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E-ISSN 1471–0676 

•Platinum Metals Rev., 2011, 55, (2), 73• 

Platinum Metals Review 

A quarterly journal of research on the platinum group metals 

and of developments in their application in industry 


APRIL 2011 VOL. 55 NO. 2 

Contents 

Microstructure Analysis of Selected Platinum Alloys 74 

By Paolo Battaini 

The 2010 Nobel Prize in Chemistry: 84 

Palladium-Catalysed Cross-Coupling 

By Thomas J. Colacot 

Dalton Discussion 12: Catalytic C–H 91 

and C–X Bond Activation 

A conference review by Ian J. S. Fairlamb 

A Healthy Future: Platinum in Medical Applications 98 

By Alison Cowley and Brian Woodward 

Fuel Cells Science and Technology 2010 108 

A conference review by Donald S. Cameron 

11th International Platinum Symposium 117 

A conference review by Judith Kinnaird 

The Discoverers of the Rhodium Isotopes 124 

By John W. Arblaster 

“Asymmetric Catalysis on Industrial Scale”, 2nd Edition 135 

A book review by Stewart Brown 

Publications in Brief 140 

Abstracts 142 

Patents 146 

Final Analysis: Flame Spray Pyrolysis: 149 

A Unique Facility for the Production of Nanopowders 

By Bénédicte Thiébaut 

Editorial Team: Jonathan Butler (Publications Manager); Sara Coles (Assistant Editor); Margery Ryan (Editorial Assistant); 

Keith White (Principal Information Scientist) 

Platinum Metals Review, Johnson Matthey Plc, Orchard Road, Royston, SG8 5HE, UK 

E-mail: jmpmr@matthey.com 

73 © 2011 Johnson Matthey

•Platinum Metals Rev., 2011, 55, (2), 74–83• 

Microstructure Analysis of Selected 

Platinum Alloys 

doi:10.1595/147106711X554008 


By Paolo Battaini 

8853 SpA, Via Pitagora 11, I-20016 Pero, Milano, Italy; 

E-mail: battaini@esemir.it 

Metallographic analysis can be used to determine the 

microstructure of platinum alloys in order to set up 

working cycles and to perform failure analyses. A 

range of platinum alloys used in jewellery and industrial 

applications was studied, including several commonly 

used jewellery alloys. Electrochemical etching 

was used to prepare samples for analysis using optical 

metallography and additional data could be obtained 

by scanning electron microscopy and energy dispersive 

spectroscopy. The crystallisation behaviour of 

as-cast alloy samples and the changes in microstructure 

after work hardening and annealing are described 

for the selected alloys. 

Introduction 

Optical metallography is a widely used investigation 

technique in materials science. It can be used to 

describe the microstructure of a metal alloy both 

qualitatively and quantitatively. Here, the term 

‘microstructure’ refers to the internal structure of the 

alloy as a result of its composing atomic elements 

and their three-dimensional arrangement over distances 

ranging from 1 micron to 1 millimetre. 

Many alloy properties depend on the microstructure, 

including mechanical strength, hardness, 

corrosion resistance and mechanical workability. 

Metallography is therefore a fundamental tool to support 

research and failure analysis (1–3). This is true 

for all industrial fields where alloys are used. A great 

deal of literature is available on the typical methods 

used in optical metallography (4–6). 

A large amount of useful information is available in 

the literature for precious metals in general (7–10). 

However, there is less information specifically 

focussed on platinum and its alloys. 

The present work aims to give some examples of 

platinum alloy microstructures, both in the as-cast 

and work hardened and annealed conditions, and to 

demonstrate the usefulness of optical metallography 

in describing them. This paper is a revised and 

updated account of work that was presented at the 


doi:10.1595/147106711X554008 

•Platinum Metals Rev., 2011, 55, (2)• 

24th Santa Fe Symposium ® on Jewelry Manufacturing 

Technology in 2010 (11). 

Materials and Methods 

A wide variety of platinum alloys are used in jewellery 

(12–18) and industrial applications (10, 19–21). 

Different jewellery alloys are used in different markets 

around the world, depending on the specific country’s 

standards for precious metal hallmarking. The 

alloys whose microstructures are discussed here 

are listed in Table I. These do not represent all the 

alloys available on the market, but were chosen as a 

representative sample of the type of results that can 

be obtained using metallographic techniques. The 

related Vickers microhardness of each alloy sample, 

measured on the metallographic specimen with a 

load of 200 gf (~2 N) in most cases, is given for each 

microstructure. 

If metallographic analysis is aimed at comparing 

the microstructure of different alloys in their as-cast 

condition, the initial samples must have the same 

size and shape. Mould casting or investment casting 

can produce different microstructures, with different 

grain sizes and shapes, depending on parameters 

such as mould shape, size and temperature, the 

chemical composition of the mould, etc. Therefore, 

whenever possible, the specimens for the present 

study were prepared under conditions which were as 

similar as possible, including the casting process. 

The specimens were prepared by arc melting and 

pressure casting under an argon atmosphere to the 

shape shown in Figure 1. A Yasui & Co. Platinum 

Investment was used, with a final flask preheating temperature 

of 650ºC. The captions of the micrographs 

specify whether the original specimen is of the type 

described above. 

The preparation of the metallographic specimens 

consists of the following four steps: sectioning, 

embedding the sample in resin, polishing the metallographic 

section, and sample etching for microstructure 

Table I 

Selected Platinum Alloys 

Composition, wt% Melting range a , Vickers microhardness b , 

ºC HV 200 

Pt 1769 65 c 

Pt-5Cu d 1725–1745 130 

Pt-5Co d 1750–1765 130 

Pt-5Au d 1740–1770 127 

Pt-5Ir d 1780–1790 95 

Pt-5Ru d 1780–1795 125 

70Pt-29.8Ir e 1870–1910 330 

70Pt-30Rh 1910 f 127 

90Pt-10Rh 1830–1850 f 95 

60Pt-25Ir-15Rh n/a 212 

a Some melting ranges are not given as they have not yet been reported 

b The microhardness value refers to the microstructure of samples measured in this 

study and reported in the captions of the Figures 

c HV 100 

d These alloys are among the most common for jewellery applications. Where it is not 

specified, it is assumed that the balance of the alloy is platinum 

e This alloy composition is proprietary to 8853 SpA, Italy 

f Solidus temperature 


doi:10.1595/147106711X554008 


Diameter: 

25 mm 

Cross-section diameter: 3 mm 

Fig. 1. General shape of specimens 

prepared by investment casting for this 

study. The microstructures of different alloys 

obtained by investment casting can be 

compared, provided that the specimens have 

the same size and shape. The dashed line 

shows the position of the metallographic 

sections examined in these samples 

detection. The detailed description of these steps 

will not be given here, as they have been discussed 

in other works (4–10). 

Further advice relevant to platinum alloys was given 

in the 2010 Santa Fe Symposium paper (11) and in 

this Journal (22). In these papers, procedures for the 

metallographic analysis of most platinum alloys are 

described. The samples for the present study were 

prepared by electrolytic etching in a saturated solution 

of sodium chloride in concentrated hydrochloric 

acid (37%) using an AC power supply, as described 

previously (22). 

Microstructures of the Platinum Alloys 

In this section the microstructures of the selected 

platinum alloys in different metallurgical conditions 

are presented. As already stated, this selection is a 

representative sample and not a complete set of the 

platinum alloys which are currently on the market. 

As-Cast Microstructures: Metallography 

of Crystallisation 

Examination of the as-cast microstructures shows 

the variation in size and shape of the grains in different 

platinum alloys. However, a noticeable dendritic 

grain structure is quite common. The largest grain 

size was found in platinum with 5 wt% copper 

(Pt-5Cu) (Figure 2) and platinum with 5 wt% gold 

(Pt-5Au) (Figure 3), with sizes up to 1 mm and 2 mm, 

respectively. The Pt-5Au alloy sample also shows 

shrinkage porosity between the dendrites. The core 

of the dendritic grains showed a higher concentration 

of the element whose melting temperature was 

the highest in both cases. This behaviour, known as 

‘microsegregation’, has been widely described (12, 

23, 24). Electrolytic etching tended to preferentially 

dissolve the interdendritic copper- or gold-rich 

regions, respectively. In a platinum with 5 wt% iridium 

(Pt-5Ir) alloy (Figure 4), since iridium has the higher 

melting temperature, the dendritic crystals were 

enriched in iridium in the first solidification stage. 

It is important to point out that the higher or lower 

visibility of microsegregation within the dendrites is 

not directly related to the chemical inhomogeneity, 

but to the effectiveness of the electrolytic etching in 

500 µm 500 µm 

500 µm 

Fig. 2. As-cast Pt-5Cu alloy showing 

dendritic grains with copper 

microsegregation (sample shape as 

in Figure 1; flask temperature 650ºC; 

microhardness 130 ± 4 HV 200 ) 

Fig. 3. As-cast Pt-5Au alloy showing 

shrinkage porosity between the 

dendrites (sample shape as in 

Figure 1; flask temperature 650ºC; 


Fig. 4. As-cast Pt-5Ir alloy with 

columnar grains (sample shape 

as in Figure 1; flask temperature 

650ºC; microhardness 

95 ± 2 HV 200 ) 


doi:10.1595/147106711X554008 


revealing it. For example, the microsegregation in the 

platinum with 5 wt% cobalt (Pt-5Co) alloy is hardly 

visible in Figure 5, despite being easily measurable by 

other techniques (24). 

Scanning electron microscopy (SEM) and energy 

dispersive spectroscopy (EDS) are very effective in 

showing the presence of microsegregation. Figure 6 

shows an as-cast sample of a platinum with 25 wt% 

iridium and 15 wt% rhodium alloy (60Pt-25Ir-15Rh). 

The SEM backscattered electron image is shown in 

Figure 7.The EDS maps in Figures 8–10 give the elemental 

distribution on the etched surface.If the maps 

were obtained on the polished surface the approximate 

concentration of each element may be different 

due to the etching process and a possible preferential 

dissolution of different phases of the alloy. 

However, because EDS is a semi-quantitative 

method, it can only give the general distribution of 

the elements on the metallographic section. It is 

worthwhile remembering that metallographic preparation 

reveals only a few microstructural features. By 

changing the preparation or the observation technique, 

some microstructural details may appear or 

become more clearly defined, while others remain 

invisible. 

The melting range of the alloy and the flask preheating 

temperature affect the size and shape of 

grains significantly. In order to decrease the dendritic 

size and obtain a more homogeneous microstructure, 

the temperature of the material containing the solidifying 

alloy is lowered as much as possible. The effectiveness 

of such an operation is, however, limited by 

50 µm 

500 µm 

Fig. 5. As-cast Pt-5Co alloy 

with small gas porosity (sample 

shape as in Figure 1; flask 

temperature 650ºC; microhardness 

130 ± 6 HV 200 ) 

200 µm 

Fig. 6. 60Pt-25Ir-15Rh alloy cast 

in a copper mould. From the 

transverse section of an ingot 

(microhardness 212 ± 9 HV 200 ) 

Fig. 7. 60Pt-25Ir-15Rh alloy: 

scanning electron microscopy 

(SEM) backscattered electron 

image of the etched sample. The 

sample is the same as that shown 

in Figure 6 

50 µm 

50 µm 

50 µm 


energy dispersive spectroscopy 

(EDS) platinum map acquired 

on the surface seen in Figure 7, 

showing the platinum microsegregation. 

The network of high 

platinum content shows this 

approximate composition (wt%): 

72Pt-14Ir-14Rh 



(EDS) iridium map acquired on 

the surface seen in Figure 7. The 

iridium concentration is lower 

where that of platinum is higher 



(EDS) rhodium map acquired on 

the surface seen in Figure 7. The 

rhodium distribution follows the 

behaviour of iridium. The zones of 

higher iridium and rhodium content 

show this approximate composition 

(wt%): 55Pt-28Ir-17Rh 


doi:10.1595/147106711X554008 


the melting range and by the chemical composition 

of the alloy. An example of the flask temperature 

effect is shown in Figure 11 for Pt-5Ir poured into a 

flask with a final preheating temperature of 890ºC. 

This microstructure is to be compared with that in 

Figure 4, in which a flask preheating temperature of 

650ºC was used. 

A smaller grain size was observed in the platinum 

with 5 wt% ruthenium (Pt-5Ru) alloy, which showed 

a more equiaxed grain (Figure 12) with a grain size 

of about 200 µm. The addition of ruthenium led to 

finer grains in the platinum alloy. 

Pouring the alloy in a copper mould produces 

a smaller grain size due to the high cooling rate, as 

visible in Figure 6 and Figures 13–15. In this case, 

the high iridium and rhodium content also contributed 

to the lower grain size in the as-cast sample. 

Homogenising thermal treatments result in a 

microstructural change. Comparing Figure 16 with 

Figure 17 highlights a reduction in microsegregation 

in Pt-5Cu as a consequence of a homogenisation 

treatment performed at 1000ºC for 21 hours. 

Work Hardened and Annealed 

Microstructures: Metallography of 

Deformation and Recrystallisation 

Optical metallography can reveal the changes in 

microstructure that occur after work hardening and 

recrystallisation thermal treatments and allows 

recrystallisation diagrams like the one in Figure 18 to 

500 µm 500 µm 

200 µm 

Fig. 11. As-cast Pt-5Ir alloy (sample 

shape as in Figure 1; flask 

temperature 890ºC; microhardness 

105 ± 2 HV 200 ) 

Fig. 12. As-cast Pt-5Ru alloy showing 

shrinkage porosity at the centre of 

the section (sample shape as in 

Figure 1; flask temperature 650ºC; 


Fig. 13. 70Pt-29.8Ir alloy: cast in a 

copper mould. From an ingot transverse 

section. A high iridium content 

contributes to grain refinement 


200 µm 

200 µm 

500 µm 

Fig. 14. 70Pt-30Rh alloy: cast in a 

copper mould. From the transverse 

section of an ingot. A high rhodium 

content enhances the grain 

refinement (microhardness 

127 ± 9 HV 200 ) 

Fig. 15. 90Pt-10Rh alloy: cast in 

a copper mould. From the transverse 

section of an ingot. The gas 

porosity is visible (microhardness 

95 ± 5 HV 200 ) 

Fig. 16. Higher-magnification image 

of as-cast Pt-5Cu alloy showing 

dendritic grains with copper microsegregation 

(microhardness 130 ± 4 

HV 200 ). Compare with Figure 17 


doi:10.1595/147106711X554008 


500 µm 

Fig. 17. 

Microstructure 

of Pt-5Cu alloy 

after thermal 

treatment at 

1000ºC for 21 

hours. The 

microsegregation 

of 

copper is 

reduced (microhardness 

120 ± 

4 HV 200 ). 

Compare with 

Figure 16 

be drawn. This makes it a valuable aid in setting up 

working cycles. It is necessary to establish the right 

combination of plastic deformation and annealing 

treatment in order to restore the material’s workability. 

This allows suitable final properties to be 

achieved. 

An example of the changes in microstructure after 

various stages of work hardening and annealing is 

shown in Figure 19 for the 60Pt-25Ir-15Rh alloy. This 

can be compared to the as-cast structure shown in 

Figure 6. 

Drawn wires show a very different microstructure 

along the drawing (longitudinal) direction in comparison 

to the transverse direction (Figures 20–22 for 

Pt-5Au). However, after annealing, the microstructure 

becomes homogeneous and the fibres formed after to 

the drawing procedure are replaced by a recrystallised 

microstructure (Figures 23 and 24). Using the techniques 

described elsewhere (11),analyses can be performed 

even on very thin wires,as shown in Figure 25 

for a platinum 99.99% wire of 0.35 mm diameter. 

It is worth pointing out that some binary platinum 

alloys have a miscibility gap at low temperatures, as 

shown by their phase diagrams (19, 20, 25). Examples 

of this are given in Figures 26 and 27 for Pt-Ir and 

Pt-Au, respectively. Similar behaviour is observed for 

Pt-Co, Pt-Cu and Pt-Rh alloys. 

As a consequence, a biphasic structure is expected 

of each of them. However, this may not occur for various 

reasons. The phase diagrams refer to equilibrium 

conditions, which hardly ever correspond to the 

as-cast conditions. One of the two phases is sometimes 

present but in low volumetric fraction, due to 

the chemical composition of the alloy, in which one 

of the two elements has a low concentration. 

Furthermore, the thermal treatments may have 

homogenised the alloy. Finally, the metallographic 

preparation may not be able to reveal such biphasic 

structures. Therefore, it is necessary to use other 

analytical techniques to detect the type and 

concentration of the alloy phases. Only in specific 

cases can the biphasic structure be revealed. 

Size of grain, mm 

1.6 

1.1 

0.6 

0.1 

0 10 20 40 60 80 

Deformation, ε % 

700 

900 

1100 

1300 

1700 

1500 

Annealing temperature, ºC 

Fig. 18. Recrystallisation 

diagram of a platinumrhodium 

alloy annealed 

at a set temperature for 

a given time after a 

deformation of ε %. 

Adapted from (10). By 

increasing the annealing 

temperature the grain size 

increases. During annealing 

the grain size also increases 

if the previous deformation 

is reduced 


doi:10.1595/147106711X554008 


200 µm 

500 µm 

500 µm 

Fig. 19. 60Pt-25Ir-15Rh alloy: from 

the transverse section of an ingot, 

after various stages of work hardening 

and annealing (microhardness 

212 ± 5 HV 200 ). Compare with the 

as-cast sample shown in Figure 6 

Fig. 20. Pt-5Au alloy: longitudinal 

section (along the drawing direction) 

of a drawn cold worked wire 


Fig. 21. Pt-5Au alloy: transverse 

section of the drawn cold 

worked wire seen in Figure 20 


50 µm 

500 µm 

50 µm 

Fig. 22. Pt-5Au alloy: detail of 

Figure 21 showing the deformation 

of the grains 

Fig. 23. Pt-5Au alloy: transverse section 

of the wire seen in Figure 21, 

after oxygen-propane flame annealing 


Fig. 24. Pt-5Au alloy: detail of 

Figure 23, showing the 

recrystallised grains 

Fig. 25. Pt 

99.99% wire: 

transverse section 

of the wire 

after various 

stages of drawing 

and annealing 

(diameter 

0.35 mm; 

microhardness 

65 ± 3 HV 100 ) 

The best results in working platinum alloys are generally 

achieved by hot forging the ingot during the 

first stages of the procedure. Metallography shows the 

differences between a material that has been cold 

worked and annealed (Figures 28 and 29 for Pt-5Cu) 

and a material that has been hot forged (Figures 30 

and 31). Hot forging more easily achieves a homogeneous 

and grain-refined microstructure, free of 

defects. This is due to the dynamic recrystallisation 

that occurs during hot forging (26). 

50 µm 

The Limits of Metallography 

Optical metallography is only the first step towards 

the study of the microstructure of an alloy. A wide 

variety of analytical techniques can be used alongside 


doi:10.1595/147106711X554008 


Iridium content, wt% 

Pt 20 40 60 80 Ir 

2454 

Gold content, at% 

Pt 20 40 60 80 Au 

1800 

2200 

Liquid 

1600 

Liquid 

Temperature, ºC 

1800 

1400 

1000 

1769 

α 

Temperature, ºC 

1400 

1200 

α 

α 1 α 2 

α 1 + α 2 

600 

Pt 20 40 60 80 Ir 

Iridium content, at% 

Fig. 26. Pt-Ir phase diagram showing a miscibility 

gap at low temperatures (20) 

1000 

800 

Pt 20 40 60 80 Au 

Gold content, wt% 

Fig. 27. Pt-Au phase diagram showing a miscibility 

gap at low temperature (25) 

2 mm 

200 µm 

2 mm 

Fig. 28. Pt-5Cu alloy: from a transverse 

section of a 19 mm × 19 mm 

ingot, which was rod milled, 

annealed in a furnace and finished 

at 10 mm × 10 mm by drawing. The 

sample shows residual coarse grain 

microstructure from the as-cast 

condition and fractures along the bar 

axis (microhardness 208 ± 13 HV 200 ). 

The small square shows the position 

of the detail seen in Figure 29 

Fig. 29. Pt-5Cu alloy: detail of 

Figure 28, with coarse grains and 

small opened cracks evident 

Fig. 30. Pt-5Cu alloy: from a transverse 

section of a 19 mm × 19 mm 

bar, which was hot hammered, 

torch annealed and finished by 

drawing. The sample has 

homogeneous microstructure with 

small grain size (microhardness 

200 ± 9 HV 200 ). The small square 

shows the position of the detail 

seen in Figure 31 


doi:10.1595/147106711X554008 


200 µm 

Fig. 31. Pt-5Cu 

alloy: detail of 

Figure 30, 

showing 

recrystallised 

grains partially 

deformed due 

to the work 

hardening 

solution of sodium chloride in concentrated 

hydrochloric acid can be successfully used for a great 

many platinum alloys, both in the as-cast condition 

and after work hardening. Optical metallography provides 

essential data on the alloy microstructure 

which can be used in setting up the working procedures. 

Other techniques can be used alongside it to 

achieve a more complete knowledge of the material, 

the effects of the working cycles on it, and to interpret 

and explain any remaining problems. 

it to provide a far more complete knowledge of the 

microstructure. One of the most widely used 

techniques is SEM. In addition to this, EDS allows the 

relative concentration of the contained chemical elements 

to be determined, as shown in Figures 8–10. 

Further studies can be performed by X-ray diffraction 

(XRD), which reveals the different crystal phases 

present in the alloy. 

When working with platinum alloys, often only 

very small specimens are available, therefore more 

recent techniques may be required in order to study 

them. One of these is the focused ion beam (FIB) 

technique, which can produce microsections of a 

specimen (27, 28). The microsections are then 

analysed by other techniques, such as transmission 

electron microscopy (TEM). In this case the details of 

microstructure can be detected due to the high spatial 

resolution of the technique. The crystal structure of 

the primary and secondary phases can be studied by 

electron diffraction. Another interesting technique is 

nano-indentation, performed with micron-sized 

indenters, which allows hardness measurements to 

be performed with a spatial resolution far better than 

that attainable with ordinary micro-indenters. The 

data obtained from these measurements allows the 

measurement of fundamental mechanical properties 

of the alloy, such as the elastic modulus (Young’s 

modulus) (29). 

Conclusions 

The metallographic analysis of platinum alloys can 

be profitably carried out by using a specimen preparation 

methodology based on the techniques used for 

gold-based alloys. However, electrochemical etching 

is required in order to reveal the alloy microstructure 

and observe it by optical microscopy. A saturated 

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Elsevier Science BV, Amsterdam, The Netherlands, 1996 

27 P. R. Munroe, Mater. Charact., 2009, 60, (1), 2 

28 E. Bemporad, ‘Focused Ion Beam and Nano-Mechanical 

Tests for High Resolution Surface Characterization: Not 

So Far Away From Jewelry Manufacturing’, in “The Santa 

Fe Symposium on Jewelry Manufacturing Technology 

2010”, ed. E. Bell, Proceedings of the 24th Symposium 

in Albuquerque, New Mexico, USA, 16th–19th May, 

2010, Met-Chem Research Inc, Albuquerque, New 

Mexico, USA, 2010, pp. 50–78 

29 D. J. Shuman, A. L. M. Costa and M. S. Andrade, Mater. 

Charact., 2007, 58, (4), 380 

The Author 

Paolo Battaini holds a degree in nuclear 

engineering and is a consultant in failure 

analysis for a range of industrial 

fields. He is responsible for research 

and development at 8853 SpA in 

Milan, Italy, a factory producing dental 

alloys and semi-finished products in 

gold, platinum and palladium alloys, 

and is currently a professor of precious 

metal working technologies at the 

University of Milano-Bicocca, Italy. 

Professor Battaini is also a recipient of 

the Santa Fe Symposium ® Ambassador 

Award and regularly presents at the 

Santa Fe Symposium ® on Jewelry 

Manufacturing Technology. 



