| | Contents | |
| | | |
| |
| | Preface | XIII |
| 1 | Introduction | 1 |
| 1.1 | Green Chemistry and Sustainable Development | 1 |
| 1.1.1 | What is ‘‘Green Chemistry’’? | 2 |
| 1.1.2 | Quantifying Environmental Impact: Efficiency, E-factors, and Atom Economy | 4 |
| 1.1.3 | Just How ‘‘Green’’ is this Process? | 6 |
| 1.1.4 | Product and Process Life-Cycle Assessment (LCA) | 9 |
| 1.2 | What is Catalysis and Why is it Important? | 10 |
| 1.2.1 | Homogeneous Catalysis, Heterogeneous Catalysis, and Biocatalysis | 12 |
| 1.2.2 | Replacing Stoichiometric Reactions with Catalytic Cycles | 19 |
| 1.2.3 | Industrial Example: The BHC Ibuprofen Process | 22 |
| 1.3 | Tools in Catalysis Research | 23 |
| 1.3.1 | Catalyst Synthesis and Testing Tools | 24 |
| 1.3.2 | Catalyst Characterization Tools | 26 |
| 1.3.3 | Tools for Modeling/Mechanistic Studies | 28 |
| 1.4 | Further Reading | 29 |
| 1.5 | Exercises | 31 |
| | References | 35 |
| 2 | The Basics of Catalysis | 39 |
| 2.1 | Catalysis is a Kinetic Phenomenon | 39 |
| 2.1.1 | Reaction Rates, Reaction Orders, Rate Equations, and Rate-Determining Steps | 40 |
| 2.1.1.1 | The Reaction Order | 42 |
| 2.1.1.2 | The Rate-Determining Step | 43 |
| 2.1.2 | The Reaction Profile and the Reaction Coordinate | 44 |
| 2.1.3 | Zero-Order, First-Order, and Second-Order Kinetics | 46 |
| 2.1.3.1 | Zero-Order Rate Equations | 46 |
| 2.1.3.2 | First-Order Rate Equations | 47 |
| 2.1.3.3 | Second-Order Rate Equations | 48 |
| 2.1.4 | Langmuir–Hinshelwood Kinetics | 49 |
| 2.1.5 | The Steady-State Approximation | 52 |
| 2.1.6 | Michaelis–Menten Kinetics | 54 |
| 2.1.7 | Consecutive and Parallel First-Order Reactions | 56 |
| 2.1.8 | Pre-Equilibrium, ‘‘Catalyst Reservoirs,’’ and Catalyst Precursors | 58 |
| 2.2 | Practical Approaches in Kinetic Studies | 60 |
| 2.2.1 | Initial Reaction Rates and Concentration Effects | 61 |
| 2.2.1.1 | Concentration Effects | 62 |
| 2.2.2 | Creating Pseudo Order Conditions | 62 |
| 2.2.3 | What You See versus What You Get | 63 |
| 2.2.4 | Learning from Stoichiometric Experiments | 64 |
| 2.3 | An Overview of Some Basic Concepts in Catalysis | 64 |
| 2.3.1 | Catalyst/Substrate Interactions and Sabatier's Principle | 65 |
| 2.3.2 | Catalyst Deactivation, Sintering, and Thermal Degradation | 66 |
| 2.3.2.1 | Catalyst Deactivation | 66 |
| 2.3.2.2 | Catalyst Sintering and Thermal Degradation | 66 |
| 2.3.3 | Catalyst Inhibition | 68 |
| 2.3.3.1 | Catalyst Poisoning | 69 |
| 2.4 | Exercises | 69 |
| | References | 73 |
| 3 | Homogeneous Catalysis | 77 |
| 3.1 | Metal Complex Catalysis in the Liquid Phase | 77 |
| 3.1.1 | Elementary Steps in Homogeneous Catalysis | 78 |
| 3.1.1.1 | Ligand Exchange: Dissociation and Coordination | 79 |
| 3.1.1.2 | Oxidative Addition | 81 |
| 3.1.1.3 | Reductive Elimination | 83 |
| 3.1.1.4 | Insertion and Migration | 84 |
| 3.1.1.5 | De-insertion and  -Elimination | 85 |
