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Tailored Metal Catalysts

'Catalysis by Metal Complexes'. 1986. Auflage. Book. …
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Titel: Tailored Metal Catalysts

ISBN: 9027718660
EAN: 9789027718662
'Catalysis by Metal Complexes'.
1986. Auflage.
Book.
Sprache: Englisch.
Herausgegeben von Y. Iwasawa
Springer Netherlands

31. Dezember 1985 - gebunden - 346 Seiten

Well tailored metal catalysts are catalysts of the new generation resulting from scientific development at the boundary between homogeneous and hetero­ geneous chemistry. The main factors involved in making tailored metal catalysts are not those of traditional impregnation in which the chemistry is in general unknown and ill-defined, or of simple ion exchange which involves long-range forces with little control on the local structure through definite and special bond direction. Tailored Metal Catalysts thus has a rather different emphasis from normal review publications in the field of catalysis. Here we concentrate more on the distinct surface chemistry and catalytic properties of important established materials with well-characterized active structures or precursors, although at the same time providing a systematic presentation of relevant data. Many pioneering works have been undertaken in the field of tailored metal catalysts since the early research on polymer-attached homogeneous metal complexes by the British Petroleum Company Ltd. and the Mobil Oil Corpora­ tion around 1969; transition metal complexes attached on polymers by Grubbs (1971), Heinemann (1971), Manassen (1971), Pittman (1971), Bursian et al. (1972), Kagan (1973), Bailar (1974); transition metal complexes attached on inorganic oxides by Allum et al. (1972), Ballard (1973), Candlin and Thomas (1974), Murrell (1974), Yermakov (1974); metal carbonyls/polymers by Moffat (1970); metal carbonyls/inorganic oxides by Parkyns (1965), Davie et al. (1969), Banks et al. (1969), Howe (1973), Burwell (1975); metal carbonyl clusters/ polymers by Colhnan (1972); metal carbonyl clusters/inorganic oxides by Robertson and Webb (1974), Anderson (1974), Smith et al. (1975).
Inorganic Oxide-attached Metal Catalysts.
- 1. Introduction.
- 2. General Features of Homogeneous and Heterogeneous Catalysts.
- 3. General Aspects of the Development of Attached Metal Catalysts.
- 3.1. First Generation Attached Catalysts.
- 3.2. Second Generation Attached Catalysts.
- 3.3. Third Generation Attached Catalysts.
- 4. Physical Techniques for the Characterization of Surface-attached Species.
- 5. Polymers and Inorganic Oxides as Supports.
- 6. Surface Hydroxyl Groups on Inorganic Oxides.
- 6.1. Silica.
- 6.2. Alumina.
- 6.3. Silica-alumina.
- 6.4. Zeolites.
- 6.5. Titania.
- 6.6. Other Inorganic Oxides.
- 7. The Functionalization of Inorganic Oxide Surfaces.
- 7.1. Silica.
- 7.2. Alumina and Zeolites.
- 7.3. Stannic Oxide and Carbon.
- 8. Attached Metal Complex Catalysts.
- 8.1. Metal Complexes Attached via Functional Ligands.
- 8.2. Transition Metal Complexes Attached Directly to Inorganic Oxide Surfaces.
- 9. Tailored Metal Catalysts.
- 9.1. Multistep Attached Metal Catalysts.
- 9.2. Transition Metal Hydride Catalysts.
- 9.3. Attached Metal Oxide Catalysts.
- 9.3.1. Surface Molybdenum Monomers.
- 9.3.2. Surface Molybdenum Dimers.
- 9.3.3. Oriented Mo03 Phases on Graphite.
- 9.3.4. Surface Chromium Monomers and Dimers.
- 9.3.5. Two-dimensional Surface CrIII Phase Attached onto SiO2.
- 9.3.6. Attached Tungsten Monomers.
- 9.3.7. Surface Cobalt Species.
- 10. Concluding Remarks.- References.- Polymer-attached Catalysts.
- 1. Introduction.
- 2. Polymer-anchored Catalysts.
- 2.1. Preparation and Characterization.
- 2.2. The Influence of the Polymer Matrix on Catalysis.
- 2.2.1. Isolation of Active Sites.
- 2.2.2. Promotion of Coordinative Unsaturation.
- 2.2.3. Concentration of the Ligand.
- 2.2.4. Stabilization of Catalysts.
- 2.2.5. Effect of Substrate Size and Shape on Selectivity.
- 2.3. Effect of the Polymer 'Field'.
- 2.3.1. Hydrophobic 'Field'.
- 2.3.2. Electrostatic 'Field'.
- 2.3.3. Asymmetric 'Field'.
- 2.4. Multifunctional Catalysts.
- 2.4.1. Cooperative Catalysis.
- 2.4.2. Multistep Catalysis.
- 3. Polymer-protected Colloidal Catalysts.
- 3.1. Preparation and Characterization.
- 3.2. Characteristic Properties of Colloidal Catalysts.
- 3.2.1. Surface Area.
- 3.2.2. Particle Size.
- 3.2.3. Effect of Protective Polymers.