The 2010 Nobel Prize in Chemistry: 

Palladium-Catalysed Cross-Coupling 

The importance of carbon–carbon coupling for real world applications 

doi:10.1595/147106711X558301 


By Thomas J. Colacot 

Johnson Matthey, Catalysis and Chiral Technologies, 

2001 Nolte Drive, West Deptford, New Jersey 08066, 

USA; 

E-mail: colactj@jmusa.com 

The 2010 Nobel Prize in Chemistry was awarded jointly 

to Professor Richard F. Heck (University of Delaware, 

USA), Professor Ei-ichi Negishi (Purdue University, 

USA) and Professor Akira Suzuki (Hokkaido University, 

Japan) for their work on palladium-catalysed crosscoupling 

in organic synthesis. This article presents a 

brief history of the development of the protocols for 

palladium-catalysed coupling in the context of Heck, 

Negishi and Suzuki coupling. Further developments in 

the area of palladium-catalysed cross-coupling are also 

briefly discussed, and the importance of these reactions 

for real world applications is highlighted. 

The 2010 Nobel Prize in chemistry was the third 

awarded during the last ten years in the area of platinum 

group metal (pgm)-based homogeneous catalysis 

for organic synthesis. Previous prizes had been 

awarded to Dr William S. Knowles (Monsanto, USA), 

Professor Ryoji Noyori (Nagoya University, Japan) and 

Professor K. Barry Sharpless (The Scripps Research 

Institute, USA) in 2001, for their development of asymmetric 

synthesis reactions catalysed by rhodium, 

ruthenium and osmium complexes, and to Dr Yves 

Chauvin (Institut Français du Pétrole, France), 

Professor Robert H. Grubbs (California Institute of 

Technology (Caltech), USA) and Professor Richard 

R. Schrock (Massachusetts Institute of Technology 

(MIT), USA) in 2005 for the development of the 

ruthenium- and molybdenum-catalysed olefin 

metathesis method in organic synthesis. 

Figure 1 shows some of the researchers who have 

made significant contributions in the area of palladium-catalysed 

cross-coupling, including 2010 Nobel 

laureate, Professor Akira Suzuki, during a crosscoupling 

conference at the University of Lyon, France, 

in 2007 (1). 

Palladium-Catalysed Reactions 

Organometallic compounds of pgms are vitally 

important as catalysts for real world applications in 


doi:10.1595/147106711X558301 


Fig. 1. From left: Professor Kohei Tamao (a significant contributor in Kumada coupling), 

Professor Gregory C. Fu (a significant contributor in promoting the bulky electron-rich 

tert-butyl phosphine for challenging cross-coupling), Professor Akira Suzuki (2010 Nobel 

Prize in Chemistry Laureate), Dr Thomas J. Colacot (author of this article) and Professor 

Tamejiro Hiyama (who first reported Hiyama coupling) in front of a photograph of 

Professor Victor Grignard (who initiated the new method of carbon–carbon coupling) in 

the library of the University of Lyon, France 

synthetic organic chemistry. Chemists are continually 

striving to improve the efficiency of industrial 

processes by maximising their yield, selectivity and 

safety. Process economics are also important, and 

chemists work to minimise the number of steps 

required and thereby reduce the potential for waste 

and improve the sustainability of the process. 

Homogeneous catalysis is a powerful tool which can 

help to achieve these goals. Of the three Nobel Prizes 

in pgm-based homogeneous catalysis, perhaps the 

most impact in practical terms has been made by 

palladium-catalysed cross-coupling (2). 

In order for an area to be recognised for the Nobel 

Prize, its real world application has to be demonstrated 

within 20 to 30 years of its discovery. Although 

the area of metal-catalysed cross-coupling was initiated 

in the early 1970s, there were a very limited number 

of publications and patents in this area before the 

1990s (see Figure 2). However, the area has grown 

rapidly from 1990 onwards, especially since 2000. 

In terms of the number of scientific publications, 

patents and industrial applications, Suzuki coupling 

is by far the largest area, followed by Heck, 

Sonogashira and Stille coupling (Figure 2). Negishi 

coupling is smaller in terms of the number of publications, 

but its popularity is growing due to the 

functional group tolerance of the zinc reagent in 

comparison to magnesium, in addition to its significant 

potential in sp 3 –sp 2 coupling, natural product 

synthesis and asymmetric carbon–carbon bond forming 

reactions (1). 

The history and development of the various types 

of palladium-catalysed coupling reactions have been 

covered in detail elsewhere (3, 4). This short article 

will focus on the practical applications of palladiumcatalysed 

coupling reactions. 

Heck Coupling 

Copyright © The Nobel Foundation. 

Photo: Ulla Montan 

Between 1968 and 

1972, Mizoroki and 

coworkers (5, 6) and 

Heck and coworkers 

(7–9) independently 

discovered the use of 

Pd(0) catalysts for 

coupling of aryl, benzyl 

and styryl halides 

with olefinic com- 


doi:10.1595/147106711X558301 


Total number of publications 

and patents 

8000 

7000 

6000 

5000 

4000 

3000 

2000 

1000 

0 

Suzuki 

Heck 

Sonogashira 

Stille 

Negishi 

Buchwald-Hartwig 

Kumada 

Hiyama 

Alpha ketone arylation 

Pre-1990 1991–2000 2001–2010 

Decades 

Fig. 2. Growth in the number of scientific publications and patents on platinum 

group metal-catalysed coupling reactions 

RX + 

R’ H 

H 

H 

Pd catalyst 

Base 

R’ H 

H 

R 

Scheme I. The Heck coupling reaction 

R, R’ = aryl, vinyl, alkyl 

X = halide, triflate, etc. 

pounds, now known as the Heck coupling reaction 

(Scheme I) as Heck was the first to uncover the mechanism 

of the reaction. 

The applications of this chemistry include the synthesis 

of hydrocarbons, conducting polymers, lightemitting 

electrodes, active pharmaceutical ingredients 

and dyes. It can also be used for the enantioselective 

synthesis of natural products. 

Heck coupling has a broader range of uses than the 

other coupling reactions as it can produce products 

of different regio (linear and branched) and stereo 

(cis and trans) isomers. Typically, olefins possessing 

electron-withdrawing groups favour linear products 

while electron-rich groups give a mixture of branched 

and linear products.The selectivity is also influenced 

by the nature of ligands, halides, additives and solvents, 

and by the nature of the palladium source.The 

reaction has recently been extended to include direct 

arylation and hydroarylation, which may have future 

potential in terms of practical applications. Heck coupling 

also has the unique advantage of making chiral 

C–C bonds,with the exception of α-arylation reactions. 

The Negishi Reaction 



During 1976–1977, 

Negishi and coworkers 

(10–12) and 

Fauvarque and Jutand 

(13) reported the use 

of zinc reagents in 

cross-coupling reactions.During 

the same 

period Kumada et al. 

(14–17) and Corriu 

et al. (18) independently 

reported that nickel–phosphine complexes 

were able to catalyse the coupling of aryl and alkenyl 

halides with Grignard reagents. Kumada and coworkers 

later reported (in 1979) the use of dichloro[1,1′- 

bis(diphenylphosphino)ferrocene]palladium(II) 

(PdCl 2 (dppf)) as an effective catalyst for the crosscoupling 

of secondary alkyl Grignard reagents with 

organic halides (19).One common limitation to both 

Ni- and Pd-catalysed Kumada coupling is that coupling 

partners bearing base sensitive functionalities 


doi:10.1595/147106711X558301 


are not tolerated due to the nature of the organomagnesium 

reagents. 

In 1982 Negishi and coworkers therefore carried out 

a metal screening in order to identify other possible 

organometallic reagents as coupling partners (20). 

Several metals were screened in the coupling of an 

aryl iodide with an acetylene organometallic reagent, 

catalysed by bis(triphenylphosphine)palladium(II) 

dichloride (PdCl 2 (PPh 3 ) 2 ). In this study, the use of 

zinc, boron and tin were identified as viable countercations, 

and provided the desired alkyne product in 

good yields. The use of organozinc reagents as coupling 

partners for palladium-catalysed cross-coupling 

to form a C–C single bond is now known as the 

Negishi reaction (Scheme II). 

Pd catalyst 

RZnY + R’X R–R’ 



Y = halide 

Scheme II. The Negishi coupling reaction 

The Negishi reaction has been used as an essential 

step in the synthesis of natural products and fine 

chemicals (21–23). 

Suzuki Coupling 



During the same 

period as the initial 

reports of the use of 

palladium–phosphine 

complexes in Kumada 

couplings, the palladium-catalysed 

coupling 

of acetylenes 

with aryl or vinyl 

halides was concurrently 

disclosed by 

three independent research groups, led by 

Sonogashira (24), Cassar (25) and Heck (26). 

A year after the seminal report on the Stille coupling 

(27, 28), Suzuki picked up on boron as the last 

remaining element out of the three (Zn, Sn and B) 

identified by Negishi as suitable countercations in 

cross-coupling reactions, and reported the palladiumcatalysed 

coupling between 1-alkenylboranes and 

aryl halides (29) that is now known as Suzuki coupling 

(Scheme III). 

Pd catalyst 

RBZ 2 + R’X R–R’ 

Base 



Z = OH, OR, etc. 

Scheme III. The Suzuki coupling reaction 

It should be noted that Heck had already demonstrated 

in 1975 the transmetallation of a vinyl boronic 

acid reagent (30). Perhaps the greatest acomplishment 

of Suzuki was that he identified PdCl 2 (PPh 3 ) 2 as 

an efficient cross-coupling catalyst, thereby demonstrating 

the relatively easy reduction of Pd(II) to 

Pd(0) during catalysis. 

The Suzuki coupling reaction is widely used in 

the synthesis of pharmaceutical ingredients such 

as losartan. Its use has been extended to include 

coupling with alkyl groups and aryl chlorides 

through the work of other groups including Fu and 

coworkers (31). Subsequent work from Buchwald, 

Hartwig, Nolan, Beller and others, including Johnson 

Matthey, has expanded the scope of this reaction. 

Other Name Reactions in Carbon–Carbon 

Coupling 

In 1976, Eaborn et al. published the first palladiumcatalysed 

reaction of organotin reagents (32), followed 

by Kosugi et al. in 1977 on the use of organotin 

reagents (33,34). Stille and Milstein disclosed in 1978 

the synthesis of ketones (27) under significantly 

milder reaction conditions than Kosugi. At the beginning 

of the 1980s, Stille further explored and improved 

this reaction protocol, to develop it into a highly versatile 

methodology displaying very broad functional 

group compatibility (28). 

In 1988, Hiyama and Hatanaka published their work 

on the Pd- or Ni-catalysed coupling of organosilanes 

with aryl halides or trifluoromethanesulfonates (triflates) 

(35). Although silicon is less toxic than tin, 

a fluoride source, such as tris(dimethylamino)- 

sulfonium difluorotrimethylsilicate (TASF) (35) or caesium 

fluoride (CsF) (36), is required to activate the 

organosilane towards transmetallation. Professor S. E. 

Denmark has also contributed significantly to this area. 

Industrial Applications 

In the early 1990s the Merck Corporation was able to 

develop two significant drug molecules, losartan, 1, 


doi:10.1595/147106711X558301 


1 Losartan 

2 Montelukast 

Fig. 3. Structures of losartan and montelukast 

(also known as Cozaar TM , for the treatment of hypertension) 

(37) and montelukast, 2, (also known as 

Singulair TM , for the treatment of asthma) (38, 39), 

(Figure 3) using Suzuki and Heck coupling processes 

respectively. This also increased awareness among 

related industries to look into similar processes. 

Today, coupling reactions are essential steps in the 

preparation of many drugs. Recent reviews by Beller 

(40) and by Sigman (41) summarise the applications 

of Pd-catalysed coupling in the pharmaceutical,agrochemical 

and fine chemicals industries. Apart from 

the major applications in the pharmaceutical and 

agrochemical industries (the boscalid process is the 

world’s largest commercial Suzuki process), crosscoupling 

is also being practiced in the electronics 

industry for liquid crystal and organic light-emitting 

diode (OLED) applications in display screens (42, 

43). 

The research and development group at Johnson 

Matthey’s Catalysis and Chiral Technologies has developed 

commercial processes for preformed catalysts 

such as PdCl 2 (dtbpf) (Pd-118), 3, (44–46), L 2 Pd(0) 

complexes, 4, (47) and precursors to twelve-electron 

species such as [Pd(µ-Br) t Bu 3 P] 2 (Pd-113), 5, (48) 

and LPd(η 3 -allyl)Cl, 6, (49, 50) (Figure 4). These catalysts 

are all highly active for various cross-coupling 

reactions which are used for real world applications. 

More details on the applications of these catalysts 

are given elsewhere (48, 51, 52). A special issue of 

Accounts of Chemical Research also covered recent 

updates of these coupling reactions from academia 

in detail (53). 

Fe 

3 

P t Bu 2 

Pd 

P t Bu 2 

Cl 

Cl 

L 

Pd 

4 

L 

Br 

t Bu 3 P–Pd Pd–P t Bu 3 

Br 

5 

P t Bu 2 

P 

6 

Pd 

Cl 

4a L = P t Bu 3 

4b L = P t Bu 2 Np 

Ph Fe Ph 

4c L = PCy 3 

4d L = Q-Phos 

4e L = A ta Ph 

Ph 

-Phos 

4f L = P(o-tolyl) 3 

4g L = PPh t Ph 

Bu 2 

Q-Phos ligand 

Me 2 N 

P t Bu 2 

A ta -Phos ligand 

Fig. 4. Examples of highly active Pd cross-coupling catalysts developed and commercialised by Johnson Matthey 


doi:10.1595/147106711X558301 


In order to address the issue of residual palladium 

in the final product, several solid-supported 

preformed palladium complexes have been developed 

and launched onto the catalyst market 

(54–56). 

Conclusions 

Palladium-catalysed cross-coupling is of great importance 

to real world applications in the pharmaceutical, 

agrochemicals, fine chemicals and electronics 

industries. The area has developed quite rapidly 

beyond the work of Heck, Negishi and Suzuki, 

though all three reactions are widely used. Academic 

groups such as those of Beller, Buchwald, Fu, Hartwig 

and Nolan as well as industrial groups such as that 

at Johnson Matthey, are now developing the field even 

further. Buchwald-Hartwig coupling has become particularly 

important for developing compounds containing 

carbon–nitrogen bonds for applications in 

industry, as well as α-arylation of carbonyl compounds 

such as ketones, esters, amides, aldehydes 

etc., and nitriles (57). The significant growth of crosscoupling 

reactions can be summarised in Professor 

K. C. Nicolaou’s words: 

“In the last quarter of the 20th century, a new 

paradigm for carbon–carbon bond formation has 

emerged that has enabled considerably the prowess 

of synthetic organic chemists to assemble complex 

molecular frameworks and has changed the way 

we think about synthesis”(58). 

More detailed articles summarising the history of 

cross-coupling in the context of the 2010 Nobel Prize 

in Chemistry with an outlook on the future of crosscoupling 

will be published elsewhere (59, 60). 

Glossary 

Ligand 

A ta -Phos 

Cy 

dppf 

dtbpf 

Np 

Ph 

Q-Phos 

t Bu 

Name 

p-dimethylaminophenyl(di-tert-butyl)phosphine 

cyclohexyl 

1,1′-bis(diphenylphosphino)ferrocene 

1,1′-bis(di-tert-butylphosphino)ferrocene 

neopentyl 

phenyl 

1,2,3,4,5-pentaphenyl-1′-(di-tert-butylphosphino)ferrocene 

tert-butyl 

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ferrocene]palladium(II)’, in “e-EROS Encyclopedia of 

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The Author 

Dr Thomas J. Colacot, FRSC, is a 

Research and Development Manager 

in Homogeneous Catalysis (Global) of 

Johnson Matthey’s Catalysis and 

Chiral Technologies business unit. 

Since 2003 his responsibilities include 

developing and managing a new catalyst 

development programme, catalytic 

organic chemistry processes, 

scale up, customer presentations and 

technology transfers of processes 

globally. He is a member of Platinum 

Metals Review’s Editorial Board, 

among other responsibilities. He has 

co-authored about 100 publications 

and holds several patents. 



Dalton Discussion 12: Catalytic 

C–H and C–X Bond Activation 

doi:10.1595/147106711X554071 


Reviewed by Ian J. S. Fairlamb 

Department of Chemistry, University of York, Heslington, 

York YO10 5DD, UK; 

E-mail: ian.fairlamb@york.ac.uk 

The 12th Dalton Discussion (DD12) conference was 

held at Durham University, UK, from 13th–15th 

September 2010 (1). It was the first Dalton Discussion 

to have been jointly organised by the Dalton and 

Organic Divisions of the Royal Society of Chemistry 

(RSC). A special issue of Dalton Transactions, containing 

refereed papers (both original and perspective 

articles), accompanied all the presentations at the 

conference (2). The DD12 meeting was supported by 

generous sponsorship from BP, Pfizer and the Dalton 

and Organic Divisions of the RSC, and poster prizes 

were provided by Springer, Dalton Transactions and 

Catalysis Science and Technology. 

The principal aim of DD12 was to bring together 

both organic and inorganic chemists from around the 

world to highlight and discuss important aspects relevant 

to the design, development and application of 

late transition metal-catalysed protocols involving the 

activation of either carbon–X (X = halogen or pseudohalogen) 

or carbon–hydrogen bonds. The investigation 

of mechanism and synthetic applications of 

catalytic processes by both experimental and theoretical 

methods underpinned many of the oral and 

poster contributions at the conference. 

Common themes discussed at DD12 included: 

• Ligand design and kinetic studies of catalytic 

processes involving C–H and C–X activation; 

• New opportunities in C–X activation; 

• Fundamental experimental aspects of C–X and 

C–H activation; 

• Mechanistic and theoretical aspects of C–X and 

C–H activation. 

It was quite fortuitous that DD12 occurred just a 

few weeks prior to the announcement on 6th October 

2010 that the Nobel Prize in Chemistry 2010 would be 

awarded to Professors Richard F. Heck, Ei-ichi Negishi 

and Akira Suzuki for work in the field of palladiumcatalysed 

cross-coupling reactions in organic synthesis 

(3), which highlights the general importance and 

timeliness of the topic. 

Over one hundred delegates attended DD12 from 

across Europe, Asia, the Middle East and North 

America. Both academic and industrial groups were 


doi:10.1595/147106711X554071 


represented at the conference, with around 25% of 

attendees being from major industrial organisations. 

The DD12 meeting comprised eight single sessions 

run over three days. Individual sessions began with 

either a Keynote lecture or an invited lecture. These 

were followed by three five-minute contributed presentations. 

With the exception of the sixth session 

(see below), questions were taken during the lively 

and lengthy discussions held after all of the session 

lectures had taken place. 

Ligand Design 

Professor Todd Marder (Durham University, UK) 

chaired the first session of the meeting. Professor 

Hans de Vries (DSM Pharmaceutical Products, The 

Netherlands) gave the Keynote lecture, which provided 

an overview of cross-coupling reactions and 

issues of ‘ligand design’ versus ‘ligand-free’ catalysis. 

His lecture nicely set the tone of the meeting and 

stimulated lots of discussion; for example, on the 

nature of the catalytically active species and the 

role of palladium nanoparticles. Professor de Vries 

then went on to present several mechanisms for the 

modified Ullmann reaction, highlighting the importance 

of copper(III) species, but also issues surrounding 

the complex catalytic reaction systems. 

A careful study of manganese-catalysed C–H oxidation 

with hydrogen peroxide showed that specially 

designed multidentate ligands were oxidised to 

pyridine-2-carboxylic acid prior to catalytic substrate 

oxidation, which explains the observed catalytic 

activity (Scheme I). This work by Wesley R. Browne 

(University of Groningen, The Netherlands) showed 

that some caution should be exerted in ligand design, 

metal catalysis and reaction mechanism analysis, 

especially where the ligand can change chemical 

form under the catalytic reaction conditions used. 

Selective Catalysis 

The second session was chaired by Warren B. Cross 

(University of Leicester, UK) who introduced a 

Keynote lecture from Professor Aiwen Lei (Wuhan 

University, China). Professor Lei discussed selective 

oxidative cross-coupling using palladium(II) catalysis 

(with a suitable oxidant) between two different 

nucleophiles (for example Process A, Scheme II) and 

N 

N 

N 

N 

CO 2 H 

N 

Mn/H 2 O 2 

Ligand oxidation 

N 

Mn/H 2 O 2 

Active 

catalyst 

species 

HO 

OH 

Scheme I. Ligand degradation in a manganese-catalysed oxidation process 

Process A 

Process B 

M 

X 

or: 

R 1 

R 1 

+ 

H 

R 2 

Pd catalyst 

R 1 

Scheme II. 

New catalytic 

cross-coupling 

processes with 

activated or 

unactivated arenes 

Process C 

H 

or: 

R 1 

R 2 

M = metal 

X = halogen or pseudohalogen 


doi:10.1595/147106711X554071 


went on to elaborate on issues surrounding the rates 

of reductive elimination processes. Crucially, fast 

reductive elimination and transmetallation rates were 

found to determine the selectivity of the heterocoupling 

reaction. 

George Fortman (University of St Andrews, UK) 

discussed work on the synthesis of gold–acetylides 

formed by alkyne C–H activation. The serendipitous 

discovery of a palladium-catalysed regioselective 

C–H functionalisation of 2-pyrones was then reported 

by Professor Fairlamb. Two catalysts were used in this 

work,namely trans-Pd(Br)N-Succ(PPh 3 ) 2 and Pd 2 (dba- 

4-OMe) 3 (N-Succ = succinimide; dba-4-OMe = 1,5-bis- 

(4′-methoxyphenyl)penta-1E,4E-dien-3-one). 

The third session of the meeting was chaired by 

Professor Fairlamb, and began with a Keynote lecture 

by Professor Jennifer Love (The University of British 

Columbia, Canada). Love presented a brief overview 

of carbon–fluorine activation processes including 

cross-coupling reactions of polyfluoroarenes. She 

focused on the development of nickel and platinum 

catalyst systems for arylboronic acid cross-coupling 

with fluoroarenes containing ortho-directing groups. 

This presentation was followed by Professor Philippe 

Dauban (Centre National de la Recherche 

Scientifique (CNRS), France), who presented studies 

of catalytic aminations involving nitrene insertion 

into C–H bonds (Scheme III). The selective C–H 

functionalisation of secondary methylene carbon 

centres in the presence of other secondary sites was 

a particular highlight. 

During the discussion session of these lectures, 

several of the pharmaceutical chemists present at the 

meeting debated the role of fluoroaryl groups in 

pharmaceutical compounds. Several viable synthetic 

methods for incorporating fluoro substituents into 

arenes were highlighted. 

Mechanistic Aspects 

The fourth session of DD12 was chaired by Professor 

Susan Gibson (Imperial College London, UK), and 

began with an invited lecture by John M. Brown 

(Oxford University, UK). Brown introduced anilide 

activation of adjacent C–H bonds in the palladiumcatalysed 

Fujiwara-Moritani reaction using catalytic 

Pd(OAc) 2 in the presence of tosic acid and p-benzoquinone. 

Kinetic aspects such as induction periods 

and palladacycle formation were presented as well as 

synthetic aspects. During the discussion session a 

number of mechanistic aspects of these processes 

were raised, which led to David (Dai) Davies 

(University of Leicester, UK) defining the ambiphilic 

metal ligand activation (AMLA) process in which the 

number of atoms thought to be involved in the transition 

state is specified, as illustrated in Scheme IV for 

AMLA-4 (4 electrons) and AMLA-6 (6 electrons) 

S (S) NH 2 + Iodine(III) 

Iodine(I) 

Rh* 

Rh*=NS (S) 

Concerted 

or stepwise? 

R 

H 

NHS (S) 

R’ 

R’ 

R 

Terpenes or 

polycyclic systems 

Yield ≤91% 

de ≤99% 

Scheme III. Selective 

carbon–hydrogen 

activation-catalytic 

amination using 

rhodium catalysis 

S (S) NH 2 = 

O 

S 

N 

NH 2 

SO2 -p-Tol 

Rh* = 

N 

O 

Rh 2 ((S)-nta) 4 

nta = nitrilotriacetate 

O 

O 

Rh 

O 

Rh 


doi:10.1595/147106711X554071 


intermediates which are of general relevance to C–H 

activation. The concerted metalation-deprotonation 

(CMD) is identical to AMLA-6. 