| 3.1.1.6 | Nucleophilic Attack on a Coordinated Substrate | 85 |
| 3.1.1.7 | Other Reaction Types | 86 |
| 3.1.2 | Structure/Activity Relationships in Homogeneous Catalysis | 88 |
| 3.1.2.1 | Steric Effects: Ligand Size, Flexibility, and Symmetry | 88 |
| 3.1.2.2 | Electronic Effects of Ligands, Substrates, and Solvents | 92 |
| 3.1.3 | Asymmetric Homogeneous Catalysis | 93 |
| 3.1.4 | Industrial Examples | 96 |
| 3.1.4.1 | The Shell Higher Olefins Process (SHOP) | 97 |
| 3.1.4.2 | The Wacker Oxidation Process | 99 |
| 3.1.4.3 | The Du Pont Synthesis of Adiponitrile | 100 |
| 3.1.4.4 | The Ciba–Geigy Metolachlor Process | 102 |
| 3.2 | Homogeneous Catalysis without Metals | 104 |
| 3.2.1 | Classic Acid/Base Catalysis | 104 |
| 3.2.2 | Organocatalysis | 105 |
| 3.3 | Scaling up Homogeneous Reactions: Pros and Cons | 108 |
| 3.3.1 | Catalyst Recovery and Recycling | 108 |
| 3.3.2 | Hybrid Catalysts: Bridging the Homogeneous/Heterogeneous Gap | 110 |
| 3.4 | ‘‘Click Chemistry’’ and Homogeneous Catalysis | 111 |
| 3.5 | Exercises | 113 |
| | References | 117 |
| 4 | Heterogeneous Catalysis | 127 |
| 4.1 | Classic Gas/Solid Systems | 129 |
| 4.1.1 | The Concept of the Active Site | 131 |
| 4.1.2 | Model Catalyst Systems | 132 |
| 4.1.3 | Real Catalysts: Promoters, Modifiers, and Poisons | 134 |
| 4.1.4 | Preparation of Solid Catalysts: Black Magic Revealed | 135 |
| 4.1.4.1 | High-Temperature Fusion and Alloy Leaching | 137 |
| 4.1.4.2 | Slurry Precipitation and Co-precipitation | 138 |
| 4.1.4.3 | Impregnation of Porous Supports | 139 |
| 4.1.4.4 | Hydrothermal Synthesis | 139 |
| 4.1.4.5 | Drying, Calcination, Activation, and Forming | 141 |
| 4.1.5 | Selecting the Right Support | 143 |
| 4.1.6 | Catalyst Characterization | 146 |
| 4.1.6.1 | Traditional Surface Characterization Methods | 146 |
| 4.1.6.2 | Temperature-Programmed Techniques | 149 |
| 4.1.6.3 | Spectroscopy and Microscopy | 149 |
| 4.1.7 | The Catalytic Converter: an Example from Everyday Life | 154 |
| 4.1.8 | Surface Organometallic Chemistry | 156 |
| 4.2 | Liquid/Solid and Liquid/Liquid Catalytic Systems | 158 |
| 4.2.1 | Aqueous Biphasic Catalysis | 159 |
| 4.2.2 | Fluorous Biphasic Catalysis | 161 |
| 4.2.3 | Biphasic Catalysis Using Ionic Liquids | 163 |
| 4.2.4 | Phase-Transfer Catalysis | 164 |
| 4.3 | Advanced Process Solutions Using Heterogeneous Catalysis | 165 |
| 4.3.1 | The BP AVADA Ethyl Acetate Process | 166 |
| 4.3.2 | The ABB Lummus/Albemarle AlkyClean Process | 168 |
| 4.3.3 | The IFP and Yellowdiesel Processes for Biodiesel Production | 168 |
| 4.3.4 | The ABB Lummus/UOP SMART Process | 172 |
| 4.4 | Exercises | 173 |
| | References | 177 |
| 5 | Biocatalysis | 189 |
| 5.1 | The Basics of Enzymatic Catalysis | 190 |
| 5.1.1 | Terms and Definitions – The Bio Dialect | 191 |
| 5.1.2 | Active Sites and Substrate Binding Models | 194 |
