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[½»Á÷] ¡¾×ÊÔ´¡¿Chem Rev 09×îÐÂ×ÛÊöCatalytic Oxidations in Dense Carbon Dioxide

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Catalytic Oxidations in Dense Carbon Dioxide†
Tsunetake Seki‡ and Alfons Baiker*
Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Ho¡§nggerberg,
HCI, CH-8093 Zurich, Switzerland


http://www.namipan.com/d/Catalyt ... 60ff64c3f1f031d3400


Contents
1. Introduction 2409
2. Properties of Carbon Dioxide-Molecular Oxygen
Mixtures
2410
2.1. Phase Behaviors 2410
2.1.1. Critical Constants of the CO2-O2 Mixtures 2410
2.1.2. Phase Behaviors of the Reacting Systems 2411
2.2. Reaction of Carbon Dioxide with Molecular
Oxygen
2411
3. Aerobic Oxidation of Alcohols 2412
3.1. Supported Palladium and Platinum Catalysts 2412
3.1.1. Batch Reactor Investigations 2412
3.1.2. Continuous-Flow-Reactor Investigations 2415
3.2. Supported Ruthenium Catalysts 2424
3.2.1. Modified Silica-Captured
Tetrapropylammonium Perruthenate
(TPAP)
2424
3.2.2. Silica-Supported Ionic Liquids Doped with
Perruthenate
2427
3.3. Other Heterogeneous Catalysts 2428
3.3.1. Chromium-Containing Molecular Sieves 2428
3.3.2. Supported Gold 2428
3.3.3. Supported Multi-Metals 2429
3.3.4. Supported Iron Oxide 2429
3.3.5. Polyoxometalate 2429
3.4. Enzyme Catalysis 2431
3.5. Photocatalytic Oxidations 2431
4. Aerobic Oxidation of Phenols 2432
4.1. Cobalt Complex Catalysts 2432
4.2. Enzyme Catalysis 2434
5. Oxidation of Alkenes 2434
5.1. Metal Complex Catalysts 2434
5.1.1. Molybdenum-Based Catalysts 2434
5.1.2. Vanadium- and Titanium-Based Catalysts 2436
5.1.3. Palladium(II) Chloride 2436
5.1.4. Iron-Based Catalysts 2438
5.1.5. Manganese-Based Catalysts 2440
5.2. Supported Metal Catalysts 2440
5.2.1. Catalytically Active Wall of a
Stainless-Steel Reactor
2440
5.2.2. Supported Palladium 2440
5.2.3. Supported Multi-Metals 2440
6. Oxidation of Alkanes Including Alkylaromatic
Compounds
2442
6.1. Catalyst-Free Autocatalytic Aerobic Oxidations 2442
6.2. Metal Complex Catalysts 2443
6.2.1. Iron(III) Porphyrins 2443
6.2.2. Cobalt(II) Fluorinated Acetate 2443
6.3. Heterogeneous Catalysts 2444
6.3.1. Catalytically Active Wall of a
Stainless-Steel Reactor
2444
6.3.2. Supported Cobalt Oxides 2445
6.3.3. Other Heterogeneous Catalysts 2447
7. Oxidation of Other Compounds 2448
7.1. Oxidation of Sulfides 2448
7.2. Oxidation of Pyridine 2449
8. Potential and Limitations of Dense CO2 as a
Medium for Catalytic Oxidations
2449
8.1. Catalysts 2449
8.1.1. Supported Metals and Oxides 2449
8.1.2. Metal Complexes and TPAP 2450
8.1.3. Enzymes 2451
8.2. Effect of Tunable Physical Properties of
Dense CO2
2451
8.2.1. Extraction and Mass and Heat Transfer 2451
8.2.2. Phase Behavior 2451
8.3. Facilitated Separation Process 2452
9. Concluding Remarks 2452
10. Abbreviations 2453
11. Acknowledgments 2453
12. References 2453

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