Heterogeneously Catalyzed Oxidation Reactions Using ... - CHEC

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CHAPTER 6 Figure 6‐3: Epoxidation of styrene with the Co‐based metal‐organic framework material STA‐12(Co) with (■) styrene conversion (□) styrene oxide selectivity, (●) benzaldehyde selectivity, (○) benzoic acid selectivity. Reaction conditions: 2.0 mmol styrene, 100 mg biphenyl, 30 mL DMF, 50 mL min ‐1 O2, 2.0 mg STA‐12(Co), 100 °C. was found. Note that the formation of a slightly higher amount of FMF in the case of styrene epoxidation took only 5 h. Apparently, FMF formation depends on the type of olefin and correlates with the conversion. FMF was also formed in the absence of a substrate but in significantly lower amounts. The selectivity to trans‐stilbene oxide was close to 90 % and a low selectivity towards benzaldehyde of ca. 5 % was found assuming that two molecules of benzaldehyde are formed from one (E)‐stilbene molecule. Co3O4 also exhibited some catalytic activity (Table 6‐1) while essentially no product formation was found in the absence of a catalyst. An analogous mixed metal STA‐12(Co,Ni) (in 1:3 ratio) was virtually not catalytically active (3 % conversion after 12 h) suggesting that the organic backbone of the MOF is inactive. In comparison to the (E)‐isomer, (Z)‐stilbene was epoxidized very slowly giving also trans‐stilbene oxide (cf. Table 6‐3, entry1). Isomerization of (Z)‐ to (E)‐stilbene was not observed. In order to assess its stability, the catalyst was tested for reusability. Some deactivation was observed that caused mainly a longer induction phase 160
6.3 Results Figure 6‐4: Epoxidation of (E)‐stilbene over STA‐12(Co) with (■) (E)‐stilbene conversion, (Δ) trans‐stilbene oxide selectivity, (●) benzaldehyde selectivity. Reaction conditions: 2.0 mmol (E)‐stilbene, 100 mg biphenyl, 30 mL DMF, 50 mL min ‐1 O2, 2.0 mg STA‐12(Co), 100 °C. Table 6‐1: Aerobic epoxidation of (E)‐stilbene in DMF. Reaction conditions: 2.0 mmol (E)‐stilbene, 6.8 µmol Co, 100mg biphenyl, 30 mL DMF, 50 mL min ‐1 O2. Catalyst Time (h) Conversion (%) Selectivity (%) ‐ 10
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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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Table 2-7: Aerobic oxidation of ami
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Table 2-8: Oxidation of hydroquinon
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Table 2-9: Oxidation of silanes wit
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Table 2-10: Oxidation reactions cat
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2.4 Strengths and opportunities of
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2.6 References 2.6 References [1] M
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2.6 References [56] H. Tumma, N. Na
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2.6 References [113] C. Keresszegi,
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2.6 References [169] Q. Zhu, Y. Lia
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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
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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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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
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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)
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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
Page 165 and 166: 5.6 References [29] I. Tsivintzelis
Page 167 and 168: 6.1 Introduction 6.1 Introduction A
Page 169 and 170: 6.2 Experimental [38]. In a typical
Page 171 and 172: 6.3 Results out in 1 mm quartz tube
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Page 177 and 178: 6.3 Results Figure 6‐6: Compariso
Page 179 and 180: 6.3 Results Figure 6‐8: Influence
Page 181 and 182: 6.3 Results investigated the epoxid
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Page 185 and 186: 6.3 Results Figure 6‐11: EXAFS an
Page 187 and 188: 6.4 Discussion would need to be for
Page 189 and 190: 6.5 Conclusions Formation of the ep
Page 191 and 192: 6.6 References [28] J. Perles, N. S
Page 193 and 194: Chapter 7 Concluding Remarks 7.1 Co
Page 195 and 196: 7.2 Final remarks and outlook speci
Page 197 and 198: Acknowledgements Acknowledgements T
Page 199: Curriculum Vitae Matthias Josef Bei
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