Esteban P. Urriolabeitia (University of Zaragoza, 

Spain) reported stoichiometric and catalytic 

regioselective C–H functionalisations including a 

palladium-catalysed oxidative etherification of iminophosphoranes. 

Finally, a combined theoretical and 

experimental study on the use of ruthenium vinylidene 

complexes as catalysts for carbon–oxygen bond 

formation was presented by Jason M. Lynam 

(University of York, UK). The role of carboxylate 

‘acetate’ ligands was discussed, and a variant of the 

AMLA/CMD mechanism proposed, namely the ligandassisted-proton 

shuttle (LAPS) (Scheme V). 

The fifth session was chaired by Anthony Haynes 

(The University of Sheffield, UK). Professor Zhang-Jie 

Shi (Peking University, China) gave an interesting 

presentation, particularly the unusual results of a 

‘metal-free’ coupling of an aryl halide with an arene 

using potassium tert-butoxide and 1,10-phenanthroline 

(4). 

Dai Davies went on to present alkyne insertion 

reactions of cyclometallated pyrazole and imine 

complexes of iridium, rhodium and ruthenium, with 

emphasis on establishing substrate/catalyst/product 

correlations through detailed structural and spectroscopic 

studies. The last speaker of the session, Xavi 

Ribas (Universitat de Girona, Spain), discussed reductive 

elimination from a ‘model’ aryl–Cu(III)–halide 

species which was triggered by a strong acid, and its 

relevance to the mechanism of Ullmann-type couplings 

(Scheme VI). 

C–H Activation 

The sixth session was chaired by Professor Peter 

Scott (The University of Warwick, UK), and the first 

invited lecture was from Professor Robin Bedford 

(University of Bristol, UK). Bedford presented an 

introduction to the field of ‘C–H activation’, and went 

on to discuss mild and selective ‘solvent-free’ aromatic 

C–H functionalisation/halogenation reactions 

catalysed by Pd(OAc) 2 . The second lecture was 

given by Professor Fairlamb on surface-catalysed 

H 

N 

O 

Pd(OAc) 2 , p-TsOH, butyl 

acrylate, p-benzoquinone 

H 

N 

O 

CO 2 Bu 

Scheme IV. Alkenylation 

chemistry (top); ambiphilic 

metal ligand activation 

(AMLA) and concerted 

metalation-deprotonation 

(CMD) mechanisms for 

carbon–hydrogen activation 

(bottom) 

Oxidative 

addition 

σ-Bond 

metathesis 

Ambiphilic metal ligand activation 

(AMLA) 

L n M 

R 

R’ 

H 

+ 

L n M 

R 

R’ 

H 

+ 

L n M 

R 

X 

H 

+ 

L n M 

R 

O 

H 

R’ 

O 

+ 

AMLA-4 

AMLA-6* 

R’ = H, hydrocarbyl, boryl 

X = heteroatom with lone pair(s) 

*AMLA-6 is essentially identical to 

concerted metalation deprotonation 

(CMD) 

O 

O 

Ru 

H 

R 

O 

O 

[Ru] 

H 

R 

[Ru] 

O 

C 

O 

R 

H 

Scheme V. Ligandassisted-proton 

shuttle (LAPS) 

mechanism 

[Ru]=Ru(κ 2 -OAc)(PPh 3 ) 2 


doi:10.1595/147106711X554071 


X 

+ 

H 

N Cu III 

( ) 3 

N 

CF 3 SO 3 H (1.5 equiv), 

CH 3 CN, 298 K,

doi:10.1595/147106711X554071 


[Rh] 

H 

R 3 P 

[Rh] 

H 

R 3 P F 

8 kcal mol –1 5 kcal mol –1 

F n 

R Rh–C/C–H = 2.15 

[Rh] 

R 3 P 

F 

H 

F 

F n 

Fig. 2. The ortho-fluorine effect in 

promoting carbon–hydrogen activation. 

R Rh–C/C–H = slope of line on plot of 

Rh–C vs. C–H bond strength (From 

T. Tanabe et al., in (2). Reproduced by 

permission of The Royal Society of 

Chemistry) 

ortho-fluorine effect 

[Rh] = Tp’Rh 

Tp’ = tris(3,5-dimethylpyrazolyl)borate 

George (The University of Nottingham, UK) presented 

a combined experimental (fast time-resolved infrared 

spectroscopy (TRIR)) and theoretical investigation of 

the C–H activation of cyclic alkanes by cyclopentadienyl 

rhodium(I) carbonyl complexes. He highlighted 

the inherent mechanistic differences in C–H activation 

of linear versus cyclic alkanes by half-sandwich 

rhodium complexes. Interestingly, C–H activation in 

cyclic alkanes depends primarily on the strength of 

alkane–metal binding. Note that this paper appeared 

in a later issue of Dalton Transactions (5). 

Poster Prizes 

Following the conference dinner in the famous 

Durham Castle, Professors Love and Perutz awarded 

four poster prizes. The poster content of the awardees 

(Figure 3)highlighted the breadth of subjects covered 

and the high standard of all of the posters presented 

at the meeting.The winning posters were: 

• ‘Hydrodefluorination of Fluoroaromatics by 

[RuH 2 (CO)(NHC)(PPh 3 ) 2 ]: An Explanation for 

the 1,2-Regioselectivity’, Julien Panetier (Heriot- 

Watt University, UK) 

• ‘Development of Chiral 4-(DAAP)-N-oxide 

Catalysts for the Sulfonylative Kinetic Resolution 

of Amines’, Toritse Bob-Egbe (Imperial College 

London, UK) 

• ‘Reversible Reactions Across the M–C Bond of 

Lanthanide NHC Complexes to Form New N–E 

and C–E Bonds’, Anne Germeroth (University of 

Edinburgh, UK) 

• ‘Novel Multidentate Phosphine-Alkene Ligands 

for Catalysis’, Amanda Jarvis (University of York, 

UK) 

Fig. 3. Poster prize winners of Dalton Discussion 12: 

Julien Panetier (Heriot-Watt University), Toritse 

Bob-Egbe (Imperial College London), Anne Germeroth 

(University of Edinburgh) and Amanda Jarvis 

(University of York) 

Concluding Remarks 

From the oral presentations, numerous posters and 

lively discussions at the DD12 meeting, there was 

overwhelming evidence that a better understanding 

of the mechanisms of metal-catalysed C–X and C–H 

functionalisation processes is emerging. Quite strikingly, 

studies in inorganic and organometallic coordination 

chemistry, theoretical and kinetic studies, new 

synthetic methodologies and applications are driving 

this understanding. The platinum group metals play 

an important role in many of the catalytic processes 

under discussion. 

As a first joint discussion conference between the 

RSC Dalton and Organic Divisions, it was a great success, 

and showed quite clearly that both the organic 


doi:10.1595/147106711X554071 


and inorganic communities need to work together to 

deliver powerful, clean and efficient methods for the 

preparation of functionalised organic building blocks 

and fine chemicals. 

K. Huang, S.-F. Zheng, B.-J. Li and Z.-J. Shi, Nature 

Chem., 2010, 2, (12), 1044 

5 M. W. George, M. B. Hall, P. Portius, A. L. Renz, X.-Z. 

Sun, M. Towrie and X. Yang, Dalton Trans., 2011, 40, 

(8), 1751 

References 

1 RSC Conferences and Events, Dalton Discussion 12: 

Catalytic C–H and C–X Bond Activation (DD12): http:// 

www.rsc.org/ConferencesAndEvents/RSCConferences/ 

dd12/index.asp (Accessed on 31 December 2010) 

2 Dalton Discussion 12: Catalytic C–H and C–X bond 

activation (DD12), Dalton Trans., 2010, 39, (43), 

10321–10540 

3 The Nobel Prize in Chemistry 2010: http://nobelprize.org/ 

nobel_prizes/chemistry/laureates/2010/ (Accessed on 31 

December 2010) 

4 C.-L. Sun, H. Li, D.-G. Yu, M. Yu, X. Zhou, X.-Y. Lu, 

The Reviewer 

Professor Ian Fairlamb is currently a 

Full Professor in Organic Chemistry at 

the University of York, UK, and has 

research interests in catalysis, synthetic 

chemistry, mechanistic understanding, 

nanocatalysis, metals in medicine, and 

applications of catalysis in chemical 

biology. In 2004, he was awarded 

both a Royal Society University 

Research Fellowship and the Royal 

Society of Chemistry Meldola Medal 

and Prize for outstanding contributions 

to the field of palladium chemistry 

in synthesis. 



A Healthy Future: Platinum in 

Medical Applications 

Platinum group metals enhance the quality of life of the global population 

doi:10.1595/147106711X566816 


By Alison Cowley 

Johnson Matthey Precious Metals Marketing, Orchard 

Road, Royston, Hertfordshire SG8 5HE, UK 

and Brian Woodward* 

Johnson Matthey Medical Products, 12205 World Trade 

Drive, San Diego, California 92128, USA; 

*E-mail: woodwbk@jmusa.com 

The world’s growing population demands increasing 

access to advanced healthcare treatments. Platinum is 

used to make essential components for a range of 

medical devices, including pacemakers, implantable 

defibrillators, catheters, stents and neuromodulation 

devices. The properties of platinum which make it 

suitable for medical device applications include its biocompatibility, 

inertness within the body, durability, electrical 

conductivity and radiopacity.Components can be 

manufactured in a variety of forms, from rod, wire and 

ribbon to sheet and foil, plus high-precision micromachined 

parts. As well as biomedical device components,platinum 

also finds use in anticancer drugs such 

as cisplatin and carboplatin. 

Introduction 

According to the United Nations Environment 

Programme (UNEP), the global population will reach 

over 9 billion by 2050 with nearly 90% of the world’s 

people located in developing countries (Figure 1) (1). 

Since the early 1970s, platinum has been used in a 

variety of medical devices for people around the 

world suffering from such ailments as heart disease, 

stroke, neurological disorders, chronic pain and other 

life threatening conditions. In 2010, some 175,000 oz 

of platinum are estimated to have been used in biomedical 

devices, of which around 80 per cent was for 

established technologies such as guidewires and cardiac 

rhythm devices. The remaining 20 per cent was 

used in newer technologies, such as neuromodulation 

devices and stents. In addition, over 25,000 oz of 

platinum are used annually in anticancer drugs (2). 

With an ageing and increasing world population, 

there will be an increasing demand for healthcare 

products and services that use components made 

from platinum, other platinum group metals (pgms) 

and their alloys. Increasing access to healthcare and 

advanced medical treatments in developing countries 

means that platinum contributes to improving 

the quality of life of people around the world. 


doi:10.1595/147106711X566816 


Global population, estimates and projections 

(billions) 

8 

6 

4 

2 

Developed countries 

Developing countries 

0 

1750 1800 1850 1900 1950 2000 2050 

Year 

Fig. 1. Trends 

in population, 

developed and 

developing 

countries, between 

1750–2050 

(estimates and 

projections) (1) 

(Image: Hugo 

Ahlenius, Nordpil) 

The Advantages of Platinum for 

Biomedical Uses 

The chemical, physical and mechanical properties of 

platinum and its alloys make them uniquely suitable 

for a variety of medical applications. Agnew et al. (3) 

and Brummer et al. (4) carried out studies which confirmed 

the low corrosivity, high biocompatibility and 

good mechanical resistance of platinum and platinum 

alloys that are used for medical applications. 

Platinum’s biocompatibility makes it ideal for 

temporary and permanent implantation in the body, 

a quality which is exploited in a variety of treatments. 

As a metal, it can be fabricated into very tiny, complex 

shapes and it has some important properties not 

shared by base metals. It is inert, so it does not corrode 

inside the body unlike metals such as nickel 

and copper, which can sometimes cause allergic 

reactions. Modern, minimally-invasive medical techniques 

often use electricity to diagnose and treat 

patients’ illnesses, and platinum’s conductivity makes 

it an ideal electrode material. It is also radiopaque, 

so it is clearly visible in X-ray images, enabling doctors 

to monitor the position of the device during 

treatment. Some examples of areas where pgms are 

used in medical devices, together with some of the 

manufacturers currently active in the medical device 

market, are shown in Table I. 

For more than forty years platinum alloys have 

been employed extensively in treatments for coronary 

artery disease such as balloon angioplasty and stenting 

where inertness and visibility under X-ray are 

crucial. In the field of cardiac rhythm disorders, 

platinum’s durability, inertness and electrical conductivity 

make it the ideal electrode material for devices 

such as pacemakers, implantable defibrillators and 

electrophysiology catheters. More recently, its unique 

properties have been exploited in neuromodulation 

devices (including “brain pacemakers”, used to treat 

some movement disorders, and cochlear implants, to 

restore hearing), and in coils and catheters for the 

treatment of brain aneurysms. 

Platinum in Biomedical Applications 

Devices for Cardiac Rhythm Management 

Abnormalities of the heart’s rhythm are common, 

often debilitating, and sometimes fatal. For example, 

bradycardia is a condition in which the heart’s 

“natural pacemaker” is set too slow, resulting in 

fatigue, dizziness and fainting. Other patients may 

be at risk of sudden cardiac death, a condition in 

which the heart’s lower chambers (the ventricles) 

“fibrillate”, or pulse in a rapid and uncoordinated 

manner. This prevents the heart from pumping 

blood and leads rapidly to death unless the victim 

receives cardioversion (a strong electric shock to the 

heart, which restores normal rhythm). 

These and other cardiac rhythm disorders can 

now be managed very successfully using implanted 


doi:10.1595/147106711X566816 


Table I 

Markets for Medical Devices and the Major Device Companies 

Medical device markets Examples of application areas Major medical device companies 

Surgical instrumentation Arthroscopic; ophthalmology; Boston Scientific; Johnson & 

endo-laparoscopic; electro-surgical Johnson; Stryker; Tyco 

Electro-medical implants Pacemakers; defibrillators; hearing Boston Scientific; Biotronik; 

assist devices; heart pumps 

Medtronic; St. Jude Medical 

Interventional Stents; angioplasty; catheter Boston Scientific; Abbott Vascular; 

ablation; distal protection 

Johnson & Johnson; Medtronic 

Orthopaedics Spinal fixation; hip implants; Biomet; Johnson & Johnson; 

knee implants 

Stryker; Zimmer 

devices such as artificial pacemakers (5, 6) and 

implantable cardioverter defibrillators (ICDs) (7–9). 

These consist of a “pulse generator”, a small box 

containing a battery and an electronic control system 

which is implanted in the chest wall, and one 

or more leads which run through a large vein into 

the heart itself. The electrodes on these leads deliver 

electrical impulses to the heart muscle – in the case 

of a pacemaker, these ensure that the heart beats 

regularly and at an appropriate pace, while in the 

case of an ICD, a much stronger electrical shock is 

delivered as soon as the device detects a dangerously 

irregular heartbeat. Each lead typically has two or 

more electrodes made of platinum-iridium alloy, 

while platinum components are also used to connect 

the pulse generator to the lead (Figure 2). 

Catheters and Stents 

Catheters are flexible tubes which are introduced 

into the body to help diagnose or treat illnesses 

such as heart disease (10–13). The doctor can perform 

delicate procedures without requiring the 

patient to undergo invasive surgical treatment, 

improving recovery time and minimising the risk of 

complications. Many catheters incorporate platinum 

components: marker bands and guidewires, which 

help the surgeon guide the catheter to the treatment 

site, or electrodes, which are used to diagnose and 

treat some cardiac rhythm disorders (arrhythmias). 

One of the most common coronary complaints in 

the developed world is atherosclerosis, the “furring 

up” of the artery walls with fatty deposits, which can 

lead to angina and heart attack (14). Blockages in the 

coronary arteries are often treated using a procedure 

called “percutaneous transluminal coronary angioplasty” 

(PTCA, also known as balloon angioplasty) 

(15, 16). This treatment uses a catheter with a tiny balloon 

attached to its end, which is guided to the treatment 

site then inflated, crushing the fatty deposits 

and clearing the artery. Afterwards, a small tubular 

device called a stent (Figure 3) is usually inserted in 

order to keep the newly-cleared artery open. 

The advent of the implantable metal stent to prop 

open the artery after angioplasty reduced the 

occurrence of restenosis (re-narrowing of the artery) 

by more than 25 per cent. In 2003 the US FDA 

approved the first drug-eluting stent for use within 

the USA (17). This type of stent is aimed at further 

lowering the rate of restenosis following angioplasty 

procedures. 

Platinum’s role in PTCA is to help ensure that the 

balloon is correctly located. First, the surgeon uses a 

guidewire to direct the balloon to the treatment site. 

This guidewire is made of base metal for most of its 

length, but has a coiled platinum-tungsten wire at 

its tip, which makes it easier to steer and ensures 

that it is visible under X-ray. Platinum is also used in 

marker bands, tiny metal rings which are placed 

either side of the balloon in order to keep track of 

its position in the body. 

Stents are usually made of base metals (typically 

stainless steel or cobalt-chromium). However, in 

2009, the American device manufacturer Boston 

Scientific introduced a cardiac stent made of a platinum 

chromium alloy (18–20). This stent has been 

approved in Europe, and the company is currently 


doi:10.1595/147106711X566816 


Pt or Pt-Ir through 

wires for multi-pin 

hermetic seal, inside 

the seal housing 

(0.015” 

(0.381 mm) 

and 0.013” 

Pt-Ir, MP35N ® or 

stainless steel 

machined parts for 

terminal connector 

(0.330 mm)) Pt or Pt-Ir wire and 

ribbon multifilar 

coils for highvoltage 

shocking 

electrodes 

Pt-Ir alloy rings for 

shocking electrodes 

Porous TiNi-coated 

Pt-Ir helix and post 

assembly for active 

fixation leads 

TiNi-coated Pt-Ir 

machined parts 

for passive 

fixation leads 

Fig. 2. An implantable cardioverter defibrillator, showing the components that are made from platinum or 

platinum group metal alloys 

seeking approval from the US Food & Drugs 

Administration (FDA). 

Catheters containing platinum components are 

also used to detect and treat some types of cardiac 

arrhythmia (21, 22). Devices called electrophysiology 

catheters (23), which contain platinum electrodes, 

are used to map the electrical pathways of the 

heart so that the appropriate treatment – such as a 

pacemaker – can be prescribed. 

Other catheters with platinum electrodes are used 

for a minimally-invasive heart treatment known as 

radio-frequency (RF) ablation (24–26). Arrhythmias 

are often caused by abnormalities in the conduction 

of electricity within the heart, and it is often possible 

Stent (stainless 

steel, Co-Cr, 

Co-Cr with Pt, 

or nitinol) 

Balloon 

supporting 

the stent 

Guidewire with 

coiled Pt-W tip 

Fig. 3. A balloon-mounted stent used in 

percutaneous transluminal coronary 

angioplasty (PTCA, or balloon angioplasty) 

procedures (Copyright © Abbott Vascular 

Devices) 

Marker band (Pt, 

Pt-Ir or Au) 


doi:10.1595/147106711X566816 


to cauterise part of the heart muscle in order to 

restore normal heart rhythm. For example, ablation 

is increasingly used to treat a very common heart 

problem called atrial fibrillation, in which the upper 

chamber of the heart (the atrium) quivers rapidly and 

erratically. Using a catheter equipped with platinumiridium 

electrodes, the surgeon “ablates” or makes 

small burns to the heart tissue, causing scarring, 

which in turn blocks the superfluous electrical 

impulses which trigger the fibrillation. 

Neuromodulation Devices 

Neuromodulation devices deliver electrical impulses 

to nerves and even directly to the brain, treating disorders 

as varied as deafness, incontinence (27, 28), 

chronic pain (29) and Parkinson’s disease (30). Many 

of these devices are based on an extension of heart 

pacemaker technology, and they are sometimes 

referred to as “brain pacemakers” (31). Like heart 

pacemakers, they have platinum-iridium electrodes 

and may also incorporate platinum components in 

the pulse generator. 

There are a number of different types of neurostimulation, 

depending on the condition that is being 

treated. Spinal cord stimulation (the commonest 

neuromodulation therapy) is used to treat severe 

chronic pain, often in patients who have already 

had spinal surgery. Small platinum electrodes are 

placed in the epidural space (the outer part of the 

spinal canal) and connected to an implanted pulse 

generator. The patient can turn the stimulation off 

and on, and adjust its intensity. 

In deep brain stimulation (DBS) (32–34), the electrodes 

are placed in the brain itself. As well as pain, 

DBS may be used to treat movement disorders such 

as Parkinson’s disease, and it is being investigated as a 

potential treatment for a wide range of other illnesses, 

including epilepsy and depression. Epileptic patients 

can also be treated using a vagus nerve stimulation 

device (the vagus nerve is situated in the neck). 

A cochlear implant (35–38) is used to restore hearing 

to people with moderate to profound hearing 

loss (many patients receive two implants, one in each 

ear). A typical device consists of a speech processor 

and coil, which are worn externally behind the ear, 

an implanted device just under the skin behind the 

ear, and a platinum electrode array which is positioned 

in the cochlea (the sense organ which 

converts sound into nerve impulses to the brain). 

The speech processor captures sound and converts it 

to digital information, which is transmitted via the 

coil to the implant. This in turn converts the digital 

signal into electrical impulses which are sent to the 

electrode array in the cochlea, where they stimulate 

the hearing nerve. These impulses are interpreted by 

the brain as sound. It is believed that around 200,000 

people worldwide have received one or more 

cochlear implants. 

At present, neuromodulation is expensive and is 

only available in a small number of specialist centres; 

even in developed countries only a small proportion 

of potentially eligible patients receive this treatment. 

However, neuromodulation can be used to help 

patients with common and sometimes difficult to 

treat conditions (such as chronic pain, epilepsy and 

migraine). Its use might therefore be expected to 

increase significantly in coming years as new indications 

for these therapies are established. 

Other Implants 

Platinum’s biocompatibility makes it ideal for temporary 

and permanent implantation in the body, 

a quality which is exploited in a variety of treatments 

in addition to the heart implants already discussed. 

Irradiated iridium wire sheathed in platinum can be 

implanted into the body to deliver doses of radiation 

for cancer therapy (39–41). This treatment takes 

advantage of platinum’s radiopacity to shield healthy 

tissues from the radiation, while the exposed iridium 

tip of the wire irradiates the tumour. Although this 

procedure is gradually being replaced by other forms 

of radio- and chemotherapy, it remains a useful 

weapon in the battle against cancer. 

A more recent development is the use of coils 

made of platinum wire to treat aneurysms, balloonings 

in blood vessels caused by weaknesses in the 

vessel walls (42).If the blood pressure rises, the vessel 

may rupture, causing a haemorrhage. Although this 

can occur anywhere in the body, platinum is mainly 

used to treat aneurysms in the brain,where surgery is 

difficult and fraught with risk. Platinum is used 

because it is inert, easy to shape, and radiopaque. 

This treatment was first introduced about 20 years 

ago. In the late 1980s, a doctor and inventor, Guido 

Guglielmi (43–45), developed a detachable platinum 

coil which could be used to treat brain aneurysms. 

Coils are delivered to the site of the aneurysm by 

microcatheter, then detached using an electrolytic 

detachment process; once in place, the coils help to 

coagulate the blood around the weak vessel wall, 


doi:10.1595/147106711X566816 


(a) (b) (c) 

Fig. 4. Detachable 

platinum coils being used 

to treat an aneurysm: 

(a) a microcatheter is used 

to deliver the platinum 

coils to the aneurysm; 

(b) the coils are detached 

using an electrolytic 

process; (c) more coils are 

added to fill the aneurysm 

and allow blood to 

coagulate, forming a 

permanent seal 

forming a permanent seal (Figure 4). The coils, numbering 

between one and around thirty depending on 

the size of the aneurysm, are left inside the patient 

indefinitely. The Guglielmi Detachable Coil (GDC ® 

Coil) device was approved in Europe in 1992 and in 

the USA in 1995, and by 2009 this and subsequent 

generations of platinum coil technology were being 

used in an estimated 30–40% of US patients treated 

for brain aneurysms. 

