Heterogeneously Catalyzed Oxidation Reactions Using ... - CHEC

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Table 2-2: <strong>Oxidation</strong> of aliphatic olefins. catalyst [Ox] OH O O + + Entry Catalyst Oxidant Solvent T (°C) Rct. time (h) Conversion Selectivity TOF (h -1 Ox ) Ref. a Ol b On c 1 Au/graphite d O2 1,2,3,5-TMB e 80 24 30% 50% 0% 26% 13 [121] 2 Au/graphite d O2 - 80 72 20% 77% 5% 5% 35 [120] 3 Au/La-OMS O2 - 80 24 48% 2.5% 40% 44% 170 [122] 4a* Au/SiNWs f,g O2 - 80 24 38% h 90% - 7% - [123] 4b* Au/SiNWs f,g O2 - 80 24 93% 0.2% 25% 75% - [123] 5a* Cu/SiNWs f,g O2 - 80 24 98% 0.1% 46% 54% - [123] 5b* Cu/SiNWs f,g O2 - 80 24 28% h 0.2% 25% 75% - [123] 6 Au/CeO2 + Ti-MCM- 41 g,i O2 - 90 5 5.3% j 88% 9.6% 230 k [124] 7* Cu2(OH)PO4 O2 - 80 4 29% 5.0% 27% 39% - [60] 8 Ag-VP-POM/ α-Al2O3 O2 trifluoro -toluene 160 1 20% 50% - - 135 [92] 9* Ag-γ-ZrP TBHP ACN 82 12 96% - 94% - 45 [125] 10 Cu-Nb2O5 TBHP ACN 60 - 14% 1.8% 2.2% 80% n.a. [126] 11* Cu3(BTC)2 TBHP ACN 50 20 50% ~ 60% - ~ 40% n.a. [127] 12* [Cu(H2btec)(bipy)]∞ TBHP DCE 75 24 65% 73% 7.7% 19% 110 [42] *No standard use reported. a Cyclohexene oxide. b Cyclohexenol. c Cyclohexenone. d Catalytic amounts of TBHP added. e Tetramethylbenzene. f Si-nanowires. g h i j k AiBN as initiator. Cis-cyclooctene as substrate. Cumene added. 1-octene as substrate. Based on the amount of Au.
2.3 Selective liquid‐phase oxidation reactions Cu2(OH)PO4 and Cu4O(PO4)2 were investigated as catalysts in O2 atmosphere at 80 °C for cyclohexene oxidation [60, 128]. A selectivity to the epoxide around 5 % for cyclohexene was found, products resulting mainly from allylic oxidation. The reaction proceeded faster with acetonitrile solvent. EPR investigations proved the presence of ∙OH radicals under reaction conditions. On the contrary, Cu/Al2O3 synthesized via impregnation was catalytically inactive for the aerobic oxidation of cyclohexene [49]. Cu catalysts obtained by impregnation feature mainly CuxO particles which might be responsible for the low activity. Aerobic epoxidation was also investigated with silver as metallic nanoparticles on a V‐containing polyoxometalate (H5PV2Mo10O40) which itself was supported on α‐ Al2O3 (Table 2‐2, entry 8) [92]. Under the harsh reaction conditions (160 °C) the catalyst deactivated rapidly. The catalyst epoxidized numerous aliphatic olefins with yields between 5‐66 %. Cyclohexene was converted with 50 % selectivity (entry 8). No primary allylic oxidation products were found. In the absence of a catalylst, the conversion was roughly the same, but peroxide formation was not detected. Milder conditions are necessary when using peroxides as oxidants; silver‐ion exchanged γ‐ZrP (Table 2‐2, entry 9) catalyzed cyclohexene oxidation with TBHP in acetonitrile to cyclohexanol [125]. Cu‐modified mesoporous Nb2O5 was used for TBHP‐epoxidation of cyclohexene in ACN [126]. Cu‐ doped Nb2O5 was more active (entry 10) than Cu‐loaded Nb2O5 exhibiting about the same conversion as unmodified Nb2O5. However, both Cu catalysts showed a high selectivity to cyclohexenone (70‐80 %), the epoxide being only a minor side product (selectivity
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 and 32: 2.3 Selective liquid‐phase oxidat
Page 33 and 34: Table 2-1: Overview over alcohol ox
Page 41: 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.
Page 91 and 92: 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
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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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