presented Ca/P ratio of calcium phosphate carbonate ranged 

from 1.46 to 1.67. The presence of polyglycolide was shown by FTIR spectra. The formation 

of the composite was indicated by sample mass which was close to the calculation mass. FTIR 

spectra of the composite showed the presence of absorption bands of calcium phosphate 

carbonate and several groups of polyglycolide. 

Keywords : Composite, precipitation, calcium phosphate, polyglycolide 

Bone is a natural composite material 

containing about 55% inorganic mineral, 30% 

organic matrix and 15% water [1]. The mineral 

component of bone is a form of calcium phosphate 

known as hydroxyapatite (HAp). The matrix 

component is comprised primarily of Type I 

collagen that is highly aligned, yielding a very 

anisotropic structure. This organic component of 

bone is predominantly responsible for its tensile 

strength and made an important role in skeletal 

system to provide the supporting structure for the 

body. Bone can remodel and adapt itself to the 

applied mechanical environment [2,3]. An accident 

or bone disease may cause bone damage that 

becomes necessary to replace or recontour the 

damage in the healing process. Many materials 

have been proposed as useful replacements. 

There are several techniques dealing with 

bone reconstruction such as allograft, autograft, and 

xenograft. Autograft is a bone reconstruction using 

one of body parts and implanted to other part from 

the same individual. Allograft is implantation from 

different individuals in the same species. Xenograft 

is implantation from different species. In many 

cases, implementation of autograft usually does not 

cause refusal response from the host body, but the 

availability is limited, moreover this can cause 

additional operation and prolongation of operation 

time, increased loss of blood, and postoperative 

pain [4-6]. On the other hand, allograft and 

xenograft sometimes cause refusal response from 

host and the availability is also limited. These may 

also become media for contagious diseases. 

Synthetical biomaterials are expected to be able to 

overcome those problems. Good biomaterial for 

bone implantation must be biocompatible, 

bioactive, no corrotion, non toxic, has long time 

stability, strength, and easy to obtain. 

Hydroxyapatite has been widely used as a 

bone replacement material in restorative dental and 

orthopaedic implant as its chemical and 

crystallographic structure being similar to that of 

bone mineral. Bone substitution needs composite of 

biomaterial within polymer and ceramics 

biomaterial. One type of polymer matching with 

this problem is Polyglycolide (PGA). Polyglycolide 

(or polyglycolic acid) is a well-known biomaterial 

with excellent biocompatibility and 

biodegradability lead to its widespread application 

in medicine as material for bone implants and bone 

fixation device. The existence of polymer as matrix 

is not forever in the body, after apatite mineral 

coalesces in bone and forms healthy bone, the 

polymer matrix will disappear. It means that 

polymer must be accepted in biological 

environment and biodegradable [7]. 

This research aimed to synthesize calcium 

phosphate carbonate-polyglicolide composite by 

precipitating calcium, phosphate, and carbonate 

compound on polyglycolide. 




Experimental 

Polymer matrix preparation 

Sodium chloroacetate was placed in a 

ceramic cup and heated using furnace with heating 

rate of 0.2 o C/minute until polymerization 

temperature, 212 o C, was reached, in nitrogen 

ambience, resulting polyglycolide (PGA) and NaCl. 

The next step was washing processes by solving 

polyglycolide powder into hot water and stirred for 

about 4 minutes. Then the polyglycolide was 

filtered and dried at 110 o C for one hour. 

Precipitation of calcium phosphate carbonate 

Solution of calcium phosphate carbonate 

was prepared from NaHCO3 and Na2HPO4.2H2O 

mixed inside a beaker glass. CaCl2.2H2O was then 

poured into the solution. Variation of 

Table 1 Concentration variation of calcium phosphate carbonate 

Sample 

code 

CaCl2. 

2H2O 

(50ml) 

NaHCO3 

(50ml) 

A 0.2 0.2 0.2 

B 0.334 0.2 0.2 

Precipitation of calcium phosphate carbonate- 

polyglycolide composite 

The calcium phosphate carbonatepolyglycolide 

composite was synthesized in the 

same way as calcium phosphate carbonate. Prior to 

the precipitation of composite, polyglycolide was 

added into NaHCO3 and Na2HPO4.2H2O solutions. 


AAS analysis was used for identifying 

concentrations of Ca, Na dan P in samples. FTIR 

analysis used to determine contain of complex 

bench in composite. 

ISBN : 978 – 979 – 19201 – 0 – 0 

concentrations to make this mixture was shown in 

Table 1. 

Precipitation processes were controlled at 

a temperature of 70 o C and N2 atmosphere. N2 

atmosphere was purposed to eliminate foreign ions 

from background. To control homogeneity of 

solution, stirring was performed during 

precipitation using magnetic stirrer. Calcium 

phosphate carbonate solution as the result of the 

precipitation was decanted for about 12 hours 

before filtering. Afterward, the precipitate was 

dried using furnace at 110 o C for 10 hours. Mass of 

precipitate was then measured using analytical 

balance. This measurement aimed to compare the 

mass of calcium phosphate carbonate mineral, the 

mass of PGA matrix and the mass of mineralmatrix 

composite. 

Na2HPO4.2H2O 

(50ml) 

Results and Discussions 

Figure 1 DSC analysis of sodium chloroacetate. 

Polymer matrix preparation 

Porous polyglycolide was obtained 

through polymerization of sodium chloroacetate at 

212 C resulting polyglycolide and sodium 

chloride (as by product). According to the analysis 

of DSC (Figure 1), sodium chloroacetate used in 

this study polymerized at 212 C. This point was 

different from previous study eventhough the type 

of sodium chloroacetate was identical (MERCK, 

98%) [7]. Therefore, it is suggested for further 

study that it is important to analyze the 

polymerization point of sodium chloroacetate. 




The pore of polyglycolide was obtained through 

the elimination of sodium chloride through out the 

immersion of polyglycolide into aquadest. It was 

assumed that the washing treatment succeeded in 

eliminating the sodium chloride in the 

polyglycolide as there was a decrease in mass of 

polyglycolide as high as 50 % wt (Table 2). This 

ISBN : 978 – 979 – 19201 – 0 – 0 

assumption was proven through FTIR spectra. 

There was no peak that indicates the presence of 

sodium chloroacetate. Although there was C=O 

band, it did not belong to sodium chloroacetate. 

XRD spectra of this obtained polyglycolide also 

showed that there was only polyglycolide peak. 

Table 2 Mass of polyglycolide before and after washing process by warm aquadest 

Mass (grams) 

Polyglycolide Before After 

The formation of composite 

The preliminary indicator of the composite 

formation was given by the measured mass which 

was close to the calculated mass. Table 3 shows 

the measured and calculated mass of the composite. 

Another indicator was given by the presence of 

absorption bands of both calcium phosphate 

carbonate and several groups of polyglycolide in 

the FTIR spectra as presented in Table 4. 

The addition of polyglycolide forming the 

composite gave an influence to the FTIR spectra, 

particularly at stretching asymmetric vibration ( 3) 

of phosphate band (around 1025 cm -1 ) and 

stretching asymmetric vibration ( 3) of carbonate 

band (around 873 cm -1 ). The occurrence of (C-O) 

Sample 

code 

Mass mineral 

from 

precipitation 

Mass lost 

(%) 

1 5.0012 2.4092 51.83 

2 4.9049 2.1817 55.52 

mineral matrix water 

Table 3 Mass of samples 

Mass 

PGA 

band of polyglycolide tended to disturb the 3 of 

phosphate band so that this band appeared as if 

there was a shoulder at around 1210 cm -1 . While the 

appearance of (COO, CH) band of polyglycolide 

tended to fades the 3 of carbonate band. At higher 

concentration, polyglycolide tended to generate the 

formation of type A carbonate apatite that occurs at 

900 cm -1 . 

Mass 

composite 

formed 

Mass 

calculation 

percentage 

(%) 

A1 55% 30% 15% 0.7263 g 1.8414 g 2.0579 g 89.48 

A2 1.3316 g 60% 30% 10% 0.6658 g 1.7406 g 1.9974 g 87.14 

A3 

70% 20% 10% 0.3806 g 1.5585 g 1.7122 g 91.02 

B1 55% 30% 15% 0.8918 g 2.1915 g 2.5268 g 86.73 

B2 1.6350 g 60% 30% 10% 0.8175 g 2.1613 g 2.4525 g 88.12 

B3 

70% 20% 10% 0.4671 g 1.8901 g 2.1021 g 89.91 

Calcium phosphate carbonate is indicated 

by the appearance of (CO3 2- ) and (PO4 3- ). In 

samples without polyglycolide, the FTIR spectra of 

those samples are similar. There is no significance 

effect in Ca/P ratio. 

However, when polyglycolide as a matrix 

was present, sample A has a distinct difference 

from sample B. Sample A1 has lower transmittance 

of all bench compared to sample B1 and so did 

sample A2 and B2. However, as the percentage of 

matrix in the composite decreased, the effect of 

Ca/P is almost undetected as there was no 

significant difference in percentage of transmission 

between sample A3 and B3. For all samples, it was 

also observed that composite of sample A (A1, A2, 

and A3) has lower Ca/P ratio compared to 

composite of sample B (B1, B2, and B3) as 

presented by Tables 5 and 6 showing the 

concentrations and ratio of Ca and P in samples. 




Table 4 Calcium phosphate carbonate and polyglycolide absorption band in samples 

ISBN : 978 – 979 – 19201 – 0 – 0 

Calsium phosphate carbonate wavenumber (cm -1 Code of 

) 

samples ACA* CO3 2- (v2) CO3 2- (v3) PO4 3- (v1) PO4 3- (v3) PO4 3- (v4) 

A 873.596 1467.65 962.305 1025.94 568.898 

A1 900.594 873.596 1043.30 568.898 

A2 900.594 873.596 1025.94 565.898, 

607.467 

A3 873.596 1060.66 561.184 

B 873.596 1467.56 958.448 1060.66 603.610 

B1 900.594 873.596 1095.37 603.610 

B2 900.594 873.596 1060.66 568.098 

B3 873.596 1035.59 568.898 

Code of 

samples (C-H) 

Polyglycolide wavenumber (cm -1 ) 

(C=O) 

in ester 

(COO, C-H) 

A1 2962.13 1751.05 1417.42 815.742 

A2 2958.27 1751.05 1417.42 806.742 

A3 2962.13 1747.19 1417.42 806.099 

B1 2962.13 1747.19 1419.35 815.742 

B2 2958.27 1747.19 1417.42 815.742 

B3 2958.27 1751.05 1419.35 815.742 

Sample code 

Ca 

Concentration (%) 

Na P 

A 28.70 3.36 14.32 

A1 18.83 2.01 9.96 

A2 15.96 2.13 8.02 

A3 22.20 2.82 11.48 

B 25.88 1.49 12.94 

B1 19.85 1.47 9.13 

B2 18.89 1.33 9.41 

B3 21.06 1.45 10.10 

Table 5 Concentrations of Ca, Na, andP 




Conclusion 

Polyglycolide and sodium chloride were 

resulted from the polymerization of sodium 

chloroacetate at 212 C. Porous polyglycolide 

obtained from elimination of sodium chloride 

through the immersion of polyglycolide into 

aquadest could be used as a matrix of calcium 

phosphate carbonate. Precipitation method enabled 

the synthesis of composite of calcium phosphate 

carbonate-polyglycolide. The appearance of 

polyglycolide indicated by the disturbance of both 

3 phosphate and carbonate bands. Phosphate band 

tended to have a shoulder occurrence at its 3, 

while carbonate band tended to fade away. 

References 

[1]. Aoki, H. 1991. Science and medical 

applications of Hydroxyapatite. Institute for 

Medical and Dental Engineering. Tokyo 

Medical and Dental University. 

[2] Mickiewicz, RA. 2001. Polymer-calcium 

phosphate composites for use as an 

Table 6 Ratio of Ca/P 

Sample code Ca/P 

A 

A1 

A2 

A3 

B 

B1 

B2 

B3 

ISBN : 978 – 979 – 19201 – 0 – 0 

injectable bone substitute. 

Department of Materials Science and 

Engineering, Massachusetts Institute of 

Technology. 


1.55 

1.46 

1.54 

1.49 

1.55 

1.67 

1.55 

1.61 

[3] Emily Y. Ho. 2005. Engineering Bioactive 

Polymers for the Next Generation of Bone 

Repair. Drexel University. 

[4] Dewi, SU. 2007. Analisis Kuantitatif, 

Kekerasan dan Pengaruh Termal Pada 

Mineral Tulang Manusia. Fakultas 

Matematika dan Ilmu Pengetahuan Alam, 

Institut Pertanian Bogor. 

[5] Langenati, R, Ngatijo, Widjaksana, Latief, 

A, Sugeng, B. 2003. Aplikasi 

Hidroksiapatit Di Bidang Medis. 

Tangerang: Batan, Puspitek Serpong. 

[6] Epple, M and Herzberg, O.1997. Porous 

Polyglycolide . J Biomed Mater Res (Appl 

Biomater) 43: 83–88. 

[7] Schwarz, K and Epple, M. 1998. 

Biomimetic Crystallization of Apatite in a 

Porous Polymer Matrix. Hamburg: Institute 

of Inorganic and Applied Chemistry, 

University of Hamburg.



ISBN : 978 – 979 – 19201 – 0 – 0 

An In-Situ Neutron Diffraction Study of β-Bi2Mo2O9 and γ-Bi2MoO6 as 

Partial Oxidation Catalysts 

Hamzah Fansui 1 and Dong-ke Zhang 2 

1 Chemistry Department, Faculty of Mathematics and Natural Sciences 

Institut Teknologi Sepuluh Nopember, 

Kampus ITS Sukolilo, Surabaya, Indonesia, 60111. 

2 Centre for Petroleum, Fuels and Energy 

The University of Western Australia, 

35 Stirling Highway, Crawley, Perth, Western Australia 6009 

Abstract 

The dynamics of lattice oxygen in β-Bi 2Mo 2O 9 and γ-Bi 2MoO 6 as catalysts for partial oxidation of 

propylene to acrolein was investigated using the neutron diffraction technique. The catalyst 

characterization experiments were carried out under reaction conditions at 300, 350 and 400 o C using 

the Medium Resolution Powder Diffraction (MRPD). The unit cell of the β-Bi 2Mo 2O 9 was seen to 

expand isotropically to the (111) face with increasing temperature, indicating that there was no 

important atomic coordinate changes in the temperature range studied. On the other hand, the unit 

cell of the γ-Bi 2MoO 6 expanded to the (110) face. The difference suggests that the two catalysts have 

different activation mechanisms in catalysing the partial oxidation reaction. Structure refinement of 

both catalysts under the in-situ conditions shows that certain lattice oxygen ions are more mobile than 

others. The Oxygen ions No. 3 and 18 in β-Bi 2Mo 2O 9 and No. 1 and 5 in γ-Bi 2MoO 6 are the mobile 

oxygen ions in the lattice. The mobile lattice oxygen ions are the most probable active oxygen for the 

selective oxidation of propylene to acrolein 

Keywords: Acrolein, Bismuth molybdate, In-Situ Neutron Diffraction, Partial Oxidation, 

Propylene.Write five keywords 

Introduction 

Bismuth molybdates have long been known as active 

catalysts for selective oxidation of olefins. There are 

several phases of bismuth molybdates but only three 

of them are known to be active for partial oxidation of 

propylene to acrolein, namely α, β and γ bismuth 

molybdates. 

Many researchers believe that lattice oxygen 

in bismuth molybdate catalysts plays an important 

role in determining the activities of bismuth 

molybdates in catalysing the partial oxidation of 

olefin. It has been proven that the oxidation reaction 

uses the lattice oxygen and follows the Mars-van 

Krevelen mechanisms [1-2]. Several studies have also 

shown that the lattice oxygen ions are involved in the 

oxidation process [1, 3-6]. Furthermore, Haber [7] 

mentioned that the ease of oxygen movement in 

bismuth molybdates, by the formation of shear plane 

and rearrangement of corner-linked metal oxides into 

edge-linked octahedrals of molybdenum as well as 

tungstate oxide, favour their activities and selectivity 

towards acrolein formation. 


Experimental 

The catalysts used in the present study were 

prepared using the co-precipitation method from 

Bi(NO3)3.5H2O and (NH4)6Mo7O24.4H2O solutions. 

Molar ratio of Bismuth to Molybdenum was 1 and 2 

for the preparation of β-Bi2Mo2O9 and γ-Bi2MoO6, 

respectively. The suspension was kept in a water bath 

at 70 o C and stirred well to evaporate the liquid 

slowly until it became a paste. The paste was then 

dried at 120 o C for 20 hrs in air. The dried cake was 

crushed and calcined in air at 250 o for 2 hrs followed 

by calcination at 650 o C for 24 hrs for β-Bi2Mo2O9 

and at 480 o C for 20 hrs for γ-Bi2MoO6. Room 

temperature structure of the catalysts thus prepared 

was characterized using both X-ray and Neutron 

diffraction techniques. XRD analysis employed Cu 

Kα radiation operated at 40 kV and 30 mA. Neutron 

diffraction analysis was carried out using the High 

Resolution Powder Diffraction (HRPD). A 

monochromatic neutron beam at a wavelength of 

1.495Å was applied. In-situ neutron diffraction 

analyses were carried out using the Medium 

Resolution Powder Diffractometer (MRPD) with a 

monochromatic neutron beam at a wavelength of 

1.665 Å. The catalyst characterisation was carried out 

at 300, 350 and 400 o C in air and in a simulated 

reaction atmosphere comprised of 1% C3H6, 2% O2 

and 97% He in a special quartz cell reactor [8] 




(Figure 1). All diffractograms were used to refine the 

lattice parameters, inter-atomic distances and thermal 

parameters, using the LHPM Rietica refinement 

method [9]. 