The Manufacture of Platinum 

Biomedical Components 

There are many technologies used to produce pgm 

components for biomedical applications, ranging 

from rod, wire, ribbon and tube drawing, to sheet 

and foil manufacture and highly precise Swiss-Type 

screw machining (micromachining) (see Figure 5). 

Rod and wire are manufactured in diameters 

ranging from 0.125" (3.175 mm) down to 0.001" 

Fig. 5. Micromachined parts made from precious 

metal alloys for biomedical device applications, with 

a pencil tip for scale 

(0.0254 mm). Dimensional consistency is assured by 

laser measurement. Rod is used as the starting material 

for a variety of machine components, with most of 

the pgm parts being used in pacemaker, defibrillator 

and other electrical stimulation products. Wire products 

are used primarily in three applications: 

(a) platinum-tungsten and platinum-nickel fine 

wires are used on balloon catheters as guidewires 

for positioning the catheter in exactly the 

right location; 

(b) other pgm wires are used as microcoils for neurovascular 

devices such as treatments for brain 

aneurysms; 

(c) platinum-iridium wires are also used as feedthrough 

wires or connector wires used to 

connect the pacemaker lead to the pulse 

generator. 

Ribbon is manufactured in the form of continuous 

strips of rolled wire in a variety of platinum alloys. 

Ribbon is often used in place of round wire to 

produce coils with minimum outside diameter, 

and is generally used for guidewire and microcoil 

applications. Ribbon is sometimes preferred over 

wire because wire can be harder to coil. It can also 

be used for markers instead of traditional cut tubing. 

Table II shows some typical specifications and 

applications for pgm rod, wire and ribbon. 

Fine diameter platinum, platinum-iridium and 

platinum-tungsten tubing (0.125" (3.175 mm) internal 

diameter and below) cut to specific lengths is used 

for markers or electrodes on angioplasty, electrophysiology 

and neurological catheter devices, 

aneurism tip coils, feed-through wires used to connect 

the pacing lead to the pulse generator (also 

known as “the can”) which houses the hybrid microelectronics 

and the battery, and pacemakers. Some 

applications of thin walled precious metal tubing 

are shown in Table III. 


doi:10.1595/147106711X566816 


Table II 

Specifications and Applications of Platinum and Platinum Alloy Rod, Wire and Ribbon Components 

Applications Types of component Specifications 

Stimulation devices Rod for manufacture of Diameters from 0.001" (0.0254 mm) 

machine components to 0.125" (3.175 mm); Cut lengths 

Balloon catheters; stent Guidewires; feed through 

from 0.02" (0.508 mm) 

delivery; stimulation leads wires; tip coils 

Table III 

Specifications and Applications of Platinum, Palladium, Gold and Precious Metal Alloy Thin Walled Tube 

Components 


Balloon catheters Radiopaque marker Inside diameter 0.0045" (0.1143 mm) to 0.250" (6.35 mm), 

bands 

(tolerance: ± 0.0005" (0.0127 mm)); Wall thickness 

0.001" (0.0254 mm) to 0.005" (0.127 mm), (tolerance: 

Electrophysiology Electrode rings 

± 0.0005" (0.0127 mm)); Length 0.015" (0.381 mm) to 

catheters; 

0.200" (5.08 mm), (tolerance: ± 0.003" (0.0762 mm)) 

stimulation devices 

Sheet and foil is mainly made from pure platinum, 

platinum-iridium alloys or rhodium. It can be shaped, 

formed and rolled to a variety of dimensions. Sheet 

or foil can be cut, formed and placed on a catheter 

for marking in a similar way to ribbon. Rhodium foil 

is used exclusively as a filter inside X-ray mammography 

equipment to enhance the viewing image. 

Table IV shows some examples of applications of 

pgm sheet and foil. 

Micromachined parts are very complex and very 

small – some are only 0.006" (0.152 mm) in diameter 

and barely visible with the naked eye (Figure 5). 

Fabrication must be extremely precise to maintain 

the necessary quality and dimensional tolerances, 

which can be as low as ± 0.0002" (0.005 mm). Highly 

specialised equipment and techniques must be used, 

such as computer numerical controlled (CNC) Swiss 

Screw machines and electrical discharge machining 

(EDM) (Figure 6). The automated high-production 

Swiss Screw machines are used to fabricate the main 

components and EDM is used to achieve the fine 

details required for many platinum parts. 

Specialty metal micromachined parts (0.8" (20 mm) 

diameter and smaller) are made from a variety of 

materials including pure platinum, platinum-iridium 

alloys and gold plus non-precious metals and 

Table IV 

Specifications and Applications of Platinum, Platinum Alloy and Rhodium Sheet and Foil Components 


Stimulation devices Electrodes; machine components; Thickness from 0.0007" (0.018 mm); 

tip coils 

Width from 1.0" (25.4 mm) to 

X-Ray equipment Imaging filters (rhodium foils) 

3.75" (95.3 mm) 


doi:10.1595/147106711X566816 


Fig. 6. The production floor at Johnson Matthey’s Medical Products micromachining facility in San Diego, 

California, USA 

alloys such as stainless steel, titanium, MP35N ® 

cobalt-nickel-chromium-molybdenum alloy, Elgiloy ® 

cobalt-chromium-nickel alloy, Kovar ® iron-nickelcobalt 

alloy, and materials such as Vespel ® , Delrin ® 

and Teflon ® (see Table V for examples). These products 

serve device applications such as coronary 

stents, pacemaker and defibrillator pulse generator 

and lead components, heart valve splices, endoscopic 

catheters, blood gas analysers, kidney dialysis, and 

other medical device and related equipment. 

Parts made from pgms are often complemented 

with a coating technology. Precious metal powders, 

Table V 

Applications and Materials for Precision Micromachined Components 

Applications Precious metals* Other materials, metals and alloys 

Stimulation Platinum; platinum alloys; Nitinol; stainless steel; MP35N ® ; 

palladium; palladium alloys 

Haynes ® alloy 25 (L605); polymers 

Manufacturing fixtures Platinum; platinum alloys Stainless steel 303/304/316; polymers 

Orthopaedic Platinum; platinum alloys Titanium; titanium alloys; stainless steel; 

ceramics 

Cardiac implants Platinum; platinum alloys; Elgiloy ® ; Nitinol 

karat golds 

Hypotubes Platinum; platinum alloys Stainless steel; Nitinol 

Precision pins, tips and Platinum; platinum alloys; silver – 

rollers 

Bushings, shafts, shims Platinum; platinum alloys Aluminium 

and spacers 

Precision fixtures and Platinum; platinum alloys; Biomed TM Brass; copper; Kovar ® 

assembly tools 

series palladium-rhenium alloys 

*Platinum alloys used include platinum-iridium, platinum-10% nickel and platinum-8% tungsten 


doi:10.1595/147106711X566816 


titanium nitride or iridium oxide are applied to 

create a more porous surface structure. The creation 

of a porous coating reduces the electrical impedance 

from the lead to the battery and allows for a good 

electrical connection, while reducing the energy 

needed to run the battery. This helps the battery to 

last longer. Most pacing lead systems manufactured 

today have some form of porous surface. The end use 

applications for coated pgm parts are the same as 

described above for uncoated parts. 

Anticancer Drugs 

As well as its use in biomedical device components, 

perhaps platinum’s most remarkable and unexpected 

quality is its ability, in certain chemical forms, to 

inhibit the division of living cells (46). The discovery 

of this property led to the development of platinumbased 

drugs (47), which are now used to treat a wide 

range of cancers. 

Although cancer remains one of the most feared 

diseases, its treatment has advanced rapidly since the 

late 1960s. Many types of cancer can now be treated 

very effectively using surgery, radiation and drugbased 

(chemo-) therapies. Chemotherapy drugs work 

by killing cells. They are designed to target cancer 

cells as specifically as possible, but inevitably cause 

damage to healthy cells as well, causing the side 

effects for which chemotherapy is well known. 

One of the most remarkable advances in the last 

few decades has been the improvement in the survival 

rate of patients with testicular cancer – it is estimated 

that 98% of men with testicular cancer will be 

alive 10 years after their diagnosis. The platinum anticancer 

drug cisplatin (47) has played a vital role in 

making testicular cancer one of the most survivable 

cancers. This drug, along with its successor drug, 

carboplatin (48), is also widely used in the treatment 

of other common tumours, including ovarian, breast 

and lung cancer. 

Summary 

For over forty years, platinum and its alloys have been 

used in a wide range of medical treatments, including 

devices such as coronary and peripheral 

catheters, heart pacemakers and defibrillators. Newer 

technologies such as neuromodulation devices and 

stents also rely on the biocompatibility, durability, 

conductivity and radiopacity of platinum to make key 

components in a variety of forms. Platinum is used in 

pharmaceutical compounds that extend the lives of 

cancer patients. Medical device manufacturers and 

pharmaceutical companies continue to invest in new 

technologies to satisfy the need for advanced medical 

treatments in both the developed world and, 

increasingly, the developing world. Platinum, the 

other pgms and their alloys will inevitably play a vital 

part in these developments. 

Acknowledgements 

The assistance of Richard Seymour and Neil Edwards, 

Technology Forecasting and Information, Johnson 

Matthey Technology Centre, Sonning Common, UK, 

in the preparation of this manuscript is gratefully 

acknowledged. 

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doi:10.1595/147106711X566816 


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and G. B. Hieshima, Surg. Neurol., 1991, 35, (1), 64 

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Further Reading 

“Biomaterials Science: An Introduction to Materials in 

Medicine”, 2nd Edn., eds. B. Ratner, A. Hoffman, F. Schoen 

and J. Lemons, Elsevier Academic Press, San Diego, CA, 

USA, 2004 

“Materials and Coatings for Medical Devices: Cardiovascular”, 

ASM International, Materials Park, Ohio, 

USA, 2009 

Granta: Materials for Medical Devices Database, Cardiovascular 

Materials and Orthopaedic Materials: http://www. 

grantadesign.com/products/data/MMD.htm (Accessed on 

10th February 2011) 

The Authors 

Alison Cowley has worked in 

Johnson Matthey’s Market Research 

department since 1990 and currently 

holds the post of Principal Analyst. 

She is Johnson Matthey’s specialist on 

mining and supplies of the platinum 

group metals (pgms). She also 

conducts research into demand for 

pgms in a number of industrial 

markets, including the biomedical 

and aerospace sectors. 

Brian Woodward has been involved in 

the electronic materials and platinum 

fabrication business for more than 

25 years and is currently the General 

Manager of Johnson Matthey’s Medical 

Products business based in San Diego, 

CA, USA. He holds BS and MBA 

degrees in Business and Management 

and has been focused on value-added 

component supply to the global 

medical device industry. 



Fuel Cells Science and Technology 2010 

Scientific advances in fuel cell systems highlighted at the semi-annual event 

doi:10.1595/147106711X554503 


Reviewed by Donald S. Cameron 

The Interact Consultancy, 11 Tredegar Road, 

Reading RG4 8QE, UK; 

E-mail: dcameroninteract@aol.com 

This was the fifth conference in the Fuel Cells 

Science and Technology series following meetings 

in Amsterdam, Munich, Turin and Copenhagen (1–4). 

It was held on 6th and 7th October 2010 at the World 

Trade Center in Zaragoza, Spain, with the theme 

‘Scientific Advances in Fuel Cell Systems’. This conference 

series alternates with the Grove Fuel Cell 

Symposium (5), placing more emphasis on the latest 

technical developments. The two-day programme 

was compiled by the Grove Symposium Steering 

Committee from oral papers and posters submitted 

from around the world, and the conference was 

organised by Elsevier (6). The meeting was attended 

by delegates from universities, research organisations 

and the fuel cell industry, and as before, many of the 

papers will be subjected to peer review and published 

in full in a special edition of Journal of Power 

Sources (7). 

There were over 200 delegates from 37 countries, 

including Spain, Germany and the UK. Although the 

majority were from Europe, the significant numbers 

from Japan, Iran and South Korea reflected the high 

level of interest in fuel cells from those countries, as 

well as others from the Middle East, Asia, Africa and 

South America. 

The Science and Technology conferences present 

the latest advances in research and development on 

fuel cells and their applications. There were three 

plenary papers, together with eight keynote speakers 

and 40 oral papers, together with 210 high-quality 

poster presentations divided into seven categories. 

Topics for the oral sessions included Fuels, Infrastructure 

and Fuel Processing; Modelling and Control; 

Materials for Fuel Cells; Fuel Cell Systems and 

Applications; Fuel Cell Electrochemistry; and finally 

Cell and Stack Technology. For this review, only 

papers involving the use of the platinum group metals 

(pgms) are discussed. 

An exhibition accompanying the conference 

included displays of demonstration fuel cell systems 

designed for education and training use (Figures 1 

and 2). 

Delegates were welcomed to Zaragoza by Pilar 

Molinero, Director General of Energy and Mining for 

the Aragon regional government, who formally 


doi:10.1595/147106711X554503 


Fig. 2. One of a series of platinum-catalysed fuel cell 

and solar hydrogen systems for educational purposes 

designed and built by Heliocentris. This company 

develops systems and turnkey solutions for training 

in industry and science, and specialises in hybrid 

energy storage comprising fuel cells, batteries and 

energy management devices 

Fig. 1. A 1 kWe polymer electrolyte fuel cell and 

control equipment designed for teaching purposes, 

exhibited at the Fuel Cells Science and Technology 

2010 conference. Operating on pure hydrogen, it 

can be used to simulate a wide variety of fuel cell 

and CHP applications. It is built by HELION, an 

AREVA subsidiary, and developed in collaboration 

with teachers from Institut Universitaire de 

Technologie (IUT) of Marseille, France 

opened the conference and briefly described activities 

in Aragon to encourage hydrogen and fuel cell 

technologies. The large number of wind farms in the 

region have created an interest in energy storage 

using water electrolysis to generate hydrogen during 

periods of power surplus. A total of 30 hydrogen and 

fuel cell projects are being supported, including a 

hydrogen highway from Zaragoza to Huesca to support 

the introduction of fuel cell vehicles. 

Plenary Presentation 

Pilar Molinero presented the 2010 Grove Medal to 

Professor J. Robert Selman (Illinois Institute of 

Technology (IIT), USA), a leading academic who has 

devoted more than 30 years to battery and fuel cell 

research and development, and to global commercialisation 

of these technologies. This has included 

the electrochemical engineering of batteries and 

high temperature fuel cells at the US Department of 

Energy’s Argonne National Laboratory and Lawrence 

Berkeley National Laboratory, and at the IIT. 

Professor Selman presented a talk on his experiences 

and advances made during this period. One 

major development is the advent of computer modelling 

which has led to improved structures and performance 

of fuel cells and their systems, although 

there is still a need to experimentally verify the predictions 

obtained at each stage. Other exciting and 

relatively new areas include the possibility of direct 

carbon oxidation fuel cells, and miniaturisation 

including biofuel systems and bioelectrochemistry. 

One of his particular interests is the use of phase 

change materials to maintain the uniform temperatures 

in batteries by absorbing or evolving heat. 

Fuels, Infrastructure and Fuel Processing 

Fuel cell technology has moved on from the largely 

research phase to commercial exploitation. A major 

market is being developed for combined heat and 

power (CHP) systems for residential domestic applications 

operating on natural gas. In a keynote presentation, 

Sascha T. Schröder (National Laboratory for 

Sustainable Energy, Technical University of Denmark) 

outlined the policy context for micro combined heat 

and power (mCHP) systems based on fuel cells. 

Systems of up to 50 kW have been considered, 


doi:10.1595/147106711X554503 


although 3–5 kW units are preferred for domestic 

installations. Low- and high-temperature polymer 

electrolyte membrane (PEM) fuel cells are the most 

advanced, although there is still a need for less 

expensive reformers to make the systems economically 

viable. Incentives in the form of a regulatory 

framework and ownership structures are of crucial 

importance to achieve widespread use of such 

devices in residential applications. A regulatory 

review has been conducted as part of the first Work 

Package of the EU-sponsored ‘FC4Home’ project, 

focused on Denmark, France and Portugal. Schröder 

outlined several types of possible support schemes, 

such as investment support in the form of capital 

grants and tax exemptions versus operating support 

in the form of feed-in tariffs, fiscal incentives and 

other payments for energy generated, and how this 

impacts on investment certainty. Also, the way in 

which incentives are offered is critical, for example 

via energy service companies, electrical network 

operators, natural gas suppliers or network operators 

or to individual house owners. Schröder reported that 

in Denmark, there are 65 fuel cell mCHP installations, 

and in France there are 832, mainly in industry. 

Most fuel cells oxidise hydrogen gas using atmospheric 

air to produce electric power and water. 

Hydrogen is generally obtained either by reforming 

natural gas or liquid hydrocarbons, or by electrolysis 

of water using surplus electrical energy. In recent 

years there has been great interest in reforming diesel 

fuel both for military and commercial purposes, 

since it uses an existing supply infrastructure. The 

pgms are often used in reforming reactions and also 

in downstream hydrogen purification. 

In a talk entitled ‘Experimental and Computational 

Investigations of a Compact Steam Reformer for 

Fuel Oil and Diesel Fuel’, Melanie Grote (OWI Oel- 

Waerme-Institut GmbH, Germany) described the optimisation 

of a compact steam reformer for light fuel 

oil and diesel fuel, providing hydrogen for PEM fuel 

cells in stationary or mobile auxiliary applications. 

Their reformer is based on a catalytically-coated 

micro heat exchanger which thermally couples the 

reforming reaction with catalytic combustion, and 

also generates superheated steam for the reaction 

(see Figure 3). Since the reforming process is sensitive 

to reaction temperatures and internal flow 

patterns, the reformer was modelled using a commercial 

computational fluid dynamics (CFD) modelling 

code in order to optimise its geometry. Fluid flow, 

Fig. 3. Steam reformer with superheater for 

supplying hydrogen to a PEM fuel cell 

(Reprinted from M. Grote et al., (7), with 

permission from Elsevier) 

heat transfer and chemical reactions were considered 

on both sides of the heat exchanger. The model 

was successfully validated with experimental data 

from reformer tests with 4 kW, 6 kW and 10 kW thermal 

inputs of low sulfur light fuel oil and diesel fuel. 

In further simulations the model was used to investigate 

co-flow, counter-flow and cross-flow conditions 

along with inlet geometry variations for the reformer. 

The experimental results show that the reformer 

design used for the validation allows inlet temperatures 

lower than 500ºC because of its internal superheating 

capability. The simulation results indicate 

that another two co-flow configurations provide fast 

superheating and high fuel conversion rates. The 

temperature increase inside the reactor is influenced 

by the inlet geometry on the combustion side. In 

current investigations the optimised geometry configurations 

are being tested in downscaled reformer 

prototypes in order to verify the simulation results. 

Because of the great detail of their model, the effect 

of mass transfer limitations on reactor performance 

can now be investigated. Hydrogen of 73% concentration 

is typically produced. 

Successful extraction of hydrogen from heavy 

hydrocarbons largely depends on the development 

of new catalysts with high thermal stability and 

improved resistance to coke formation and sulfur 

poisoning. A new range of ruthenium-containing 

perovskite oxide catalysts is being examined for 

diesel fuel reforming. In a talk entitled ‘Hydrogen Production 

by Oxidative Reforming of Diesel Fuel over 

Catalysts Derived from LaCo 1−x Ru x O 3 (x = 0.01–0.4)’, 


doi:10.1595/147106711X554503 


Noelia Mota (Instituto de Catálisis y Petroleoquímica 

del Consejo Superior de Investigaciones Científicas 

(CSIC), Spain) explained how under reforming conditions 

these LaCo oxides form well-dispersed cobalt 

metallic particles over a matrix of lanthana. This 

increases hydrogen formation and prevents deactivation 

by coke and sulfur. To improve the activity and 

stability of LaCoO 3 -derived catalysts, structural and 

electronic modifications can be introduced by 

partial substitution of Co by other transition metals, 

and among these, ruthenium is a highly effective catalyst. 

This work studied the influence of the partial 

substitution of Co over the physicochemical properties 

of LaCo 1−x Ru x O 3 perovskite where x = 0, 0.01, 

0.05, 0.1, 0.2 or 0.4 and the effect on the structure 

and activity of the derived catalysts in the reforming 

of diesel fuel to produce hydrogen. There was an 

increase in the rate of hydrogen production associated 

with the higher ruthenium content. 

Fuel Cell Systems and Applications 

The fourteen member countries of the International 

Energy Agency Hydrogen Implementing Agreement 

(IEA–HIA) have been instrumental in summarising 

and disseminating information on integrated fuel cell 

and electrolyser systems. In a keynote presentation 

entitled ‘Evaluation of Some Hydrogen Demonstration 

Projects by IEA Task 18’, Maria Pilar Argumosa 

(Instituto Nacional de Técnica Aeroespacial (INTA) 

Spain) summarised some of their findings since the 

programme was established in 2003. In addition to 

establishing a database of demonstration projects 

worldwide, the programme has reported in detail on 

lessons learned from several demonstrations of 

hydrogen distribution systems. The project concentrated 

on fuel cells in the power range 2–15 kW and 

exceptionally up to 150 kW. PEM and alkaline electrolysers 

were studied as hydrogen generators. No 

safety incidents occurred during the project, 

although the fuel cells tested showed relatively high 

performance degradation in field operation. Capital 

costs of electrolysers are still high, and maintenance 

costs for some systems have ranged up to €15,000 per 

year although the warranty protocol was stipulated 

to be less than €3000 per year for the first 

three years. Electrolysers ranged from 50% to 65% 

efficiency based on the higher heating value of 

the fuel. 

Future electrical networks will need active distributed 

units able to ensure services like load following, 

back-up power, power quality disturbance compensation 

and peak shaving. In his talk ‘PEM Fuel Cells 

Analysis for Grid Connected Applications’, Francesco 

Sergi (Consiglio Nazionale delle Ricerche, Italy) outlined 

their investigation of PEM fuel cell systems as 

components of power networks. The paper highlighted 

the performances of PEM fuel cells using MEAs 

supplied by ETEK containing 30% Pt on Vulcan XC, 

and their behaviour during grid connected operation, 

particularly the phenomena of materials degradation 

that can appear in these applications. Several 

tests were conducted both on fuel cell systems and 

single cells to compare the performances obtained 

with DC and AC loads. Power drawn by single phase 

grids contains low frequency fluctuations which 

cause a large ripple on the stack output current. 

During tests on single cells, degradation of the MEA 

catalysts has been observed due to these dynamic 

loads. A dedicated inverter designed to minimise 

the ripple current effect on the fuel cell stack has 

enabled durability tests to be performed on a 5 kW 

Nuvera PowerFlow TM PEM fuel cell system which 

showed no decay in the ohmic region of operation of 

the cell after 200 hours, even with the fuel cell systems 

operating on the utility grid. 

Materials handling using forklift vehicles is proving 

to be one of the most exciting early markets for fuel 

cells, with over 70 publicly reported demonstration 

programmes since 2005 (8). In this application, lifetime 

and reliability are key parameters. A typical 

forklift work cycle is characterised by heavy and fast 

variations in power demand, for example additional 

power is required during lifting and acceleration. 