| 5.1.3 | Intramolecular Reactions and Proximity Effects | 195 |
| 5.1.4 | Common Mechanisms in Enzymatic Catalysis | 197 |
| 5.2 | Applications of Enzyme Catalysis | 199 |
| 5.2.1 | Whole-Cell Systems versus Isolated Enzymes | 200 |
| 5.2.2 | Immobilized Enzymes: Bona Fide Heterogeneous Catalysis | 202 |
| 5.2.2.1 | Binding Enzymes to Solid Supports | 202 |
| 5.2.2.2 | Trapping Enzymes in Polymers or Sol/Gel Matrices | 203 |
| 5.2.2.3 | Cross-Linking of Enzymes | 204 |
| 5.2.3 | Replacing ‘‘Conventional Routes’’ with Biocatalysis | 205 |
| 5.2.4 | Combining ‘‘Bio’’ and ‘‘Conventional’’ Catalysis | 207 |
| 5.3 | Developing New Biocatalysts: Better than Nature's Best | 210 |
| 5.3.1 | Prospecting Natural Diversity | 210 |
| 5.3.2 | Rational Design | 211 |
| 5.3.3 | Directed Evolution | 211 |
| 5.4 | Nonenzymatic Biocatalysts | 213 |
| 5.4.1 | Catalytic Antibodies (Abzymes) | 213 |
| 5.4.2 | Catalytic RNA (Ribozymes) | 214 |
| 5.5 | Industrial Examples | 215 |
| 5.5.1 | High-Fructose Corn Syrup: 11 Million Tons per Year | 215 |
| 5.5.2 | The Mitsubishi Rayon Acrylamide Process | 217 |
| 5.5.3 | The BMS Paclitaxel Process | 218 |
| 5.5.4 | The Tosoh/DSM Aspartame Process | 220 |
| 5.6 | Exercises | 221 |
| | References | 224 |
| 6 | Computer Applications in Catalysis Research | 231 |
| 6.1 | Computers as Research Tools in Catalysis | 231 |
| 6.2 | Modeling of Catalysts and Catalytic Cycles | 233 |
| 6.2.1 | A Short Overview of Modeling Methods | 233 |
| 6.2.2 | Simplified Model Systems versus Real Reactions | 236 |
| 6.2.3 | Modeling Large Catalyst Systems Using Classical Mechanics | 236 |
| 6.2.4 | In-Depth Reaction Modeling Using Quantum Mechanics | 238 |
| 6.3 | Predictive Modeling and Rational Catalyst Design | 240 |
| 6.3.1 | Catalysts, Descriptors, and Figures of Merit | 241 |
| 6.3.2 | Three-Dimensional (3D) Descriptors | 242 |
| 6.3.2.1 | Comparative Molecular Field Analysis (CoMFA) | 243 |
| 6.3.2.2 | The Ligand Repulsive Energy Method | 244 |
| 6.3.3 | Two-Dimensional (2D) Descriptors | 245 |
| 6.3.4 | Generating Virtual Catalyst Libraries in Space A | 248 |
| 6.3.5 | Understanding Catalyst Diversity | 250 |
| 6.3.6 | Virtual Catalyst Screening: Connecting Spaces A, B, and C | 253 |
| 6.3.7 | Predictive Modeling in Heterogeneous Catalysis | 255 |
| 6.3.8 | Predictive Modeling in Biocatalysis | 256 |
| 6.4 | An Overview of Data-Mining Methods in Catalysis | 257 |
| 6.4.1 | Principal Components Analysis (PCA) | 259 |
| 6.4.2 | Partial Least-Squares (PLS) Regression | 260 |
| 6.4.3 | Artificial Neural Networks (ANNs) | 262 |
| 6.4.4 | Classification Trees | 264 |
| 6.4.5 | Model Validation: Separating Knowledge from Garbage | 264 |
| 6.4.5.1 | Cross-Validation and Bootstrapping | 265 |
| 6.4.5.2 | Mixing the Dependent Variables ( -Randomizing) | 266 |
| 6.4.5.3 | Defining the Model Domain | 266 |
| 6.5 | Exercises | 266 |
| | References | 268 |
| | Index | 275 |