Figure 1. A schematic of the special sample 

cell for the in-situ MRPD analyses 


Figure 2 shows HRPD diffractograms and 

refinement fit of room temperature -Bi2Mo2O9 and 

-Bi2MoO6. Search and Match results using Jade 6.0 

and PDF (Powder Data File) database version 2 

reveals that the bismuth molybdate catalysts prepared 

in this experiment are -Bi2Mo2O9 and -Bi2MoO6. 

The beta phase corresponds to ICSD 

(Inorganic Crystal Structure Database) collection No. 

201742 based on structural model reported by Chen 

and Sleight [10]. The unit cell in the model is 

monoclinic with unit cell parameters a=11.972(3), 

b=10.813(4), c=11.899(2), =90.0 =90.1(0) 

=90.0 and unit cell volume V=1540.4. Meanwhile, 

the gamma phase corresponds to ICSD collection No. 

47139 where the unit cell is orthorhombic and 

ISBN : 978 – 979 – 19201 – 0 – 0 

a=5.482(0), b=16.199(1), c=5.509(0), =90.0 

=90.0 =90.0 and unit cell volume V=489.2 as 

reported by Teller et al. [11]. Structure refinement 

results of the beta and gamma phases from their room 

temperature HRPD and XRD using their 

corresponding structural model give slightly different 

unit cell parameters as shown in Table 1. 

) 

Figure 2. Graphical representation of the 

refinement results of room temperature 

HRPD diffractograms. (A) β-Bi2Mo2O9 

and (B) γ-Bi2MoO6. 

Table 1. Refined unit cell parameters of bismuth molybdates of room temperature X-ray and Neutron 

(HRPD) diffractograms. 

Parameters 

β-Bi2Mo2O9 

γ-Bi2MoO6 

X-ray Neutron X-ray Neutron 

Volume (Å 3 ) 1534.05(9) 1538.27(5) 489.41(3) 490.84(2) 

a (Å) 11.954(0) 11.965(0) 5.484(0) 5.489(0) 

b (Å) 10.799(0) 10.810 (0) 16.209(0) 16.225(0) 

c (Å) 11.883(0) 11.893 (0) 5.506(0) 5.511(0) 

α ( o ) 90.000 90.000 90.000 90.000 

β ( o ) 90.143(3) 90.139(2) 90.000 90.000 

The dynamic changes on the structure of 

beta and gamma phases under reaction condition 

 

90.000 90.000 90.000 90.000 

(increasing temperature and reaction atmosphere) 

were studied by HRPD. The unit cell of the β- 


(b) 

(a



Bi2Mo2O9 expanded isotropically as the temperature 

increased (Figure 2.a). The isotropic unit cell 

expansion revealed that there is no important atomic 

coordinate change in the temperature range studied. 

The thermal parameters did not increase as the 

temperature increased. However, some oxygen ions 

(No. 3 and 18) in the lattice had larger thermal 

parameters than the others. These oxygen atoms were 

laid in the cavities of the β-Bi2Mo2O9 crystal and 

bonded to molybdenum and bismuth ions. On the 

other hand, the unit cell of the γ-Bi2MoO6 expanded 

more in the a and c directions than in the b direction 

(Figure 2.b). Some oxygen ions in the lattice (No. 1 

and 5) experienced greater increases in their thermal 

parameters than the others. Oxygen No 1 was 

a, b, c, and beta 

0.80% 

0.70% 

0.60% 

0.50% 

0.40% 

0.30% 

0.20% 

0.10% 

0.00% 

a 

b 

c 

beta 

Cell Volume 

275 300 325 350 375 400 425 

Temperature ( o C) 

2.50% 

2.00% 

1.50% 

1.00% 

0.50% 

0.00% 

Cell Volume 

ISBN : 978 – 979 – 19201 – 0 – 0 

situated between the Mo-O and Bi(2)-O layers while 

Oxygen No 5 was on the Mo-O layer and closer to 

the Bi(1) layer than the other oxygen ions in the Mo- 

O layer. The specific thermal parameters of Oxygen 

ions No 1 and 5 indicate that they are probably the 

key in controlling the catalyst activity for the 

selective partial oxidation. In addition, the less lattice 

expansion in the b direction suggests that oxygen 

atoms bridging the layers were strongly bonded to 

molybdenum and/or bismuth, except Oxygen No 1. 

The lattice oxygen atoms with high thermal 

parameters at high temperatures are the source of the 

oxidising oxygen responsible for the selective 

oxidation of propylene to acrolein. 

a, b and c 

1.00% 

0.90% 

0.80% 

0.70% 

0.60% 

0.50% 

0.40% 

0.30% 

0.20% 

0.10% 

0.00% 

a 

b 

c 

Cell Volume 

275 300 325 350 375 400 425 

Temperature ( o C) 

(a) 

(b) 

Conclusion 

Figure 2. Percentage of unit cell extensions of a) β-Bi2Mo2O9 and b) γ-Bi2MoO6 

4. Y.-H. Han, W. Ueda, Y. Moro-Oka, Applied 

Catalysis A: General 176 (1999) 

5. L. D. Krenzke, The Kinetics and Mechanism 

The in-situ neutron diffraction study revealed 

of Propylene Oxidation over Bismuththat 

the most probable active lattice oxygen ions 

Molybdate, 

responsible for the partial oxidation of propylene 

Bismuth(1)Molybdenum(1)Oxygen(12), 

to acrolein are oxygen No 3 and 18 in -Bi2Mo2O9 

and No. 1 and 5 in -Bi2MoO6. The active oxygen 

atoms in both bismuth molybdates are slightly 

different in their nature. In the phase, active 

oxygen ions are laying in the crystal’s cavity and 

directly bonded to molybdenum and bismuth ions, 

while in the phase, the active oxygen are 

sandwiched between molybdenum and bismuth 

oxide layers. 

6. 

7. 

Bismuth(3)Iron(1)Molybdenum(2)Oxygen(12) 

and Uranium(1)Antimony(3)Oxygen(10), in 

Chemistry. 1977, The University of 

Wisconsin: Milwaukee, USA. p. 163-175. 

E. Ruckenstein, D. B. Dadyburjor, The 

Journal of Physical Chemistry 84 (1980) 26 

J. Haber, in R. K. Grasselli, J. F. Brazdil (Ed.), 

Catalysis by Transition Metal Oxides, 

American Chemical Society, Washington, D. 

C., 1985, p. 1-19 

References 

8. H. Fansuri, Catalytic Partial Oxidation of 

Propylene to Acrolein: The Catalyst Structure, 

1. J. M. Thomas, W. J. Thomas, Principles and 

Practice of Heterogeneous Catalysis, VCH 

Verlagsgesellschaft mbH, Weinheim, 1997 

2. A. Bielanski, J. Haber, Oxygen in Catalysis, 

Marcel Dekker, Inc., New York, 1991, p. 472- 

479. 

3. M. M. Bettahar, G. Constentin, L. Savary, J. 

C. Lavalley, Applied Catalysis A: General 145 

(1996) 

Catalyst', Journal of Solid State Chemistry, vol. 63, pp. 70-75. 

Reaction Mechanisms and Kinetics, Ph.D 

Thesis, Curtin University of Technology, 2005, 

p. 49 

9. C. J. Howard, B. A. Hunter, LHPM Manual, A 

Computer Program for Rietveld Analysis of 

X-ray and Neutron Powder Diffraction 

Patterns, Australian Institute of Nuclear 

Science and Engineering, Sydney, 1997. 

10. Chen, H-Y & Sleight, AW, 1986, 'Crystal 

Structure of Bi2Mo2O9: A Selective Oxidation 


2.50% 

2.00% 

1.50% 

1.00% 

0.50% 

0.00% 

Cell Volume



11. Teller, RG, Brazdil, JF & Grasselli, RK, 1984, 

'The Structure of -Bismuth Molybdate, 

Bi2MoO6, by Powder Neutron Diffraction', 

Acta Crystallographica C, vol. 40, pp. 2001- 

2005. 

ISBN : 978 – 979 – 19201 – 0 – 0 




ISBN : 978 – 979 – 19201 – 0 – 0 

A Neutron Diffraction Study of Co and Mn Incorporation into 

AlPO4-5 Lattice 

Hamzah Fansuri 1 , Mei Dong 2 , Sawsan Jamil Freij 3 , Jianguo Wang 2 and Dong-ke Zhang 4 

1 Chemistry Department, Faculty of Mathematics and Natural Sciences 

Institut Teknologi Sepuluh Nopember, 

Kampus ITS Sukolilo, Surabaya, Indonesia, 60111. 

2 State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. 

Box 165, Taiyuan, Shanxi 030001, China 

3 Centre for Fuels and Energy-Curtin University of Technology, GPO Box U1987, WA 6845, Australia 

4 Centre for Petroleum, Fuels and Energy, The University of Western Australia, 

35 Stirling Highway, Crawley, Perth, Western Australia 6009 

h.fansuri@chem.its.ac.id 

Abstract 

Incorporation of Co 2+ and Mn 2+ into the lattice of AlPO 4-5 to alter its acidity and redox properties in 

order to improve the AlPO catalytic activity was studied using the neutron diffraction and analysed 

using the Rietveld refinement method. Several Co 2+ and Mn 2+ substituted AlPO 4-5 samples were 

synthesised using a hydrothermal method and then calcined at 550 o C in air before the neutron 

diffraction analyses. Electron microscopy images of the AlPOs showed that they were mainly 

agglomerates of hexagonal plates and prisms where no clear difference was observed between Co and 

Mn substituted AlPO 4-5. Rietveld refinement of the neutron diffraction data in the Pcc2 group 

showed that the substitution of aluminium with either cobalt or manganese did not affect the structure 

of AlPO 4-5 significantly and no other phases of Mn or Co were detected. This is an indication that 

the Co and Mn ions were homogenously distributed in the AlPO 4-5 framework and will have similar 

catalytic selectivity to that of unsubstituted AlPO 4-5. Further refinements are required to fully 

understand the Co 2+ and Mn 2+ incorporation into the AlPO 4-5 lattice. 

Keywords: Neutron diffraction, Aluminophosphate molecular sieves, Transition metal 

incorporation. 

Introduction 

Aluminophosphate molecular sieves (AlPOs) are 

important materials for their potential applications in 

catalysis, adsorption and separation. The AlPO4-5 

generally consists of a tetrahedral structure of AlO4 

and PO4, which corner-share an oxygen atom to build 

a three-dimensional framework with molecule-sized 

channels [1]. However, the framework lacks acidic 

and redox active sites and thus does not possess 

catalytic activity. Incorporation of transition metal 

ions can alter the AlPO catalytic activity. For 

example, CoAPO-5 is an excellent catalyst for 

selective oxidation of alkanes due to its highly 

dispersed redox centres and proper pore structure [2]. 

Although many publications have reported the 

synthesis of MeAPOs, little is known about the 

detailed nature of the metal incorporation in the 

framework. Progress in the designed synthesis of 

these microporous catalysts with desired locations of 

active sites and well defined atomic environment is 

limited due to the lack of adequate knowledge of the 

transient active ions from the precursor gel to the 

templated solid microporous materials. 

This paper reports our effort in the 

determination of metal incorporation in AlPO4-5 

using a neutron diffraction technique. Neutron 

diffraction is a sensitive probe for this incorporation 

since Al and P have different scattering lengths. The 

initial structure model of the Co- and Mn-AlPO4 was 

deduced from the unsubstituted AlPOs with a 

hexagonal symmetry and strict alternation of Al and P 

in the framework (space group P6cc) [3, 4]. 


Experimental 

The Co- and Mn-AlPO4 were synthesised according 

to the verified method [5]. Samples were crystallised 

at 200 o C for 2, 8, 16 and 24 hours. They were then 

calcined in a muffle furnace in air (flow rate: 100 

ml/min) with a heating rate of 10 ºC per minute to 550 

o C and kept at this temperature for 6 hours. 

The XRD analyses of all samples were performed 

using Cu Kα radiation operating at 40 kV and 30 mA. 

Neutron Diffraction was used to characterise the Co 2+ 

and Mn 2+ substituted molecular sieves at room 




temperature in air using the Medium Resolution 

Powder Diffractometer (MRPD) over 3 o – 138 o of 

two-theta. A Ge crystal monochromator was used to 

provide a monochromatic neutron beam at 1.665 Ǻ. 

Unit cell parameters were refined using RIETICA, a 

rietveld refinement software 6 . The SEM images were 

also taken using a Philips XL30 Scanning Electron 

Microscope fitted with a SE, BSE and EDS detectors. 


Figures 1 and 2 show diffractograms of Neutron- 

Medium Resolution Powder Diffraction (MRPD) and 

XRD, respectively, collected at room temperature for 

10 samples of cobalt and manganese 

aluminophosphate. The patterns have shown that the 

crystallinity of of Mn-AlPO increases with the 

crystallization time while the crystallinity of Co-AlPO 

reaches a maximum at 8 hour of crystallization and 

decreases with longer crystallization time. The 

crystalinity is taken as the ratio between the peak 

heights versus FWHM (Full Width of Half 

Maximum). 

Figure 1 Diffractograms of Neutron-Medium 

Resolution Powder Diffraction (MRPD) 

Blue line = CoAlPO4-5 and Red line = 

MnAlPO4-5. 

The data from diffractograms (MRPD and XRD) 

were refined in Pcc2 group using Rietica Software to 

investigate the effect of metal substitution on the 

crystal structure and parameters. An example of 

refinement results is shown in Figures 3 and 4 for the 

MRPD data for Co and Mn aluminophosphate, 

respectively. 

3000 

2500 

2000 

1500 

1000 

500 

3500 

3000 

2500 

2000 

1500 

1000 

ISBN : 978 – 979 – 19201 – 0 – 0 

0 

5 15 25 35 45 55 65 75 85 95 105 115 125 

500 

Figure 5 The refined data for Co-AlPO4-5 

crystallised for 16 hours 

0 

5 25 45 65 85 105 125 

Figure 6 The refined data for Mn-AlPO4-5 

crystallised for 16 hours 

Analysis of the X-ray diffractogram of Co- and 

Mn-AlPO4 reveals that their structure are better 

described as having a Pcc2 rather than P6cc 

symmetry. Preliminary refinements, either with X-ray 

or neutron diffraction patterns, have shown that 

substitution of aluminium with either cobalt or 

manganese did not affect the bulk structure of AlPO4- 

5 significantly and no other phases of Mn or Co were 

detected. It indicates that Co and Mn are 

homogenously distributed in the AlPO4-5 framework. 

Table 1 compares the crystal lattice parameters for the 

unsubstituted and metal-substituted 

aluminophosphate samples studied. Further 

refinements are required to fully understand the 

structure by varying the atomic positions with degree 

of substitution 




ISBN : 978 – 979 – 19201 – 0 – 0 

Table 1. Unit cell parameters for pure AlPO4-5 and the metal-substituted AlPO4-5 

Phase 

Unit cell (Pcc2) 

a ∆ b ∆ c ∆ 

AlPO(Unsubsituted 

) 13.794 23.901 8.417 

CoAlPO (2 hrs) 13.770 8 23.859 13 8.389 2 

CoAlPO (8 hrs) 13.775 6 23.868 10 8.392 1 

CoAlPO (16 hrs) 13.771 6 23.876 10 8.391 1 

CoAlPO (24 hrs) 13.771 5 23.879 9 8.393 1 

MnAlPO (2 hrs) 13.772 6 23.888 11 8.396 1 

MnAlPO (8 hrs) 13.778 6 23.882 11 8.396 1 

MnAlPO (16 hrs) 13.778 6 23.871 11 8.395 1 

MnAlPO (24 hrs) 13.773 6 23.880 11 8.394 2 

. 

The possibility that the Co- and Mn-AlPO4- different crystallographic faces. This may induce 

5 having preferred orientation is justified by their preferred orientation effect in the diffraction patterns 

electron microscope images as shown in Figures 5 as some faces would be expressed more than others, 

and 6. 

depending on the overall composition of the samples 

Electron microscopic images show that the 

AlPO4 mainly consists of agglomerates of hexagonal 

plates and some prisms. It is also shown that both 

Co-AlPO4-5 and Mn-AlPO4-5 have two main 

morphologies; each morphology is dominated by 

analysed. 

Figure 3 SEM Images of CoAlPO4-5, crystallised for 24 hours 




Conclusion 

Figure 4 SEM Images of MnAlPO4-5, crystallised for 24 hours 

The present study has shown that crystals of Co 

and Mn substituted aluminophosphates consist 

mainly of agglomerates of hexagonal plates and 

prisms. No clear difference was observed between 

Co and Mn substituted AlPO4-5. Preliminary 

refinements of the neutron diffraction data in the 

Pcc2 group have shown that the substitution of 

aluminium with either cobalt or manganese did not 

affect the structure of AlPO4-5 significantly and no 

other phases of Mn or Co were detected. This is 

an indication that Co and Mn are homogenously 

distributed in the AlPO4-5 framework and may 

suggest similar selectivity to that of the 

unsubsituted AlPO4-5. 