This is not ideal for a fuel cell and hence it is preferred 

to form a hybrid with an energy store. In his 

talk ‘Integrated Fuel Cell Hybrid Test Platform in 

Electric Forklift’, Henri Karimäki (VTT Technical 

Research Centre of Finland) described how a hybrid 

power source has been developed for a large counterweight 

forklift consisting of a pgm-catalysed PEM 

fuel cell, ultracapacitors and lead-acid batteries. The 

project was carried out in two phases, firstly in the 

laboratory with an 8 kW PEM fuel cell,a lead-acid battery 

and ultracapacitor to validate the system, then a 

second generation 16 kW hybrid system was built into 

a forklift truck (Figure 4). The latter power source 

consisted of two 8 kW NedStack platinum-catalysed 

PEM fuel cells with two 300 ampere-hour (Ah) leadacid 

batteries and two Maxwell BOOSTCAP ® 165F 

48V ultracapacitors, providing 72 kW of power. 


doi:10.1595/147106711X554503 


PEM fuel cells 

Lead-acid 

batteries 

Ultracapacitors 

Brake 

resistor 

Fig. 4. Hybrid forklift power 

source with 2 PEM fuel cell 

stacks (total fuel cell peak 

power 16 kW); 2 lead-acid 

battery packs (total battery 

capacity 24 kWh); 2 ultracapacitor 

modules (capacity 

~72 kWs assuming 20% 

utilisation). Hybrid system 

peak power in the forklift is 

~50 kWe (Reprinted from 

‘Integrated PEMFC Hybrid 

Test Platform for Industrial 

Vehicles’, Fuel Cell Seminar 

2010, 18th–21st October 

2010, San Antonio, Texas, 

USA, by courtesy of 

T. Keränen, VTT Technical 

Research Centre of Finland) 

Hydrogen for the PEM fuel cell is stored on board in 

metal hydride canisters connected in common with 

the liquid cooling circuit. The energy stores were 

connected directly in parallel without intermediate 

power electronics to achieve a simple structure and 

avoid conversion losses. Drawbacks of this arrangement 

include limited ultracapacitor utilisation and 

lack of direct control over the load profile seen by 

the PEM fuel cell. The fuel cell voltage varied from 

96 V to 75 V during operation. Control system hardware 

and software were developed in-house and are 

available as open source. The 16 kW system was 

tested both in the laboratory with an artificial load 

and outdoors installed in a real forklift (Kalmar 

ECF556) utilising regenerative braking. After start-up 

from warm indoor conditions, outdoor driving tests 

were performed in typical southern Finnish winter 

weather (−5ºC to −15ºC). The experimental results 

allow direct comparison of system performance to 

the original lead-acid battery installation. 

Many submarines currently under construction are 

being fitted with fuel cell power plants and existing 

boats are being retrofitted, following pioneering work 

by Siemens in Germany and United Technologies 

Corporation in the USA. A contract has been awarded 

by the Spanish Ministry of Defence to design, develop 

and validate an air-independent propulsion (AIP) 

system as part of the new S-80 submarine. This programme 

was described by A. F. Mellinas (Navantia SA, 

Spain). It is intended that S-80 submarines will exhibit 

many performance features currently only available 

in nuclear-powered attack boats, including threeweek 

underwater endurance and the possibility of 

firing cruise missiles while submerged. The system is 

based on an on-board reformer supplying hydrogen 

to a fuel cell power module. Their system will operate 

as a submarine battery charger, generating regulated 

electrical power to allow long submerged periods. 

This application imposes the strictest safety constraints 

while performing under the most demanding 

naval requirements including shock, vibration and a 

marine environment. It is also intended to combine 

high reliability with a minimum acoustic signature to 

provide a stealthy performance. 

Fuel cell/electrolyser systems are being actively 

developed as a means to support astronauts on the 

surface of the moon, as explained by Yoshitsugu Sone 

(Japan Aerospace Exploration Agency (JAXA)). JAXA 

is developing a regenerative fuel cell system that 

can be applied to aerospace missions (Figure 5). For 

lunar survival, a large energy store is essential to 

allow for the 14 day-14 night lunar cycle. The limited 

energy density of the lithium-ion secondary cells 

(currently 160–180 Wh kg −1 , and likely to be less than 

300 Wh kg −1 even in the future) means that over a 

tonne of batteries would be needed to last the lunar 

night, even for modest power demands. 

Initially, PEM fuel cell systems that can be operated 

under isolated low-gravity and closed environments 

have been studied. Subsystems and operating methods 

such as closed gas circulation, with the working 

gases in a counter-flow configuration, and a dehydrator 

were developed to simplify assembly of the fuel 

cell system. Fuel cells were combined with electrolysers 

and water separators to form regenerative fuel 

cell systems, and the concept has been demonstrated 


doi:10.1595/147106711X554503 


Charge 

O 2 

Discharge 

O 2 

Discharge 

Charge 

Charge Discharge 

Discharge 

Electrolyser H 2 O Fuel cell H 2 O Unitised regenerative fuel cell 

Charge 

Charge 

H 2 H 2 

Discharge 

Charge 

Discharge 

Separated type regenerative fuel cell 

Unitised regenerative fuel cell 

Fig. 5. Schematic of the concept for a 100 W regenerative fuel cell system for use in lunar 

and planetary missions (Reprinted from Y. Sone, (7), with permission from Elsevier) 

for 1000 hours in an isolated, closed environment. 

Practical performance has also been demonstrated, 

initially using a thermal vacuum chamber, and also in 

a stratospheric balloon in August 2008. 

In addition to separate fuel cell stacks and electrolysers, 

JAXA has developed a regenerative fuel 

cell, where the polymer electrolyte fuel cell is combined 

with the electrolyser to fulfil both functions. 

A 100 W-class regenerative fuel cell has been built 

and demonstrated as a breadboard model for over 

1000 hours. A 17 cell stack of 27 cm 2 electrodes provides 

an output of 100 W at 12 V, while in the electrolysis 

mode,‘charging’ is at 28 V. 

Fuel Cell Electrochemistry 

One of the main challenges facing PEM fuel cells is to 

increase the three-phase interface between catalysts, 

electrolyte and gases, in order to thrift the amount 

of pgm catalyst required. These catalysts are typically 

platinum nanoparticles uniformly dispersed on porous 

carbon support materials also of nanometre scale. In 

her talk entitled ‘Synthesis of New Catalyst Design for 

Proton Exchange Membrane Fuel Cell’, Anne-Claire 

Ferrandez (Commissariat à l’énergie atomique (CEA) 

Le Ripault, France) described grafting polymeric synthon 

to the surfaces of the platinum nanoparticles, 

allowing creation of new architectures of catalyst 

layers that promote both ionic conduction between 

the solid electrolyte and electronic conduction to the 

carbon support. The resulting materials appear to be 

oxidation resistant and stable to voltage cycling up 

to +1.0 V. By adjusting synthesis parameters, it is 

possible to optimise the electrical, chemical and mass 

transfer properties of the electrodes and also reduce 

the platinum content. 

For automotive applications of PEM fuel cells, the 

US Department of Energy has published a target 

platinum loading of less than 0.2 mg cm −2 for combined 

anode and cathode by 2015, with performance 

characteristics equating to a platinum content of 

0.125 g kW −1 by this date (Figure 6). This is most 

likely to be achieved by optimising a combination 

of parameters including catalyst, electrode and membrane 

structures as well as operating conditions. Ben 

Millington (University of Birmingham, UK) described 

their efforts in a talk entitled ‘The Effect of Fabrication 

Methods and Materials on MEA Performance’. Various 

methods and materials have been used in the fabrication 

of catalyst coated substrates (CCSs) for membrane 

electrode assemblies (MEAs). Different solvents 

(ethylene glycol, glycerol, propan-2-ol, tetrahydrofuran 

and water), Nafion ® polymer loadings (up to 

1 mg cm −2 ) and anode/cathode Pt loadings have 

been used in the preparation of catalyst inks 

deposited onto various gas diffusion layers (GDLs) 

sourced from E-TEK, Toray and Freudenberg, and the 

performance of the resulting MEAs were reported. 

Several methods of CCS fabrication such as painting, 

screen printing, decal and ultrasonic spraying were 

investigated. All MEAs produced were compared to 

both commercial MEAs and gas diffusion electrodes 

(GDEs). They found that MEA performance was dramatically 

affected by the solvent type, the deposition 

method of the catalyst ink on the GDE, the GDE 


doi:10.1595/147106711X554503 


Fig. 6. Status of estimated 

total pgm content in fuel 

cell stacks from 2005 to 

2009 compared to DOE 

targets (J. Spendelow, 

K. Epping Martin and 

D. Papageorgopoulos, 

‘Platinum Group Metal 

Loading’, DOE Hydrogen 

Program Record No. 9018, 

US Department of Energy, 

Washington, DC, USA, 

23rd March, 2010) 

type (woven or nonwoven), the drying process and 

the amount of Nafion ® added to the GDE during 

fabrication. Currently, the university is able to produce 

MEAs with similar performance to commercial 

products. 

More widespread commercial development of fuel 

cells has identified new challenges such as the effects 

of impurities in fuel supplies and the atmospheres in 

which the devices have to operate. One of these has 

been studied in detail at the Technical University of 

Denmark, and the results were presented in a paper 

by Syed Talat Ali entitled ‘Effect of Chloride Impurities 

on the Performance and Durability of PBI 

(Polybenzimidazole)-Based High Temperature 

PEMFC’. Chlorides derived from sea salt are present in 

the atmosphere as an aerosol in coastal areas and salt 

is also used for deicing roads in many countries during 

winter. Small traces of chlorides may originate 

from phosphoric acid in the PBI membrane and from 

platinum chloride precursors used to prepare some 

platinum catalysts, while substrate carbons such as 

Cabot Vulcan ® XC72R carbon black contain trace 

impurities. The possible effect of halogen ions on 

platinum catalysts are unknown, since they may promote 

dissolution as complex ions, thereby enhancing 

metal oxidation and re-deposition processes. The 

group’s present work is devoted to a systematic study 

at temperatures from 25ºC to 180ºC. Firstly, determination 

of the chloride content of Pt-based catalysts 

was carried out using ion chromatography. Secondly, 

the effect of chloride on the dissolution of a smooth 

Pt electrode was studied in 85% phosphoric acid at 

70ºC using cyclic voltammetry. It was found that the 

presence of chlorides is likely to be very harmful to 

the long-term durability of acid doped PBI-based 

high-temperature PEM fuel cells. 

Materials for Fuel Cells 

The pgms are also finding applications in hydrogen 

generation by water electrolysis as a means of reducing 

electrode overvoltage and thereby improving 

operating efficiency. This represents not only a clean 

method of hydrogen production, but also an efficient 

and convenient way of storing surplus energy from 

renewable sources such as solar, wind and hydroelectric 

power. In his talk ‘An Investigation of Iridium 

Stabilized Ruthenium Oxide Nanometer Anode 

Catalysts for PEMWE’, Xu Wu (Newcastle University, 

UK) described the synthesis and characterisation 

of these catalysts. The electrochemical activity of 

Ru x Ir 1−x O 2 materials in the range 0.6 < x < 0.8 was 

investigated. A nanocrystalline rutile structure solid 

solution of iridium oxide in ruthenium oxide was 

identified. When x was 0.8, 0.75, and 0.7, Ru x Ir 1−x O 2 

exhibited remarkable catalytic activity, while increasing 

the amount of iridium resulted in improved stability. 

A PEM water electrolysis (PEMWE) single cell 

achieved a current density of 1 A cm −2 at 1.608 V with 

Ru 0.7 Ir 0.3 O 2 on the anode, a Pt/C catalyst on the 

cathode and Nafion ® 117 as the membrane. 

Cell and Stack Technology 

Considerable progress has been made in developing 

high-temperature solid polymer electrolyte 

fuel cells, with particular advances in membrane 

technology. 

In a keynote presentation entitled ‘High Temperature 

Operation of a Solid Polymer Electrolyte Fuel Cell 

Stack Based on a New Ionomer Membrane’, Antonino 

S.Aricó (Consiglio Nazionale delle Ricerche – Istituto 

di Tecnologie Avanzate per l’Energia (CNR-ITAE), 

Italy) gave details of tests on PEM fuel cell stacks as 

part of the European Commission’s Sixth Framework 


doi:10.1595/147106711X554503 


Programme ‘Autobrane’ project. These were assembled 

with Johnson Matthey Fuel Cells and SolviCore 

MEAs based on the Aquivion TM E79-03S short-side 

chain (SSC) ionomer membrane, a chemically stabilised 

perfluorosulfonic acid membrane developed 

by Solvay Solexis (Figure 7). An in-house prepared 

catalyst consisting of 50% Pt on Ketjen black was used 

for both anode and cathode, applied at 67 wt% catalyst 

with a Pt loading of 0.3 mg cm –2 . Electrochemical 

experiments with fuel cell short stacks were performed 

under practical automotive operating conditions at 

absolute pressures of 1–1.5 bar and temperatures 

ranging up to 130ºC, with relative humidity varying 

down to 18%. The stacks using large area (360 cm 2 ) 

MEAs showed elevated performance in the temperature 

range from ambient to 100ºC, with a cell power 

density in the range of 600–700 mW cm −2 , with a moderate 

decrease above 100ºC. The performances and 

electrical efficiencies achieved at 110ºC (cell power 

density of about 400 mW cm −2 at an average cell 

voltage of about 0.5–0.6 V) are promising for automotive 

applications. Duty-cycle and steady-state galvanostatic 

experiments showed excellent stack stability 

for operation at high temperature. 

Poster Exhibits 

The poster session was combined with an evening 

reception to maximise the time available for oral 

papers and over 200 posters were offered. These 

included a wide range of applications of the pgms in 

Fig. 7. Polymer structure of long side-chain Nafion ® 

and short side chain Aquivion TM perfluorosulfonic 

ionomer membranes (Reprinted from A. Stassi 

et al., (7), with permission from Elsevier) 

fuel processing, fuel cell catalysis and sensors. There 

were a considerable number of posters featuring the 

preparation and uses of pgm fuel cell catalysts, which 

were too numerous to mention in detail. 

Several posters featured preparation of Pt and PtRu 

catalysts supported on carbon nanofibres. It is evident 

that while materials such as graphitised carbon 

nanofibres can be highly stable and oxidation resistant, 

with existing catalyst preparation techniques it is 

difficult to make high surface area, uniform platinum 

dispersions which can compete with catalysts on more 

conventional carbon supports such as Vulcan ® XC72. 

One poster which highlighted this difficulty was 

‘Durability of Carbon Nanofiber Supported Electrocatalysts 

for Fuel Cells’, by David Sebastián et al. 

(Instituto de Carboquímica, CSIC, Spain). 

Other posters featured studies of the effects of 

carbon monoxide on high-temperature PEM fuel 

cells, and the effects of low molecular weight 

contaminants on direct methanol fuel cell (DMFC) 

performance. Studies are also in progress on more 

fundamental aspects such as catalyst/support interactions, 

for example ‘Investigation of Pt Catalyst/Oxide 

Support Interactions’, by Isotta Cerri et al. (Toyota 

Motor Europe, Belgium). 

Summary 

Conclusions from the Fuel Cells Science and Technology 

2010 conference were summed up by José Luis 

García Fierro (Instituto de Catálisis y Petroleoquímica, 

CSIC, Spain). He remarked that the high level of interest 

in the conference partly reflects more strict environmental 

laws combined with the high prices of gas 

and oil (oil was US$75 per barrel at the time of the 

conference), emphasising the need for the best possible 

efficiency in utilising fuels. Biofuels appear to be 

making a more limited market penetration than originally 

expected.He also mentioned that of the posters 

exhibited at the conference, no fewer than 45 involved 

PEM fuel cell catalysts and components, direct 

methanol and direct ethanol fuel cells. One potentially 

large market for fuel cells is in shipping, where 

marine diesel engines currently produce 4.5% of the 

nitrogen oxides (NOx) and 1% of particulates from all 

mobile sources. This becomes a sensitive issue, especially 

when vessels are in port. The marine market 

consists of some 87,000 vessels, the majority of which 

have propulsion units of less than 2 MWe. Among the 

actions currently in progress to promote exploitation 

of hydrogen technology and fuel cells are hydrogen 


doi:10.1595/147106711X554503 


refuelling stations for vehicles together with codes 

and standards for the retail sales of hydrogen fuel, 

with support for early market opportunities. 

References 

1 D. S. Cameron, Platinum Metals Rev., 2003, 47, (1), 28 




5 The Grove Fuel Cell Symposium: http://www.grovefuelcell. 

com/ (Accessed on 5th January 2011) 

6 Fuel Cells Science and Technology: http://www. 

fuelcelladvances.com/ (Accessed on 5th January 2011) 

7 J. Power Sources, 2011, articles in press 

8 V. P. McConnell, Fuel Cells Bull., 2010, (10), 12 


Donald Cameron is an independent 

consultant on fuel cells and electrolysers, 

specialising in electrocatalysis. 



11th International Platinum 

Symposium 

“PGE in the 21st Century: Innovations in Understanding Their Origin and Applications to 

Mineral Exploration and Beneficiation” 

doi:10.1595/147106711X554512 


Reviewed by Judith Kinnaird 

School of Geosciences, University of the Witwatersrand, 

Private Bag 3, 2050 Wits, South Africa; 

E-mail: judith.kinnaird@wits.ac.za 

Every few years an International Platinum Symposium 

is organised to provide a forum for discussion of 

the geology, geochemistry, mineralogy and beneficiation 

of major and minor platinum group element 

(PGE) deposits worldwide. The theme of the 11th 

International Platinum Symposium, which took place 

in Sudbury, Canada, from 21st–24th June 2010 (1), 

was “PGE in the 21st Century: Innovations in 

Understanding Their Origin and Applications to 

Mineral Exploration and Beneficiation”. 

Participants from mining and exploration companies, 

geological surveys, consulting companies and 

universities on all continents attended to listen to 

85 papers and read 54 posters. Such meetings normally 

take place every four years although it is five 

years since the previous meeting in Oulu, Finland in 

2005, with a smaller interim meeting held in India. 

The organisation was impeccable throughout, for 

field trips, poster sessions, the social programme 

and the main conference. The committee was led by 

Professor C. Michael Lesher (Laurentian University, 

Canada), Edward Debicki (Geoscience Laboratories, 

Canada), Pedro Jugo (Laurentian University), James 

Mungall (University of Toronto, Canada) and Heather 

Brown (Ontario Geological Survey, Canada). Sudbury 

proved an excellent venue, a mining town that has 

developed into a pleasant tree-rich area that has 

overcome all the earlier issues of environmental 

degradation. 

Delegates were told in an overview of the global 

pgm industry that the Bushveld Complex in South 

Africa and the Norilsk deposit in Russia together 

account for roughly 90% of newly mined platinum 

and 85% of newly mined palladium supply. The 

Stillwater Complex in the USA is a significant source 

of palladium but not platinum, while the Great Dyke 

in Zimbabwe offers the possibility of significant 

expansion (Figure 1).Russian stockpiles of palladium 

are thought to be nearly exhausted, but recycling is 

growing rapidly to become another dominant source 

of supply. Demand for platinum, palladium and the 


doi:10.1595/147106711X554512 


Zimbabwe 

craton 

200 km 

Bulawayo 

Mimosa 

Harare 

Hartley Platinum 

Mhondoro and Zinca 

Unki 

Ngezi 

Snake’s Head 

East Dyke 

Zambesi Mobile Belt 

East Dyke 

Harare 

Selous 

Wedza 

Subchamber 

Selukwe 

Subchamber 

Musengezi 

Subchamber 

Sebakwe 

Subchamber 

South Chamber 

Darwendale 

Subchamber 

North Chamber 

16ºS 

17ºS 

18ºS 

19ºS 

Mafic sequence 

Ultramafic sequence 

Satellite dykes 

Craton & cover rocks 

Mobile belts 

Major faults & fractures 

Fig. 1. Large-scale map of 

the Great Dyke in 

Zimbabwe, showing major 

lithological subdivisions 

and areas of current 

exploitation. The Great 

Dyke is the largest resource 

of platinum outside the 

Bushveld Complex of 

South Africa. Its size has 

encouraged active 

exploration and mining, 

and in 2010 there were 

three major mines in 

operation and several 

intensive exploration 

initiatives (Courtesy of 

A. H. Wilson and 

A. J. du Toit, from ‘Great 

Dyke Platinum in the Region 

of Ngezi Mine, Zimbabwe: 

Characteristics of the Main 

Sulphide Zone and 

Variations that Affect 

Mining’, 11th International 

Platinum Symposium, 

Sudbury, Ontario, Canada, 

21st–24th June, 2010) 

North Marginal Zone 

of the Limpopo Belt 

Southern 

satellites 

29ºE 31ºE 

0 50 100 

km 

other pgms is expected to grow strongly, however, and 

new deposits of PGEs are of interest as possible 

sources of future supply. It is therefore interesting that 

the PGEs attract just 2% of overall global exploration 

spending, which is focused on Africa, Canada and 

Russia. 

It was therefore not surprising that several recent 

discoveries of deposits of PGEs around the world 

were discussed at this meeting, with much progress 

made towards understanding their geological origins 

and their potential for exploitation as future ore 

bodies. Existing deposits were also discussed, but data 

on grades were sometimes lacking, and data were 

presented as tenors (i.e. the grade calculated in 100% 

sulfide only). Other studies focused on experimental 

measurements, analytical techniques and results, 

new geochemical criteria for the identification of 

PGE-enriched deposits, characterisation of platinum 

group mineral assemblages and the processes that 

extract platinum from ore. 

Papers of particular interest have been collated 

and summarised below, according to geographical 

region. All abstracts are available on the conference 

website (1). It is important to note that there are six 

platinum group elements (PGEs): platinum, palladium, 

rhodium, iridium, osmium and ruthenium. 

Geologists use the term ‘PGM’ to mean platinum 

group minerals as the PGEs occur in minerals rather 

than metallic form in natural deposits, whereas metallurgists 

use ‘pgm’ to mean platinum group metals. 


doi:10.1595/147106711X554512 


Southern Africa 

The opening day of the symposium focused on South 

Africa’s Bushveld Complex and Zimbabwe’s Great 

Dyke, as is fitting for the largest producers of platinum. 

For the Bushveld, chromitite layers were described 

from at least six cyclic units of ultramafic Lower Zone 

in the northeastern limb, that have previously been 

regarded as Marginal Zone but no platinum grades 

were given. Profiles of PGEs through chromitites in 

the layered mafic-ultramafic suite showed that platinum 

per unit metre through the complex was highest 

in the north west.The atypical stratigraphic sequence 

of the ‘contact-type’ basal nickel-copper-PGE mineralisation 

of the satellite Sheba’s Ridge at the western 

extremity of the eastern limb is unique with discontinuous 

UG2 Reef and Merensky Reef analogues above 

a basal ‘Platreef’-style sulfide-rich ore body with 

grades of

doi:10.1595/147106711X554512 


The PGE deposits of the Lac des Iles Complex in 

Canada (the Roby, Twilight and High-Grade Zones) 

differ from most other PGE deposits as they occur in 

a small, concentrically-zoned mafic intrusion rather 

than in a large layered intrusion and the ore zone is 

∼900 m by 700 m in size and open at depth rather 

than thin and tabular. Pentlandite controls 30% of 

whole-rock palladium, the rest is present as PGMs. 

