Preface xiii
1 Introduction 1
Leon Lefferts, Ulf Hanefeld, and Harry Bitter
1.1 A FewWords at the Beginning 1
1.2 Catalysis in a Nutshell 1
1.3 History of Catalysis 3
1.3.1 Industrial Catalysis 4
1.3.2 Environmental Catalysis 5
1.4 Integration Homo–Hetero-Biocatalysis 5
1.5 Research in Catalysis 10
1.5.1 S-Curve, Old Processes Improvement Is Knowledge Intensive 10
1.5.2 Interdependence with Other Fields 11
1.5.3 Recent and Future Issues 12
1.6 Catalysis and Integrated Approach or How to Use this Book 14
References 14
2 Heterogeneous Catalysis 15
Leon Lefferts, Emiel Hensen, and Hans Niemantsverdriet
2.1 Introduction 15
2.1.1 Concept of Heterogeneous Catalysis 15
2.1.2 Applications of Heterogeneous Catalysis 16
2.1.3 Catalytic Cycle 23
2.2 Adsorption on Surfaces 23
2.2.1 Physisorption and Chemisorption 24
2.2.2 Adsorption Isotherms 26
2.2.3 Chemisorption and Chemical Bonding 28
2.2.4 Connecting Kinetic andThermodynamic Formulations 33
2.3 Surface Reactions 35
2.3.1 Reaction Mechanism and Kinetics 35
2.4 Types of Heterogeneous Catalysts 41
2.4.1 Supported Metals 41
2.4.2 Oxides and Sulfides 51
2.4.3 Solid Acid Catalysts 62
Question 1 69
Question 2 69
References 70
3 Homogeneous Catalysis 73
Elisabeth Bouwman,Martin C. Feiters, and Robertus J. M. Klein Gebbink
3.1 Framework and Outline 73
3.1.1 Outline of this Chapter 73
3.1.2 Definitions and Terminology 74
3.2 Coordination and Organometallic Chemistry 75
3.2.1 Coordination Chemistry: d Orbitals, Geometries, Crystal Field Theory 75
3.2.2 σ and π donors and back-donation: CO, alkene, phosphane, H2 77
3.2.3 Organometallics: Hapticity, Metal–Alkyl/Allyl, Agostic Interaction, Carbenes 80
3.2.4 Electron Counting: Ionogenic or Donor-Pair versus Covalent or Neutral-Ligand 81
3.2.5 Effect of Binding on Ligands andMetal Ions, Stabilization of Oxidation States 83
3.3 Elementary Steps in Homogeneous Catalysis 84
3.3.1 Formation of the Active Catalyst Species 84
3.3.2 Oxidative Addition and Reductive Elimination 85
3.3.3 Migration and Elimination 87
3.3.4 Oxidative Coupling and Reductive Cleavage 90
3.3.5 Alkene or Alkyne Metathesis and σ-Bond Metathesis 90
3.3.6 Nucleophilic and Electrophilic Attack 92
3.4 Homogeneous Hydrogenation 95
3.4.1 Background and Scope 95
3.4.2 H2 DihydrideMechanism:Wilkinson’s Catalyst 96
3.4.3 H2 Monohydride Mechanism and Heterolytic Cleavage 97
3.4.4 Asymmetric Homogeneous Hydrogenation 98
3.4.5 Transfer Hydrogenation with 2-Propanol 100
3.4.6 Other Alkene Addition Reactions 102
3.5 Hydroformylation 104
3.5.1 Scope and Importance of the Reaction and Its Products 104
3.5.2 Cobalt-Catalyzed Hydroformylation 105
3.5.3 Rhodium-Catalyzed Hydroformylation 107
3.5.4 Asymmetric Hydroformylation 110
3.6 Oligomerization and Polymerization of Alkenes 112
3.6.1 Scope and Importance of Oligomerization and Polymerization 112
3.6.2 Oligomerization of Ethene (Ni, Cr) 113
3.6.3 Stereochemistry and Mechanism of Propene Polymerization 115
3.6.4 Metallocene Catalysis 117
3.6.5 Polymerization with Non-Metallocenes (Pd, Ni, Fe, Co) 118
3.7 Miscellaneous Homogeneously Catalyzed Reactions 118
3.7.1 Cross-Coupling Reactions: Pd-Catalyzed C–C Bond Formation 118
3.7.2 Metathesis Reactions 120
Question 1 (total 20 points) 122
Question 2 (total 20 points) 122
References 123
Further Reading 124
4 Biocatalysis 127
Guzman Torrelo, Frank Hollmann, and Ulf Hanefeld
4.1 Introduction 127
4.2 Why Are Enzymes So Huge? 129
4.3 Classification of Enzymes 137
4.3.1 Oxidoreductases (EC 1) 139
4.3.2 Transferases (EC 2) 147
4.3.3 Hydrolases (EC 3) 147
4.3.4 Lyases (EC 4) 157
4.4 Concepts and Methods 157
4.4.1 Cofactor Regeneration Systems 158