References 

1. Ribeiro, F.R., F. Alvarez, C. Henriques, F. 

Lemos, J.M. Lopes, and M.F. Ribeiro, J. Mol. 

Catal. A, 96 (1995) 245. 

2. G. Sanker, R. Raja, J. M. Thomas, Catal. Lett., 

55 (1998) 15. 

3. Bennet JM, Cohen JP, Flanigen EM, Pluth JJ, 

Smith JV, Am Chem Soc Symp Ser 218 

(1983)109. 

4. Qiu S, Pang W, Kessler H, Guth JL, Zeolites 8 

(1989) 440. 

5. Harry Robson (Editor), “Syntheses of Zeolitic 

Materials”, Elsevier B.V., Amsterdam, 2001. 

p.90. 

6. C. J. Howard, B. A. Hunter, LHPM Manual, A 

Computer Program for Rietveld Analysis of 

X-ray and Neutron Powder Diffraction 

Patterns, Australian Institute of Nuclear 

Science and Engineering, Sydney, 1997 

ISBN : 978 – 979 – 19201 – 0 – 0 




ISBN : 978 – 979 – 19201 – 0 – 0 

Relation Between Addition of Alumino-Silicate with Alkali-Silica Reaction and 

Geopolimer Product 

Anggaria Maharani, Lukman Atmaja 1 and Hamzah Fansuri 

Laboratories of Physical Chemistry, Department of Chemistry, Faculty of Mathematic and Natural Sciences, Sepuluh 

Nopember Institut of Technology (ITS), Surabaya, Indonesia. 


email: lukman_at@chem.its.ac.id, 

Introduction 

Abstract 

Geopolymers have been studied for several decades due to their excellent mechanical and thermal properties, 

as well as chemical and fire resistance. Geopolymer were synthesized via reaction of aluminosilicate 

material, fly ash, with alkalinesilicate solution at ambient temperature. In this paper, geopolymers was 

modified by the addition the amount of insoluble additive, α-Al 2O 3 (Corundum) and SiO 2 (Quartz) to Si/Al 

variation. The result show that the geopolymer product (Si/Al=5.0) has highest strength (65 MPa) as compare 

to other sample. The current work used XRD, the quartz and mullite were found both of fly ash and 

geopolymer product. This study also indicates that not only amorphous phases but also crystalline phases 

involve in the geopolymerization process. 

Keywords : crystalline phase reactivity in geopolymerization, fly ash utilization, geopolymers, alkali-silica 

reaction 

Power stations, using coal like-fuels, are 

worldwide energy source, including Indonesia will 

dramatically increase its coal fired-power station to 

produce 10000 MW electricity. The generation of 

electricity by coal combustion produces fly ash (80- 

90%) and bottom ash (10-20%) [1,2]. It is considered 

that volume of fly ash production will reach 800 

MTon in around the world) in 2010 where only a 

small part (20-30%) of these ashes are used at present 

[3]. Thus, the increase of coal fired power station will 

give serious problems to particularly our environment 

like air pollution, contaminant of water and decrease 

of ecosystem quality. 

The important advances in the search for 

new application for fly ashes are being achieved. 

Among the main achievements is a new inorganic 

material which is called geopolymer. Geopolymer is a 

synthetic material analogues of natural zeolite. 

Geopolymer materials has excellent mechanical 

properties, including fire and acid resistance [4]. 

These properties make geopolymer an alternative 

construction material compared to Portland cement. 

Geopolymer has better strength than Portland cement 

[5]. 

Fly ashes contain sufficient amount of 

alumina and silica that can be used as source 

materials for geopolymerisation reaction. It was 

reported that the type and nature of the starting 

materials will directly affect the final physical and 

chemical properties of a geopolymer [6]. Moreover, 

the main mineral component in fly ash like quartz and 

mullite might also affect the geopolymer product due 

to their activation reaction [7]. Geopolymer from Fly 

ash with more amorphous phases are more reactive 

than those contains more crystalline phases [8]. Xu 

and van Deveneter also reported that Si and Al in 

amorphous phase are more dissolvable in an alkaline 

solution than the crystalline phase [9]. 

The aim of the present study is to prove the 

role of Si and Al in crystalline phases and their 

contribution to Si/Al ratio in the geopolymerisation 

process and product. The present study explores the 

effect of the insoluble silicone and aluminium content 

in a series of composition on the mechanical strength, 

microstructural and to identify and quantify such 

products. 

Experimental 

Materials 

Fly ash class F (according to ASTM C 618- 

03) used in the synthesis of all geopolymer matrices 

was obtained from Asam-asam power station in South 

Kalimantan, Indonesia. Its chemical composition is 




shown in Table 1. The composition of fly ash was 

determined by X-ray fluorescence (XRF) method. 

Quartz/SiO2 (Merck, 99%), Corrundum/α-Al2O3 

(Merck, 95%), sodium silicate, distilled water and 

analytical-grade NaOH were used throughout all 

experiment. 

Geopolymerisation 

The ash and either quartz or corundum in the 

required proportions were mixed with the activating 

solution to prepare cylindrical specimens (15x30 

mm). Alkaline solution (NaOH, sodium silicate and 

H2O) and source materials were mixed for 3 minutes. 

The mixture was cast in plastic moulds and vibrated 

for 10 second. Specimens was cured at 60°C for 24h. 

At the end of the curing process, the specimens were 

removed from the oven and kept in the mould for 7, 

14, 21 and 28 days. 

Compressive strength testing 


ISBN : 978 – 979 – 19201 – 0 – 0 

Compressive strength testing was carried out 

on the molded, cylindrical speciments with 1:2 

diameter to length ratio. Three cylinders of each 

sample were tested and the experimental values being 

averaged. All samples were tested at 7, 14, 21 and 28 

days. An Torsee Universal Testing Machine Au-5 

20490 was used for all tests. 

Morphology, FT-infrared analysis and X-ray 

diffraction 

The samples were studied by SEM/EDX 

using a JEOL JSM-6360LA scanning microscope 

equipped with an energy dispersive X-ray at the 

accelerating voltage of 10 kV. FT-infrared spectra 

were recorded on a spectrometer using the KBr pellet 

technique. X-ray powder diffraction data were 

obtained using a Phillips PW 1800 diffractometer 

with Cu Kα radiation (40 kV, 30 mA) with scanning 

rate 2°/min from 5° to 70°. 

Table 1 Elemental composition Fly ash, expressed as oxides (%) 

Mechanical strength 

Fig. 1 shows the variation in compressive 

strength with curing time for the various working 

system (3 cube per test were tested). At short curing 

time (7 day), an increase in the soluble silica content 

at Si/Al = 5.0 favored the development of high 

mechanical strength in material (compressive strength 

> 50 MPa). At slightly longer curing times (14 day), 

however, a substantial increase was observed in the 

strength of systems. Longer curing times had a 

consistently beneficial effect on the mechanical 

strength of the all matrices. 




Compressive strength (MPa) 

70 

65 

60 

55 

50 

45 

40 

35 

30 

25 

7 d 

14 d 

21 d 

28 d 

ISBN : 978 – 979 – 19201 – 0 – 0 

20 

1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 

The mol ratio of Si/Al 

Fig. 1. Mechanical strength vs mol ratio of Si/Al for various curing time 

The geopolymerisation of fly ash, fly ash-corundum, 

and fly ash-quartz was conducted with the mol ratio 

of Si/Al was varied from 1.5 to 6.0 in NaOH and 

Na2SiO3 solutions. It was found that all geopolymer 

products have satisfactory compressive strength 

(Fig.1). When a mixture of fly ash and corundum was 

geopolymerised, theere was no significant change in 

the compressive strength, namely around 34 MPa. On 

the other hand, addition of SiO2 (Quartz) results in 

dramatic increase in the compressive strength. It was 

faound that the strength reached up to 65 MPa, 

doubled than those prepared by corrundum addition. 

The Figure also shows that the increase in Si/Al ratio 

improve the compressive strength of geopolymers. 

However, when the ratio is higher that 5 it start to 

declines. 

The variation in mechanical strength as a 

result of variation in Si/Al ratio has a relation with 

material reactivity. The propety can be analysed by 

elemental analysis using ICP for silicone and 

aluminium dissolved from the material in a strong 

alkaline solution. The analysis results showed that the 

solubility of aluminium in corundum was only 

0.067% while in fly ash it was 4.57%. The same trend 

was also shown by quartz where the solubility of 

silicone was only 2.06%. Thus, it can be seen that a 

high reactivity raw materials were needed to produce 

a high performance geopolymer. 

3.2 Sample crystallinity and FT-Infrared 

Characteristics 

X-ray powder diffraction pattern for the 

material studied, including original fly ash, SiO2 and 

corundum, are shown in Fig. 2. In contrast to the 

other two, the fly ash shows a substantial amorphous 

phase (hump registered between 2θ = 20° and 2θ = 

30°) in its structure with the peaks of the quartz 

(SiO2, JCPDS 03-0444) and mullite (3Al2O3.2SiO2, 

JCPDS 15-0776) as a remainder. It has been reported 

[9] that source materials like fly ash are usually have 

a higher reactivity in geopolymerization process. 




Fig. 3 shows the XRD pattern of the 

geopolymer synthesized at Si/Al molar ratio =3.0; 

3.5 and 5.0. The Figure shows crystalline phases 

detected in the product of geopolymer, namely quartz 

. 

Si/Al=5.0 + TiO 2 

Si/Al=3.5 + TiO 2 

Si/Al=1.5 + TiO 2 

Q 

Q 

R 

R 

5 10 15 20 25 30 35 40 45 50 55 60 65 70 

5 10 15 20 25 30 35 40 45 50 55 60 65 70 

2θ 

ISBN : 978 – 979 – 19201 – 0 – 0 

Fly ash 

Quartz 

Corundum 

Fig. 2. The XRD pattern of fly ash, quartz and corundum 

R M 

R 

R Q 

M 

Q 

M 

R 

MM 

Q/M 

R 

Q M R 

M 

M 

Fig. 3. The XRD pattern of some geopolymer 

products. Q= quartz, M= mullite, and R= Rutile 

2θ 

M 

R 

and mullite. The addition of insoluble material 

(Quartz and Corundum) increased the intensity of 

quartz (in 2θ = 27, increase from 438 to 487) and 

mullite (in 2θ = 42, increase from 89 to 291). 

The FTIR spectra of the original fly ash and 

geopolymer products are shown in Fig. 4. The fly ash 

spectrum shows one broad absorbance registered at 

1089cm -1 which is ascribed to T-O asymmetric 

stretching vibration (T=Si or Al). Absorbance at 

466cm -1 ascribed to υ4 (O-Si-O) bending modes of 

SiO4 tetrahedra and around 782 cm -1 is assigned as 

symmetrical stretching of Si-O-Si [6,10]. An 

absorbance at 679 cm -1 is assigned for quartz as a 

part of the fly ash component[11]. There was no 

significant differences between the FTIR pattern of 

fly ash and the geopolymer products which means 

that the most vibrant forms of the molecular chains 

existing in the raw materials are retained in the 

geopolymer product 




1464 

1427 784 690 

1081 1018 560 

1089 

Wave number (cm -1 ) 

On the other hand, the geopolymer products either 

with or without insoluble material additives were 

found to have vitreous phases comprising of SiO2 and 

Al2O3 namely quartz and mullite. The presence of 

quartz in the FTIR spectra is shown by a series of 

bands located at around 1081, 784 (double band), 690 

and 460 cm -1 . Meanwhile, the presence of mullite is 

shown by bands at around at 560 cm -1 (band 

associated with the octahedral aluminium present in 

mullite) [12]. Absorption band which is appeared at 

around 1427 cm -1 has been assigned to the presence 

of the sodium bicarbonate [10] as a result of the 

reaction between excess sodium with atmospheric 

carbondioxide. The geopolymer absorption band at 

around 1089 cm -1 (asymmetric stretching vibration of 

459 

782 679 466 

ISBN : 978 – 979 – 19201 – 0 – 0 

Si/Al = 6.0 

Si/Al = 5.0 

Si/Al = 3.5 

Si/Al = 3.0 

Si/Al = 1.5 

Fly ash 

Fig. 4. FTIR spectra of fly ash and geopolymers product 

T-O) is shifted to between 1081 and 1018 cm -1 . The 

shift indicates that the vitreous components in fly ash 

are reacted with the alkali activator and the alkaline 

aluminosilicate gels are being formed [11]. 

Microscopic morphology 

The micrographs presented in this paper 

depict the typical microstructure by the material at 

Si/Al ratio (Fig. 5 and 6). Fig. 5 is a SEM image 

showing the characteristic morphology of the original 

fly ash, quartz and corundum. The ash (a) consists of 

a series of spherical vitreous particles of different 

sizes (diameter ranging from 0.2 to 5 µm). While 

quartz powder (b) shows a prismatic shape with 

particle size mostly larger than 50 µm and corundum 




powder displays hexagonal shapes with particle size mostly smaller than 5 µm. 

(a) (b) 

(c) 

Fig. 5. SEM Picture (a) original fly ash, (b) Quartz, (c) Corundum 

Fig. 6a shows the geopolymer product 

without insoluble material additives. The picture 

correspond to a geopolymer cured for 28 days. Fly 

ash particles which have reacted with the alkali 

solution are observed to co-exist with some unreacted 

sphere (see ). Fig. 6b shows the geopolymer 

product with corundum addition. Corundum crystals 

(see ) are detected under the matrix layer on the 

broken surface. Fig. 6c shows the product with quartz 

additive. Almost all quartz particles reacted with the 

alkali solution. 

ISBN : 978 – 979 – 19201 – 0 – 0 

The main reaction product from 

geopolymerization in alkaline condition is sodiumalumino-silicate 

gel that are getting compacted during 

precipitation step with more gel proceeding from 

other particles giving place to a geopolymer matrix. 

The EDX analyses for the geopolymer matrix show 

that the Si/Al ratio in the main reaction products is 

3.5 in the geopolymer with no additive), 3.0 with 0.03 

mol corundum additive and 5.0 with 0.3 mol quartz 

additive. This phenomenon suggests that some added 

corrundum and quartz may still exist in the 

geopolymer product. 




Conclusion 

(a) (b) 

Product of geopolymers from fly ash and 

insoluble material (Quartz and corundum) has been 

successfully synthesized. It is found that there is an 

interrelationship among the insoluble additives that 

affect the final structure and properties of geopolymer 

products. It was shown that the reactivity of starting 

material affect the mechanical properties where 

highly reactive starting material produces high 

mechanical strength. The lower reactivity of the 

quartz, the interaction between the source material 

and the alkaline solution and the reinforcing effect 

caused by the unreacted quartz particles give 

satisfactory mechanical strength of the formed 

geopolymers. The Si/Al ratio (5.0) gives the highest 

mechanical strength. This study also indicates that not 

(c) 

Fig. 6. SEM images of Geopolymer product 

(a) Si/Al=3.5, (b) Si/Al=3.0 and (c) Si/Al=5 

ISBN : 978 – 979 – 19201 – 0 – 0 

only amorphous phases but also crystalline phases 

involve in the geopolymerization process. 


The authors gratefully acknowledge funding 

from the Directorate General of Higher Education, 

Indonesia, under Hibah Pasca grant. 

References 

[1] Bankowski, P., Zou, L., Hodges, R.,”Using 

inorganic polymer to reduce leach rates of 

metals from brown coal fly ash”, Mineral 

Engineering, 17 (2004) 159-166. 

[2] Perera, D. S., Uchida, O., Vance, E.R., 

Finnie, K.S., (2007), “Influence of Curing 

Schedule on the Integrity og Geopolymers”, 




Journal of Material Science, 42 (2007) 

3099-3106. 

[3] Bakharev, T., “Thermal Behaviour of 

Geopolymers Prepared using Class F Fly 

Ash and Elevated Temperature Curing”, 

Cement and Concrete Research, 36 (2006) 

1134-1147. 

[4] Fletcher, A.R., MacKenzie, K. J. D., 

Nicholson, L. C., Shimida, Shiro, “The 

composition range of aluminoslicate 

geopolymers”, Journal of European 

Ceramic Society, 25 (2005) 1471-1477. 

[5] Fernandez-Jimenez, A., Palomo, A., and 

Criado, M., “Microstructure Development 

of Alkali-Activated Fly Ash Cement : A 

Descriptive Model”, Cement and Concrete 

Research, 35 (2005) 1204-1209. 

[6] Van Jaarsveld, J.G.S., van Deventer, J.S.J. 

and G.C. Lukey., “The Effect of 

Composition and Temperature on The 

Properties of Fly Ash- and Kaolinite-Based 

Geopolymers”, Chemical Engineering 

Journal, 8 (2002) 63-73. 

[7] Xu, Hua, Lukey, G. C., van Deventer, J. S. 