In spite of more than a century of mining in the 

Sudbury district of Canada, new discoveries are still 

being made. The principal styles of Cu-Ni sulfide 

mineralisation that have been mined are: 

(a) in the Sublayer at the lower contact of the 

Sudbury Igneous Complex; 

(b) in quartz diorite Offset Dykes (with grades of

doi:10.1595/147106711X554512 


(a) 

Surface 

D 

A 

A 

B 

C 

D 

Contact 

Footwall type 

Low sulfide 

Capre footwall 

New discovery 

C 

Massive sulfide 

Low sulfide PGE-Au 

Disseminated Ni sulfide 

Undifferentiated gneiss 

Granite breccia 

Sudbury breccia 

Sudbury igneous complex 

Diabase 

Granite 

Fault 

B 

0 250 

m 

(b) 

Surface 

C 

A 

B 

A 

B 

C 

D 

Contact 

Footwall type 

Breccia belt type 

109 FW 

New discovery 

0 100 

D 

Inclusion massive/ 

breccia sulfide 

Siliceous zone 

Disseminated Ni-Cu sulfide 

Low sulfide, high PGE 

mineralisation 

Metasediments 

Metavolcanic 

Sudbury breccia 

Granite 

Quartz diorite 

Norite 

Trap dyke 

Shear zone 

Fig. 2. Composite cross-sections of typical geological settings for Footwall Deposits of PGEs and sulfide 

in the Sudbury Igneous Complex, Canada, in (a) the North and East Range and (b) the South Range (Courtesy 

of P. C. Lightfoot and M. C. Stewart, from ‘Diversity in Platinum Group Element (PGE) Mineralization at 

Sudbury: New Discoveries and Process Controls’, 11th International Platinum Symposium, Sudbury, Ontario, 

Canada, 21st–24th June, 2010) 


doi:10.1595/147106711X554512 


Table I 

Platinum Group Element Abundances of the Jinchuan Deposit in China 

Ore type Platinum Palladium Rhodium Iridium Ruthenium 

grade, ppb grade, ppb grade, ppb grade, ppb grade, ppb 

Disseminated 35.8–853 74.8–213 2.5–19.5 5.1–38.5 4.2–33.1 

Net-textured 12.7–1757 a 171–560 0.7–5.1 0.4–4.0 1.5–3.5 

Massive 11.6–102 218–1215 78.1–201 211–644 91–553 

a One exceptional occurrence of 3343 ppb 

in cratonic areas, several clusters or lineaments 

of mafic and mafic-ultramafic intrusions where 

feeder dykes and the lowermost parts of layered 

intrusions are exposed, a continental-scale province 

of flood basalts,and several areas of extensive komatiitic 

magmatism in Precambrian greenstone belts. 

The Fortaleza de Minas komatiite-hosted Ni-Cu 

deposit is quoted as an estimated resource of 6 Mt at 

grades of 0.7 ppm combined Pt, Pd and Au, 0.4% Cu 

and 2.5% Ni. The layered mafic-ultramafic lithologies 

of the Tróia Unit of the Cruzeta Complex in northeastern 

Brazil have been the focus of platinum exploration 

for more than 30 years. Local chromitite 

horizons, 0.3 m to 3 m thick, contain up to 8 ppm Pt 

and 21 ppm Pd. 

Other Occurrences 

Komatiite-hosted Ni-Cu deposits with PGEs from 

Australia and Canada were discussed. PGE-bearing 

chromitites from eastern Cuba and elsewhere were 

described. Data from the Al’Ays ophiolite complex in 

Saudi Arabia have shown that podiform chromitites 

with high PGE concentrations (above 1.4 ppm) also 

have distinctive minor element concentrations that 

provide an improved fingerprint for further exploration. 

The Ambae chromites of the Vanuatu Arc in 

the south-west Pacific have grades of 75.8 ppb Rh, 

52.1 ppb Ir, 36.8 ppb Os and 92.6 ppb Ru, whereas 

Pd, Pt and Au are below the detection limit. These 

values account for 56% of the Ir, over 90% of the 

Ru and 22% of the Rh present in the Ambae lavas. 

Reconnaissance studies of the PGEs potential of four 

chromite mining districts in southern Iran showed 

that chromites have concentrations of 6 PGEs (combined 

Pt, Pd, Rh, Ir, Os and Ru) from 57 ppb to 

5183 ppb with an average of 456 ppb. 

New Discoveries 

New Cu-Au-PGE mineralisation was reported from the 

Togeda macrodyke in the Kangerlussuaq region of 

East Greenland. A metasediment-hosted deposit from 

Craignure, Inverary, in Scotland hosts sulfide mineralisation 

with PGE concentrations locally exceeding 

3 ppm and, although small, this raises the possibility 

of other metasediment-hosted Ni-Cu-PGE mineralisation 

in Scotland. Amphibolites and their weathered 

equivalents on the northwest border of the Congo 

Craton in South Cameroon have a PGEs plus Au content 

of 53 ppb to 121 ppb. The Pd:Pt ratios are ∼ 3. 

Ni-Cu-PGE mineralisation was described from the 

Gondpipri area of central India but Ni and Cu dominate 

and PGE content is low. 

Process Mineralogy in the Platinum 

Industry and Future Trends 

This was perhaps a new topic for these events. 

Laser ablation inductively coupled plasma mass 

spectrometry (LA-ICP-MS) mapping provides critical 

information on the distribution of the PGEs in and 

around magmatic sulfides and is useful in characterising 

PGE deposits. As an example of the insights 

that can be gained with this technique, new data 

for samples from the Merensky Reef and Norilsk- 

Talnakh show that the behaviour of Pt is very different 

from that of Pd and Rh, which are generally 

hosted by pentlandite. Pt often forms a plethora of 

discrete phases in association with the trace and 

semi-metals. The variable distribution of these phases 

has implications for geometallurgical models and 

PGE recoveries. 

While the PGEs are most often concentrated in 

sulfide minerals such as pyrrhotite, pentlandite and 

chalcopyrite, there were several reports at the 


doi:10.1595/147106711X554512 


symposium of pyrite hosting appreciable amounts of 

Rh and Pt. Pyrite from the McCreedy and Creighton 

deposits of Sudbury has a similar Os, Ir, Ru, Re 

(rhenium) and Se (selenium) content to that of coexisting 

pyrrhotite and pentlandite, whereas Rh (at up 

to 130 ppm), arsenic (up to 30 ppm), Pt and Au show 

a stronger preference for pyrite than for pyrrhotite or 

pentlandite. In the Canadian Cordilleran porphyry 

copper systems, up to 90% of the Pd and Pt in mineralised 

samples occurs in pyrite. 

Concluding Remarks 

With reports of a number of new discoveries alongside 

much new information on existing resources, 

the 11th International Platinum Symposium provided 

the industry with the most comprehensive 

overview yet of platinum group element deposits 

worldwide. While many of these deposits have relatively 

low grades of PGEs, they may still prove to be 

viable and valuable sources of pgms in the future. 

Exploration efforts are also expected to become more 

efficient as a greater understanding of the geological 

process behind the formation of PGE deposits is 

gained. 

Reference 

1 The 11th International Platinum Symposium at Laurentian 

University: http://11ips.laurentian.ca/Laurentian/Home/ 

Departments/Earth+Sciences/NewsEvents/11IPS/ (Accessed 

on 7th January 2011) 


Judith Kinnaird is a Professor of 

Economic Geology at the School of 

Geosciences at the University of the 

Witwatersrand, South Africa, and 

Deputy Director of the University’s 

Economic Geology Research Institute 

(EGRI). Her research interests include 

Bushveld Complex magmatism and 

mineralisation especially of the 

Platreef in the northern limb, while 

her research team is currently 

conducting studies on chromitite 

geochemistry, mineralogy and PGE 

grade distribution; tenor variations; 

zircon age-dating; Lower Zone 

mineralogy and geochemistry of the 

Bushveld Complex in South Africa. 



The Discoverers of the Rhodium 

Isotopes 

The thirty-eight known rhodium isotopes found between 1934 and 2010 

doi:10.1595/147106711X555656 


By John W. Arblaster 

Wombourne, West Midlands, UK; 

E-mail: jwarblaster@yahoo.co.uk 

This is the fifth in a series of reviews on the circumstances 

surrounding the discoveries of the isotopes 

of the six platinum group elements. The first review 

on platinum isotopes was published in this Journal 

in October 2000 (1), the second on iridium isotopes in 

October 2003 (2), the third on osmium isotopes in 

October 2004 (3) and the fourth on palladium isotopes 

in April 2006 (4). 

Naturally Occurring Rhodium 

In 1934, at the University of Cambridge’s Cavendish 

Laboratory, Aston (5) showed by using a mass spectrograph 

that rhodium appeared to consist of a single 

nuclide of mass 103 ( 103 Rh). Two years later Sampson 

and Bleakney (6) at Princeton University, New Jersey, 

using a similar instrument, suggested the presence of 

a further isotope of mass 101 ( 101 Rh) with an abundance 

of 0.08%. Since this isotope had not been discovered 

at that time, its existence in nature could not 

be discounted. Then in 1943 Cohen (7) at the 

University of Minnesota used an improved mass spectrograph 

to show that the abundance of 101 Rh must be 

less than 0.001%. Finally in 1963 Leipziger (8) at the 

Sperry Rand Research Center, Sudbury, Massachusetts, 

used an extremely sensitive double-focusing mass 

spectrograph to reduce any possible abundance to 

less than 0.0001%. However by that time 101 Rh had 

been discovered (see Table I) and although shown to 

be radioactive, no evidence was obtained for a longlived 

isomer. This demonstrated conclusively that 

rhodium does in fact exist in nature as a single 

nuclide: 103 Rh. 

Artificial Rhodium Isotopes 

In 1934, using slow neutron bombardment, Fermi 

et al. (9) identified two rhodium activities with halflives 

of 50 seconds and 5 minutes. A year later the 

same group (10) refined these half-lives to 44 seconds 

and 3.9 minutes. These discoveries were said to be 

‘non-specific’ since the mass numbers were not 


doi:10.1595/147106711X555656 


determined, although later measurements identified 

these activities to be the ground state and isomeric 

state of 104 Rh, respectively. In 1940 Nishina et al. 

(11, 12), using fast neutron bombardment, identified 

a 34 hour non-specific activity which was later identified 

as 105 Rh. In 1949 Eggen and Pool (13) confirmed 

the already known nuclide 101 Pd and identified the 

existence of a 4.7 day half-life rhodium daughter 

product. They did not comment on its mass although 

the half-life is consistent with the isomeric state of 

101 Rh. Eggen and Pool also identified a 5 hour half-life 

activity which was never subsequently confirmed. 

Activities with half-lives of 4 minutes and 1.1 hours, 

obtained by fast neutron bombardment, were identified 

by Pool, Cork and Thornton (14) in 1937 but 

these also were never confirmed. 

Although some of these measured activities represent 

the first observations of specific nuclides, the 

exact nuclide mass numbers were not determined 

and therefore they are not considered to represent 

actual discoveries. They are however included in 

the notes to Table I. The first unambiguous identification 

of a radioactive rhodium isotope was by 

Crittenden in 1939 (15) who correctly identified 

both 104 Rh and its principal isomer. Nuclides where 

only the atomic number and atomic mass number 

were identified are considered as satisfying the discovery 

criteria. 

Discovery Dates 

The actual year of discovery is generally considered 

to be that when the details of the discovery were 

placed in the public domain, such as manuscript 

dates or conference report dates. However, complications 

arise with internal reports which may not be 

placed in the public domain until several years after 

the discovery, and in these cases it is considered that 

the historical date takes precedence over the public 

domain date. Certain rhodium isotopes were discovered 

during the highly secretive Plutonium Project of 

the Second World War, the results of which were not 

actually published until 1951 (16) although much of 

the information was made available in 1946 by Siegel 

(17, 18) and in the 1948 “Table of Isotopes”(19). 

Half-Lives 

Selected half-lives used in Table I are generally those 

accepted in the revised NUBASE evaluation of 

nuclear and decay properties in 2003 (20) although 

literature values are used when the NUBASE data are 

not available or where they have been superseded by 

later determinations. 

Table I 

The Discoverers of the Rhodium Isotopes 

Mass number a Half-life Decay Year of Discoverers References Notes 

modes discovery 

89 ps b EC + β + ? 1994 Rykaczewski et al. 21, 22 

90 15 ms EC + β + 1994 Hencheck et al. 23 A 

90m 1.1 s EC + β + 2000 Stolz et al. 24 A 

91 1.5 s EC + β + 1994 Hencheck et al. 23 B 

91m 1.5 s IT 2004 Dean et al. 25 B 

92 4.7 s EC + β + 1994 Hencheck et al. 23 C 

92m 0.5 s IT? 2004 Dean et al. 25 C 

93 11.9 s EC + β + 1994 Hencheck et al. 23 D 

94 70.6 s EC + β + 1973 Weiffenbach, Gujrathi and Lee 26 

94m 25.8 s EC + β + 1973 Weiffenbach, Gujrathi and Lee 26 

95 5.02 min EC + β + 1966 Aten and Kapteyn 27 

95m 1.96 min IT, EC + β + 1974 Weiffenbach, Gujrathi and Lee 28 

Continued 


doi:10.1595/147106711X555656 


Table I 

The Discoverers of the Rhodium Isotopes (Continued) 



96 9.90 min EC + β + 1966 Aten and Kapteyn 27 

96m 1.51 min IT, EC + β + 1966 Aten and Kapteyn 27 

97 30.7 min EC + β + 1955 Aten and de Vries-Hamerling 29 

97m 46.2 min EC + β + , IT 1971 Lopez, Prestwich and Arad 30 

98 8.7 min EC + β + 1955 Aten and de Vries-Hamerling 29 E 

98m 3.6 min EC + β + 1966 Aten and Kapteyn 31 

99 16.1 d EC + β + 1956 Hisatake, Jones and Kurbatov 32 F 

99m 4.7 h EC + β + 1952 Scoville, Fultz and Pool 33 

100 20.8 h EC + β + 1944 Sullivan, Sleight and Gladrow 34, 35 G 

100m 4.6 min IT, EC + β + 1973 Sieniawski 36 

101 3.3 y EC 1956 Hisatake, Jones and Kurbatov 32 F 

101m 4.34 d EC, IT 1944 Sullivan, Sleight and Gladrow 34, 37 G 

102 207.0 d EC + β + , β − 1941 Minakawa 38 

102m 3.742 y EC + β + , IT 1962 Born et al. 39 

103 Stable – 1934 Aston 5 

103m 56.114 min IT 1943 (a) Glendenin and Steinberg (a) 40, 41 H 

(b) Flammersfeld (b) 42 

104 42.3 s β − 1939 Crittenden 15 I 

104m 4.34 min IT, β − 1939 Crittenden 15 I 

105 35.36 h β − 1944 (a) Sullivan, Sleight and Gladrow (a) 34, 43 J 

(b) Bohr and Hole (b) 44 

105m 42.9 s IT 1950 Duffield and Langer 45 

106 30.1 s β − 1943 (a) Glendenin and Steinberg (a) 40, 41 K 

(b) Grummitt and Wilkinson (b) 46 

(c) Seelmann-Eggebert (c) 47 

106m 2.18 h β − 1955 Baró, Seelmann-Eggebert 48 L 

and Zabala 

107 21.7 min β − 1954 (a) Nervik and Seaborg (a) 49 M 

(b) Baró, Rey and (b) 50 

Seelmann-Eggebert 

108 16.8 s β − 1955 Baró, Rey and 50 N 

Seelmann-Eggebert 

108m 6.0 min β − 1969 Pinston, Schussler and Moussa 51 

Continued 


doi:10.1595/147106711X555656 


Table I 

The Discoverers of the Rhodium Isotopes (Continued) 



109 1.33 min β − 1969 Wilhelmy et al. 52, 53 

110 28.5 s β − 1969 (a) Pinston and Schussler (a) 54 

(b) Ward et al. (b) 55 

110m 3.2 s β − 1963 Karras and Kantele 56 

111 11 s β − 1975 Franz and Herrmann 57 

112 3.4 s β − 1969 Wilhelmy et al. 52, 53 

112m 6.73 s β − 1987 Äystö et al. 58 

113 2.80 s β − 1988 Penttilä et al. 59 

114 1.85 s β − 1969 Wilhelmy et al. 52, 53 

114m 1.85 s β − 1987 Äystö et al. 58 

115 990 ms β − 1987 Äystö et al. 60, 61 

116 680 ms β − 1987 Äystö et al. 58, 60, 61 

116m 570 ms β − 1987 Äystö et al. 58, 60, 61 

117 394 ms β − 1991 Penttilä et al. 62 

118 266 ms β − 1994 Bernas et al. 63 O 

119 171 ms β − 1994 Bernas et al. 63 P 

120 136 ms β − 1994 Bernas et al. 63 Q 

121 151 ms β − 1994 Bernas et al. 63 P 

122 ps b β − ? 1997 Bernas et al. 64 

123 ps b β − ? 2010 Ohnishi et al. 65 See Figures 1 

and 2 


and 2 


and 2 


a m = isomeric state 

b ps = particle stable (resistant to proton and neutron decay) 

and 2 


doi:10.1595/147106711X555656 


Fig. 1. The superconducting ring cyclotron (SRC) in the Radioactive Isotope Beam Factory (RIBF) at the 

RIKEN Nishina Center for Accelerator-Based Science where the newest isotopes of palladium, rhodium 

and ruthenium were discovered (65) (Copyright 2010 RIKEN) 

Dr Toshiyuki Kubo 

Fig. 2. Dr Toshiyuki Kubo 

(Copyright 2010 RIKEN) 

Toshiyuki Kubo is the team leader of the Research Group at RIKEN. 

He was born in Tochigi, Japan, in 1956. He received his BS degree 

in Physics from The University of Tokyo in 1978, and his PhD 

degree from the Tokyo Institute of Technology in 1985. He joined 

RIKEN as an Assistant Research Scientist in 1980, and was promoted 

to Research Scientist in 1985 and to Senior Research Scientist 

in 1992. He spent time at the National Superconducting Cyclotron 

Laboratory of Michigan State University in the USA as a visiting 

physicist from 1992 to 1994. In 2001, he became the team leader for 

the in-flight separator, dubbed ‘BigRIPS’, which analyses the fragments 

produced in the RIBF. He was promoted to Group Director 

of the Research Instruments Group at the RIKEN Nishina Center in 

2007. He is in charge of the design, construction, development and 

operation of major research instruments, as well as related infrastructure 

and equipment, at the RIKEN Nishina Center. His current 

research focuses on the production of rare isotope beams, in-flight 

separator issues, and the structure and reactions of exotic nuclei. 


doi:10.1595/147106711X555656 


Notes to Table I 

A 

B 

C 

D 

E 

90 Rh and 90m Rh Hencheck et al. (23) only proved that the isotope was particle stable. Stolz et al. 

(24) in 2000 identified both the ground state and an isomer. The half-life determined 

by Wefers et al. in 1999 (66) appears to be consistent with the ground 

state. The discovery by Hencheck et al. is nominally assigned to the ground state. 

91 Rh and 91m Rh Hencheck et al. (23) only proved that the isotope was particle stable. Wefers et al. 

(66) first determined a half-life in 1999 but Dean et al. (25) remeasured the halflife 

in 2004 and identified both a ground state and an isomer having identical 

half-lives within experimental limits. The discovery by Hencheck et al. is nominally 

assigned to the ground state. 

92 Rh and 92m Rh Hencheck et al. (23) only proved that the isotope was particle stable. Wefers et al. 

(66) incorrectly determined the half-life in 1999 with more accurate values being 

determined by both Górska et al. (67) and Stolz et al. (24) in 2000. Dean et al. 

(25) showed that these determinations were for the ground state and not for the 

isomeric state which they also identified. The discovery by Hencheck et al. is nominally 

assigned to the ground state. 

93 Rh Hencheck et al. (23) only proved that the isotope was particle stable. Wefers et al. 

in (66) incorrectly measured the half-life in 1999 with more accurate values being 

obtained by both Górska et al. (67) and Stolz et al. (24) in 2000. 

98 Rh Aten et al. (68) observed this isotope in 1952 but could not decide if it was 

96 Rh or 98 Rh. 

F 

99 Rh and 101 Rh Farmer (69) identified both of these isotopes in 1955 but could not assign mass 

numbers. 

G 

100 Rh and 101m Rh For these isotopes the 1944 discovery by Sullivan, Sleight and Gladrow (34) was 

not made public until its inclusion in the 1948 “Table of Isotopes” (19). 

H 

I 

J 

103m Rh 

Although both Glendenin and Steinberg (40) and Flammersfeld (42) discovered 

the isomer in 1943 the results of Glendenin and Steinberg were not made public 

until their inclusion in the 1946 table compiled by Siegel (17, 18). 

104 Rh and 104m Rh Both the ground state and isomer were first observed by Fermi et al. (9) in 1934 

and by Amaldi et al. (10) in 1935 as non-specific activities. Pontecorvo (70, 71) 

discussed these activities in detail but assigned them to 105 Rh. EC + β + was also 

detected as a rare decay mode (0.45% of all decays) in 104 Rh by Frevert, 

Schöneberg and Flammersfeld (72) in 1965. 

105 Rh For this isotope the 1944 discovery by Sullivan, Sleight and Gladrow (34) was not 

made public until its inclusion in the 1946 table of Siegel (17, 18). The isotope 

was first identified by Nishina et al. (11, 12) in 1940 as a non-specific activity. 

K 106 Rh The discovery by Glendenin and Steinberg (40) in 1943 was not made public until 

Continued 


doi:10.1595/147106711X555656 


Notes to Table I (Continued) 

its inclusion in the 1946 table of Siegel (17, 18) and therefore the discovery of this 

isotope by both Grummitt and Wilkinson (46) and Seelmann-Eggebert (47) in 

1946 are considered to be independent. 

L 

106m Rh 

Nervik and Seaborg (49) also observed this isotope in 1955 but tentatively 

assigned it to 107 Rh. 

M 107 Rh First observed by Born and Seelmann-Eggebert (73) in 1943 as a non-specific 

activity and also tentatively identified by Glendenin (74, 75) in 1944. 

N 

108 Rh Although credited with the discovery, the claim by Baró, Rey and Seelmann- 

Eggebert (50) is considered to be tentative and a more definite claim to the 

discovery was made by Baumgärtner, Plata Bedmar and Kindermann (76) 

in 1957. 

O 

118 Rh Bernas et al. (63) only confirmed that the isotope was particle stable. The half-life 

was first determined by Jokinen et al. (77) in 2000. 

P 

119 Rh and 121 Rh Bernas et al. (63) only confirmed that the isotopes were particle stable. The halflives 

were first determined by Montes et al. (78) in 2005. 

Q 

120 Rh Bernas et al. (63) only confirmed that the isotope was particle stable. The half-life 

was first determined by Walters et al. (79) in 2004. 

Some of the Terms Used for This Review 

Atomic number 

Mass number 

Nuclide and isotope 

Isomer/isomeric state 

Half-life 

Electron volt (eV) 

The number of protons in the nucleus. 

The combined number of protons and neutrons in the nucleus. 

A nuclide is an entity containing a unique number of protons and neutrons in the 

nucleus. For nuclides of the same element the number of protons remains the same 

but the number of neutrons may vary. Such nuclides are known collectively as the 

isotopes of the element. Although the term isotope implies plurality it is sometimes 

used loosely in place of nuclide. 

An isomer or isomeric state is a high energy state of a nuclide which may decay 

by isomeric transition (IT) as described in the list of decay modes below, although 

certain low-lying states may decay independently to other nuclides rather than the 

ground state. 

The time taken for the activity of a radioactive nuclide to fall to half of its previous 

value. 

The energy acquired by any charged particle carrying a unit (electronic) charge when it 

falls through a potential of one volt, equivalent to 1.602 × 10 –19 J. The more useful 

unit is the mega (million) electron volt (MeV). 


doi:10.1595/147106711X555656 


Decay Modes 

α 

β – 

β + 

EC 

IT 

p 

n 

Alpha decay is the emission of alpha particles which are 4 He nuclei. Thus the atomic 

number of the daughter nuclide is two lower and the mass number is four lower. 

Beta or electron decay for neutron-rich nuclides is the emission of an electron (and an 

anti-neutrino) as a neutron in the nucleus decays to a proton. The mass number of the 

daughter nuclide remains the same but the atomic number increases by one. 

Beta or positron decay for neutron-deficient nuclides is the emission of a positron (and a neutrino) 

as a proton in the nucleus decays to a neutron. The mass number of the daughter nuclide remains 

the same but the atomic number decreases by one. However this decay mode cannot occur unless 

the decay energy exceeds 1.022 MeV (twice the electron mass in energy units). Positron decay is 

always associated with orbital electron capture (EC). 

Orbital electron capture in which the nucleus captures an extranuclear (orbital) electron 

which reacts with a proton to form a neutron and a neutrino, so that, as with positron 

decay, the mass number of the daughter nuclide remains the same but the atomic number 

decreases by one. 

Isomeric transition in which a high energy state of a nuclide (isomeric state or isomer) 

usually decays by cascade emission of γ (gamma) rays (the highest energy form of electromagnetic 

radiation) to lower energy levels until the ground state is reached. 

