Catalysis

Gadi Rothenberg is Professor and Chair of Heterogeneous Catalysis and Sustainable Chemistry at the Van't Hoff Institute for Molecular Sciences at the University of Amsterdam, and teaches courses on catalysis, thermodynamicsand scientific writing. He has published over 180 papers in peer-reviewed journals, was awarded 15 patents, and co-founded the companies Sorbisense A/S, Yellow Diesel BV and Plantics BV. Rothenberg?s current research interestsinclude fuel cells, biomass conversion and multifunctional materials. His latest invention is a simple catalytic process for removing cyanide from industrial waste streams.

• Preface xi1 Introduction 11.1 Green Chemistry and Sustainable Development 11.1.1 What Is ‘Green Chemistry’? 21.1.2 Quantifying Environmental Impact: Efficiency, E-Factors, and Atom Economy 41.1.3 Just How ‘Green’ Is This Process? 61.1.4 Product and Process Life-Cycle Assessment (LCA) 101.2 What Is Catalysis and Why Is It Important? 121.2.1 Homogeneous Catalysis, Heterogeneous Catalysis, and Biocatalysis: Definitions and Examples 141.2.2 Connecting Catalysis and Sustainability: Saving Resources by Using Catalytic Cycles 201.2.3 Industrial Example: the BHC Ibuprofen Process 221.3 Tools in Catalysis Research 241.3.1 Catalyst Synthesis and Testing Tools 241.3.2 Catalyst Characterisation Tools 271.3.3 Modelling/Mechanistic Studies Tools 281.4 Exercises 30References 38Further Reading 412 The Basics of Catalysis 432.1 Catalysis Is a Kinetic Phenomenon 432.1.1 Reaction Rates, Reaction Orders, Rate Equations and Rate-Determining Steps 452.1.2 The Reaction Profile and the Reaction Coordinate 492.1.3 Zero-Order, First-Order and Second-Order Kinetics 522.1.4 Langmuir–Hinshelwood Kinetics 582.1.5 The Steady-State Approximation 612.1.6 Michaelis–Menten Kinetics 622.1.7 Consecutive and Parallel First-Order Reactions 662.1.8 Pre-equilibrium, ‘Catalyst Reservoirs’, and Catalyst Precursors 672.2 Practical Approaches in Kinetic Studies 702.2.1 Initial Reaction Rates and Concentration Effects 702.2.2 Creating Pseudo-Order Conditions 712.2.3 What You See vs. What You Get 722.2.4 Learning from Stoichiometric Experiments 732.3 An Overview of Some Basic Concepts in Catalysis 742.3.1 Catalyst-Substrate Interactions and Sabatier’s Principle 742.3.2 Catalyst Deactivation, Sintering, and Thermal Degradation 752.3.3 Catalyst Inhibition 782.4 Exercises 79References 853 Homogeneous Catalysis 893.1 Metal Complex Catalysis in the Liquid Phase 903.1.1 Elementary Steps in Homogeneous Catalysis 913.1.2 Structure-Activity Relationships in Homogeneous Catalysis 1003.1.3 Asymmetric Homogeneous Catalysis 1063.1.4 Industrial Examples 1093.2 Homogeneous Catalysis without Metals 1173.2.1 Classic Acid/Base Catalysis 1173.2.2 Organocatalysis 1173.3 Scaling Up Homogeneous Reactions: Pros and Cons 1193.3.1 Catalyst Recovery and Recycling 1203.3.2 Immobilised Complexes and Ship-In-A-Bottle Catalysts 1223.4 ‘Click Chemistry’ and Homogeneous Catalysis 1223.5 Exercises 124References 1314 Heterogeneous Catalysis 1374.1 Classic Gas/Solid Systems 1394.1.1 The Concept of the