<p>Preface xi</p> <p><b>1 Introduction 1</b></p> <p>1.1 Green Chemistry and Sustainable Development 1</p> <p>1.1.1 What Is ‘Green Chemistry’? 2</p> <p>1.1.2 Quantifying Environmental Impact: Efficiency, E-Factors, and Atom Economy 4</p> <p>1.1.3 Just How ‘Green’ Is This Process? 6</p> <p>1.1.4 Product and Process Life-Cycle Assessment (LCA) 10</p> <p>1.2 What Is Catalysis and Why Is It Important? 12</p> <p>1.2.1 Homogeneous Catalysis, Heterogeneous Catalysis, and Biocatalysis: Definitions and Examples 14</p> <p>1.2.2 Connecting Catalysis and Sustainability: Saving Resources by Using Catalytic Cycles 20</p> <p>1.2.3 Industrial Example: the BHC Ibuprofen Process 22</p> <p>1.3 Tools in Catalysis Research 24</p> <p>1.3.1 Catalyst Synthesis and Testing Tools 24</p> <p>1.3.2 Catalyst Characterisation Tools 27</p> <p>1.3.3 Modelling/Mechanistic Studies Tools 28</p> <p>1.4 Exercises 30</p> <p>References 38</p> <p>Further Reading 41</p> <p><b>2 The Basics of Catalysis 43</b></p> <p>2.1 Catalysis Is a Kinetic Phenomenon 43</p> <p>2.1.1 Reaction Rates, Reaction Orders, Rate Equations and Rate-Determining Steps 45</p> <p>2.1.2 The Reaction Profile and the Reaction Coordinate 49</p> <p>2.1.3 Zero-Order, First-Order and Second-Order Kinetics 52</p> <p>2.1.4 Langmuir–Hinshelwood Kinetics 58</p> <p>2.1.5 The Steady-State Approximation 61</p> <p>2.1.6 Michaelis–Menten Kinetics 62</p> <p>2.1.7 Consecutive and Parallel First-Order Reactions 66</p> <p>2.1.8 Pre-equilibrium, ‘Catalyst Reservoirs’, and Catalyst Precursors 67</p> <p>2.2 Practical Approaches in Kinetic Studies 70</p> <p>2.2.1 Initial Reaction Rates and Concentration Effects 70</p> <p>2.2.2 Creating Pseudo-Order Conditions 71</p> <p>2.2.3 What You See vs. What You Get 72</p> <p>2.2.4 Learning from Stoichiometric Experiments 73</p> <p>2.3 An Overview of Some Basic Concepts in Catalysis 74</p> <p>2.3.1 Catalyst-Substrate Interactions and Sabatier’s Principle 74</p> <p>2.3.2 Catalyst Deactivation, Sintering, and Thermal Degradation 75</p> <p>2.3.3 Catalyst Inhibition 78</p> <p>2.4 Exercises 79</p> <p>References 85</p> <p><b>3 Homogeneous Catalysis 89</b></p> <p>3.1 Metal Complex Catalysis in the Liquid Phase 90</p> <p>3.1.1 Elementary Steps in Homogeneous Catalysis 91</p> <p>3.1.2 Structure-Activity Relationships in Homogeneous Catalysis 100</p> <p>3.1.3 Asymmetric Homogeneous Catalysis 106</p> <p>3.1.4 Industrial Examples 109</p> <p>3.2 Homogeneous Catalysis without Metals 117</p> <p>3.2.1 Classic Acid/Base Catalysis 117</p> <p>3.2.2 Organocatalysis 117</p> <p>3.3 Scaling Up Homogeneous Reactions: Pros and Cons 119</p> <p>3.3.1 Catalyst Recovery and Recycling 120</p> <p>3.3.2 Immobilised Complexes and Ship-In-A-Bottle Catalysts 122</p> <p>3.4 ‘Click Chemistry’ and Homogeneous Catalysis 122</p> <p>3.5 Exercises 124</p> <p>References 131</p> <p><b>4 Heterogeneous Catalysis 137</b></p> <p>4.1 Classic Gas/Solid Systems 139</p> <p>4.1.1 The Concept of the Active Site 141</p> <p>4.1.2 Model Catalyst Systems 143</p> <p>4.1.3 Real Catalysts: Promoters, Modifiers, and Poisons 144</p> <p>4.1.4 Preparation of Solid Catalysts: Black Magic Revealed 146</p> <p>4.1.5 Selecting the Right Support 154</p> <p>4.1.6 Catalyst Characterisation 157</p> <p>4.1.7 The Catalytic Converter: an Example from Everyday Life 166</p> <p>4.1.8 