Proton decay in which a proton is emitted from the nucleus so both the atomic number and mass 

number decrease by one. Such a nuclide is said to be ‘particle unstable’. 

Neutron decay in which a neutron is emitted from the nucleus so the atomic number remains 

the same but the atomic mass is decreased by one. Such a nuclide is said to be ‘particle 

unstable’. 

Erratum: In the previous reviews (1–4) the alpha and beta decay modes were described in terms of ‘emittance’. This should 

read ‘emission’. 

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The Author 

John W. Arblaster is interested in 

the history of science and the 

evaluation of the thermodynamic and 

crystallographic properties of the 

elements. Now retired, he previously 

worked as a metallurgical chemist in a 

number of commercial laboratories 

and was involved in the analysis of a 

wide range of ferrous and non-ferrous 

alloys. 



“Asymmetric Catalysis on Industrial 

Scale”, 2nd Edition 

Edited by Hans-Ulrich Blaser (Solvias AG, Switzerland) and Hans-Jürgen Federsel 

(AstraZeneca, Sweden), Wiley-VCH, Weinheim, Germany, 2010, 580 pages, 

ISBN: 978-3-527-32489-7, £140, €168, US$360 (Print version); e-ISBN: 9783527630639, 

doi:10.1002/9783527630639 (Online version) 

doi:10.1595/147106711X558310 


Reviewed by Stewart Brown 

Johnson Matthey Precious Metals Marketing, 

Orchard Road, Royston, Hertfordshire SG8 5HE, UK; 

E-mail: stewart.brown@matthey.com 

Introduction 

“Asymmetric Catalysis on Industrial Scale:Challenges, 

Approaches and Solutions”, edited by Hans-Ulrich 

Blaser and Hans-Jürgen Federsel, builds and 

expands upon its first edition, which was published 

in 2004 (1). The second edition provides the reader 

with a comprehensive examination of the industrially 

important aspects of asymmetric catalysis, an area of 

organic chemistry that introduces chirality (a molecule 

that is non-superimposable upon its mirror 

image) to a molecule.This is especially important for 

pharmaceuticals, as biologically active compounds 

are often chiral molecules. 

One of the book’s co-editors, Hans-Ulrich Blaser, 

is currently Chief Technology Officer at Solvias in 

Basel, Switzerland, having previously spent twenty 

years at Ciba and three years at Novartis.The other coeditor, 

Hans-Jürgen Federsel, is Director of Science for 

Pharmaceutical Development at AstraZeneca in 

Sweden. He is recognised as a specialist in process 

research and development where he has worked for 

over 30 years. 

The monograph is divided into 28 chapters, each 

containing stand-alone case studies of a particular 

chemical or biocatalytic process. This makes the text 

very easy to dip in and out of, or alternatively to look 

for specific examples of interest. The book highlights 

real world processing issues, showing how each has 

been tackled and solved by the authors. The main 

aim of this book is to show that asymmetric catalysis 

is not merely the preserve of academic research; 

rather, it is a large-scale production tool for industrial 

manufacturing. However, just as importantly it provides 

support and ideas for those suffering with similar 

issues in optimising industrial syntheses. 

The reader of this book is required to have a relatively 

advanced knowledge of organic chemistry in 

order to fully appreciate the complexities of the vast 

range of reactions covered. It is aimed primarily at 


doi:10.1595/147106711X558310 


postgraduate level and particularly at those involved 

in the pharmaceutical and process chemistry industries.The 

book combines both organic chemistry and 

biochemistry in almost equal measure and so a good 

understanding of biological compounds and reactions 

is also required. 

Asymmetric Catalysis by the 

Platinum Group Metals 

The chapters are written by a grand total of 87 different 

authors from a plethora of pharmaceutical 

companies around the world, as well as a few chemicals 

companies and universities. The lengths of the 

chapters are such that a solid overview is provided, 

without overloading the reader with information. All 

reaction schemes are well drawn and are generally 

complemented with graphs and spectra of the synthesised 

compounds, as well as some photographs and 

process flow sheets to demonstrate some very elegant 

engineering solutions. Furthermore, the chapters are 

well referenced, allowing easy access to further information 

and literature should the reader so require. 

Due to the broad scope of this book, in terms of 

the variety of reactions and processes covered, this 

review will only focus on those involving platinum 

group metal (pgm) catalysts. It will not cover nonpgm 

catalytic processes or those involving biological 

catalysis, of which there are many interesting 

examples. 

In terms of coverage, as expected in this particular 

field, the pgms feature heavily throughout, with one 

or more of the metals being referred to in 17 of the 

28 chapters. In fact, Chapter 20, which examines 

asymmetric hydrogenation for the design of drug 

substances, features all five of the pgms that are 

most widely used for catalytic applications: platinum, 

palladium, rhodium, iridium and ruthenium. 

Interestingly, the book is arranged by process rather 

than perhaps a more orthodox method of segmenting 

by catalyst type or chemical transformation. The reasoning 

behind this is that it enables readers to find 

out how particular issues have been solved on a 

process level, which should prove useful to the industrial 

practitioner. 

The chapters are grouped into three sections: 

• Part I:‘New Processes for Existing Active 

Compounds (APIs)’; 

• Part II:‘Processes for Important Building Blocks’; 

• Part III:‘Processes for New Chemical Entities 

(NCEs)’. 

Throughout this book the importance of process 

development and scale-up, taking laboratory-scale 

products to pilot plant and subsequently full-scale 

production of active, pure products is impressed 

upon the readers. 

The range of enantioselective catalysis shown in 

this book highlights the growing importance of 

developing more selective, active and ultimately 

more cost-effective processes for the production of 

specific biologically active compounds. 

New Processes for Existing Active Compounds 

The first section of the book contains five chapters, 

each of which examines either new catalysts or new 

routes to produce existing compounds for such products 

as cholesterol-lowering, cough-relieving or antiobesity 

drugs, as well as vitamins and indigestion 

remedies. Asymmetric hydrogenations catalysed by 

Ru, Ir or Rh feature heavily, especially in Chapter 2 in 

which Kurt Püntener and Michelangelo Scalone 

(F. Hoffmann-La Roche Ltd, Switzerland) present five 

example syntheses showing how the hydrogenation 

of different functional groups has led to significant 

improvements in the production of active pharmaceutical 

intermediates (APIs). 

Chapter 3 takes a detailed look at the use of asymmetric 

hydrogenation in the production of (+)–biotin 

(vitamin H). This compound has three stereocentres 

that need to be controlled to produce the pure, 

active compound that can produce full biological 

activity in the body. The reader is led through the 

history of biotin production (today a 100 tonne per 

year industry) from the original eleven-step Goldberg- 

Sternbach concept involving a palladium-catalysed 

hydrogenation step, through to the much shorter and 

more elegant Lonza process, utilising a rhodiumcatalysed 

asymmetric hydrogenation step (Scheme I). 

The often lengthy reaction schemes are very well 

drawn out and highlight the complexities associated 

with this particular synthesis. 

Chapter 5 covers the important reaction of asymmetric 

ketone reduction, which despite being academically 

well understood poses significant issues 

in complex biological molecules on an industrial 

scale. This chapter highlights the groundbreaking 

work by Ryoji Noyori, who won the 2001 Nobel Prize 

in Chemistry with William S. Knowles for their work 

on chiral hydrogenation reactions catalysed by Rh 

and Ru complexes (2). This has influenced the work 

in this chapter and much of the rest of the book. 


doi:10.1595/147106711X558310 


Scheme I. The Lonza 

concept: (+)-biotin 

process using 

asymmetric 

hydrogenation 

catalysed by a 

rhodium(I) complex 

Andreas Marc Palmer (Nycomed GmbH, Germany) 

and Antonio Zanotti-Gerosa (Johnson Matthey 

Catalysis and Chiral Technologies, UK) tell the story of 

how selectivity and activity can be tuned by the optimisation 

of ruthenium phosphine complexes such as 

those shown in Figure 1 for large-scale reactions. 

Processes for Important Building Blocks 

The second section contains fourteen chapters categorised 

as new catalyst and process developments 

for synthetically important building blocks, nine of 

which mention pgms. Chapter 16 in particular 

demonstrates the effectiveness of pgms with mention 

given to Pd, Rh, Ir and Ru in a particularly in-depth 

analysis of asymmetric transfer hydrogenation. 

The technique of asymmetric transfer hydrogenation 

is an important method for producing optically 

active alcohols and amines (for example, Scheme II). 

The authors spend considerable time in this chapter 

discussing the reaction components before moving 

on to some case studies to illustrate their use. This is 

certainly one of the most detailed chapters, and it is 

well supported by a series of tables, reaction schemes 

and graphs. 

Processes for New Chemical Entities 

The final section is the least relevant in terms of 

pgm use, with five of the remaining nine chapters not 

featuring the metals. However, one of the standout 

reviews in terms of pgm catalysis is Chapter 20. 

Fig. 1. Two examples 

of ruthenium phosphine 

complexes 

used as catalysts for 

the asymmetric 

reduction of ketones 


doi:10.1595/147106711X558310 


Scheme II. Rhodium-catalysed asymmetric 

transfer hydrogenation reaction 

investigated for the synthesis of a key 

intermediate of duloxetine 

This chapter, entitled ‘Enabling Asymmetric 

Hydrogenation for the Design of Efficient Synthesis of 

Drug Substances’ and written by Yongkui Sun, Shane 

Krska, C. Scott Shultz and David M. Tellers (Merck & 

Co, Inc, USA), includes examples of catalysed steps 

involving platinum, palladium, rhodium, iridium and 

ruthenium during the course of the text. 

The chapter begins with an introduction once 

again paying tribute to the great work by Knowles 

and Noyori in the field of asymmetric hydrogenation. 

It then talks about the work done by Merck chemists 

to increase the use of asymmetric catalysis in drug 

discovery programmes within the company.The chapter 

drives home the key message that by identifying 

and having a concerted effort to utilise and improve 

a particular reaction, unprecedented progress could 

be made. 

Three detailed case studies born out of Merck’s 

‘Catalysis Initiative’ are then recounted: laropiprant, 

an API in the cholesterol-lowering drug Tredaptive TM ; 

taranabant, an API in the treatment of obesity; and 

sitagliptin, an API in the treatment of type 2 diabetes 

(Figure 2) (Scheme III). All three demonstrate the 

vital importance of high-throughput screening to 

optimise both catalyst and reaction conditions 

within a constrained time-frame.The whole chapter is 

a success story for the Merck ‘Catalysis Initiative’ and 

should serve as inspiration to other companies in 

the search for new methods for large-scale drug 

production. 

Conclusions 

This book contains a comprehensive examination of 

a wide range of industrially important asymmetric 

reactions. It clearly shows the difficulties and challenges 

associated with these reactions, and more 

importantly how scientists and engineers have managed 

to successfully overcome them. The pgms feature 

in a large proportion of the syntheses and 

processes mentioned, with palladium-catalysed 

hydrogenations and the work of Knowles and Noyori 

being particularly significant. 

The book is easy to read and well illustrated and 

referenced throughout. The decision to group the 

chapters by the nature of the process works well, 

with the tables at the front of the book easily 

directing readers to subjects of interest. The key aim 

of this book, to show that asymmetric catalysis is not 

merely the preserve of academic research, is driven 

home in every chapter. The relevance of each reaction 

and synthesis to the industrial environment is 

made abundantly clear through a wide array of case 

studies. 

Overall, this book will be of interest to both industrial 

specialists and academics as it contains a good 

mix of chemistry and engineering. It provides comfort 

and inspiration to those working in this field 

through the numerous success stories told and is 

undoubtedly a useful source of potential contacts 

for those struggling with a particular asymmetric 

synthesis issue. 

Fig. 2. The structures of laropiprant, taranabant and sitagliptin 


doi:10.1595/147106711X558310 


Scheme III. First generation route to sitagliptin. BINAP = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl; 

EDC = N-(3-dimethylaminopropyl)-N‘-ethylcarbodiimide hydrochloride; DIAD = di-isopropyl azodicarboxylate; 

NMM = N-methylmorpholine 

“Asymmetric 

Catalysis on 

Industrial 

Scale”, 2nd 

Edition 

References 

1 “Asymmetric Catalysis on Industrial Scale: Challenges, 

Approaches and Solutions”, eds. H.-U. Blaser and 

E. Schmidt, Wiley-VCH, Weinheim, Germany, 2004 

2 ‘Advanced Information on the Nobel Prize in Chemistry 

2001, Catalytic Asymmetric Synthesis’, The Royal 

Swedish Academy of Sciences, Stockholm, Sweden, 

10th October, 2001 


Dr Stewart Brown graduated with an MChem 

(Hons) and a PhD in Chemistry from the 

University of Liverpool, UK. He joined Johnson 

Matthey in 2004 and spent 5 years as a 

Process Development Chemist, involved in the 

scale-up of new catalysts and processes for the 

Emission Control Technologies business unit. 

In 2009 he transferred to Precious Metals 

Marketing and is currently a Market Analyst 

within the Market Research team, focusing 

on the chemical, electronics, automotive and 

petroleum refining sectors. 


doi:10.1595/147106711X570631 


Publications in Brief 

BOOKS 

“Healthy, Wealthy, Sustainable World” 

J. Emsley (UK), Royal Society of 

Chemistry, Cambridge, UK, 2010, 

248 pages, ISBN 978-1-84755-862-6, 

£18.99 

The themes of this general reader 

book relate to the importance 

of chemistry in everyday 

life, the benefits chemicals currently 

bring, and how the use of 

chemicals can continue on a 

sustainable basis. Topics covered 

include: health, food (the role of agrochemicals 

and food chemists),water (drinking water; the seas as 

a source of raw materials),fuels,plastics (can they be 

sustainable?), cities and sport. 

“Modern Electroplating”, 5th Edition 

Edited by M. Schlesinger (University 

of Windsor, Windsor, Ontario, 

Canada) and M. Paunovic (USA), 

John Wiley & Sons, Inc, Hoboken, 

New Jersey, USA, 2010, 736 pages, 

ISBN 978-0-470-16778-6, £100.00, 

€120.00, US$149.95; e-ISBN: 

9780470602638 

This expanded new edition 

places emphasis on electroplating 

and electrochemical plating in nanotechnologies, 

data storage and medical applications. It 

includes chapters on ‘Palladium Electroplating’ and 

‘Electroless Deposition of Palladium and Platinum’. 

“Pharmaceutical Process Chemistry” 

Edited by T. Shioiri (Japan), K. Izawa 

(Ajinomoto Co, Inc, Japan) and 

T. Konoike (Shionogi & Co, Ltd, 

Japan), Wiley-VCH Verlag GmbH & 

Co KGaA, Weinheim, Germany, 2011, 

526 pages, ISBN 978-3-527-32650-1, 

£125.00, €150.00, US$210.00; 

e-ISBN 9783527633678 

This book covers the basic 

chemistry needed for future 

developments and key techniques 

in the pharmaceutical industry, as well as 

morphology, engineering and regulatory issues. 

Recent examples of industrial production of active 

pharmaceutical ingredients are given. It includes 

chapters on ‘Development of Palladium Catalysts for 

Chemoselective Hydrogenation’, ‘Silicon-Based 

Carbon–Carbon Bond Formation by Transition Metal 

Catalysis’ and ‘Direct Reductive Amination with 

Amine Boranes’. 

JOURNALS 

Geoscience Frontiers 

Editor-in-Chief: X. X. Mo (China 

University of Geosciences (Beijing), 

China); China University of 

Geosciences (Beijing), Peking 

University and Elsevier BV; ISSN 

1674-9871 

Geoscience Frontiers (GSF) is a 

new quarterly journal under the 

joint sponsorship of the China 

University of Geosciences 

(Beijing) and Peking University. Co-published with 

Elsevier, GSF publishes original research articles and 

reviews of recent advances in all fields of earth sciences. 

Technical papers, case histories, reviews and 

discussions are included. 

Greenhouse Gases: Science and Technology 

Edited by Mercedes Maroto-Valer 

(Centre for Innovation in Carbon 

Capture and Storage (CICCS), University 

of Nottingham, UK) and 

Curtis Oldenburg (Geologic Carbon 

Sequestration (GCS) Program, 

Lawrence Berkeley National Laboratory, 

USA); Society of Chemical 

Industry and John Wiley & Sons, Ltd; 

e-ISSN 2152-3878 

Greenhouse Gases: Science and Technology (GHG) is 

a new quarterly online journal from the Society of 

Chemical Industry (SCI) and Wiley. GHG is dedicated 

to the management of greenhouse gases through capture, 

storage, utilisation and other strategies. GHG will 

explore subject areas such as: 

(a) Carbon capture and storage; 

(b) Utilisation of carbon dioxide (CO 2 ); 

(c) Other greenhouse gases: methane (CH 4 ), nitrous 

oxide (N 2 O), halocarbons; 

(d) Other mitigation strategies. 


doi:10.1595/147106711X570631 


High-Temperature Materials 

JOM, 2010, 62, (10) 

The theme of this issue of JOM 

is high-temperature materials 

which includes the following 

four articles on the topic of 

nickel-based superalloys: 

The Thermodynamic Modeling of 

Precious-Metal-Modified Nickel 

Based Superalloys 

F. Zhang, J. Zhu, W. Cao, C. Zhang and Y. A. Chang, JOM, 

2010, 62, (10), 35 

Precious-Metal-Modified Nickel-Based Superalloys: 

Motivation and Potential Industry Applications 

A. Bolcavage and R. C. Helmink, JOM, 2010, 62, (10), 41 

The Use of Precious-Metal-Modified Nickel-Based 

Superalloys for Thin Gage Applications 

D. L. Ballard and A. L. Pilchak, JOM, 2010, 62, (10), 45 

A Combined Mapping Process for the Development of 

Platinum-Modified Ni-Based Superalloys 

A. J. Heidloff, Z. Tang, F. Zhang and B. Gleeson, JOM, 2010, 

62, (10), 48 

21st International Symposium on Chemical Reaction 

Engineering (ISCRE 21) 

Ind. Eng. Chem. Res., 2010, 49, (21), 

10153–11120 

ISCRE 21 was held in 

Philadelphia, Pennsylvania, USA, 

from 13th–16th June 2010. The 

symposium focused on the role 

of chemical reaction engineering 

in addressing resource sustainability, 

environmental and 

life science challenges. The topics covered included 

rational design of catalysts, computational catalysis, 

reaction path analysis, dynamics of chemical reactors, 

multiphase and reacting flows, environmental 

reaction engineering, microreactors, membrane reactors, 

process intensification, fuel cells, bioderived 

chemicals and fuels, clean coal conversion processes, 

CO 2 capture and utilisation,hydrogen production and 

utilisation, and novel functional materials. This ISCRE 

21 special issue of Industrial & Engineering Chemistry 

Research consists of Invited Perspectives by the 

plenary speakers, as well as regular, full-length contributed 

papers by the other authors. 

Recent Advances in the in-situ Characterization of 

Heterogeneous Catalysts 

Chem. Soc. Rev., 2010, 39, (12), 

4541–5072 

The 28 review articles of this 

themed issue of Chemical 

Society Reviews cover the advantages, 

limitations, challenges 

and future possibilities of in situ 

characterisation techniques for 

“elucidating the ‘genesis’ and 

working principles of heterogeneous catalysts”. Bert 

Weckhuysen (Inorganic Chemistry and Catalysis 

Group, Debye Institute for Nanomaterials Science, 

Utrecht University, The Netherlands) assembled this 

issue on in situ characterisation of catalytic solids. 

ON THE WEB 

Global Emissions Management 

Latest issue: Volume 3, Issue 01 

(November 2010) 

Johnson Matthey Environmental 

Catalysts and Technologies’ 

Global Emissions 

Management (GEM) publication 

featuring developments in emissions control is 

now online. Free subscription to GEM online allows 

subscribers to: 

(a) Read up-to-date news and features; 

(b) Access all previous articles from Global 

Emissions Management; 

(c) Create a bespoke issue using MyGEM; 

(d) Print, download and share all articles. 

Find this at: http://www.jm-gem.com/ 


doi:10.1595/147106711X570479 


Abstracts 

CATALYSIS – APPLIED AND PHYSICAL 

ASPECTS 

Controlled Synthesis of Pt Nanoparticles via Seeding 

Growth and Their Shape-Dependent Catalytic Activity 

X. Gong, Y. Yang, L. Zhang, C. Zou, P. Cai, G. Chen and 

S. Huang, J. Colloid Interface Sci., 2010, 352, (2), 379–385 

Octahedral,cuboctahedral,branched and ‘rice-like’Pt 

NPs were synthesised using a seed-mediated growth 

route. Pt NPs (3 nm) were prepared and dispersed in 

oleyl amine to form a seed solution and then 

Pt(acac) 2 was added. By adjusting the molar ratio of 

Pt from Pt(acac) 2 and seed NPs, the seed diameter 

and the addition route of Pt(acac) 2 , the NPs growth 

could be controlled to fall into in a kinetic or thermodynamic 

growth regime. The obtained NPs were 

supported on C black (Vulcan XC-72). The catalysts 

synthesised from branched NPs were found to have 

higher catalytic activity and stability for the oxidation 

of methanol. 

Pyrophoricity and Stability of Copper and Platinum 

Based Water-Gas Shift Catalysts during Oxidative 

Shut-Down/Start-Up 

R. Kam, J. Scott, R. Amal and C. Selomulya, Chem. Eng. Sci., 

2010, 65, (24), 6461–6470 

In this investigation Cu/ZnO exhibited high levels of 

pyrophoricity.This manifested as a sharp temperature 

rise of the catalyst bed upon air introduction. Severe 

sintering of the bulk and metallic phases of the catalyst 

resulted in catalyst deactivation.No pyrophoricity 

was observed for Pt-based catalysts; however, there 

was sintering of the metallic phase in Pt/TiO 2 and 

Pt/ZrO 2 . Pt/CeO 2 retained its activity, displaying no 

loss in specific surface area or metal dispersion. 

Shape-Selective Formation and Characterization of 

Catalytically Active Iridium Nanoparticles 

S. Kundu and H. Liang, J. 

Colloid Interface Sci., 2011, 

354, (2), 597–606 

Sphere, chain, flake and 

needle shaped Ir NPs 

were synthesised via 

reduction of Ir(III) ions in 

cetyltrimethylammonium 

bromide micellar 

media containing alkaline 

2,7-dihydroxynaphthalene under UV irradiation. The 

NPs’ morphology was tuned by changing the surfactant:metal 

ion molar ratios and altering other parameters.The 

Ir nano-needles were a good catalyst for the 

reduction of organic dyes in presence of NaBH 4 . 

CATALYSIS – REACTIONS 

Selective Oxidation of Glucose Over Carbon- 

Supported Pd and Pt Catalysts 

I. V. Delidovich, O. P. Taran, L. G. Matvienko, A. N. Simonov, 

I. L. Simakova, A. N. Bobrovskaya and V. N. Parmon, Catal. 

Lett., 2010, 140, (1–2), 14–21 

Pt/C exhibited lower specific activity and provided 

poor selectivity of glucose oxidation to gluconic acid 

by O 2 in comparison with Pd/C.The finely dispersed 

Pd/C catalysts are prone to deactivation due to oxidation 

of their surface, while larger metal particles are 

more tolerant and stable. The activity of Pd nanoparticles 

can be maintained when the process is 

controlled by diffusion of O towards the active component 

of the catalyst. 

Carbonates: Eco-Friendly Solvents for Palladium- 

Catalysed Direct Arylation of Heteroaromatics 

J. J. Dong, J. Roger, C. Verrier, T. Martin, R. Le Goff, C. Hoarau 

and H. Doucet, Green Chem., 2010, 12, (11), 2053–2063 

Direct 2-,4- or 5-arylation of heteroaromatics with aryl 

halides using PdCl(C 3 H 5 )(dppb) as catalyst precursor/base 

was shown to proceed in moderate to good 

yields using the solvents diethylcarbonate (see the 

Figure) or propylene carbonate.The best yields were 

obtained using benzoxazole or thiazole derivatives 

(130ºC). The arylation of furan, thiophene, pyrrole, 

imidazole or isoxazole derivatives was found to 

require a higher reaction temperature (140ºC). 