Active Site 1414.1.2 Model Catalyst Systems 1434.1.3 Real Catalysts: Promoters, Modifiers, and Poisons 1444.1.4 Preparation of Solid Catalysts: Black Magic Revealed 1464.1.5 Selecting the Right Support 1544.1.6 Catalyst Characterisation 1574.1.7 The Catalytic Converter: an Example from Everyday Life 1664.1.8 Surface Organometallic Chemistry 1684.2 Liquid/Solid and Liquid/Liquid Catalytic Systems 1714.2.1 Aqueous Biphasic Catalysis 1714.2.2 Fluorous Biphasic Catalysis 1734.2.3 Biphasic Catalysis Using Ionic Liquids 1754.2.4 Phase-Transfer Catalysis 1764.3 Advanced Process Solutions Using Heterogeneous Catalysis 1784.3.1 The BP AVADA Ethyl Acetate Process 1784.3.2 The CB&I Lummus/Albemarle AlkyClean Process 1794.3.3 The IFP and Yellowdiesel Processes for Biodiesel Production 1804.3.4 The ABB Lummus/UOP SMART Process 1844.4 Exercises 186References 1965 Biocatalysis 2055.1 The Basics of Enzymatic Catalysis 2065.1.1 Terms and Definitions – the Bio Dialect 2065.1.2 Active Sites and Substrate Binding Models 2105.1.3 Intramolecular Reactions and Proximity Effects 2125.1.4 Common Mechanisms in Enzymatic Catalysis 2135.2 Applications of Enzyme Catalysis 2155.2.1 Whole-Cell Systems vs. Isolated Enzymes 2165.2.2 Immobilised Enzymes: Bona Fide Heterogeneous Catalysis 2185.2.3 Replacing ‘Conventional Routes’ with Biocatalysis 2215.2.4 Combining ‘Bio’ and ‘Chemo’ Catalysis 2235.3 Developing New Biocatalysts: Better than Nature’s Best 2255.3.1 Prospecting Natural Diversity 2265.3.2 Rational Design 2265.3.3 Directed Evolution 2275.4 Non-enzymatic Biocatalysts 2295.4.1 Catalytic Antibodies (Abzymes) 2295.4.2 Catalytic RNA (Ribozymes) 2305.5 Industrial Examples 2325.5.1 High-Fructose Corn Syrup: 11 Million Tons per Year 2325.5.2 The Mitsubishi Rayon Acrylamide Process 2335.5.3 The BMS Paclitaxel Process 2355.5.4 The Tosoh/DSM Aspartame Process 2365.6 Exercises 237References 2436 Computer Applications in Catalysis Research 2496.1 Computers as Research Tools in Catalysis 2496.2 Modelling of Catalysts and Catalytic Cycles 2516.2.1 A Short Overview of Modelling Methods 2516.2.2 Simplified Model Systems vs. Real Reactions 2536.2.3 Modelling Large Catalyst Systems Using Classical Mechanics 2546.2.4 In-Depth Reaction Modelling Using Quantum Mechanics 2566.3 Predictive Modelling and Rational Catalyst Design 2586.3.1 Catalysts, Descriptors, and Figures of Merit 2596.3.2 Three-Dimensional (3D) Descriptors of Homogeneous Catalysts 2606.3.3 Two-Dimensional (2D) Descriptors of Homogeneous Catalysts 2636.3.4 Descriptors of Heterogeneous (Solid) Catalysts 2676.3.5 Predictive Modelling in Biocatalysis 2716.3.6 Generating Virtual Catalyst Libraries in Space A 2726.3.7 Understanding Catalyst Diversity 2736.3.8 Virtual catalyst Screening: connecting Spaces A, B, and c 2766.4 An Overview of Data Mining Methods in Catalysis 2776.4.1 Principal Components Analysis (PCA) 2796.4.2 Partial Least-Squares (PLS) Regression 2816.4.3 Artificial Neural Networks (ANNs) 2836.4.4 Classification Trees 2846.4.5 Model Validation: Separating Knowledge from Garbage 2846.5 Exercises 287References 291Index 297