J., (2006), “The effect of Ca on Activation of 

ISBN : 978 – 979 – 19201 – 0 – 0 

Class C-, Class F-Fly ash and Blast Furnace 

Slag, Cement and Concrete Research, xx 

(2006) xxx-xxx. 

[8] Xu, Hua, Van Deventer, J.S.J., “The 

geopolymerisation of aluminosilicate 

minerals”, International Journal of Mineral 

Processing, 59 (2000) 247-266. 

[9] Xu, Hua dan J.S.J., Van Deventer, 

“Geopolymerisation of Multiple Minerals”, 

Journal of Mineral Engeneering, 15 (2002) 

1131-1139. 

[10] Lee, W. K. W., J.S.J., Van Deventer, “The 

effect of the inorganic salt contamination on 

the strength and durability of geopolymers”, 

Colloidal and Surface A : Physicochem. 

Eng. Aspects., 211 (2002) 115-126. 

[11] Fernandez-Jimenez, A., Palomo, A., 

“Composition and Microstructure of Álcali 

Activated Fly Ash Binder : Effect the 

Activator”, Cement and Concrete Research, 

35 (2005) 1984-1992. 

[12] Criado, M., Fernández-Jiménez, A., Palomo, 

A., (2007), “Alkali activation of fly ash : 

Effect of the SiO2/Na2O ratio Part I : FTIR 

study”, Microporous and Mesoporous 

Materials, 106 (2007) 180-191. 




ISBN : 978 – 979 – 19201 – 0 – 0 

Dye Sensitized Solar Cell Building by Anchored-Tio2 

Wahyuningsih, 1,2 Joshua Watts 3 , Indriana Kartini, 2 Narsito 2 , Lianzhou Wang 3 , Max Lu 3 

1 Department of Chemistry, Faculty Mathematic and Natural Science Sebelas Maret University 

Ir. Sutami Street, 36A, Kentingan, Surakarta, Indonesia. 

E-mail: w.sayekti.yahoo.com, phone: 62-274-368381 

2 Department of Chemistry, Faculty Mathematic and Natural Science Gadjah Mada University 

Sekip Utara, Yogyakarta 55281, Indonesia 

3 ARC Centre of Excellence for Functional Nanomaterials, Level 5 AIBN Building 74 Brisbane Qld 4072 

Australia 

Abstract 

In this study, mesoporous TiO 2 with 30 nm pore size diameter synthesized using the template method 

with a short-range ordered-framework structure was successfully used as an electrode material in 

dye-sensitized solar cells. The higher light-to-electricity energy conversion efficiency is attributed to 

the novel physicochemical properties of mesoporous TiO 2, which include high surface area, anchored 

by silyl agent, and uniform nanochannels. The high surface area adsorbs large quantities of the 

sensitized dye, resulting in the generation of a higher photocurrent density. A significant influence of 

the mesopore structure on photovoltaic performance was also observed based on these novel 

properties. The photovoltaic performance of the dye-sensitized solar cells composed of mesoporous 

TiO 2 is expected to be further improved through the use of an anchor group, which has higher thermal 

stability. Therefore, mesoporous TiO 2, used as an electrode material in DSSCs, may provide a means 

of obtaining higher efficiencies in dye sensitized solar cells, possibly approaching their theoretical 

efficiency value in future. 

Keywords: belum ada 

Introduction 

Since the powering work of Regan and Gratzel (1), a 

great attention has been paid to dye sensitized solar 

cell (DSSC) as cheap, effective and environmentally 

benign candidates for a new generation of solar 

power. Solar cells based on dye-sensitization of TiO2 

electrodes are regarded as a regenerative low-cost 

alternative to conventional solid-state devices. DSSC 

is a photoelectrochemical device which effectively 

utilizes a property of nanocrystaline wide bandgap 

metal oxide semiconductor porous electrode. 

Nanocrystalline TiO2, particularly in the anatase 

phase, has been extensively investigated as a potential 

material for dye-sensitized solar cells (DSSCs) (1). 

Currently, this kind of solar cell reaches an efficiency 

exceeding 10% offering a realistic option for 

converting light to electrical energy. However, it is 

not easy to gain 10% efficiency, which is still far 

from the theoretical efficiency of 33%. 

Generally, a DSSC consists of indium tin oxide, 

(ITO), dye modified TiO2 electrode, electrolyte, and a 

counter electrode. To establish high energy 

conversion efficiency, mesoporous TiO2 electrode of 

a large surface area have been investigated 

extensively as a key material for DSSC (1). The 

efficiency of 10% was obtained by using mesoporous 

TiO2 as electrode materials (12). Over the whole 

range of 0–40 mm, the amount of dye adsorbed by the 

mesoporous TiO2 films was about 1.5–2 times greater 

than that by the P-25 films (12). This high efficiency 

is attributable to the physicochemical properties of 

mesoporous TiO2, such as surface area, ordered 

structure, particles size and uniform pore size (12). In 

this study, mesoporous TiO2 was synthesized with 

triblock copolymer Pluronic P123 as the structure 

direction template to satisfy this need. In order to 

make breakthroughs in progress, a great deal of 

attention has also been focused on developing new 

sensitizers (2,3), new electrolytes (4,8,16,17), new 

model counter electrodes (5,10,15) and new 

semiconductor electrode materials (2,6,9). Recently, 

an efficiency of 10.2% was obtained using a N719 

dye as a sensitizer (7), and a new record efficiency of 

11.04% was achieved using a modified electrolyte 

(11). One of the strategies to improve conversion 

efficiency is to increase high harvesting efficiency by 

increasing the amount of dye in the TiO2 electrode 

using anchoring group onto TiO2 surface. 

In this article, we present the photophysic and 

photoelectrochemical characteristics of mesoporous 

TiO2, anchored by silyl agent, abbreviated as 

anchored-TiO2. Photosensitizer was anchored onto 

TiO2 surface via anchor group to gain chemical 

bonding between TiO2 and dye. Compared to 

nanowires or nanorods, mesoporous anchored-TiO2 

has a high surface area (approx. 140.1 m 2 g -1 after 

calcinated at 400 o C), and also uniform nanochannels 

that can be easily accessed by the electrolyte for I3 - 

ion transport. Sensitized anchoring-TiO2 was applied 




for the electrode of DSSC. The incident photon to 

current conversion efficiency (IPCE) of the cell made 

from anchored TiO2 was investigated. There are many 

factors limiting the cell performance, among which 

light harvesting efficiency is the most important. 


Materials 

Nanocrystaline TiO2 was synthesized via self 

assembly-sol–gel technique adopted followed 

previous work (19). Titanium tetra isopropoxide 

(TTIP) was purchased from Aldrich, triblock 

copolymer HO(CH2CH2O)20(CH2CH(CH3)O)70 

(CH2CH2O)20H (Mav = 5750, designated 

EO20PO70EO20; Pluronic P123) was received as a gift 

from BASF, acetylacetonate (acac) was purchased 

from Merck, 2-propanol (iPr) and hydrochloric acid 

(HCl) 37% was purchased from Merck. TiO2 film 

prepared on indium tin oxide (resistivity: 10 Ω/cm 2 ) 

conductive glass (Asahi Glass, Japan) and Pt coated 

FTO conducting glass (Dyesol). Complexes 

compound were prepared using CoCl2 from Merck, 

aminopropyltrimethoxysilane (APTS) from Aldrich, 

and 4-(2-piridilazoresorcinol) (PAR) from Aldrich. 

Methanol used as solution of in situ complexes 

sensitizer formation was purchased from Merck. 

Sealant spacer, aluminum back cover, electrolyte (EL- 

HSE) and N719 dye were purchased from Dyesol. 

Instrumental 

Crystal structure of TiO2 powders were 

analyzed by X-ray diffraction (XRD) measurements 

using Cu Kα radiation (Shimadzu XRD-6000). 

Differential thermal analysis (DTA) and thermal 

gravimetric analysis (TGA) and fourier transform 

infra red spectrophotometer (FTIR) were used to 

observe template replacing process. Pore size 

distribution and surface area were calculated using N2 

adsorption-desorption data from Autosorp NOVA 

1000. Scanning Electron Microscope (SEM) 

including Energy Dispersive X Ray Analysis (EDX) 

specimen (Joel JSM 6360LA) was employed to 

investigate the morphology of the anchored TiO2 film. 

The absorption and reflectant spectrum was analyzed 

by UV-Vis spectrophotometer (SHIMADZU UV 

1799 Pharma-Spec) equipped with specularreflectance 

accessories. Annealing process of TiO2 

film preparation was carried out using a Furnace 

Carbolite CWF 1300 with a heating rate of 5 o C/min 

at 400 o C for 2 hour. 

Preparation of Anchored-TiO2 Photoelectrodes 

ISBN : 978 – 979 – 19201 – 0 – 0 

TiO2 film was fabricated on the indium tin 

oxide (ITO) covered glass substrate (Asahi Glass 

Japan, 10 Ω/cm 2 ) by doctor bland technique. Anatase 

TiO2 particles (7-8 nm in size) were prepared by 

using a published method (19). TiO2 pastes were 

prepared by adding water, acetylacetonate, and triton- 

X 100 (10:1:2 v/v). The film thickness was prepared 

by SEM. The apparent film size was 5 mm x 5 mm. 

The films were annealed at 400 o C for 2 hour with a 

rising rate of 5 o C/min. TiO2 film was immersed in the 

anchoring ligand aminopropyltrimethoxysilane (5%) 

for 5 times, and then rinsed with methanol creating 

anchored-TiO2. Anchored-TiO2 film was immersed in 

the Co 2+ solution (10 -4 M), then in the 4-(2piridylazo) 

resorcinol (10 -4 M) for 2 hour. After dye 

adsorption via in situ complexes formation, the colour 

of the thin films changed to a deep red. 

Solar cell assembly 

Stepwise of DSSC building including (1) 

preparation of dye sensitised photoanode cell, (2) the 

use of Pt-coated on conductive glass electrode, and 

(3) assembly of sandwiched dye sensitized solar cell. 

The dye-sensitized TiO2 electrode was 

incorporated into a thin-layer, sandwiched solar cell 

(Fig.8). The area of the TiO2 electrodes was 0.5 x 0.5 

cm 2 . The Pt sputtered on a transparent conducting 

glass (SnO2-F) (Dyesol) was used as the counter 

electrode. A thermoplastic sealant film spacer (50 µm 

nominal thickness, TPS 109129-50 from Dyesol) was 

used to prevent the cell from short-circuiting when 

the counter- and working electrodes were clamped 

together. The electrolyte (EL-HSE electrolyte from 

Dyesol) was placed inside counter and working 

electrodes through a small hole in counter electrode. 

Electrolyte addition was kept in vacuum desiccators. 

After electrolyte addition (without air bubble 

formation), the cell was pressed together with 

electrolyte sealer (thermoplastic backed aluminium 

strip) in the back side. DSSC cell was tested with a 

solar simulator, which has an input power of 250 watt 

and able to reach a voltage range of about 0.2-0.5 V. 

This indicates that the cell is ready for IPCE 

measurement. 

Fig 1. Building component of dye sensitized solar cell 

IPCE measurement 

Action spectra of the monochromatic 

incident photon to current conversion efficiency 




(IPCE) for the solar cells were measured with a Oriel 

QE/IPCE measurenment kit Model QE-PV-SI from 

Newport Corporation. We employed an AM1.5 solar 

simulator with 300 watt Xenon Lamp as the light 

source. The incident light intensity was calibrated 

with a standard solar cell for silicon solar cell 

produced by Japan Quality Assurance Organization 


A monochromatic incident photon to current 

conversion efficiency (%IPCE) of 0.9 was obtained 

at 655 nm composed of mesoporous TiO2. The 

photocurrent yield measured at 655 nm was found to 

depend on the counter ion of the iodine/triiodine 

redox electrolyte. 

IPCE% 

1 

0.9 

0.8 

0.7 

0.6 

0.5 

0.4 

0.3 

0.2 

0.1 

0 

350 450 550 650 750 850 950 1050 

Wevelength (nm) 

IPCE(%) 

10 

9 

8 

7 

6 

5 

4 

3 

2 

1 

0 

IPCE(%) 

. 

IPCE (%) 

0.2 

0.18 

0.16 

0.14 

0.12 

0.1 

0.08 

0.06 

0.04 

0.02 

0 

. 

1 

0.8 

0.6 

0.4 

0.2 

ISBN : 978 – 979 – 19201 – 0 – 0 

0 

350 450 550 650 750 850 950 1050 

750 850 950 1050 

Wavelength (nm) 


350 450 550 650 750 850 950 1050 


Fig. 2. Incident photon to electron conversion efficiency (IPCE) of (a) mesoporous TiO2/aminosilyl-Co II - 

piridylazoresorcinol and (b) P25 TiO2/aminosilyl-Co II -piridylazo resorcinol (c) mesoporous TiO2/N719. 

Insert: row photocurrent action spectra along visible region. 

Based on the figures, there are correlations 

between IPCE spectra (Fig. 10) and UV VIS 

absorption spectra of related cell (Fig. 11). 

Excitation dyes electrons seen in UV VIS 

absorption will be injected to the conduction band 

of electrode TiO2. The cell performance improves 

significantly if the dye acts not only as an absorber 

but also as an efficiency blocking layer (Schmith- 

Mende et al, 2005). The recombination of 

photogeneration electrons and hole in the band of 

all solar cells are the main reasons for their less 

efficiency. DSSCs, in which the electrons and hole 

exist in separate chemical phases, are subject 

almost exclusively to interfacial recombination. We 

suggest the lower result of aminosilyl anchored- 

TiO2 based DSSC compared to mesoporous 

TiO2/N719 is due to inefficient blocking layer as a 

consequence of the recombination of 

photogeneration electrons and holes. The sluggish 

efficient interfacial charge transfer between the 

TiO2 and dye complexes anchored to the TiO2 

surface also propose the lower result of anchored- 

TiO2 based DSSC. Unfortunately, for the second 

periods transition metals Co II used in this study, the 

ratio of injection over recapture ratio kinj/kb lower 

that 10 3 . 

The nanocrystaline films with particles size 

commensurate or smaller that their Bohr radius 

exhibits quantum size properties, which can be 

illustrated in photocurrent action spectra of 




mesoporous TiO2/aminosilyl-Co II - 

piridylazoresorcinol (Fig. 2a) and of mesoporous 

TiO2/N719 (Fig 2c).. This means that there is a 

potential barrier between the particles and that the 

particles constituting the film can, in some respect, 

be regarded as individual entities. Quantum size 

effect occur if crystal size of TiO2 less than 10 nm. 

Fig.3 shows dependency of crystal size on 

annealing temperature. Annealing until 400 O C still 

get quantum size TiO2. In the absent of quantum 

size effect, the extinction spectrum is described by 

the Mie’s Theory (26). By Mie’s Theory, a very 

small colloidal semiconductor particle removes 

light from the incident beam both by scattering and 

absorption. 

Crystal Size (nm) 

25 

20 

15 

10 

5 

0 

0 200 400 600 800 1000 

Temperature (C) 

Fig. 3. Dependency of TiO2 crystal size on 

annealing temperature. Annealing 

temperature rate 5 o C/min. ( ____anatase, --- 

rutile) 

The BET surface area of mesoporous TiO2 

(140.1 m 2 g -1 ) is higher than that of P-25 (approx. 

55 m 2 g -1 ), resulting in more dye being adsorbed 

per unit thickness of film. The high-adsorption 

property of mesoporous TiO2 allows high 

photocurrent action spectra properties of DSSC 

based mesoporous TiO2 (Fig. 2a and Fig. 2b). The 

higher efficiency is attributable to the 

physicochemical properties of mesoporous TiO2, 

such as high surface area, ordered structure, particle 

size and uniform pore size. The results of the 

characterization of the mesoporous TiO2 are 

depicted in Fig. 4 (data calculations were shown in 

Table 1). The pore size distribution was very 

narrow and the highest pore diameter was estimated 

to be 30 nm. The isotherm is of type IV, 

characteristic of mesoporous materials. The 

hysteresis loop exhibited by the specimen is mainly 

between the H1- and H2-types.The character of 

small size distribution explains the low efficiency 

in the P25 film, because of the diffusion of I 3- ion in 

electrolyte become a slow and limits the current 

production. 

Experiment results can be illustrated in the form of 

figures (graphics or picture, see example Figure 1). 

Title of figure (10 pts) is set under the figure. 

Figure can be formatted single or double column. It 

ISBN : 978 – 979 – 19201 – 0 – 0 

should set centered alignment, and the resolution of 

scanned picture has to be not less then 300 dpi. 

(a) 

(b) 

Fig 4. Characteristic of (a) isotherm adsorptiondesorption 

N2 and (b) pore size distribution 

of mesoporous TiO2 (synthesized at molar 

ratio of TTIP/P123/acac/H2O/iPr = 

1/0,051/0,53/12/30) 

Table 1. The BET data and pore characteristic of 

TiO2 used in DSSCs cells 

Surface 

area 

(m 2 Pore 

volume 

/g) cm 3 Average 

pore size 

/g (nm) 

mesoporous 140.1 216.6 6.2 

TiO2 

TiO2 P25 58 0.291 1.04 

Many researchers have tried to reproduce the 

overall efficiency of 10% for N719 DSSC, reported 

in 1993 (13). However, this record remained 

unmatched for several years until 2001, when a 

black dye-adsorbed DSSC gave an efficiency of 

10.4 % (14). Sensitization of mesoporous TiO2 

using N719 dyes can increase photocurrent action 

spectra compared with mesoporous 

TiO2//aminosilyl-Co II -pyridilazoresorcinol (Fig 2c). 

