Catalytic Chemistry. Bruce C. Gates. John Wiley & Sons, Inc. New York Chichester Brisbane Toronto Singapore. University of Delaware ^.'-'.

Transcription

1 : s / ; '.... ;. : : ^.'-'. Catalytic Chemistry Bruce C. Gates University of Delaware John Wiley & Sons, Inc. New York Chichester Brisbane Toronto Singapore

2 Contents List of Notation xix 1 INTRODUCTION References 12 Further Reading 12 Problems 12 2 CATALYSIS IN SOLUTIONS Introduction Acid-Base Catalysis Catalysis in the Gas Phase Catalysis in Dilute Aqueous Solution General and Specific Acid and Base Catalysis Catalysis in Concentrated Strong Acid Solutions Catalysis by Bases Stepwise and Concerted Reactions Catalysis by Metal Ions Hydrocarbon Conversion 40 Carbenium Ion Reactions 40 Catalytic Reactions Involving Carbenium Ion Intermediates Catalysis by Electron Transfer Simple Redox Reactions Oxidation Involving Free-Radical Intermediates Organometallic Catalysis Introduction 67 xiii

3 Xiv CONTENTS Bonding and Structure of Transition Metal Complexes 68 Reactions of Transition Metal Complexes 77 Patterns of Reactivity of the Transition Metals Examples of Organometallic Catalysis 79 Olefin Hydrogenation 79 Olefin Hydroformylation 91 Methanol Carbonylation 98 Olefin Polymerization 102 Olefin Metathesis 109 Partial Oxidation 112 C-H Bond Activation Catalysis by Metal Clusters Catalysis by Macromolecules Phase Transfer Catalysis Catalysis by Micelles The Influence of Diffusion Process Engineering Separation Corrosion Heat Transfer 133 References 134 Further Reading 137 Problems CATALYSIS BY ENZYMES Introduction Composition and Structure of Enzymes Reactions Catalyzed by Enzymes Nature of Catalytic Sites: the Uniqueness of Enzymes as Catalysts Examples of Enzyme Structure and Catalysis Organic Catalysis 159 Lysozyme 160 Ribonuclease Metalloenzyme Catalysis 169 Carbonic Anhydrase 173 A Free-radical Reaction Catalyzed by Vitamin B ) Summary Supported Enzymes 177

4 CONTENTS XV References 178 Further Reading 179 Problems CATALYSIS BY POLYMERS The Nature of Polymers Attachment of Catalytic Groups to Polymer Supports Catalysis in Polymer Gels Adsorption and the Kinetics of Polymer-Catalyzed Reactions Interactions of Catalytic Groups: the Role of the Support Bifunctional and Multifunctional Catalysis Porous Polymers and Surface Catalysis Intraparticle Transport Influence The Thiele Model: the Influence of Intraparticle Mass Transport on Catalysis The Influence of Intraparticle Heat Transport Applications of Polymer Catalysts Extraparticle Transport Influence 240 References 244 Further Reading 246 Problems CATALYSIS IN MOLECULAR-SCALE CAVITIES Structures of Crystalline Solids Structures of Zeolites (Crystalline Aluminosilicates) Silicalite and ZSM Zeolite A Zeolites X and Y (Faujasites) Families of Zeolites Pore Sizes and Molecular Sieving Aluminum Content and Acidity Adsorption and Diffusion in Zeolites The Solventlike Nature of Zeolite Pores Catalysis by Zeolites Acid-Base Catalysis 275 Cracking 276 Other Reactions of Olefins 283

5 Xvi CONTENTS Steric and Transport Effects: Molecular Sieving and Shape-selective Catalysis 285 Influence of Steric and Transport Effects on Catalyst Deactivation Catalysis by Zeolites Containing Metal Complexes and Clusters 295 Transition Metal Complexes 295 Metal Clusters and Aggregates Summary Nonzeolite Molecular Sieves Clays and Other Layered Materials 300 References 301 Further Reading 304 Problems CATALYSIS ON SURFACES Introduction Surface Structures Single-Crystal Surfaces of Metals Experimental Methods of Determining Surface Structures of Single Crystals High-Surface-Area Amorphous Solids 317 Macroscopic Structures of Porous Solids 317 Surface Structures of Metal Oxides Adsorption Adsorption Isotherms Structures of Adsorbed Species on Single-Crystal Metal Surfaces Adsorption on Complex Surfaces Functionalized Surfaces Surface Catalysis Catalysis on Functionalized Surfaces: Connections to Molecular Catalysis 340 Catalysis by Silica-Supported Rh Complexes 340 Wacker Oxidation of Ethylene on V Surfaces Functionalized with Pd 340 Olefin Metathesis Catalyzed by Metal-Oxide- Supported Metal Complexes 340 Olefin Polymerization on Surfaces Functionalized with Cr Complexes 342 Catalysis by Multicenter Surface Sites Olefin Polymerization Catalysis on Titanium Trichloride Surfaces: Further Links Between Molecular and Surface Catalysis 346

6 CONTENTS XVÜ Catalysis on Metal Surfaces 351 CO Oxidation on Pd 356 NH 3 Synthesis on Fe 362 Hydrocarbon Conversion on Pt Catalysis on Metal Oxide Surfaces 371 Alcohol Dehydration on 7-AI2O3 371 Reactions of Olefins on ZnO Catalysis by Supported Metals 378 The Nature of Supported Metals 378 Structure-Insensitive and Structure-Sensitive Reactions 387 Ethylene Oxidation on Silver 392 Bifunctional Catalysis and the Reforming of Naphtha Hydrocarbons Catalysis by Mixed Metal Oxides: Ammoxidation of Propylene Catalysis by Metal Sulfides: Hydrodesulfurization and Related Petroleum Hydroprocessing Reactions 406 References 417 Further Reading 422 Problems 422 Glossary 430 Reading List 433 Acknowledgments 437 Index 445