Surface Organometallic Chemistry 168</p> <p>4.2 Liquid/Solid and Liquid/Liquid Catalytic Systems 171</p> <p>4.2.1 Aqueous Biphasic Catalysis 171</p> <p>4.2.2 Fluorous Biphasic Catalysis 173</p> <p>4.2.3 Biphasic Catalysis Using Ionic Liquids 175</p> <p>4.2.4 Phase-Transfer Catalysis 176</p> <p>4.3 Advanced Process Solutions Using Heterogeneous Catalysis 178</p> <p>4.3.1 The BP AVADA Ethyl Acetate Process 178</p> <p>4.3.2 The CB&I Lummus/Albemarle AlkyClean Process 179</p> <p>4.3.3 The IFP and Yellowdiesel Processes for Biodiesel Production 180</p> <p>4.3.4 The ABB Lummus/UOP SMART Process 184</p> <p>4.4 Exercises 186</p> <p>References 196</p> <p><b>5 Biocatalysis 205</b></p> <p>5.1 The Basics of Enzymatic Catalysis 206</p> <p>5.1.1 Terms and Definitions – the Bio Dialect 206</p> <p>5.1.2 Active Sites and Substrate Binding Models 210</p> <p>5.1.3 Intramolecular Reactions and Proximity Effects 212</p> <p>5.1.4 Common Mechanisms in Enzymatic Catalysis 213</p> <p>5.2 Applications of Enzyme Catalysis 215</p> <p>5.2.1 Whole-Cell Systems vs. Isolated Enzymes 216</p> <p>5.2.2 Immobilised Enzymes: Bona Fide Heterogeneous Catalysis 218</p> <p>5.2.3 Replacing ‘Conventional Routes’ with Biocatalysis 221</p> <p>5.2.4 Combining ‘Bio’ and ‘Chemo’ Catalysis 223</p> <p>5.3 Developing New Biocatalysts: Better than Nature’s Best 225</p> <p>5.3.1 Prospecting Natural Diversity 226</p> <p>5.3.2 Rational Design 226</p> <p>5.3.3 Directed Evolution 227</p> <p>5.4 Non-enzymatic Biocatalysts 229</p> <p>5.4.1 Catalytic Antibodies (Abzymes) 229</p> <p>5.4.2 Catalytic RNA (Ribozymes) 230</p> <p>5.5 Industrial Examples 232</p> <p>5.5.1 High-Fructose Corn Syrup: 11 Million Tons per Year 232</p> <p>5.5.2 The Mitsubishi Rayon Acrylamide Process 233</p> <p>5.5.3 The BMS Paclitaxel Process 235</p> <p>5.5.4 The Tosoh/DSM Aspartame Process 236</p> <p>5.6 Exercises 237</p> <p>References 243</p> <p><b>6 Computer Applications in Catalysis Research 249</b></p> <p>6.1 Computers as Research Tools in Catalysis 249</p> <p>6.2 Modelling of Catalysts and Catalytic Cycles 251</p> <p>6.2.1 A Short Overview of Modelling Methods 251</p> <p>6.2.2 Simplified Model Systems vs. Real Reactions 253</p> <p>6.2.3 Modelling Large Catalyst Systems Using Classical Mechanics 254</p> <p>6.2.4 In-Depth Reaction Modelling Using Quantum Mechanics 256</p> <p>6.3 Predictive Modelling and Rational Catalyst Design 258</p> <p>6.3.1 Catalysts, Descriptors, and Figures of Merit 259</p> <p>6.3.2 Three-Dimensional (3D) Descriptors of Homogeneous Catalysts 260</p> <p>6.3.3 Two-Dimensional (2D) Descriptors of Homogeneous Catalysts 263</p> <p>6.3.4 Descriptors of Heterogeneous (Solid) Catalysts 267</p> <p>6.3.5 Predictive Modelling in Biocatalysis 271</p> <p>6.3.6 Generating Virtual Catalyst Libraries in Space A 272</p> <p>6.3.7 Understanding Catalyst Diversity 273</p> <p>6.3.8 Virtual catalyst Screening: connecting Spaces A, B, and c 276</p> <p>6.4 An Overview of Data Mining Methods in Catalysis 277</p> <p>6.4.1 Principal Components Analysis (PCA) 279</p> <p>6.4.2 Partial Least-Squares (PLS) Regression 281</p> <p>6.4.3 Artificial Neural Networks (ANNs) 283</p> <p>6.4.4 Classification Trees 284</p> <p>6.4.5 Model Validation: Separating Knowledge from Garbage 284</p> <p>6.5 Exercises 287</p> <p>References 291</p> <p>Index 297</p>