This report proves that anchoring of carboxylic 

group more favour than silyl group, except of metal 

ion and ligand influence. Further explanation need 

observation of two dyes with the equivalent metal 

ions and ligand. 




The photovoltaic performance of DSSCs 

depends largely on the film thickness (12). Wei et. 

al. (12) have showed Jsc of the cells composed of 

mesoporous TiO2 and P-25 initially increased with 

film thickness but then fell off with further 

increases in thickness. The film thickness 

approximately 20 µm for the mesoporous TiO2 film 

and that for the P-25 film is fixing with sealant used 

as spacer between working electrode and counter 

electrode. On the other hand, the electron 

recombination between the electrons injected from 

the excited dye to the conduction band of electrode 

TiO2 and the I3 - ions in the electrolyte becomes 

more serious in the thicker films. It should be 

pointed out that this IPCE tendency of the cells 

made of P-25 less than those of mesoporous TiO2, 

indicating that the electron recombination between 

the transported electrons and I3 - ions in the P-25 

film is more serious than that in the mesoporous 

TiO2 film (Fig 2). This may contribute to the 

differences in electrode material morphology. As 

mentioned above, the particle size of P-25 is 

approximately 20 nm, while mesoporous TiO2 has a 

short-range ordered-framework structure and a 

smaller particle size (approx. 7–8 nm, calculated by 

Scherrer equation from Fig. 8), and thus contains a 

large number of grain boundaries of homogeneous 

nanocrystalline TiO2 along the framework (Fig.5). 

Nakade et al.(18,19) report that the diffusion 

coefficients of electrons increased with TiO2 

particle size. The increasing diffusion coefficients 

of electrons were related to the decreased film 

surface area and the condition of the grain 

boundaries. On the other hand, they also found that 

the electron lifetimes decreased with increasing 

TiO2 particle size. Therefore, an electrode film 

composed of mesoporous TiO2 is conductive to 

decreased diffusion coefficients of electrons and 

increased electron lifetimes. 

Fig. 5. SEM picture of mesoporus TiO2 synthesized 

by Pluronic P123 templated at molar ratio of 

TTIP/P123/acac/H2O/IPr = 

1/0,051/0,53/12/30 (a) magnitification 

50.000x (b) magnitification 95.000x, and 

SEM picture of TiO2 P25 at (a) 

ISBN : 978 – 979 – 19201 – 0 – 0 

magnitification 50.000x (d) magnitification 

90.000x 

Fig.6. SEM photograph of cross section of 

ITO/mesoporousTiO2. The ITO/meso 

porous TiO2 film was calcinated at 400 o C 

for 2 hour. 

Fig 6. Illustration of mesoporous TiO2 in 30 nm 

average pore diameter size with numerous 

uniform aminosilyl nanochannels. 

Aminosilyl nanochannels absorb monolayer 

dyes 

Our experimental results suggest that the 

mesoporous structure plays a key role and is 

responsible for the improvement in the performance 

parameters. Compared with P-25 nanoparticles, 

mesoporous TiO2 has numerous uniform aminosilyl 

nanochannels 30 nm in average pore size (Fig 6). 

Assuming that the adsorbed dye forms a monolayer 

on the inner surfaces of the aminosilyl 

nanochannels, and the molecular size of PAR as 

organic ligand is approximately 1.20 Å nm - 2.4 Å 

(24), big space is left for electrolyte diffusion. If the 

adsorbed dye molecules were stuck in the inner 

surface of the channels as a bilayer or aggregated in 

the entrances of the nanochannels, the space for 

electrolyte diffusion will not further reduced. Under 

these conditions, it only need short time for the 

electrolyte solution to penetrate and fill all the 

nanochannels. Using a little dye of Co 2+ complexes 

the aggregated adsorption dye molecules in the 

entrances of the nanochannels can not hampers dye 

adsorption on the inner surface of the 

nanochannels. Based on the assumptions mentioned 

above, part of the inner surface is be covered by 

dye molecules and the electrode film can be used 

efficiently. However, over time, the rearrangement 

of adsorbed dye might occur accompanied with the 




diffusion of electrolyte solution. On the other hand, 

due to anchoring group addition cooperated in TiO2 

surface as well as in Co 2+ -pyridilazoresorcinol 

complexes, removing dye together within 

electrolyte can be reduced. But aminosilyl 

nanochannels with high concentration may increase 

cell resistivity due to silyl condensation. 

The XRD pattern of mesoporous TiO2 

synthesized by self assembly-sol gel method 

adopted followed previous work (19) was shown in 

Fig. 7. It can be seen that the phase of mesoporous 

TiO2 annealed at 400 o C show well-crystallized both 

anatase (90%) and rutile (10%) peak. The average 

crystal size of TiO2 calculated using the Scherer 

equation is about 7 nm. 

Fig. 7. X-ray diffraction pattern of TiO2 thin film 

on indium tin oxide glass. Synthesized at 

molar ratio of P123/acac/HCl/H2O/iPr = 

0.05:0.53:1.25:12.00:30.00. 

Clean up of template occur at 400 o C, due to 

organic group burning at that temperature. These 

phenomena show at infra red spectra’s (Fig. 9), 

differential thermal analysis (Fig. 10a.) and 

thermograph metric analysis (Fig.10b.). 

Fig 9. Infra red spectra of TiO 2 annealed at (a) 150 o C, (b) 

300 o C, and (c) 400 o C. 

M icrovolt Endo up (m icrovolt) 

W eight % (% ) 

400 

350 

300 

250 

200 

150 

100 

50 

ISBN : 978 – 979 – 19201 – 0 – 0 

0 

0 100 200 300 400 500 600 700 800 

100 

80 

60 

40 

20 


0 

0 200 400 600 800 


Fig.10. Thermal analysis of TiO2 xerogel (a) 

differential thermal analysis, and (b) 

thermographymetric analysis 

We report here a novel dyes, cobalt-based 

photosensitizer, was prepared via in situ complexes 

formation. The UV Vis spectra of Co 2+ , Co 2+ -APTS 

complexes, and Co 2+ -APTS-PAR complexes in 

methanol show in Fig. 11. It exposed that visible 

absorption of Co 2+ -APTS-PAR complexes is very 

far above the ground due to chromophore ligand of 

4-(2-piridylazo)resorcinol. The specular absorption 

spectra of the TiO2 sample show in Fig. 11a. The 

band gap of the anatase crystal as calculated for the 

absorption edge in the visible region was found to 

be 3.02 eV, respectively. This result is appropriate 

with Eg value of TiO2 anatase and rutile literatures 

about 2.99 – 3.32 eV (20, 21, 22). Addition of 

anchoring ligand of APTS, and Co 2+ complexes can 

move absorption spectra at visible region slightly 

(Fig 12c). 


a 

b



Fig 11. UV VIS spectra’s of (a) Co 2+ ion in 

methanol solution, (b) Co 2+ -APTS 

complexes solution in methanol, and (c) 

Co 2+ -APTS-PAR complexes in methanol 

Fig 12. UV VIS spectras of (a) TiO2 film onto ITO 

glass, (b) aminosilane-TiO2 film onto 

ITO glass, and (c) aminosilane-TiO2/dye 

film onto ITO glass 

High absorption spectra at ultraviolet region, 

shown in Fig. 12, exhibits one pyridyl based ð-ð* 

transition (245 nm) and one metal-to-ligand charge 

transfer (MLCT) bands at 550 nm superimposed 

with weakly d-d transition. Like those of bipyridyl 

complexes of ruthenium(II), their intense visible 

absorptions are due to excitation into initially 

singlet metal-to-ligand charge transfer (1MLCT) 

states via t2g ð* electronic transitions. However, 

cobalt’s weaker ligand field places the metalcentered 

antibonding eg orbitals lower in energy 

than the ligand ð* orbitals. As a consequence, 

unlike ruthenium complexes, for which a 3 MLCT 

state is populated via intersystem crossing and 

persists for nano - to microseconds, cobalt 

complexes crossover to a ligand field (LF) state. 

There is a concurrent and substantial loss of excited 

state energy: for the tris-substituted complexes, the 

LF state is only 0.9 eV above the ground state (23). 

Conclusion 

An improvement photocurrent action spectrum 

was achieved by applying anchored-mesoporous 

ISBN : 978 – 979 – 19201 – 0 – 0 

TiO2 as an electrode material. This high efficiency 

can be attributed to the novel physicochemical 

properties of mesoporous TiO2, which include high 

surface area, uniform nanochannels and a 

homogeneous nanocrystalline TiO2 several nm in 

size arranged along the framework. The high 

surface area anchored-TiO2 allows adsorption of a 

large volume of dye, resulting in a higher incident 

photon to current efficiency. The photovoltaic 

performance of the dye-sensitized solar cells 

composed of mesoporous TiO2 is expected to be 

further improved through the use anchor group, 

which has higher thermal stability. Therefore, 

mesoporous TiO2, used as an electrode material in 

DSSCs, may provide a means of obtaining higher 

efficiencies in dye sensitized solar cells, possibly 

approaching their theoretical efficiency value in 

future. 


This work was supported by Minister of 

Education of Indonesia under Sandwich Program 

2008 visiting in ARC Centre of Excellence for 

Functional Nanomaterials, Australian Institute for 

Bioengineering and Nanotechnology, University of 

Queensland. 

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Jiang, Daoben Zhau, 2004, Influence of small 

moleculs in conducting polyaniline on the 

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conversion efficiency of N719 dye-sensitized 

solar cell, Coordination Chemistry Reviews, 

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Berginc, 2008, U.O. Krasovec , D. Gerhard, P. 

Wasserscheid, A.Hinsch, H. J. Gores, 2008, 

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Chemistry, 164 3–12. M. Wei, Y. Konishi, H. 

Zhou, M. Yanagida, H.Sugihara and H. 

Arakawa, 2006, Highly efficient dye-sensitized 

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dioxide, Journal of Materials chemistry, J. 

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1320. 




Introduction 

ISBN : 978 – 979 – 19201 – 0 – 0 

Synthesis and Characterization Of PVA/Montmorillonite 

Khoirul Himmi Setiawan 1 , Is Fatimah 2 

1 Research and Development Unit for Biomaterials LIPI, Bogor, Indonesia, 

Email: khoirul_himmi@yahoo.com 

2 Chemistry Dept., Islamic University of Indonesia, Yogyakarta, Indonesia, 

Email: isfatimah@fmipa.uii.ac.id 

Abstract 

Polyvinyl alcohol (PVA)/montmorillonite composites were prepared by intercalation in solution 

system. Their physicochemical properties as the function of PVA to montmorillonite mass ratio were 

investigated with X-ray diffraction (XRD), surface area analyzer and Fourier Transform Infra Red. The 

results showed that PVA chains could be intercalated into the silica interlayer space of montmorillonite 

and the properties are affected by the PVA to montmorillonite mass ratio. Due to FTIR and surface area 

analyzer data, it can be concluded that there are no significant surface properties of 

PVA/montmorillonite within the range of 1% to 3% w.t clay content. However, the XRD pattern of 

materials show the effect of the mass ratio in that the highest d 001 produced at the ratio of 1% PVA in 

the PVA/montmorillonite synthesis. These data are the indication of intercalation process to exfoliating 

process as the PVA concentration increase controlled by the cation exchange capacity. 

Keywords: intercalation, montmorillonite, PVA/Montmorillonite 

Nanocomposite materials, consisting of inorganic 

nanolayers of montmorillonite (MMT) clay and organic 

polymers, have evoked intense interest lately because 

their unique characteristics have the potential to be used 

in many commercial applications. Nanostructured 

polymer-inorganic composites, mixed at the molecular 

level or near molecular level, are much different from 

the conventional composites with incorporation of a 

variety of additives in the polymer matrices. In the 

polymer-inorganic nanocomposites, strong chemical 

bonds or interactions such as van der Waals forces, 

hydrogen bonding, or electrostatic forces, often exist 

between the polymer and inorganic components (Jung 

et al., 2006). 

Several useful polymer/clay nanocomposite 

materials have been produced. At present, polymer/clay 

hybrids are one of the most important classes of 

synthetically engineered materials. They can be 

transformed into new materials possessing the 

advantages of both organic materials, such as light 

weight, flexibility, and good moldability, and inorganic 

materials, such as high strength, heat stability, and 

chemical resistance (Chang et al., 2003). The flexibility 

and processability of polymer matrices based on watersoluble 

polymer such as poly-vinyl alcohol (PVA) with 

excellent optical properties and good compatibility with 

additives can provide good mechanical properties. 

Poly-vinyl alcohol (PVA) is a water-soluble 

polymer extensively used in paper coating, textile 

sizing, and flexible water-soluble packaging films. 

These applications stimulate interest in improving the 

mechanical, thermal, and permeability properties of thin 

nanocomposite films, ultimately with the hope of 

retaining the optical clarity of PVA (Strawhecker & 

Manias, 2000). PVA nanocomposite materials may 

offer a viable alternative for these applications to heat 

treatments or conventionally filled PVA materials. The 

flexibility and processability of polymer matrices based 

on water-soluble polymer such as poly-vinyl alcohol 

(PVA) with excellent optical properties and good 

compatibility with additives can provide good 

mechanical properties. There are several publications 

associated with the preparation and properties of 

PVA/clay nanocomposites prepared by solution 

dispersion technique (Carrado et al.,1996, Wang & 

Wu, 1997, Strawhecker & Manias, 2000). 

Recently, PVA/clay nanocomposites are found to 

display novel properties, which can be observed from 

two dissimilar chemical components combining at the 

molecular level. Kokabi reported that nanocomposite 

hydrogels based on PVA and organically modified 

montmorillonite clay were introduced as novel wound 

dressings, which prepared by the cyclic freezing– 

thawing method. PVA/clay nanocomposite hydrogels 

showed excellent physical and mechanical properties 

which met the essential requirements of ideal wound 




dressings. Based on swelling measurements, they 

exhibited high capability in absorbing fluid, so 

recommended for exudative wounds. Because of their 

unique mechanical properties, i.e. very high elasticity, 

they could be excellent candidates for wounds under 

high stresses. The proper values of the water vapor 

transmission rates of PVA nanocomposite hydrogels 

indicated that they could keep moist environment on 

interface of the wound and dressing to accelerate the 

healing process (Kokabi, Sirousazar, & Hassan, 2007). 

And though many research about poly/clay have 

been reported, sinthesis and characterization of 

nanocomposite hydrogels based on clay is not yet 

studied in Indonesia. With enormous clay resources, 

Indonesia need more advanced and sustaine research in 

developing poly/clay, leads to some novel 

nanocomposites with improved performance properties, 

which may be potentially used in wide range application 

such as optics and biomedicinal technology. This paper 

will focus on review the unique structural properties of 

PVA/Montmorillonite (MMT) clays made by 

intercalation system. Physiochemical properties of 

PVA/MMT will be analyzed by FT-IR, X ray 

diffractometer, and Surface Area Analyzer. 


Experimental 

The starting clay used for synthesis was natural 

montmorillonite supplied by PT. Tunas Inti Makmur 

Semarang, Indonesia. The cation exchange capacity of 

clay is 68 meq/100 g. Particle sizes of less than 200 

mesh were used in synthesis process. Chemicals consist 

of H2SO4 and Poly-vinyl alcohol (PVA) was purchased 

from E.Merck. 

Synthesis of PVA-montmorillonite 

The starting material, montmorillonite was dispersed in 

water in the concentration of 10 % w.t and then refluxed 

with H2SO4 0.01 M for 6 hours in order to purify clay 

from impurities. Sample was filtered and neutralized 

until the filtrate was free from Cl - and pH=7. Solid was 

dried in oven at 130 o C followed by grounding to 200 

mesh in particle size. PVA intercalating solution was 

prepared by diluting PVA solution with deionized water. 

Clay suspension was made by dispersing 

montmorillonite in water with the concentration of 5% 

w.t and stirred for 24 h. PVA intercalation was 

performed by slow titration of a PVA solution of under 

vigorously stirring at room temperature for 24 hours. 

PVA concentrations were varied at 1, 2 and 3 w.t % clay 

content. After washing by centrifugation and filtration, 

the intercalated solids were dried by heating in oven at 

ISBN : 978 – 979 – 19201 – 0 – 0 

80 o C for 24 hours. Dry sample resulted was washed 

with aquadest. Further, PVA-clay composite are 

designated as PVA/MMT 1%, 2% and 3% respectively 

and for comparison purpose, montmorillonite clay 

encoded by MMT. 

Physiochemical characterisation of the samples was 

studied including surface area analysis (nitrogen 

adsorption at 77 K), X-ray diffraction (XRD), and 

Fourier Transform Infra Red (FT-IR) identification. Xray 

powder diffraction patterns were obtained by using a 

Shimadzu X6000 diffractometer, at 40 kV and 30 mA, 

and employing Ni filtered Cu Kα radiation 


Material structure of Montmorillonit clay was identified 

by X-Ray Diffractmeter to study precursor effect from 

PVA toward physiochemical properties of 

Montmorillonit. Figure 1 shows XRD curves of 

Montmorillonit and PVA hybrids with different clays at 

1, 2 and 3 w.t % clay content. Wide-angle X-ray 

diffraction (XRD) measurements were performed at 

room temperature on a Shimadzu X6000 X-ray 

diffractometer using Ni filtered Cu Kα radiation. The 

scanning rate was 2°/min over a range of 2θ = 3–25°. 