4.4.2 Methods to Shift Unfavorable Equilibria 159
4.4.3 Two-Liquid-Phase Systems (and Related) 164
4.4.4 (Dynamic) Kinetic Resolutions and Desymmetrization 164
4.4.5 Enantiomeric Ratio E 168
4.5 Applications and Case Studies 169
4.5.1 Oxidoreductases (E.C. 1) 169
4.5.2 Transferases (EC 2) 177
4.5.3 Hydrolases (EC 3) 179
4.5.3.1 Lipases and Esterases (EC 3.1.1) 179
4.5.4 Lyases (EC 4) 181
Question 1 186
Question 2 186
Question 3 187
Question 4 188
Further Reading 188
5 Chemical Kinetics of Catalyzed Reactions 191
Freek Kapteijn, Jorge Gascon, and T. Alexander Nijhuis
5.1 Introduction 191
5.2 Rate Expressions – Quasi-Steady-State Approximation and Quasi-Equilibrium Assumption 193
5.3 Adsorption Isotherms 198
5.3.1 One-Component Adsorption 198
5.3.2 Multicomponent Adsorption 199
5.3.3 Dissociative Adsorption 200
5.4 Rate Expressions – Other Models and Generalizations 200
5.5 Limiting Cases – Reactant and Product Concentrations 202
5.6 Temperature and Pressure Dependence 206
5.6.1 Transition-StateTheory 207
5.6.2 Forward Reaction – Temperature and Pressure Dependence 208
5.6.3 Forward Reaction – Limiting Cases 209
5.7 Sabatier Principle – Volcano Plot 213
5.8 Concluding Remarks 214
Notation 216
Greek 217
Subscripts 217
Superscripts 217
Question 1 217
Question 2 218
Question 3 218
References 219
6 Catalytic Reaction Engineering 221
Freek Kapteijn, Jorge Gascon, and T. Alexander Nijhuis
6.1 Introduction 221
6.2 Chemical Reactors 222
6.2.1 Balance and Definitions 222
6.2.2 Batch Reactor 224
6.2.2.1 Multiple Reactions 226
6.2.3 Continuous Flow Stirred Tank Reactor (CSTR) 228
6.2.4 Plug-Flow Reactor (PFR) 231
6.2.5 Comparison between Plug-flow and CSTR reactor 233
6.3 Reaction and Mass Transport 236
6.3.1 External Mass Transfer 237
6.3.2 Internal Mass Transport 242
6.3.3 Gas–Liquid Mass Transfer 248
6.3.4 Heat Transfer 254
6.4 Criteria to Check for Transport Limitations 257
6.4.1 Numerical Checks 257
6.4.2 Experimental Checks 260
Notation 264
Greek symbols 265
Subscripts 265
Question 1 265
Question 2 266
Question 3 267
References 269
7 Characterization of Catalysts 271
Guido Mul, Frank de Groot, Barbara Mojet-Mol, and Moniek Tromp
7.1 Introduction 271
7.1.1 Importance of Characterization of Catalysts 271
7.1.2 Overview of the Various Techniques 271
7.2 Techniques Based on Probe Molecules 273
7.2.1 Temperature-Programmed Techniques 273
7.2.2 Physisorption and Chemisorption 275
7.3 Electron Microscopy Techniques 280
7.4 Techniques from Ultraviolet up to Infrared Radiation 283
7.4.1 UV/Vis Spectroscopy 283
7.4.2 Infrared Spectroscopy 286
7.4.3 Raman Spectroscopy 289
7.5 Techniques Based on X-Rays 291
7.5.1 Introduction 291
7.5.2 Interaction of X-Rays with Matter 293
7.5.3 X-Ray Photoelectron Spectroscopy (XPS) 294
7.5.4 X-ray Absorption Spectroscopy (XAS) 295
7.5.5 X-Ray Scattering 299
7.5.6 X-Ray Microscopy 302
7.6 Ion Spectroscopies 303
7.7 Magnetic Resonance Spectroscopy Techniques 304
7.7.1 NMR 304
7.7.2 EPR 306
7.8 Summary 310
Question 1 310
Question 2 311
Question 3 312
References 313
8 Synthesis of Solid Supports and Catalysts 315
Petra de Jongh and Krijn de Jong
8.1 Introduction 315
8.2 Support Materials 317
8.2.1 Mesoporous Metal Oxides 318
8.2.2 Ordered Microporous Materials 326
8.2.3 Carbon Materials 331
8.2.4 Shaping 333
8.3 Synthesis of Supported Catalysts 333
8.3.1 Colloidal Synthesis Routes 334
8.3.2 Chemical Vapor Deposition 335
8.3.3 Ion Adsorption 338
8.3.4 Deposition Precipitation 341
8.3.5 Co-Precipitation 345
8.3.6 Impregnation and Drying 349
Question 1 357
Question 2 357
Question 3 358
References 358
Index 361
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