Heterogeneously Catalyzed Oxidation Reactions Using ... - CHEC

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CHAPTER 2 amount of transition metal. Thus, metal dispersions etc. will not be taken into account as these data are only rarely available. Especially in oxidation catalysis, the meaning of a TOF as a microkinetic description of chemical processes at the active site is limited since the nature of the active site is often unknown and, even more, many oxidation reactions are at the origin of a radical autoxidation which was merely induced by the transition metal catalyst. Thus, the TOF will function primarily as a performance comparison. TOFs presenting essentially a reaction rate are highly dependent on the experimental conditions, varying greatly for the same reaction when measured at high or low conversion. Thus, the respective tables will not only give TOFs but also the conversions at which these were obtained. 2.3.1 Alcohol oxidation Scheme 2‐2: Schematic overview over the covered oxidation reactions. The oxidation of alcohols with molecular oxygen has been intensively studied in the recent years with a great interest in gold catalysis and is described extensively in a number of reviews [5, 6, 95]. The strength of gold catalysts compared to e.g. Pt group members is the high selectivity to the 18
Table 2-1: Overview over alcohol oxidation reactions. R 1 Entry Catalyst Substrate Product Oxidant Solvent T (°C) Rct. time (h) Conversion Selectivity TOF (h -1 ) Reference 1 8%Cu/SiO2 3-octanol 3-octanone - toluene 90 20 100% 100% 0.3 [100] 2 8%Cu/Al2O3 3-octanol 3-octanone styrene toluene 90 1.5 100% 100% 4 [101] 3 8%Cu/Al2O3 carveol carvone styrene toluene 90 1.5 100% 95% 3.5 [101] 4 7%Cu/MgO 1-octanol octanal styrene mesitylene 150 3 58% >99% 1.7 [51] 5 8%Cu/La2O3 1-octanol octanal styrene mesitylene 150 2 63% 100% 2.4 [53] 6 CuAl/HT 7 CuAl/HT benzyl alcohol + benzamine benzyl alcohol + pnitro-benzamine dibenzyl amine - - 150 14 72% c - 1.3 [102] N-benzyl-N-(4nitrophenyl)amine - - 160 9 98% c - 2.7 [102] 8 Cu/HT cyclooctanol cyclooctanone - - 180 8 85% c - 390 [52] 9 Ag/HT benzyl alcohol benzaldehyde - xylene 130 24 >99% 90% 250 [86] 10 5%Ag/Al2O3 benzyl alcohol benzaldehyde - toluene 111 24 100% 82% 2.1 [67] 11 Cu-OMS-2 2-propanol acetone O2 water 55 3 40% Ca. 50% - [84] 12 CuxMnyOz /Al2O3 benzyl alcohol benzaldehyde O2 toluene 100 4 91% 99% 0.8 [61] 13a CuO 1-phenylethanol acetophenone O2 - 200 1 78% 100% 1.6 [103] 13b CuO/Y 1-phenylethanol (E)-1,2-dimethylstilbene O2 - 200 1 100% 85% 2.1 [103] 14* Cu0.4Co0.6Fe2O4 benzyl alcohol benzaldehyde H2O2 ACN 60 8 80% 98% - [104] 15 CuCr/LDH (layered double OH) benzyl alcohol benzaldehyde TBHP - 94 5 51% 75% - [105] 16 Cu-Al-HT/BINOL d benzyl alcohol benzaldehyde O2 - RT 10 99% c - - [106] 17 0.5% Ag-zeolite 2-propanol acetone O2 water 55 5 30% 80% - [84] 18 0.6%Ag/pumice benzyl alcohol benzaldehyde O2 ACN 75 - - - 0.5 [69] 19 10%Ag/SiO2 + CeO2 benzyl alcohol benzaldehyde O2 xylene 140 2 98% 95% 21 [71] 20 Ag-V-MPA cinnamyl alcohol cinnamaldehyde O2 toluene 90 10 93% c - 1.2 [94] 21 2%Ag/Al2O3 + TEMPO MGP MGPA b PDS water 25 15 78% 99% 8 [107] 22 OH catalyst R 2 CuCl2-SILP-SiO2 + TEMPO O [Ox] R 1 R 2 benzyl alcohol benzaldehyde O2 dibutyl-ether 65 14 99% 99% 1.4 [108] *No standard use reported. a Methyl-α-D-glucopyranoside. b Methyl-α-D-glucopyrasiduronic acid. c Yield. d K2CO3 added.
Page 1 and 2: TECHNICAL UNIVERSITY OF DENMARK (DT
Page 3 and 4: Preface The present dissertation su
Page 5 and 6: the carboxylic acid, ceria inhibite
Page 7 and 8: Resume Denne afhandling giver indle
Page 9 and 10: hvorimod mængden af katalysator ku
Page 11 and 12: 2.3.8 Oxidation of sulfides .......