Figure 1. XRD patterns of (a) Montmorillonit 

(MMT) and (b)-(d) PVA/MMT 1%, 2% and 

3% respectively 

XRD pattern of MMT shows typical peak of 

montmorillonite at 2θ = 5,9275 o (d = 14,898 Ǻ) and 2θ 

= 19,915 o (d = 4,454 Ǻ) with significant intensity. Other 

typical peaks such as 2θ = 20,18 o and 2θ = 23,57 o , 

confirm montmorillonite content. Compared to XRD 

pattern of Boyolali clay reported by Simpen et. al. 

(2003), the intensity of typical peak from 

montmorillonite used in this study shows less 

crystalline. Beside of montmorillonite typical peak, 

other mineral content such as caolinite showed at 2θ = 

12,2 o (d = 7,24Ă); 2θ = 24,86 o (d = 3,57 Å); and 2θ = 

19,88 o (d = 4,46 Å). Generally, XRD pattern showed 




that clay used in this research classified into 

montmorillonite mineral. 

The main basal spacing (d001) peak reflections of 

montmorillonte (MMT) are well defined, indicating a 

very ordered structure. Figure 1 shows that intercalation 

of PVA into Montmorillonite cause basal spacing 

displacement to the left along with the increasing of d001 

from PVA/MMT 1% w.t and PVA/MMT 2% w.t. In the 

presence of PVA, the peaks for both clays show the 

characteristics of a moderately disordered material, 

ISBN : 978 – 979 – 19201 – 0 – 0 

indicating the PVA presence in the interlaminar spaces 

though not throughout, since if this were the case, the 

degree of disorder would be much greater. In other 

hand, PVA/MMT 3% w.t shows less d001 than 

Montmorillonite (MMT). This is caused by polymer 

grafting which form agregrat in the interlaminar spaces 

of aluminosilicate structure. The data about interlayer 

spacings of clay modified by PVA with various 

intercalation agent concentration showed on table 1. 

Table 1. interlayer spacings of Montmorillonit and PVA/MMT Nanocomposite 

SAMPLE 2 θ (FWHM) Basal spacing d001 

MMT 6.30 14.47 

PVA/MMT 1% (w.t) 6.15 14.82 

PVA/MMT 2% (w.t) 6.06 15.04 

PVA/MMT 3% (w.t) 6.70 13.61 

Figure 2 shows the FT-IR spectrum for MMT, 

PVA hybrids with different clays at 1, 2 and 3 w.t % 

MMT content It is well known that pure MMT shows 

three strong peaks at 455, 520, and 1045 cm −1 . These 

peaks are associated with the bending mode of Si-O, 

the stretching vibration of Al-O, and the stretching 

vibration of Si-O, respectively. 

Figure 2. FT-IR spectra of (a) MMT, (b) PVA/MMT 1%, (c) PVA/MMT 2%, (d) PVA/MMT 3% 

Sample Active Surface Area (m 2 /g) 

FT-IR spectrum all of the PVA/MMT 

nanocomposite microspheres show the presence of 

the -OH stretching vibration in the region of 3000- 

3600 cm −1 after the intercalation process. It indicates 

that the surfaces of the PVA/MMT nanocomposite 

microsphere were covered with the hydroxyl groups. 

While FT-IR spectrum of PVA/MMT 3% show 

significant intensity of alkyl typical peak (C–H sp 3 ) 

on 2800 – 3000 cm -1 , other both PVA/MMT 1% and 

2% show no significant peak there. 

Table 2. Surface area of Montmorillonit and 

PVA/MMT 

MMT 

45,684 

PVA/MMT 1% (w.t) 

188.05 


215.72 


251.77 

Surface area of Montmorillonite (MMT), PVA 

hybrids with different clays at 1, 2 and 3 w.t % MMT 

content showed on table 2. It is obvious that specific 

surface area increase along with the increase of PVA 

concentration intercalated. Information about the 

influence of PVA concentration toward increasing of 

specific surface area can’t definitely explaine the 

physiochemical properties of material sinthesized. So, 




it needs more explanation about pore distribution 

presented on figure 3. 

Figure 3. Pore distribution of PVA/MMT hybrids 

material 

PVA/MMT 1% show formation of new specific 

pore at 32 Å (mesopore), while PVA/MMT 2% show 

no dominant pore formed. Preconception about the 

effect of polymer grafting which form agregrat in the 

interlaminar spaces of aluminosilicate structure is 

confirmed by formation of two kind dominant pore 

mode from PVA/MMT 3%, around 32 Å dan 56Å. It 

can be assumed that there is grafting structure 

forming clay layer aggregation which is responsible 

to form mesopore. 

Conclusion 

PVA intercalation into montmorilonite structure 

to form PVA/MMT composite shown the effect of 

PVA precentage in composite to the physicochemical 

characters of materials. From the XRD and surface 

area analysis data it is concluded that the 

intercalation with 1% and 2% PVA give the clay 

structure intercalation followed by increasing spesific 

surface area of materials. These physicochemical 

character gained grafting structure by the use PVA of 

3% as revealed by XRD, pre distribution analysis and 

FTIR analysis. 

References 

Carrado, K. A., Thiyagarajan, P., & Elder, D. L. 

(1996). Clays Clay Miner,44 , 506. 

Chang, J. H., Jang, T. G., Ihn, K. J., Lee, W. K., & 

Sur, G. S. (2003). Journal of Applied Polymer 

Science, 90 , 3208–3214. 

Jung, H. M., Lee, E. M., Ji, B. C., Sohn, S. O., Ghim, 

H. D., Cho, H., et al. (2006). Fibers and 

Polymers, 7 , 229-234. 

Kokabi, M., Sirousazar, M., & Hassan, Z. M. (2007). 

European Polymer Journal,43 , 773–781. 

ISBN : 978 – 979 – 19201 – 0 – 0 

Strawhecker, K. E., & Manias, E. (2000). Chem 

Mater, 12 , 2943. 




ISBN : 978 – 979 – 19201 – 0 – 0 

Structure and Characterizations TiO2/TS-1 with Variation of 

Calcination Temperature 

Maria Ulfa * Didik Prasetyoko 

Chemistry Department of Mathematic and Science Faculty 

Institut Teknologi Sepuluh Nopember 

Surabaya 

* e-mail: mariaulfa8@gmail.com 

Abstract 

Cathechol and hidroquinon are used in a broad range application from pharmaceuticals, 

photography to polimer industries. Cathechol and hidroquinon can be synthesized from 

phenol hydroxylation with H2O2 as oxidant and Titanium Silicalite (TS-1) as catalyst. TS-1 

has great properties, such as high activity and selectivity to oxidation reaction. However, its 

hydrophobic site leads to slow H2O2 adsorption toward the active site of TS-1. 

Consequently, the reaction rate of whole reaction is low. Titanium oxide (TiO2) as metal 

oxide can give acid site to catalysts. TiO2 has acidic properties, which is depend on 

calcination temperature due to phases transformation of anatase-rutile. In this research, 

The TiO2 is impregnated into TS-1 then its prepared with variation of calcination 

temperature. The novel catalyst, TiO2/TS-1, will be more hydrophilic at certain calcination 

temperature compared to TS-1 and rate of the hydroxylation phenol reaction will be faster. 

Keywords: TiO2/TS-1, hydroxylation of phenol, calcination temperature 

Introduction 

Cathechol and hidroquinon are used in a large application 

of the modern chemical industry such us pharmaceuticals, 

photography to polimer industries (1). TS-1 which was 

firest synthesized by Taramasso et al in 1983 has shown 

excellent catalytic activity in organic oxidation reactions 

using hydrogen peroxide as oxidant under mild conditions. 

In organic oxidation reactions such us hydroxylation 

phenol, many work have been done to enhance the the 

phenol selectivity due to the industrial importance of 

hydroxylation of phenol in the synthesis hydroquinone and 

cathechol. The ability of TS-1 to catalyze a wide variety of 

oxidation transformation including hydroxylation of phenol 

with aqueous hydrogen peroxide had led to extensive 

research worldwide on the synthesis of related heterogenous 

catalyst for liquid phase oxidations (2) 

The catalytic activity of TiO2 is strongly 

influenced by its structure. TiO2 is usually obtained 

by hydrolysis of titanium oxide, followed by 

annealing in the presence of oxygen. Porter et al. [3] 

studied microstructural changes in commercial 

Degussa P-25 TiO2 due to heat-treatment. The 

powder was annealed from 600 to 1000 °C. With the 

increasing calcination temperature the apparent 

crystallite size and rutile content in the catalyst 

increased, whereas the specific surface area and the 

rate of phenol photodecomposition under UV 

irradiation decreased. The same effect was observed 

by Reddy et al. [4] for catalytic activity obtained by 

TiCl4 hydrolysis and calcination at low temperatures, 

between 100 and 600 °C. A marked increase in the 

crystallite size and a decrease in lattice strain were 

observed for catalysts annealed above 600 °C. The 

rate of methylene blue degradation in UV increased 

with increasing calcination temperature from 400 to 

700 °C. Calcination above 700 °C resulted in a 

smaller rate constant, mainly due to partial 

transformation of anatase to rutile. The catalytic 

activity of the titanium oxide is related mainly to its 

acid properties. Some author have reported that the 

catalyst contain Lewis acid sites which are 

responsible for the activity [10,11,14]. In this study, 

TS-1 loaded with titanium oxide has been synthesized 

and used as acidic catalysts in which the Ti atoms in 

TS-1 acts as oxidative acid sites while titanium oxide 

deposited on the surface of TS-1 acts as Lewis acid 

sites. The effect of calcinations temperature of 

titanium oxide on the the structure and properties of 

the catalyst was investigated. 


Preparation of sample 

TS-1 containing 1% mol of titanium was prepared 

according to a procedure describe earlier using 

tetraethyl ortosilicates (Merck,98%), tetraethyl 

ortotitanat (Merck 98%, TEOT) in 2-propanol, 

tetrapropylammonium hydroxide (Merck 20% 

TPAOH in water) and distilled water. The gel was 

charged into a 150 mL autoclave and heated at 175 o C 




under static condition. The material was recovered 

after 4 days by centrifugation and washed with excess 

distilled water. A white powder was obtained after 

drying in air at 100 o C overnight. The solid material 

was then calcined in air at 550 o C for 4 h. 

Sample TS-1 loaded with titanium oxide 

(TiO2/TS-1) was prepared by the impregnation 

method using tetraethyl ortotitanat TEOT precusor. 

TS-1 calcined was dried in oven at 110 o C overnight 

for 24 h. After that, the necessary amount of titanium 

oxide was dissolved in 2-propanol (Merck 98%) to 

obtain the desired metal loaidng and the required 

quantity of pre-dried of TS-1 was immediately added 

to the clear solution with stirring. The mixture was 

stirred at room temperature for 3 h. The solid was 

recovered by evaporating the 2-propanol at 80 o C. 

The acid hydrolysis was performed by addtion of 20 

mL solution of 0,5 M HNO3 in disttiled water and 

aged overnight, followed by heating at 120 o C until 

dryness. The solid was then washed with distilled 

water for three times and finally dried at 110 o C for 24 

h. The white solid was calcined at 400, 500, 600, and 

700 o C for 4 h. 

Titanium oxide was prepared by hydolysis of 

tetraethyl ortotitanat (TEOT) at room temperature. 

The white solid was revcovered by filtration, washing 

with water and drying at 100oC overnight. Finally, 

the solid was calcined at 550oC for 4h. 

Characterizations 

All sample were characterized by powder X-ray 

diffraction(XRD) for crystallinity and phase content 

of the solid material, using Bruker Advance D8 

difractometer with Cu K Cu Kα (λ = 1.5405 Å) as the 

diffracted monochromatic beam at 40 kV and 30 

mA,. The patern was scanned in the 2θ ranges 

between 5–50 o at a step 0,02 o and step time 1s. 

Infrared (IR) spectra of the samples were collected on 

Shimadzu Fourier Transform Infrared (FTIR)n 

spectrometer with a spectral resolution of 2 cm −1 , 

scan 10s, at temperature 20 o C with KBr wafer 

ISBN : 978 – 979 – 19201 – 0 – 0 

methode. Infrared spectra of the samples were 

recorded at room temperature in the hydroxyl region 

of 1400-400 cm −1 . 

Hydrophobycity of catalyst was also analisized by 

using water adsorption technique. In a typical 

experiment, the catalysts were dried in an oven at 

110 o C for 24 h to remove all the physically adsorbed 

water. After dehydration, the sample was exposed to 

water vapor at room temperature, folllowed by the 

determination of the percentage of adsorbed water as 

function of time. 


X-ray diffraction 

Fig. 1 shows the XRD pattern of XTiO 2/TS-1 samples. The 

samples are noted as XTiO 2/TS-1 where X denoted the 

calcination temperature. The diffraction pattern for the 

samples with 400, 500, 600 and 700 o C of calcination 

temperature show similar pattern to that of the parent TS-1 

as indicated by the diffraction peaks at 2θ = 7,92º; 7,94º; 

8,80º; 23,06º; 23,08º; 23,10º; 23,24º; 23,26º; dan 23,28º. 

The presenceof all the typical XRD peaks for TS-1 

indicates the framework structure has been retained after 

calcination. Fig 1 shown that no diffraction lines for 

anatase-rutil phases of titanium oxide are observed 

indicating that TiO 2 is highly dispersed on the surface of 

TS-1. It is found that the MFI structure of TS-1 was 

maintained after the impregnation titanium oxide and 

calcination preparation. However, the XRD peak intensities 

of TS-1 decreased when calcination temperature was 

increased. This might be due to the decreased in the 

precentage amount of TS-1 in the samples as calcination 

temperature of TiO 2 increased 

Table can be illustrated using double (Table 1) or 

single (Table 2) column, if necessary. Table started by 

table title (10 pts) that set above the table. Table is set 

centered alignment, and table limit must not exceed 

margin of the page. If the title of the table more than 

one row, the second row should be formatted using 

hanging indent following the above limit. 

Table. 1 The phase dan peak intensities of samples from XRD 

Samples Intensities at 2Ө = 23,06 

Cps 

TS-1 

400 TiO2/TS-1 

500 TiO2/TS-1 

600 TiO2/TS-1 

700 TiO2/TS-1 

TiO2 

2696 

2652 

2635 

2619 

2604 

0 

The XRD pattern of TiO2 samples indicated that 

structure of TiO2 was rutile. There is no diffraction 

line assigned for crystalline phase of titanium 

oxide present. This indicated that niobium oxide 

was well dispersed on the TS-1. In addition, the 

Phase Intensities at 2Ө = 27,52 

( rutile phase) 

MFI 

MFI 

MFI 

MFI 

MFI 

Rutil 

Cps 

180 

413 

427 

438 

450 

1971 

peak intensities of TS-1 decreased up to 0,4- 0,9 % 

(table 1) as increased calcination temperature. It is 

suggested that titanium oxide is either located on 

the surface of TS-1 or crystalline phase of TiO2 

covering the surface of TS-1 of TS-1.Since of Ti 




site of TiO2 is larger than size pore entrance of TS- 

1, they should be attached to the external surface of 

TS-1. The peak intensities of rutil phase at 2θ = 

27,52º increased up to 0,77-0,79% (table 2) as 

increased calcination temperature. It is suggested 

that TiO2 which are dispersed in the surface of TS-1 

mainly due to partial transformation of anatase to 

rutile 

Fig 1. XRD pattern of the samples 

Tabel 1. Increased precentage peak intensities of 

samples TS-1 and TiO2/TS-1 

Sampel 

Persentase 

pengurangan 

intensitas pola 

difraksi TS-1 

(%) 

Persentase 

pengurangan 

intensitas pola 

difraksi fase 

rutil 

(%) 

TS-1 

- 

0,036 

400 TiO2/TS-1 0,458 

0,771 

500 TiO2/TS-1 0,635 

0,777 

600 TiO2/TS-1 0,082 

0,783 

700 TiO2/TS-1 0,958 

0,791 

TiO2 

- 

- 

Infrared Spectroscopy 

2θ, degree 

The infrared of spectra zeolite lattice vibration 

between 1400 and 400 cm -1 are depicted in Fig 2. 

According to Flanigen, the absorpstion bands at 

around 1100, 800, dan 450 cm -1 are lattice modes 

associated with internal linkage in SiO4 or AlO4 

tetrahedral and are sensitive to structural changes. 

