Heterogeneously Catalyzed Oxidation Reactions Using ... - CHEC

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CHAPTER 3 [60] Z.P. Qu, M.J. Cheng, W.X. Huang, X.H. Bao, J. Catal. 229 (2005) 446. [61] M. Caravati, J.‐D. Grunwaldt, A. Baiker, Phys. Chem. Chem. Phys. 7 (2005) 278. [62] C. Keresszegi, T. Burgi, T. Mallat, A. Baiker, J. Catal. 211 (2002) 244. [63] A. Abad, A. Corma, H. Garcia, Chem. Eur. J. 14 (2008) 212. [64] J.‐D. Grunwaldt, M. Caravati, A. Baiker, J. Phys. Chem. B 110 (2006) 25586. [65] P. Fristrup, L.B. Johansen, C.H. Christensen, Catal. Lett. 120 (2008) 184. [66] A.N. Pestryakov, Catal. Lett. 28 (1996) 239. [67] A.N. Pestryakov, N.E. Bogdanchikova, A. Knop‐Gericke, Catal. Today 91‐92 (2004) 49. [68] P.R. Sarode, K.R. Priolkar, P. Bera, M.S. Hegde, S. Emura, R. Kumashiro, Mater. Res. Bull. 37 (2002) 1679. [69] S. Imamura, H. Yamada, K. Utani, Appl. Catal. A 192 (2000) 221. [70] K. Ebitani, H.‐B. Ji, T. Mizugaki, K. Kaneda, J. Mol. Catal. A 212 (2004) 161. [71] L. Kundakovic, M. Flytzani‐Stephanopoulos, J. Catal. 179 (1998) 203. [72] A. Trovarelli, G.J. Hutchings (Ed.), “Catalysis by ceria and related materials”, Imperial College Press, London, 2002. [73] T. Burgi, M. Bieri, J. Phys. Chem. B 108 (2004) 13364. [74] C. Keresszegi, D. Ferri, T. Mallat, A. Baiker, J. Phys. Chem. B 109 (2005) 958. [75] C. Mondelli, D. Ferri, J.‐D. Grunwaldt, F. Krumeich, S. Mangold, R. Psaro, A. Baiker, J. Catal. 252 (2007) 77. 100
Chapter 4 Selective Side-Chain <strong>Oxidation</strong> of Alkyl Aromatic Compounds <strong>Catalyzed</strong> by Cerium Modified Silver Catalysts Abstract Silver supported on silica was found to effectively catalyze the aerobic side‐chain oxidation of alkyl aromatic compounds under solvent‐free conditions. Toluene, p‐ xylene, ethylbenzene and cumene were investigated as model substrates. Typically, the reaction was performed at ambient pressure; only for toluene an elevated pressure was required. Carboxylic acids, such as benzoic acid or p‐ Flame made silver catalysts. toluic acid, additionally increased the reaction rate while CeO2 could act both as a promoter and an inhibitor depending on the substrate and the reaction conditions. Silver catalysts were prepared both by standard impregnation and flame spray pyrolysis. Addition of a Ce precursor to the FSP catalyst resulted in significantly smaller silver particles. Ce‐ doped FSP catalysts in general exhibited higher catalytic performance with TONs up to 2000 except for cumene oxidation that appeared to proceed mainly by homogeneous catalysis. In addition, flame‐ made catalysts were more stable against silver leaching compared to the impregnated catalysts. The structure of the silver catalysts was studied in detail both by X‐ray absorption spectroscopy and transmission electron microscopy suggesting metallic silver to be required for catalytic activity. Catalytic studies point to a radical mechanism which differs depending on the type of substrate. 101
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TECHNICAL UNIVERSITY OF DENMARK (DT
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Preface The present dissertation su
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the carboxylic acid, ceria inhibite
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Resume Denne afhandling giver indle
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hvorimod mængden af katalysator ku
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2.3.8 Oxidation of sulfides .......
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5.3.5 Macroscopic mass transport in
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Chapter 1 Introduction With its gre
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1. Introduction Scheme 1‐1: High
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1. Introduction Figure 1‐2: Phase
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1. Introduction [28] S. Bawaked, N.
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2.1 Introduction 2.1 Introduction E
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2.2.1 Synthesis of gold catalysts 2
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2.2 Catalyst synthesis for oxidatio
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2.2 Catalyst synthesis for oxidatio
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2.3 Selective liquid‐phase oxidat
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Table 2-1: Overview over alcohol ox
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Ph O O Ph (4) (5) 2.3 Selective liq
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Table 2-4: Side-chain oxidation of
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2.3.4 Oxidation of cyclohexane 2.3
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Table 2-5: Oxidatin of cyclohexane.
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Table 2-6: Ring hydroxylation of ar
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Page 63 and 64: Table 2-7: Aerobic oxidation of ami
Page 65 and 66: Table 2-8: Oxidation of hydroquinon
Page 67 and 68: 2.3 Selective liquid‐phase oxidat
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.
Page 91 and 92: Chapter 3 Selective Liquid-Phase Ox
Page 93 and 94: 3.2 Experimental 3.2.1 Catalyst pre
Page 95 and 96: 3.3 Results Scattering amplitudes a
Page 97 and 98: Absorption (a.u.) 1.2 1.0 0.8 0.6 0
Page 99 and 100: Conversion (%) 100 90 80 70 60 50 4
Page 101 and 102: 3.3 Results Figure 3‐5: In situ X
Page 103 and 104: 3.3 Results Table 3‐2: Conversion
Page 105 and 106: 3.3 Results In order to gain insigh
Page 107 and 108: 3.3 Results the cost of selectivity
Page 109 and 110: 3.4 Discussion synergetic interacti
Page 111 and 112: 3.5 Conclusions to corroborate the
Page 113: 3.6 References [29] T. Mitsudome, Y
Page 117 and 118: 4.2 Experimental single‐step flam
Page 119 and 120: 4.2 Experimental alcohol (Aldrich,
Page 121 and 122: 4.3 Results Scheme 4‐1: Oxidation
Page 123 and 124: 4.3 Results Figure 4‐2: Formation
Page 125 and 126: 4.3 Results oxidation by either 2,6
Page 127 and 128: Absorption (a.u.) Absorption (a.u.)
Page 129 and 130: 4.3 Results atomic mixing of Ag and
Page 131 and 132: 4.3 Results Figure 4‐7: Influence
Page 133 and 134: 4.4 Discussion and mechanistic cons
Page 135 and 136: 4.5 Conclusions heterogeneous radic
Page 137 and 138: 4.6 References [29] S.I. Zabinsky,
Page 139 and 140: Chapter 5 Experimental Determinatio
Page 141 and 142: 5.2 Experimental The most important
Page 143 and 144: 5.2 Experimental Eurotherm 2216e te
Page 145 and 146: Figure 5-1: Schematic view of the e
Page 147 and 148: (Eq. 5‐5) AB i j ε AB i j β 5.2
Page 149 and 150: (a) (b) (c) (d) (e) (f) (g) (h) (i)
Page 151 and 152: 5.3 Results two association sites o
Page 153 and 154: Pressure (bar) 150 145 140 135 5.3
Page 155 and 156: 5.3 Results Figure 5‐7: Oxidation
Page 157 and 158: Weight (g) 5.3 Results Figure 5‐8
Page 159 and 160: 5.4 Discussion catalytic reactions
Page 161 and 162: 5.4 Discussion corresponding CO2‐
Page 163 and 164: 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
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Curriculum Vitae Matthias Josef Bei
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