- 3.3. Colloidal Catalysts Protected by Functionalized Polymers.
- 4. Concluding Remarks.- References.- The Preparation of Heterogeneous Catalysts from Mononuclear Carbonyl Complexes on Inorganic Supports.- General Aspects of Catalyst Preparation.
- 2.1. Support Materials.
- 2.1.1. Silica.
- 2.1.2. Alumina.
- 2.1.3. Zeolites.
- 2.1.4. Other Supports.
- 2.2. Introduction of the Carbonyl Complex.
- 2.3. Catalyst Activation.
- 3. Group VI Carbonyl Complexes.
- 3.1. Preparation and Characterization.
- 3.1.1. Mo(CO)6-Alumina.
- 3.1.2. Cr(CO)6-Alumina.
- 3.1.3. W(CO)6-Alumina.
- 3.1.4. Mo(CO)6-Silica.
- 3.1.5. Cr(CO)6-Silica.
- 3.1.6. W(CO)6-Silica.
- 3.1.7. Mo(CO)6-Zeolite Y.
- 3.1.8. Cr(CO)6-Zeolite Y.
- 3.1.9. W(CO)6-Zeolite Y.
- 3.1.10. Mo(CO)6-Magnesia.
- 3.1.11. Cr(CO)6- and W(CO)6 Magnesia.
- 3.2. Catalytic Properties.
- 3.2.1. Olefin Metathesis.
- 3.2.2. Olefin Polymerization.
- 3.2.3. Olefin Hydrogenation.
- 3.2.4. Hydrogenolysis of Alkanes.
- 3.2.5. Deuterium Exchange Reactions.
- 3.2.6. Hydrogenation of Carbon Monoxide.
- 3.2.7. Hydrodesulphurization.
- 4. Group VIII Carbonyl Complexes.
- 4.1. Preparation and Characterization.
- 4.1.1. Fe(CO)5-Alumina.
- 4.1.2. Fe(CO)5-Magnesia.
- 4.1.3. Fe(CO)5-Zeolite Y.
- 4.1.4. Fe(CO)5-Graphite.
- 4.1.5. Ni(CO)4-Alumina.
- 4.1.6. Ni(CO)4-Zeolite.
- 4.2. Catalytic Properties.
- 5. Group V Carbonyl Complexes.
- 6. Concluding Remarks.
- 7. Literature Update.- References.- Surface-supported Metal Clusters and their Catalysis in CO-based Reactions.
- 1. Introduction.
- 2. Preparation and Characterization of Surface-supported Metal Clusters.
- 2.1. Rhodium and Platinum Carbonyl Clusters Impregnated on Metal Oxides.
- 2.2. Ruthenium, Osmium and Iridium Carbonyl Clusters Impregnated on Metal Oxides.
- 2.3. Iron, Cobalt and Nickel Carbonyl Clusters Impregnated on Metal Oxides.
- 2.4. Zeolite-entrapped Cluster Catalysts.
- 2.5. Reactivity and Catalysis of Surface-supported Metal Cluster Species.
- 2.6. Bimetallic Clusters Impregnated on Metal Oxides.
- 3. Selectivity Aspects of Fischer-Tropsch (F-T) Synthesis with Supported Metal Carbonyls.
- 4. Carbonylation Reactions Catalyzed by Cluster-impregnated Catalysts.
- 4.1. Activities and Selectivities in Ethylene and Propylene Hydro- formylation Catalyzed by Cluster-derived Catalysts from Different Carbonyl Clusters on Zinc Oxide.
- 4.2. Effect of Metal Oxide Support on Catalytic Behavior of Rhodium Clusters.
- 4.3. Bimetallic Rhodium-Cobalt and Cobalt Carbonyl Clusters Supported on Zinc Oxide and Carbon.
- 5. Synthesis of Oxygenated Carbon Compounds from Synthesis Gas.
- 5.1. Rhodium Carbonyl Cluster-derived Catalysts in CO-H2 Reactions.
- 5.2. The Role of Bifunctional Metal Oxides in Modifying the Formation of Oxygenated Species by Rhodium Cluster-impregnated Catalysts.
- 5.3. Bimetallic Rh-Co Cluster-derived Catalysts in CO-H2 Conversion.
- 5.4. Methanol Synthesis by Rhodium, Platinum and Iridium Cluster-impregnated Catalysts.- References.- Asymmetrically Modified Nickel Catalysts.
- 1. Introduction.
- 2. General Considerations in Reactions Relating to MNi.
- 2.1. Stereo-differentiating Reactions.
- 2.2. Catalysts for Enantio-differentiating Hydrogenation Reactions.
- 3. MNi as a Practical Enantio-differentiating Hydrogenation Catalyst.
- 3.1. Development and Improvement of Catalyst and Reaction Conditions.
- 3.1.1. The Discovery of MNi.
- 3.1.2. Modification Variables.
- 3.1.3. Preparation Variables of the Metal Catalyst.
- 3.1.4. Reaction Variables.
- 3.1.5. Supplementary Modifying Reagents.
- 3.1.6. Preparation of TA-NaBr-MRNi and its Use for the Hydrogenation of MAA.
- 3.2. Application of MNi for the Preparation of Optically Pure Materials.
- 3.2.1. Hydrogenation of ?-Ketoester.
- 3.2.2. Hydrogenation of ?-Diketones.
- 3.2.3. Hydrogenation of Miscellaneous Carbonyl Compounds.
- 4. MNi, its Structure and Mode of Action.
- 4.1. Enantio-differentiating and Hydrogenation Steps in the Reaction Path.
- 4.2. Mode of Adsorption of Modifying Reagent on Nickel Catalysts.
- 4.2.1. ?-Hydroxy Acids.
- 4.2.2. ?-Amino Acids.
- 4.3. Enantio-differentiating and Non-enantio-differentiating Sites on MNi.
- 4.3.1. Surface Condition of Catalyst and Proportion of Enantio-differentiating Sites.
- 4.3.2. Control of Non-enantio-face Differentiating Sites by Partial Poisoning.
- 4.4. Mode of Enantio-face Differentiation on MNi.
- 5. Conclusions.- References.

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