Page 13 and 14: 5.3.5 Macroscopic mass transport in
Page 15 and 16: Chapter 1 Introduction With its gre
Page 17 and 18: 1. Introduction Scheme 1‐1: High
Page 19 and 20: 1. Introduction Figure 1‐2: Phase
Page 21 and 22: 1. Introduction [28] S. Bawaked, N.
Page 23 and 24: 2.1 Introduction 2.1 Introduction E
Page 25 and 26: 2.2.1 Synthesis of gold catalysts 2
Page 27 and 28: 2.2 Catalyst synthesis for oxidatio
Page 29 and 30: 2.2 Catalyst synthesis for oxidatio
Page 31: 2.3 Selective liquid‐phase oxidat
Page 35 and 36: 2.3 Selective liquid‐phase oxidat
Page 45 and 46: Ph O O Ph (4) (5) 2.3 Selective liq
Page 51 and 52: Table 2-4: Side-chain oxidation of
Page 53 and 54: 2.3.4 Oxidation of cyclohexane 2.3
Page 55 and 56: Table 2-5: Oxidatin of cyclohexane.
Page 59 and 60: Table 2-6: Ring hydroxylation of ar
Page 63 and 64: Table 2-7: Aerobic oxidation of ami
Page 65 and 66: Table 2-8: Oxidation of hydroquinon
Page 69 and 70: Table 2-9: Oxidation of silanes wit
Page 71 and 72: Table 2-10: Oxidation reactions cat
Page 73 and 74: 2.4 Strengths and opportunities of
Page 81 and 82: 2.6 References 2.6 References [1] M
Page 83 and 84:
2.6 References [56] H. Tumma, N. Na
Page 85 and 86:
2.6 References [113] C. Keresszegi,
Page 87 and 88:
2.6 References [169] Q. Zhu, Y. Lia
Page 89 and 90:
2.6 References [223] M. Fetizon, M.
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Chapter 3 Selective Liquid-Phase Ox
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3.2 Experimental 3.2.1 Catalyst pre
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3.3 Results Scattering amplitudes a
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Absorption (a.u.) 1.2 1.0 0.8 0.6 0
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Conversion (%) 100 90 80 70 60 50 4
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3.3 Results Figure 3‐5: In situ X
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3.3 Results Table 3‐2: Conversion
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3.3 Results In order to gain insigh
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3.3 Results the cost of selectivity
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3.4 Discussion synergetic interacti
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3.5 Conclusions to corroborate the
Page 113 and 114:
3.6 References [29] T. Mitsudome, Y
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Chapter 4 Selective Side-Chain Oxid
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4.2 Experimental single‐step flam
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4.2 Experimental alcohol (Aldrich,
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4.3 Results Scheme 4‐1: Oxidation
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4.3 Results Figure 4‐2: Formation
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4.3 Results oxidation by either 2,6
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Absorption (a.u.) Absorption (a.u.)
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4.3 Results atomic mixing of Ag and
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4.3 Results Figure 4‐7: Influence
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4.4 Discussion and mechanistic cons
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4.5 Conclusions heterogeneous radic
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4.6 References [29] S.I. Zabinsky,
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Chapter 5 Experimental Determinatio
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5.2 Experimental The most important
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5.2 Experimental Eurotherm 2216e te
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Figure 5-1: Schematic view of the e
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(Eq. 5‐5) AB i j ε AB i j β 5.2
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(a) (b) (c) (d) (e) (f) (g) (h) (i)
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5.3 Results two association sites o
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Pressure (bar) 150 145 140 135 5.3
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5.3 Results Figure 5‐7: Oxidation
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Weight (g) 5.3 Results Figure 5‐8
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5.4 Discussion catalytic reactions
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5.4 Discussion corresponding CO2‐
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5.5 Conclusions 5.5 Conclusions The
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5.6 References [29] I. Tsivintzelis
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6.1 Introduction 6.1 Introduction A
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6.2 Experimental [38]. In a typical
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6.3 Results out in 1 mm quartz tube
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6.3 Results Figure 6‐2: Structure
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6.3 Results Figure 6‐4: Epoxidati
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6.3 Results Figure 6‐6: Compariso
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6.3 Results Figure 6‐8: Influence
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6.3 Results investigated the epoxid
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6.3 Results Figure 6‐10: Co‐epo
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6.3 Results Figure 6‐11: EXAFS an
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6.4 Discussion would need to be for
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6.5 Conclusions Formation of the ep
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6.6 References [28] J. Perles, N. S
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Chapter 7 Concluding Remarks 7.1 Co
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7.2 Final remarks and outlook speci
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Acknowledgements Acknowledgements T
Page 199:
Curriculum Vitae Matthias Josef Bei
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