The absorpition bands at around 1230 dan 547 cm -1 

are characteristic of the MFI type zeolite structure 

and are sensitive to structure changes. All samples 

showed a band at around 970 cm -1 . the vibrational 

modes at around this frequency may be the result of 

several contribution, i.e. the asymmetric streching 

modes of Si-O-Ti linkages, terminal Si-O streching 

of Si-O-H-(HO)Ti” defective sites” and tytanyl 

ISBN : 978 – 979 – 19201 – 0 – 0 

(Ti=O) vibrations[16,17,18,19]. However, this 

band can be attributed to the titanium in the 

framework, since silicate, a Ti free zeolite, did not 

shoe any band at aroud this frequency. In addition, 

impregnation and increased temperature calcination 

titanium oxide gave rise to no band around 970 cm - 

1 . Therefore, it is concluded that the TS-1 sample 

contains Si-O-Ti connections. There is no band 

shifting or additional band observed after 

impregnation of titanium oxide on TS-1. Ths 

finding suggest that both the MFI structure and 

titanium framework were still maintained after both 

of impregnation and calcination temperature 

preparation of titanium oxide. 

Fig 2. FTIR Spectra of the samples 

c 

a b d 

Fig 3. Hydrophobicity testing before stirring: a. TS- 

1; b. 400 TiO2/TS-1; C, 500 TiO2/TS-1; D. 

600 TiO2/TS-1; E. 700 TiO2/TS-1, F.TiO2 

a b e 

c d f 

Fig 4. Hydrophobicity testing before stirring: a. 

TS-1; b. 400 TiO2/TS-1; c, 500 TiO2/TS-1; 

d. 600 TiO2/TS-1; e. 700 TiO2/TS-1, f.TiO2 


e 

f



As shown in Fig 3 and , it was clearly observed 

that the amount of adsorbed water on 700 and 600 

TiO2/TS-1 was significantly lower than 400 and 

500TiO2/TS-. This might be indicated that 

increased calcinations temperature mainly due to 

the transformation anatase-rutil phase. The highly 

rutil phase of sample at high calcinations 

temperature might be due to the agglomeration 

titanium oxide (8) in the surface of TS-1.Fig 3 and 

4 a, show that TS-1 not well dispersed to aqueous 

water. It is indicates that TS-1 have naturally 

hydrophobic behavior. Impregnation titanium oxide 

to the surface of TS-1 enhanced hidrophylicity 

behavior. 

Conclusion 

Acidid catalyst have been sussesfuly prepared 

by the dispersion of titaniumoxide on TS-1 at 

modified of calcination temperature increased up to 

400 and 700 o C. The catalyst have oxidative site due 

to titanium located in the framework os silicates, 

while octahedral titanium containing hidrophilic 

site. The best incresing hidrophilic behavior at 500 

TiO2/TS-1 due to highly dispersion of titanium 

oxide in the surface of TS-1. Temperature 

Calcination at 600-700 o C due to decreasing 

hydrophilic behavior mainly transformation phase 

of anatase-rutil. 


We gratefully acknowledgement funding from 

Directoration General of Highler Education 

Indonesiaunder Hibah Paska grant No 

1108/12.7/PM/2008. 

References 

[1] Almeida, R.M., Noda, L.K., Goncalves, N.S., 

Meneghetti, S.M.P, dan Meneghetti, M.R., 

“Transesterification Reaction of Vegetable 

Oils, Using Superacid sulfated TiO2-Base 

Catalysts”, Applied Catalysis A : General , 

Vol. 347, hal. 100–105. 

[2] Atoguchi, T., Yao, S. (2001), “Phenol 

Oxidation over Titanosilicalite- 

1:Experimental and DFT Study of Solvent”, 

Journal of Molecular Catalysis A: Chemical, 

Vol. 176, hal. 173-178. 

[3] Bhattacharyya, A.,Kawi, S.,dan Ray, M.B. 

(2004),”Photocatalytic Degradation of 

Orange II by TiO 2 Catalysts supported on 

Adsorbents”, Catalysis Today, Vol. 98, hal. 

470-479. 

[4] Bonelli, B., Cozzolino, M., Tesser, R., Serio, 

M.D., Piumetti, M., dan Garrone, E. (2007), 

“Study of The surface acidity of TiO2/SiO2 

ISBN : 978 – 979 – 19201 – 0 – 0 

Catalyst by Means of FTIR Measurements of 

CO and NH3 Adsorption”, Journal of 

Catalysis, Vol. 246, hal 293-300. 

[5] Belessi. V., Lambropoulou, D., Konstantinou, 

I., Katsoulidis, A., Pomonis, P., Petridis, D., 

dan Albanis, T. (2007),” Stucture and 

Photocatalytic Performance of TiO2/Clay 

Nanocomposites for The Degradation of 

Dimethachlor”, Applied Catalysis B : 

Enviromental, Vol. 73, hal. 292–299. 

[6] Chen, J., Eberlein, L., Langford, C.H. (2002), 

“Pathways of Phenol and Benzene 

Photooxidation Using TiO2 supported on A 

Zeolite”, Journal of Photochemistry and 

Photobiology, Vol. 148, hal 183 -189. 

[7] Chun, S.W., Jang, J.Y., Park, D.W., Woo, H.C., 

dan Chung, J.S. (1998), “Selective Oxidation 

of H2S to Elemental Sulfur Over TiO2/SiO2 

Catalysts”, Applied Catalysis B : 

Environmental , Vol. 16, hal. 235–243. 

[8] Corma, A., dan Garcia, H. (2002), “ Lewis Acid 

as Catalysts in Oxidation Reaction: From 

Homogenous to Heterogenous System”, 

Chemical Review, Vol. 102, hal 3837-3892. 

[9] Contsantine, M., Popa, J.M., dan Gubelmann. 

(1993), “Hydroxylation of Phenols/Phenol 

Ethers”, (US.Patents 5.254.746). 

[10] Drago, R. S., Dias, S. C., McGilvray, J. M., 

dan Mateus, A. L. M. L. (1998), “Acidity 

and Hydrophobicity of TS-1”, Journal of 

Physical Chemistry, Vol. 102, hal. 1508- 

1514. 

[11] Esposito, A., Taramasso, M. and Neri, C. 

(1983). “Hydroxylating Aromatic 

Hydrocarbons”. (US Patent No. 4,396,783). 

[12] Huang, D.G., Liao, S.J., Liu, J.M, Dang, Z., 

dan Petrik, L. ( 2006), ” Preparation of 

Visible- Light Responsive N-F-codoped 

TiO2 Photocatalyst by A Sol Gel 

Solvothermal Method”, Journal of 

Photochemistry and Photobiology, Vol. 164, 

hal 242-266. 

[13] Indrayani, S. (2008), Aktivitas Katalitik 


menggunakan H2O2 , Tesis M.Sc., Jurusan 

Kimia, FMIPA Institut Teknologi Sepuluh 


[14] Kung. H. H. (1989), “Transition Metal Oxides: 

Surface Chemistry and Catalysis”, Study 

Surface Science and Catalysis. 45. 

[15] Lamberti, C., Bordiga, S., Zecchina, A., 

Artioli, G., Marra, G. and Spano, G., 

(2001), “Ti Location in the MFI Framework 

of Ti-Silicalite-1: A Neutron Powder 

Diffraction Study”. Journal of Am. Chem. 

Soc., Vol. 123, hal. 2204-2212. 

[16] Li, G., Wang, X., Guo, X., Liu, S., Zhao, Q., 

Bao, X., and Lin, L. (2000). “Titanium 

Species in Titanium Silicalite TS-1 Prepared 




By Hydrothermal Method”, Materials 

chemistry and Physics, Vol. 71, hal 195- 

201. 

[17] Machado, N.R.C, dan Santana, S.V. (2005), 

“Influence of Thermal Treatment on The 

stucture and Photocatalytic Activity of TiO2 

P25”, Catalysis Today, Vol 107-108, hal. 

595-698. 

[18] Nur, H., Prasetyoko, D., Ramli, Z., Endud, S. 

(2004), “Sulfation: A simple Method to 

enhance the Catalytic Activity of TS-1 in 

Epoxidation of 1-octene with Aqueous 

Hydrogen Peroxide”, Catalysis 

Communications . Vol.5, hal. 725–728. 

[19] Nur, H., (2006), Heterogeneous 

Chemocatalysis: Catalysis by Chemical 

Design, Ibnu Sina Institute for Fundamental 

Science Studies Universiti Teknologi 

Malaysia, Johor Bahru. 

ISBN : 978 – 979 – 19201 – 0 – 0 




ISBN : 978 – 979 – 19201 – 0 – 0 

Improved Properties of SnTiO3 Thin Film Light Sensor 

Prepared by Sol-Gel Method 

Tulus Ikhsan Nasution 1,2* , Zaliman Sauli 1 , Hasnizah Aris 1 and Eddy Marlianto 2 

1 School of Microelectronic Engineering 

Universiti Malaysia Perlis, 02600 Kangar, Perlis, Malaysia 

2 Faculty of Mathematics and Natural Sciences 

Universitas Sumatera Utara, Medan 20155, Indonesia 

*e-mail ikhsan@unimap.edu.my 

Abstract 

Thin films based on SnTiO3 sensing material have been successful to deposit on the silicon 

(Si) substrates. The films were annealed at 700 o C in air for 30 s. The surface roughness of 

the films was observed by using an Atomic Force Microscopic (AFM). The current-voltage 

characteristics were measured at the relative low positive voltages under the condition 

without and with light exposure. It was found that the electrical currents of SnTiO3 

composite are higher compared with those of single phase SnO2 both without and with light 

exposure. The improved properties of SnTiO3 composites are related to its smoother 

surface and smaller grain size than SnO2. 

Keywords: Thin film, Sensitivity, Sol-gel, Tin dioxide, Tin Titanate 

Introduction 

Tin dioxide (SnO2) has been well known as a high 

performance n-type semiconductor with a large band 

gap. Thus, light will be easy to penetrate into this 

material and generate the free carriers [1-2]. An 

improvement of the electrical properties can be done 

if the semiconductor oxide adsorbs the light because 

the adsorption can result in a photoexcitation, 

affecting the charge transport across the grain 

boundaries [3]. This provides an advantage which 

enables the sensors based on semiconductor oxide 

have high performance. However, a strong demand of 

the commercial market for reliable and low cost 

sensors leads to the need of continuously developing 

new sensing materials with the improved properties. 

The sensor fabrication in small size is also to be 

important work because it makes easy to integrate it 

into an electrical circuit [4]. 

Many methods can be utilized to produce a variety 

of new sensing materials, especially including 

chemical processes. In this work, sol-gel method is 

considered to be the most suitable method to prepare 

SnTiO3 composite as a sensing material due to this 

method offers some significant advantages such as 

purity and homogeneity that can be obtained by the 

distillation. The low capital cost of the equipment and 

simplicity make it an excellent technique for 

formulating new compositions [5-6]. 

The electrical conductance of SnTiO3 thin film 

sensors are examined under light exposure (photo 

current) and no light exposure (dark current) to 

investigate the effect of light intensity to the 

photocurrent. The characterizations of its structural 

and electrical properties are also carried out to explain 

an important role of grain size distribution, grain 

boundaries and surface state in increasing the 

sensitivity of SnO2-TiO3 thin film sensors. 


Tin acetate [Sn(CH3COO)2] and titanium 

isopropoxide [Ti(OC3H7)4] were used as starting 

materials to prepare the precursor solution of SnTiO3. 

The 2-methoxyethanol (2-MOE) was used as a 

solvent. Titanium isopropoxide was dissolved in the 

2-MOE, then tin acetate was added into the titanium 

solution. After agitating the mixture of tin-titanium 

(Sn-Ti) in 2-MOE for 4 hours, Sn-Ti complex 

solution was obtained. 

The precursor solution was then spin-coated onto 

Al/SiO2/Si substrate at 3000 rpm for 30 s. The spincoated 

wet films were pre-baked at 90 o C for 30 

minutes over a hot-plate to remove the organic 

contaminations. This procedure was performed 

several times to obtain the appropriate thickness. The 

films were final-annealed at 700 o C for 15 s in a rapid 

thermal annealing processor. The surface roughness 

and grain size of SnO2 and SnTiO3 thin films were 

characterized by atomic force microscope (AFM). 

The current-voltage (I-V) measurements of the SnO2 

and SnTiO3 thin films were carried out by using 

semiconductor parametric analyzer (SPA) from 0 to 1 

V in air. 





Figure 1 (a) and (b) show the three-dimensional 

micrographs of SnO2 and SnTiO3 thin films deposited 

by using a sol-gel deposition technique. The AFM 

observation was carried out in contact mode with a 

scan area of 5000 nm x 5000 nm and a scan speed of 

2 Hz. The micrographs indicate that SnTiO3 has the 

smoother surface roughness compared with SnO2. 

Fig. 1 Three-dimensional AFM images of the 

surface of the BST thin film pre-sintered at 

(a) 400 o C and (b) 600 o C. 

This is evident from the three-dimensional 

micrographs, where the z-scale range increased from 

100 nm (Fig. 1 (a) to 150 nm (Fig. 1 (b). This is also 

confirmed with the grain size of SnO2 decreased from 

about 220 nm to about 95 nm. Beside that, no 

microcracks are observed on the surface of both films 

that enables to get the reliable data when the electrical 

measurement is repeated. 

The addition of Ti elements into SnO2 caused the 

grain growth rate to be slower during annealing 

process. The degree of roughness is represented by 

mean roughness which is the mean value relative to 

the centre line or plane. The surface area difference is 

defined as a percentage increase in a comparison of 

the 3-dimensional surface area produced by 

projecting the surface onto the threshold plane. The 

mean grain size is statistically calculated from the 

total number of grains [7]. 

Figure 2 shows the behavior of electrical current 

of SnO2 and SnTiO3 thin films without and with light 

exposure as a function of varying voltages. The 

currents increased steeply with increasing the applied 

voltage up to around 0.55 V and above 0.55 V, the 

current increased modestly with the increase of the 

applied voltage. The current difference between SnO2 

and SnTiO3 is less without light illumination. 

Whereas under light illumination, SnTiO3 shows 

higher current values compared with SnO2. This 

result indicates the Ti elements in SnO2 is surely 

acting as a light absorbing elements. The 

measurements were done under the constant energy 

irradiation. It was also found that both SnO2 and 

SnTiO3 have fast response to the light that falls on 

ISBN : 978 – 979 – 19201 – 0 – 0 

their surface. The similar results are obtained for 

repeated measurement. 

Current (mA) 

800 

700 

600 

500 

400 

300 

200 

100 

SnO 2 (Without Light) 

SnO 2 (With Light) 

SnTiO 3 (Without Light) 

SnTiO 3 (With Light) 

0 

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 

Voltage (V) 

Fig. 2: I-V curves for SnO2 and SnTiO3 thin films. 

Fig 3. The sensitivity of SnO2 and SnTiO3 to the light 

Comparing the current values under light 

illumination and without light illumination provides 

the sensitivity values as depicted in Figure 3. It was 

found that the sensitivity of SnTiO3 is higher than that 

of SnO2. It is believed that the increase in sensitivity 

of SnO2 with the incorporation of Ti element is 

affected by the reduction of particle size which causes 

SnTiO3 is to be more porous compared with SnO2. 

Therefore, the higher sensitivity of SnTiO3 is ascribed 

to an enhancement of light adsorption by the light 

confinement within porous SnTiO3 layer as 

previously reported for porous TiO2 thin film [8]. The 

Ti activities in light adsorption or the change in 

Fermi-level can be considered to be responsible for 

the increased sensitivity. However, the further 

investigations are needed to prove the correctness of 

these preliminary expectations. 

Conclusion 

The conclusion of this study can be summarized as 

the following: 




The addition of Ti element into SnO2 structure has an 

effect to increase it’s electrical current and in turns, 

causes the sensitivity of SnTiO3 is higher compared 

with that of SnO2. It is believed that the smoother 

surface roughness of SnTiO3 than SnO2 plays an 

important role for the improved electrical properties. 

Adding the thickness of the films is believed can 

increase the sensitivity to be much higher from the 

present results. 


The financial support from Universiti Malaysia Perlis 

(UniMAP), Universitas Sumatera Utara (USU) and 

FRGS 9003-00184 is greatfully acknowledged. 

References 

[1] Nishikawa, S., Hashimoto, H., Chikamoto, M., 

Horikoshi, K., Aoki, M., Arima, K., Uchikosi, 

J. and Morita, M. 2006. Photo current through 

SnO2/SiC/p-Si(100) structures, Thin Solid 

Films, 508, 385-388. 

[2] Wu, C. L., Chou, J. C., Chung, W. Y., Sun, T. 

P. and Hsiung, S. K. 2000. Study on 

SnO2/Al/SiO2/Si ISFET with a metal light 

shield, Materials Chemistry and Physics, 63, 

153-156. 

[3] Comini, E, Faglia, G. and Sberveglieri. 2001. 

UV light activation of tin oxide thin films for 

NO2 sensing at low temperatures, Sensors and 

Actuators B, 78, 73-77. 

[4] Nasution, T. I, Sauli, Z. and Omar, R. 2006. 

Electrical and sensing properties of 

SnO2(4mol%ZnO)/CuO(4mol%ZnO) heterocontact 

gas sensor having the sensitivity to CO 

gas, Proceedings of the International 

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Sciences (ICMNS), Bandung, Indonesia, ISBN 

979-3507-91-8. 

[5] Nasution, T. I., Zaliman, Johari, Azhar, Z., 

Taking, S. Hikam, M. N. and Idris, M. A. 2007. 