J. J. Dong et al., Green Chem., 2010, 12, (11), 2053–2063 


doi:10.1595/147106711X570479 


EMISSIONS CONTROL 

A Global Description of DOC Kinetics for Catalysts 

with Different Platinum Loadings and Aging Status 

K. Hauff, U. Tuttlies, G. Eigenberger and U. Nieken, Appl. 

Catal. B: Environ., 2010, 100, (1–2), 10–18 

Five Pt/γ-Al 2 O 3 DOCs with different Pt loadings and 

ageing steps were characterised with regards to Pt 

particle diameter, active surface area and conversion 

behaviour for CO, propene and NO oxidation. 

HR-REM showed that the Pt particles have diameters 

larger than 8 nm. The catalyst activity was shown to 

be directly proportional to the catalytically active surface 

area, which was determined by CO chemisorption 

measurements. In order to model the CO and 

propene oxidation kinetics, only the catalytically 

active surface has to be changed in the global 

kinetic models. The same was true for NO oxidation 

at higher temperatures. 

FUEL CELLS 

High Platinum Utilization in Ultra-Low Pt Loaded 

PEM Fuel Cell Cathodes Prepared by Electrospraying 

S. Martin, P. L. Garcia-Ybarra and J. L. Castillo, Int. J. 

Hydrogen Energy, 2010, 35, (19), 10446–10451 

The title cathodes with Pt loadings as low as 0.012 mg 

Pt cm –2 were prepared by the electrospray method. 

SEM of these layers showed a high dispersion of the 

catalyst powders forming fractal deposits made by 

small clusters of Pt/C NPs, with the clusters arranging 

in a dendritic growth. Using these cathodes in MEAs, 

a high Pt utilisation in the range 8–10 kW g –1 was 

obtained for a fuel cell operating at 40ºC and atmospheric 

pressure.Moreover,a Pt utilisation of 20 kW g –1 

was attained at 70ºC and 3.4 bar over-pressure. 

Effect of MEA Fabrication Techniques on the Cell 

Performance of Pt–Pd/C Electrocatalyst for Oxygen 

Reduction in PEM Fuel Cell 

S. Thanasilp and M. Hunsom, Fuel, 2010, 89, (12), 

3847–3852 

The effect of three different MEA fabrication techniques: 

catalyst-coated substrate by direct spray 

(CCS), catalyst-coated membrane by direct spray 

(CCM-DS) or decal transfer (CCM-DT), on the O 2 

reduction in a PEMFC was investigated under identical 

Pt-Pd/C loadings. The cells prepared by the CCM 

methods, and particularly by CCM-DT, exhibited a significantly 

higher open circuit voltage (OCV) but a 

lower ohmic and charge transfer resistance. By using 

CV with H 2 adsorption, it was found that the electrochemically 

active area of the electrocatalyst prepared 

by CCM-DT was higher than those by CCS and 

CCM-DS. Under a H 2 /O 2 system at 0.6 V, the cells 

with an MEA made by CCM-DT provided the highest 

cell performance (~350 mA cm –2 ). 

METALLURGY AND MATERIALS 

Shape Memory Effect and Pseudoelasticity of TiPt 

Y. Yamabe-Mitarai, T. Hara, S. Miura and H. Hosoda, 

Intermetallics, 2010, 18, (12), 2275–2280 

Martensitic transformation behaviour and SM properties 

of Ti-50 at%Pt SMA were investigated using 

high-temperature XRD and loading–unloading compression 

tests. The structures of the parent and 

martensite phases were identified as B2 and B19, 

respectively. Strain recovery was observed during 

unloading at RT and at 1123 K, which was below the 

martensite temperature. Shape recovery was investigated 

for the samples by heating at 1523 K for 1 h. The 

strain recovery rate was 30–60% for the samples tested 

at RT and ~11% for the samples tested at 1123 K. 

Role of Severe Plastic Deformation on the Cyclic 

Reversibility of a Ti 50.3 Ni 33.7 Pd 16 High Temperature 

Shape Memory Alloy 

B. Kockar, K. C. Atli, J. Ma, M. Haouaoui, I. Karaman, M. 

Nagasako and R. Kainuma, Acta Mater., 2010, 58, (19), 

6411–6420 

The effect of microstructural refinement on the thermomechanical 

cyclic stability of the title HTSMA 

which was severely plastically deformed using equal 

channel angular extrusion (ECAE) was investigated. 

The grain/subgrain size of the high temperature 

austenite phase was refined down to ~100 nm. The 

increase in strength differential between the onset of 

transformation and the macroscopic plastic yielding 

after ECAE led to enhancement in the cyclic stability 

during isobaric cooling–heating. The reduction in 

irrecoverable strain levels is attributed to the increase 

in critical stress for dislocation slip due to the 

microstructural refinement during ECAE. 

CHEMISTRY 

The Chemistry of Tri- and High-Nuclearity 

Palladium(II) and Platinum(II) Complexes 

V. K. Jain and L. Jain, Coord. Chem. Rev., 2010, 254, 

(23–24), 2848–2903 


doi:10.1595/147106711X570479 


This review gives an overview of the title complexes 

and reports developments. Three or more squareplanar 

metal atoms can be assembled in several ways 

resulting in complexes with a myriad of geometric 

forms.These square planes may be sharing a corner, 

an edge and two edges or even separated by ligands 

having their donor atoms incapable of forming 

chelates, yielding dendrimers and self-assembled 

molecules. Synthetic, spectroscopic and structural 

aspects of these complexes together with their applications 

are described. (Contains 554 references.) 

ELECTRICAL AND ELECTRONICS 

Dissolution and Interface Reactions between 

Palladium and Tin (Sn)-Based Solders: 

Part I. 95.5Sn-3.9Ag-0.6Cu Alloy 

P. T. Vianco, J. A. Rejent, G. L. Zender and P. F. Hlava, Metall. 

Mater. Trans. A, 2010, 41, (12), 3042–3052 

The interface microstructures and dissolution behaviour 

which occur between Pd substrates and molten 

95.5Sn-3.9Ag-0.6Cu (wt%) were studied. The solder 

bath temperatures were 240–350ºC, and the immersion 

times were 5–240 s.As a protective finish in electronic 

assemblies, Pd would be relatively slow to 

dissolve into molten Sn-Ag-Cu solder. The Pd-Sn intermetallic 

compound (IMC) layer would remain sufficiently 

thin and adherent to a residual Pd layer so as 

to pose a minimal reliability concern for Sn-Ag-Cu 

interconnections. 

Dissolution and Interface Reactions between 

Palladium and Tin (Sn)-Based Solders: 

Part II. 63Sn-37Pb Alloy 

P. T. Vianco, J. A. Rejent, G. L. Zender and P. F. Hlava, Metall. 

Mater. Trans. A, 2010, 41, (12), 3053–3064 

The interface microstructures as well as the rate 

kinetics of dissolution and IMC layer formation were 

investigated for couples formed between molten 

63Sn-37Pb (wt%) and Pd sheet. The solder bath temperatures 

were 215–320ºC, and the immersion times 

were 5, 15, 30, 60, 120 and 240 s. The extents of Pd 

dissolution and IMC layer development were significantly 

greater for molten Sn-Pb than the Pb-free 

Sn-Ag-Cu (Part I, as above) at a given test temperature. 

ELECTROCHEMISTRY 

The Effect of Gold on Platinum Oxidation in 

Homogeneous Au–Pt Electrocatalysts 

S. D. Wolter, B. Brown, C. B. Parker, B. R. Stoner and J. T. 

Glass, Appl. Surf. Sci., 2010, 257, (5), 1431–1436 

Ambient air oxidation of Au-Pt thin films was carried 

out at RT and then the films were characterised by 

XPS. The homogeneous films were prepared by RF 

cosputtering with compositions varying from Au 9 Pt 91 

to Au 89 Pt 11 and compared to pure Pt and Au thin 

films. The predominant oxidation products were PtO 

and PtO 2 . Variations in Pt oxide phases and/or concentration 

did not contribute to enhanced electrocatalytic 

activity for oxygen reduction observed for the 

intermediate alloy stoichiometries. 

A Feasibility Study of the Electro-recycling of 

Greenhouse Gases: Design and Characterization of a 

(TiO 2 /RuO 2 )/PTFE Gas Diffusion Electrode for the 

Electrosynthesis of Methanol from Methane 

R. S. Rocha, L. M. Camargo, M. R. V. Lanza and R. Bertazzoli, 

Electrocatalysis, 2010, 1, (4), 224–229 

The title GDE was designed to be used in the electrochemical 

conversion of CH 4 into MeOH under 

conditions of simultaneous O 2 evolution. The GDE 

was prepared by pressing and sintering TiO 2 (0.7)/ 

RuO 2 (0.3) powder and PTFE. CH 4 was inserted into 

the reaction medium by the GDE and electrosynthesis 

was carried out in 0.1 mol l –1 Na 2 SO 4 . Controlled 

potential experiments showed that MeOH concentration 

increased with applied potential, reaching 

220 mg l –1 cm 2 ,at 2.2V vs. a calomel reference electrode. 

Current efficiency for MeOH formation was 30%. 

PHOTOCONVERSION 

Cyclometalated Red Iridium(III) Complexes 

Containing Carbazolyl-Acetylacetonate Ligands: 

Efficiency Enhancement in Polymer LED Devices 

N. Tian, Y. V. Aulin, D. Lenkeit, S. Pelz, O. V. Mikhnenko, P. W. 

M. Blom, M. A. Loi and E. Holder, Dalton Trans., 2010, 39, 

(37), 8613–8615 

New red emitting cyclometalated Ir(III) complexes 

containing carbazolyl-acetylacetonate ligands (1, 2) 

were prepared and then compared to the commonly 

used reference emitter [(btp) 2 Ir(III)(acac)]. For a 

range of concentrations the new complexes 

revealed better luminous efficiencies than 

[(btp) 2 Ir(III)(acac)]. The phosphorescence decay 

times of the newly designed triplet emitters are 

significantly shorter making them attractive 

candidates for applications in advanced organic and 

polymer LEDs. 


doi:10.1595/147106711X570479 


N. Tian et al., Dalton Trans., 2010, 39, (37), 8613–8615 

1 

2 


doi:10.1595/147106711X570398 


Patents 

CATALYSIS – APPLIED AND PHYSICAL 

ASPECTS 

Palladium(0) Complex Catalyst 

Johnson Matthey Plc, World Appl. 2010/128,316 

A Pd(0)L n complex, where L is a ligand and 

n = 2, 3 or 4, is prepared by reacting a Pd(II) complex 

in a solvent with a base and ligand L. Further base, 

optionally in a solvent, may be added to form the 

Pd(0)L n complex. The pre-formed Pd(0) complex 

can be prepared on an industrial scale and used as a 

catalyst in Pd-catalysed cross-coupling reactions. 

When n = 2, the Pd(II) complex may not be 

[(o-tol) 3 P] 2 PdCl 2 . The Pd(0)L n complex may be, for 

example, Pd[ t Bu 2 (p-PhMe 2 N)P] 2 or Pd[ t Bu 2 (Np)P] 2 . 

Polymer-Supported Ruthenium Catalysts 

C.-M. Che and K.-W. M. Choi, US Appl. 2011/0,009,617 

Non-crosslinked soluble polystyrene-supported Ru 

nanoparticles were prepared by reacting 

[RuCl 2 (C 6 H 5 CO 2 Et)] 2 with polystyrene in air. The 

supported Ru nanoparticles can be used to catalyse 

intra- and intermolecular carbenoid insertion into 

C–H and N–H bonds, alkene cyclopropanation and 

ammonium ylide/[2,3]-sigmatropic rearrangement 

reactions and can be recovered and reused ten times 

without significant loss of activity. 

Dinuclear Osmium-Rhodium Photocatalyst 

Toyota Motor Corp, Japanese Appl. 2010-209,044 

A dinuclear metal complex,for example 1,containing 

a light-harvesting Os(tpy) 2 2+ moiety and a catalytically 

active diphosphine Rh moiety can be used as a 

N 

N 

N 

Os 

N 

N 

N 

Japanese Appl. 2010-209,044 

R 2 

P 

P 

R 2 

(PF 6 ) 2 

Rh 

R =phenyl, isopropyl, ethyl, tert-butyl, cyclohexyl, 

propyl or naphthyl 

1 

Cl 

CO 

photocatalyst for decomposing H 2 O to produce H 2 . 

The photocatalyst is prepared by cross-coupling a terpyridyl 

Os complex with phenylboronic acid pinacol 

ester having a phosphinothioyl group in the presence 

of a Pd catalyst to obtain the corresponding phosphine 

sulfide.This is reacted with Raney Ni to give a 

diphosphine ligand having an Os(tpy) 2+ 

2 moiety. 

This ligand is mixed with a transition metal complex 

such as [RhCl(CO) 2 ] 2 in a suitable solvent at room 

temperature to obtain the dinuclear metal complex. 

CATALYSIS – INDUSTRIAL PROCESS 

Palladium-Catalysed Preparation of Intermediates 

Bayer CropScience AG, World Appl. 2011/003,530 

Substituted and unsubstituted (2,4-dimethylbiphenyl- 

3-yl)acetic acids and their esters are prepared via a 

selective Suzuki cross-coupling reaction using 

homogenous or heterogeneous Pd catalysts. 4-tert- 

Butyl-2,6-dimethylphenyl acetic acid and 4-tert-butyl- 

2,6-dimethyl mandelic acid, useful as intermediates 

for pharmaceutical compounds or agricultural chemicals, 

are produced in good yield from inexpensive 

starting materials. 

Fixed-Bed Platinum Catalyst for Hydrosilylation 

Gelest Technol. Inc, US Appl. 2010/0,280,266 

A recyclable fixed-bed catalyst complex containing a 

silica-supported Pt carbene catalyst is claimed for use 

in a hydrosilylation process between an olefin, silicone 

or alkyne and a silicone to produce an 

organofunctional silane and/or a crosslinked silicone 

which contains

doi:10.1595/147106711X570398 


produced under standard hydroformylation reaction 

conditions of 75–125ºC and 1–70 bar (15–1000 psig). 

EMISSIONS CONTROL 

High Palladium Content Diesel Oxidation Catalysts 

Umicore AG & Co KG, World Appl. 2010/133,309 

Pd-enriched DOCs are claimed for the oxidation of 

CO and HC emissions from a compression ignition/ 

diesel engine. A first washcoat covers 25–95% of the 

substrate from the inlet and may contain Pt:Pd in a 

ratio for example 1:1; a second washcoat is richer in 

Pd than the first washcoat,with a Pt:Pd ratio for example 

1:2, and covers 5–75% of the substrate from the 

inlet.The catalysts are described as having increased 

performance and hydrothermal durability under cold 

start conditions. 

Platinum-Palladium Diesel Oxidation Catalyst 

BASF Corp, US Patent 7,875,573 (2011) 

An exhaust gas treatment system includes a DOC 

containing two washcoat layers coated onto a high 

surface area support substantially free of silica. The 

bottom washcoat layer contains Pt:Pd in a ratio 

between 2:1–1:2 and does not contain a HC storage 

component. The top washcoat layer contains Pt:Pd 

in a ratio between 2:1–10:1 and one or more HC storage 

components. A soot filter is located downstream 

of the DOC and a NOx conversion catalyst is located 

downstream of the soot filter. 

FUEL CELLS 

Platinum and Palladium Alloy Electrodes 

Danmarks Tekniske Univ., World Appl. 2011/006,511 

Electrode catalysts formed from Pt or Pd, preferably 

Pt, alloyed with Sc,Y and/or La on a conductive support 

material are claimed for use in a PEMFC.The catalysts 

are described as having increased ORR activity, 

comparable active site density and lower cost compared 

to pure Pt. The activity enhancement is stable 

over extended periods of time. 

Binary and Ternary Platinum Alloy Catalysts 

California Inst. Technol., US Appl. 2011/0,003,683 

Pt-based alloys containing

doi:10.1595/147106711X570398 


Platinum Apparatus for Producing Glass 

Nippon Electric Glass Co Ltd, Japanese Appl. 2010-228,942 

Glass manufacturing apparatus which reduces the 

formation of bubbles in optical or display glass is 

claimed. A dry coating containing a glass powder and 

a ceramic powder is formed on the outer surface of a 

Pt container. The coated Pt container is then surrounded 

by a refractory layer containing >97 wt% 

Al 2 O 3 and SiO 2 and fired. 

MEDICAL AND DENTAL 

Ruthenium Compounds for Treating Cancer 

Univ. Strasbourg, World Appl. 2011/001,109 

Ru compounds for treating proliferative diseases, in 

particular cancer, are claimed, together with pharmaceutical 

compositions containing the same. Preferred 

compounds include 1 and 2. 

ELECTRICAL AND ELECTRONICS 

World Appl. 2011/001,109 

Gas Discharge Lamp with Iridium Electrode 

Koninklijke Philips Electronics NV, US Appl. 2010/0,301,746 

A gas discharge lamp includes a gas discharge vessel 

filled with S, Se, Te or a compound thereof and an 

electrode assembly in which the electron-emissive 

material is 80–100 wt% Ir optionally alloyed with Ru, 

Os, Rh, Pd or Pt. The Ir-based electrode has a high 

melting point and resists chemical reaction with the 

gas filling, providing a long-lived, efficient, compact 

and high intensity white light source for applications 

such as general and professional illumination. 

O 

O 

N 

N 

Ru 

N 

N 

N 

+ 

– 

PF 6 

1 

+ 

Integrated Rhodium Contacts 

IBM Corp, US Patent 7,843,067 (2010) 

A microelectronic structure contains an interconnect 

barrier layer of Ta, Ti, W, Mo or their nitrides, between 

a Rh contact structure and a Cu interconnect structure. 

Interdiffusion between Rh and Cu is prevented 

and low resistance in microelectronic devices can be 

achieved. 

N 

N 

Ru 

N 

N 

N 

– 

PF 6 

2 


doi:10.1595/147106711X567680 


Flame Spray Pyrolysis: A Unique 

Facility for the Production of 

Nanopowders 

FINAL ANALYSIS 

Flame spray pyrolysis can be used to produce a 

wide array of high purity nanopowders ranging 

from single metal oxides such as alumina to more 

complex mixed oxides, metals and catalysts. The 

technique was first developed by the research group 

of Sotiris E. Pratsinis at ETH Zurich, Switzerland (1). 

Since then it has been used to create new and 

sophisticated materials for catalysis and other 

applications (2). 

Johnson Matthey has developed its own Flame 

Spray Pyrolysis Facility (Figure 1) which produces 

a range of nanopowders using the flame spray pyrolysis 

technique. It has the capacity to produce up to 

100 g h −1 of nanopowder product, depending on the 

material composition, and a number of process variables 

enable the preparation of well-defined target 

materials. 

How it Works 

Flame spray pyrolysis is a one step process in which 

a liquid feed – a metal precursor(s) dissolved in a 

solvent – is sprayed with an oxidising gas into a flame 

zone. The spray is combusted and the precursor(s) 

are converted into nanosized metal or metal oxide 

particles, depending on the metal and the operating 

conditions. The technique is flexible and allows the 

use of a wide range of precursors, solvents and 

process conditions, thus providing control over particle 

size and composition. 

Materials Synthesised 

A range of oxide-based materials have been prepared 

using the technique and some examples are illustrated 

in Table I. Some of these materials find uses 

in catalysis, electronics, thin film applications and 

Fig. 1. Johnson Matthey’s development-scale Flame Spray Pyrolysis Facility, housed at the Johnson 

Matthey Technology Centre, Sonning Common, UK. It offers a unique facility for the production 

for nanopowders 


doi:10.1595/147106711X567680 


Table I 

Properties of Selected Metal Oxides Prepared by Flame Spray Pyrolysis 

Material Particle size a , Specific surface Phase identification 

nm area b , m 2 g −1 

Al 2 O 3 10–15 ~100 Mixture of γ- and δ-Al 2 O 3 

CeO 2 10–15 80–100 Cubic CeO 2 

ZnO 8–15 60–90 Mainly tetragonal ZrO 2 

TiO 2 25 80–100 Mainly anatase and trace of rutile 

Doped TiO 2 30 90–100 Mainly rutile and traces of anatase 

a Determined by TEM analysis 

b Determined by BET analysis 

other areas. Additionally the transferable knowledge 

gained can be applied to the synthesis of pgm catalysts 

and supported pgm catalysts by the flame spray 

method. 

Case Study: A Palladium Catalyst for 

Fine Chemicals Synthesis 

A 2 wt% Pd/Al 2 O 3 catalyst was prepared from an 

organometallic palladium compound and an aluminium 

alkoxide in a organic solvent. The solution 

5 nm 

Fig. 2. Transmission electron microscopy (TEM) image 

of a flame made Pd/Al 2 O 3 catalyst with Pd nanoparticles 

highlighted by red arrows 

was fed into the spray at 5 ml min −1 in an oxygen 

stream of 5 l min −1 . The spray was then combusted 

with a pre-ignited flame of methane/oxygen. The 

resulting product (Figure 2) had a specific surface 

area of 145 m 2 g −1 with a Pd dispersion around 30% as 

determined by CO chemisorption. 

The catalyst was tested in the hydrogenation of 

nitrobenzene to produce aniline, using 0.5 g of 

nitrobenzene in 5 ml of ethanol at 3 bar and 50ºC. Its 

performance was found to be comparable to that of 

commercially available Pd/Al 2 O 3 and Pd/C catalysts. 

This demonstrates that the Pd particles in the flame 

spray samples are well dispersed throughout the support 

and give rise to a high metal surface area available 

for catalysis. 

Study of the effects of the process parameters 

including spray conditions and precursor chemistry 

on catalyst characteristics is ongoing. 

Conclusion 

The flame spray pyrolysis technique allows for the 

preparation of a vast range of materials, including 

metastable phases, due to the rapid quenching 

process. Johnson Matthey has dedicated much effort 

to the application of the technique to the synthesis of 

catalysts. Further scale-up will be critical and work is 

ongoing via an EU funded project aimed at achieving 

a production capacity over 10 kg h −1 .To increase our 

know-how and satisfy other interest areas, more work 

utilising the technique is also ongoing via other EU 

and UK Technology Strategy Board (TSB) funded 

projects. 


doi:10.1595/147106711X567680 


Acknowledgement 

The creation of the development-scale Flame Spray 

Pyrolysis Facility at JMTC, Sonning Common, was 

partly funded by a grant provided by the UK’s former 

Department of Trade and Industry (DTI) under 

its Micro and Nano Technology (“MNT”) Network 

initiative. 

DR BÉNÉDICTE THIÉBAUT 

Johnson Matthey Technology Centre, Blounts Court, 

Sonning Common, Reading RG4 9NH UK 

E-mail: thiebb@matthey.com 

References 

1 R. Strobel, A. Baiker and S. E. Pratsinis, Adv. Powder 

Technol., 2006, 17, (5), 457 

2 R. Strobel and S. E. Pratsinis, Platinum Metals Rev., 

2009, 53, (1), 11 

The Author 

Dr Bénédicte Thiébaut joined Johnson Matthey twelve years ago 

and worked on numerous projects specialising in the last seven 

years in the nanotechnology area. She initially investigated the 

synthesis of nanomaterials by solution routes and turned her 

interest to other methodologies including the flame spray pyrolysis 

(FSP) technique. 


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EDITORIAL TEAM 

Jonathan Butler 

Publications Manager 

Sara Coles 

Assistant Editor 

Margery Ryan 

Editorial Assistant 

Keith White 

Principal Information Scientist 


Platinum Metals Review is the quarterly E-journal supporting research on the science and technology 

of the platinum group metals and developments in their application in industry 

http://www.platinummetalsreview.com/

Platinum Metals Review 

Johnson Matthey Plc, Precious Metals Marketing, Orchard Road, Royston, Hertfordshire SG8 5HE, UK 


http://www.platinummetalsreview.com/

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