Heterogeneously Catalyzed Oxidation Reactions Using ... - CHEC

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Si OH TOF 130 h -1 Ag/HAP CHAPTER 2 H2O H2O SiH (n-Bu) 3SiH Scheme 2‐17: <strong>Oxidation</strong> of aliphatic and aromatic silanes over Ag/HAP [87] and Au/HAP [235]. 2.4 Strengths and opportunities of coinage metals as oxidation catalysts A great deal of the success of gold is certainly connected to the high effort which was put in this field of research. Simple synthesis methods like impregnation are hardly used and achieve poor dispersions [200]. Hence, newly developed more sophisticated synthesis strategies [24] allow tuning of the Au nanoparticles size [239]. This can also be a disadvantage: in addition to the high raw material costs of Au, more sophisticated methods are also more expensive. On the contrary, Cu combines low cost of the metal with a high efficacy of simple synthesis methods like ion‐exchange and coprecipitation. This way also mixed oxides are easily accessible. Due to the often high importance of isolated sites, optimal catalyst loadings can be very low. Silver lies somewhere between these two; though many metallic silver catalysts studied in the open literature were prepared by impregnation, more elaborate techniques usually afforded better catalysts. Potentially due to sintering, calcination times should be chosen with care for silver catalysts [71]. Calcination in air is apparently an important activation step as silver‐oxygen species are formed [73, 74]. As outlined in section 2.2, different catalyst types exist depending e.g. on the oxidation state of the metal. Table 2‐10 gives an overview over the reactivities of the different catalyst types emphasizing that – except for alcohol oxidation – the structural difference between gold and copper is big, gold being metallic and copper in the most cases ionic during the oxidation reaction. This causes a significant difference in reactivity. Both Cu and Au catalysts apparently feature areas where they are dominating. For gold, this would e.g. be the aerobic oxidation of alcohols offering high selectivity and often good reusability while the capability of Cu to generate hydroxyl radicals [170] make it a preferred catalyst material for benzene hydroxylation. Also the other oxidation reactions described 56 Au/HAP H 2O Si OH TOF 40 h -1 (n-Bu) 3Si OH TOF 20 h -1
Table 2-10: <strong>Oxidation</strong> reactions catalyzed by different catalyst types (cf. Figure 2-1) prepared from the coinage metals. Note that the classification of catalysts described by the reviewed literature was not unambiguously possible in some cases. metallic (nano)particles oxidic (nano)particles subsurface-mod. metals (homo)disperse ions mixed oxides MOFs Anaerobic alcohol oxidation Cu Ag Ag Aerobic alcohol oxidation Ag Au Cu Ag Ag Cu Epoxidation Ag Au Cu Cu Ag (Cu) Cu Allylic oxidation Au Ag Cu Cu Ag (Cu) Cu Side-chain oxidation of alkyl aromatic compounds Ag (Au) Cu Ag Cu Cu Cu Cyclohexane oxidation Ag Au Cu Cu Ag Cu Hydroxylation of aromatics Cu Cu (Ag) Amine oxidation Au Hydroquinone oxidation Au Cu Ag (Cu) Cu Sulfide oxidation Ag Silane oxidation Ag Au
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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
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 and 32: 2.3 Selective liquid‐phase oxidat
Page 33 and 34: Table 2-1: Overview over alcohol ox
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: Table 2-9: Oxidation of silanes wit
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 and 114: 3.6 References [29] T. Mitsudome, Y
Page 115 and 116: Chapter 4 Selective Side-Chain Oxid
Page 117 and 118: 4.2 Experimental single‐step flam
Page 119 and 120: 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
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Curriculum Vitae Matthias Josef Bei
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