Effect of Pre-Sintering Temperature on the 

Electrical Properties of Ba0.5Sr0.5TiO3 Thin 

Films Derived from a Solution Deposition, 

Proceedings of IEEE Regional Symposium on 

Microelectronics, ISBN 9-789839-933543. 

[6] Nasution, T. I., Zaliman, Johari, Azhar, Z., 

Taking, S. Hikam, M. N. and Idris, M. A. 2007. 

The Electrical Properties of Ba0.5Sr0.5TiO3 Thin 

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ISBN : 978 – 979 – 19201 – 0 – 0 

Application of Chitin and Chitosan Isolated from Waste of 

Java Sea White Shrimp (penaeus merguensis) as Adsorbent 

Khabibi, Rum Hastuti, Sri Syufa’ati 

Department of Chemistry, University of Diponegoro 

Abstract 

Research of adsorption rhodamine by chitin and chitosan that isolated from waste of java sea white 

shrimp (penaeus merguensis) have been done. The purpose of this research is to isolate chitin from 

the waste of white shrimp skin, transformation of chitin to chitosan, and that application as adsorbent 

rhodamine in pH, time of optimum contact and determine the maximum adsorption capacity of 

rhodamine. Chitin was isolated from waste of java sea white shrimp (penaeus merguensis) through 

deproteination, demineralization, and depigmentation processes. transformation of chitin to chitosan 

through deacetylation processes. Chitin and chitosan usage as adsorbent of rhodamine is conducted 

in pH variation of 2, 3, 4, 5, 6, 7, 8, and 10, contact time of 15, 30, 45, and 60 minutes. Concentrate of 

60, 120, 180, 240, and 300 ppm with volume of sample 20 ml, stiring speed 150 rpm and the amount 

of chitin/chitosan 1 g. Analysis of chitin and chitosan using FTIR spectrometer to determine the 

groups that found on chitin and chitosan. The quantity residu of rhodamine which not adsorb by chitin 

and chitosan were analyzed usely UV-Vis, while to determine the maximum adsorption capacity 

using the Langmuir isotherm equalization. 

The result of extraction is gained white-colour chitin and white-grayish chitosan obtained contained 

70.48%. The optimum adsorption pH of chitin into rhodamine occurs in pH of 5 and the optimum 

adsorption of chitosan into rhodamine in pH 3. Time of adsorption optimum contact of rhodamine by 

chitin and chitosan occurs in 30 minutes. The maximum adsorption capacity chitin of rhodamine 5.69 

mg/g and the maximum adsorption capacity chitosan of rhodamine 6.55 mg/g. it is concluded that 

chitosan more effective as adsorbent rhodamine than chitin. 

Keywords: chitin, chitosan, adsorption, rhodamine, white shrimp 

Introduction 

Rhodamine is one of dye that used widely for 

papers, textile and snacks industries (Isminingsih, 

1973). Rhodamine is resistant to sunlight effect and 

difficult to be degraded biologically because its 

relative stable aromatic structure. Rhodamine waste 

is very dangerous for human life because it can be 

accumulated in a body and cause liver cancer. 

(C2H5)2N 

O 

C 

COOH 

N + (C2H5)2Cl - 

Figure 1. Structure of Rhodamine 

Besides waste from dyeing at textile, there 

is another source of Rhodamine waste that is from 

shrimp processing as an export commodity in a 

form of shrimp without head and shell so that the 

shrimp waste are head and shell of shrimp as 

additional product. 

North Java Ocean as a shrimp producer 

produces more than 50 thousand tons a year. 

Shrimp producing produces shrimp waste that is 

30-40 % from the whole shrimp weight (Moeljanto, 

1984). Since now, shrimp shell waste uses for 

fodder or food industry such as shrimp chips 

(Benjakul and Shophanodora, 1993). 

Shrimp shells contains chitin (Muzzarelli 1985) 

functioning as adsorption of organic compound and 

pigment substance because chitin has amide bunch 

(-NHCO) and Hydroxyl bunch (-OH) as active site. 

Chitin can be isolated from shrimp shell through 

de-proteinasi, demineralization, and depigmentation 

processes. 

H 

CH2OH 

H 

OH 

H 

O 

H 

NHCOCH3 

H 

O 

H 

CH2OH 

H 

OH 

H 

O 

H 

NHCOCH3 

kii 

Figure 2. Structure of Chitin 

Chitin can be changed into chitosan 

through deasitilasi, that causes N-acetyl released so 

that it changes an unit of N-acetyl glucosamine into 

an unit of glucosamine (Robert, 1992) because 

chitosan has amine bunch (-NH2) and Hydroxyl (- 

OH) as active bunch so that chitosan can be used as 

adsorbent either organic or inorganic compounds. 


H 

CH 2OH 

H 

OH 

H 

O 

H 

NH 2 

H 

O 

H 

CH 2OH 

H 

OH 

H 

O 

H 

NH 2 

H 

O 

H 

O 

n 

n



Figure 3. Structure of Chitosan 

Filipkowska (2007) had used chitin as 

adsorbent of black 8 and black 5 colors with 

optimum adsorption at pH 6 while Chiou et al 

(2003) argued that chitosan can be used as pigment 

substance of AAVN (Acid Alizarin Violet N) and 

RB4 (Reactive Blue 4) at pH 3. Setyadi (2005) was 

made chitosan as pigment adsorbent of indigo 

carmine through chromatography method with 

maximum adsorption chitosan toward indigo 

carmine at pH 4. Indigo carmine, AAVN, RB4 and 

Rhodamine have similar structure. Those are 

aromatic compounds. Thus, Rhodamine is expected 

capable to be adsorbed by chitin and chitosan. The 

objective of this research is to isolate chitin from 

white shrimp shell waste, from Java sea, and 

transform to be chitosan, and determine its effect as 

rhodamine adsorbent. 


Materials 

Dry white shrimp (penaeus merguensis) shell 

powder from java sea, NaOH (p.a merck), HCl (p.a 

merck), H2O2 (p.a merck), citric acid (p.a merck), 

Na2HPO4 (p.a merck). 

Chitin and Chitosan Extraction 

Two hundred grams of dry shrimp shell powder is 

added by a liter of 3,5 % NaOH, then heat at 65°C 

for 2 hours along mixing. Then, the mixture is 

filtered and washed by aquades. Residue is added to 

HCL 1 N heated at temperature of 65°C for 2 hours. 

Residue is put at 250 ml of 3% H2O2 for 24 hours 

by 2 times of soaking. The mixture is filtered and 

residue is washed by aquadest then dried by oven at 

80°C for 8 hours of chitin purifying process. 

Chitin transformation to become chitosan: 

Residue is added by 500 ml of 50 % NaOH solution 

then heated at 100°C for 2 hours with mixing. The 

mixture is filtered and residue is washed by 

aquadest until neutral. The residue is dried at 80°C 

for 8 hours to get chitosan powder. Characterizing 

of result (Chitin and chitosan) is analyzed using 

spectrophotometer FTIR. 

Rhodamine adsorption by chitin and chitosan 

with various pH 

A gram of chitin/ chitosan powder put in 

Erlenmeyer. Then, 20 ml solution of 660 ppm 

Rhodamine sample with various pH i.e. 

2,3,4,5,6,7,8 and 10 is added into it and shake it by 

bath shaker during 30 minutes, room temperature. 

The solution, the result of adsorption, is measured 

absorbency using spectrophotometer UV-vis at 570 

nm. 

ISBN : 978 – 979 – 19201 – 0 – 0 

Rhodamine adsorption by chitin and chitosan with 

various time-contacts 

Each of 4 Erlenmeyer is added with 20 ml of 60 

ppm Rhodamine and a gram of Chitin/ Kitosan at 

optimum pH and then shakes with bath shaker for 

15, 30, 45 and 60 minutes. The solution, the result 

of adsorption, is measured quantitatively using 

spectrophotometer UV-vis at 570 nm. 

Rhodamine adsorption by chitin and chitosan with 

various concentration. 

Rhodamine solution in different concentration: 60, 

120, 180, 240, and 330 ppm is added with a gram of 

chitin/ chitosan then shake using bath shaker at 

optimum time and pH. The solution, the result of 

adsorption, is measured quantitatively using 

spectrophotometer UV-vis at 570 nm. 


Chitin and chitosan Extraction 

Chitin subtracts from shrimp shells by doing chitin 

extraction from shrimp shell powder through 

process of de-proteinasi, demineralization while to 

get chitosan can do by deasetilasi process. Deproteinasi 

process can cause the bunch of protein 

and chitin released. Demineralization is the process 

of the elimination toward mineral of shrimp shells. 

Mineral of shrimp shells is CaCO3. Thus, using 

HCL, the mineral of shrimp shells can be 

eliminated because the forming of CaCl2 that can be 

eliminated. The equation of reaction is: 

2HCL + CaCO3 CaCl2 + H2CO3 

De-pigmentation process is a process to eliminate 

pigment so that it becomes white residue. The depigmentation 

is a process using 3% of H2O2 that 

functioning as strong oxidant. The result of 

extraction is gained white-colour chitin. The final 

residue outcome is Chitin and analyzed using 

spectrosphometer FTIR, with result as in Figure 1. 

Figure 4. Spectra FTIR of chitin 




Table 1 Wave number and prediction groups 

funtional in chitin 

Wave Number (cm - 

Prediction funtional 

1 

) 

groups 

3443,74 Stretching N-H 

overlapp O-H 

2927,05 Stretching C-H 

alifatik 

1653,11 

Stretching C=O 

1559,87 

N-H sekunder 

1379,34 Stretching CH3 

1157,14 Stretching C-O eter 

1073,26 dan 

1029,62 

Stretching C-N 

Figure 5. Spectra FTIR of chitosan 

Table 2 Wave number and prediction groups 

funtional in chitosan 

Wave Number (cm -1 ) Prediction funtional 

groups 

3442,91 Stretching N-H overlapp 

2922,39 

1652,98 

1558,51 

O-H 

Stretching C-H alifatik 

Stretching C=O 

Stretching N-H 

1034,98 Stretching C-N 

Obtained Chitin is then deasetilated, is a 

process of reducing acetyl (-COCH3) groups 

substituted with hydrogen groups so that amide (- 

NHCOCH3) change to amina (-NH2) group 

(Tokura,1995). Deasetilation degree is determined 

by base line method and obtained 70,48%. 

The result of deasetilation is white-grayish chitosan 

Analysis outcome of chitosan Spectra FTIR (Figure 

2), show correspondence of some groups chitosan 

function according to Sastrohamidjojo, 1991; 

Khopkar, 1990; and Fessenden, 1992. Chitosan 

function groups resulted in Spectra FTIR seen in 

Table 2. 

The Determination of Optimum pH of Rhodamine 

Adsorption by Chitin and chitosan 

pH is one of factors that influence 

adsorption process. From data of determination of 

colour essence of rhodamine textile that been 

adsorbed because of pH influence. Figure 3 shows 

pH influence toward adsorption of color essence of 

ISBN : 978 – 979 – 19201 – 0 – 0 

rhodamin by chitin and chitosan for 30 minutes. In 

chitin rhodamine adsorption more increases 

significantly at pH 2-5. After pH 5, colour essence 

of rhodamin that been adsorbed more decreases, 

rhodamine adsorption in chitin occurs because of 

interaction of amide group that being proton by N + 

group from rhodamine. 

Figure 3 correlation between Rhodamine that 

adsorbed (q) chitin with pH 

Figure 4 correlation between Rhodamine that 

adsorbed chitosan (q) with pH 

Figure 4 shows that rhodamine adsorption 

by kitosan. At pH 2-3 more increases, but after pH 

4 color essence of rhodamine that being adsorbed 

decreases. This is because chitosan has amina 

(NH2) groups that has one set of dependent electron 

in atom N. This amina group serves as lewis base 

by sharing its set of dependent electron, so that at 

pH acid/base will enable protonation very 

small/even doesn’t occur. According to Suhardi 

(1993) that amina groups at chitosan, can fasten 

color essence because chitosan has character of 

cationic so that in acid condition amina groups 

(NH2) will be protoned become (NH3 + ). The more 

increasing of rhodamin that is adsorbed, the more 

many amina groups that is protoned (Chiou, 2003). 

The Determination of Optimum Contact Time 

toward Rhodamine Adsorption by Chitin and 

Chitosan 

Study about this influence of contact time aims to 

know optimum contact time at adsorption of color 

essence of rhodamine by chitin and chitosan. 

Contact time is varied from 15, 30, 45, and 60 




minutes with compound volume 20 ml at pH 5 

(chitin) and pH 3 (chitosan). In Figure 5 and 6 show 

the influence of time toward rhodamin adsorption 

by Chitin and chitosan. The longer contact time, the 

more color essence that is absorbed by Chitin and 

chitosan, then further occurs decreasing of 

adsorption of color essence of rhodamin. 

Figure. 5 correlation between contact time with 

rhodamine that adsorbed by chitin (q) 

Figure. 6 correlation between contact time with 

rhodamine that adsorbed by chitosan 

(q) 

This shows that stability has been 

achieved. And the adsorption tends to decrease after 

it goes on for 30 minutes, probably it occurred 

resulted in interaction of adsorben with adsorbat 

that too much full. Contact time of 30 minutes 

seems have the most optimum adsorption. 

The Adsorption by Chitin and chitosan with 

Variation of Rhodamin Concentration 

Rhodamine adsorption by chitin and chitosan is 

conducted by variation of concentration between 

60, 120, 180, 240, and 300 ppm with pH 5 for 

Chitin and pH 3 for kitosan during 30 minutes. 

Maximum rhodamin adsorption by Chitin and 

kitosan are 5.695 mg/g and 6.549 mg/g (based on 

isotherm Langmuir equalization). At rhodamin 

adsorption by Chitin can be seen from Figure 7 and 

chitosan from figure 8, adsorbtion outcome shows 

that increasing of chitosan adsorbing power occurs 

with increasing of rhodamin solution concentration. 

The bigger rhodamin concentration, kitosan power 

tends to more increase, and at certain concentration 

that results in equal condition thus the increasing of 

concentration doesn’t influence adsorbing power 

anymore. 

ISBN : 978 – 979 – 19201 – 0 – 0 

Figure 7 correlation between rhodamine that 

adsorbed (q) by chitin with various 

concentration of rhodamine 

Figure 8. corelation between rhodamine that 

adsorbed 

(q) by chitosan with various concentration 

of 

rhodamine 

According to Robert (1992) chitin has – 

NHCOCH3 (amida) active groups, and involves 

interaction of hydroxyl (-OH) group as active site 

that fasten the color essence and chitosan has either 

hydroxyl (-OH) active groups or amina (NH2). 

Interaction of Chitin and chitosan with 

rhodamine can occur because of electrostatic 

interaction (Longhinotti, dkk., 1998). Electrostatic 

interaction of chitin and rhodamine due to a set of 

dependent electron at N-amida (-NHCOCH3) 

groups that is shared at N-rhodamine (N + -(C2H5)2) 

groups, while electrostatic interaction at chitosan 

because of groups from rhodamin -COO - 

(Annadurai, 2002) and (-NH3 + ) positive groups at 

chitosan. So that rhodamine adsorption by chitosan 

more increases by more many amina groups that is 

protoned (Chiou, 2003). 

Result of the study shows alteration of the 

color occurring after adsorption process. The color 

of Chitin that is formerly yellowish-white changes 

to red and the color of chitosan that is formerly 

brownish-white changes to red. While rhodamine 

solution is formerly red changes to more 

transparent (bright). That alteration suggests that 

rhodamine in the solution has been absorbed by 

either chitin or chitosan. 




ISBN : 978 – 979 – 19201 – 0 – 0 

The prediction of interaction that occurs between chitin and chitosan with rhodamine is: 

• Chitin-N (amida)+ + N(C2H5)2-rhod →Kit-(amida)N + N(C2H5)2-rhod 

• Chitosan-NH3 + + - OOC-rhod→Kit-NH3 + + - OOC-rhod 

Based on estimation using isotherm Langmuir 

equalization, maximum capacity of rhodamin that is 

absorbed by Chitin and chitosan is 5.695 mg/g and 

6.549 mg/g. this suggests that chitosan is more 

effective than chitin for adsorbing rhodamine. 

Conclusion 

The result of extraction is gained whitecolour 

chitin and white-grayish chitosan obtained 

contained 70.48%. The optimum adsorption pH of 

chitin into rhodamine occurs in pH of 5 and the 

optimum adsorption of chitosan into rhodamine in 

pH 3. Time of adsorption optimum contact of 

rhodamine by chitin and chitosan occurs in 30 

minutes. The maximum adsorption capacity chitin 

of rhodamine 5.69 mg/g and the maximum 

adsorption capacity chitosan of rhodamine 6.55 

mg/g. it is concluded that chitosan more effective as 

adsorbent rhodamine than chitin. 

References 

Annadurai, G., 2002, Adsorption of Basic Dye on 

Strongly Chelating Polymer: Batch 

Kinetics Studies, Journal Iranian Polymer. 

vol 11, no. 4 

Benjakul, S. dan P. Shophanodora, 1993, Chitosan 

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no. 4 

Chiou, M., ho, P., dan Li, H., 2003, Adsorption 

Behavior of Dye AAVN and RB4 in Acid 

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Universiti Kebangsaan Malaysia

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