Catalysis

Ulf Hanefeld is Professor of Biocatalysis at the Department of Biotechnology at Delft University of Technology, The Netherlands. His research focuses on the hydroxynitrile lyase enzymes, heterogeneous catalysis combined with biocatalysis, and more broadly on the catalytic formation of carbon-carbon bonds. Besides his extensive research portfolio, Hanefeld is an important figurehead for education in biocatalysis. Leon Lefferts was appointed Professor at Twente University in 1999, after having worked at the industrial laboratories of DSM for 12 years. He has been visiting professor at both Tokyo Institute of Technology, 2005?2007, as well at at Aalto University in Helsinki since 2011. His research interests are within the field of applied heterogeneous catalysis, with emphasis on activation of stable molecules, e.g. methane, carbon dioxide and water, heterogeneous catalyst in gas-liquid systems as well as catalytic upgrading of biomass based feeds, e.g. flash pyrolysis oil.

• Preface xiii1 Introduction 1Leon Lefferts, Ulf Hanefeld, and Harry Bitter1.1 A FewWords at the Beginning 11.2 Catalysis in a Nutshell 11.3 History of Catalysis 31.3.1 Industrial Catalysis 41.3.2 Environmental Catalysis 51.4 Integration Homo–Hetero-Biocatalysis 51.5 Research in Catalysis 101.5.1 S-Curve, Old Processes Improvement Is Knowledge Intensive 101.5.2 Interdependence with Other Fields 111.5.3 Recent and Future Issues 121.6 Catalysis and Integrated Approach or How to Use this Book 14References 142 Heterogeneous Catalysis 15Leon Lefferts, Emiel Hensen, and Hans Niemantsverdriet2.1 Introduction 152.1.1 Concept of Heterogeneous Catalysis 152.1.2 Applications of Heterogeneous Catalysis 162.1.3 Catalytic Cycle 232.2 Adsorption on Surfaces 232.2.1 Physisorption and Chemisorption 242.2.2 Adsorption Isotherms 262.2.3 Chemisorption and Chemical Bonding 282.2.4 Connecting Kinetic andThermodynamic Formulations 332.3 Surface Reactions 352.3.1 Reaction Mechanism and Kinetics 352.4 Types of Heterogeneous Catalysts 412.4.1 Supported Metals 412.4.2 Oxides and Sulfides 512.4.3 Solid Acid Catalysts 62Question 1 69Question 2 69References 703 Homogeneous Catalysis 73Elisabeth Bouwman,Martin C. Feiters, and Robertus J. M. Klein Gebbink3.1 Framework and Outline 733.1.1 Outline of this Chapter 733.1.2 Definitions and Terminology 743.2 Coordination and Organometallic Chemistry 753.2.1 Coordination Chemistry: d Orbitals, Geometries, Crystal Field Theory 753.2.2 σ and π donors and back-donation: CO, alkene, phosphane, H2 773.2.3 Organometallics: Hapticity, Metal–Alkyl/Allyl, Agostic Interaction, Carbenes 803.2.4 Electron Counting: Ionogenic or Donor-Pair versus Covalent or Neutral-Ligand 813.2.5 Effect of Binding on Ligands andMetal Ions, Stabilization of Oxidation States 833.3 Elementary Steps in Homogeneous Catalysis 843.3.1 Formation of the Active Catalyst Species 843.3.2 Oxidative Addition and Reductive Elimination 853.3.3 Migration and Elimination 873.3.4 Oxidative Coupling and Reductive Cleavage 903.3.5 Alkene or Alkyne Metathesis and σ-Bond Metathesis 903.3.6 Nucleophilic and Electrophilic Attack 923.4 Homogeneous Hydrogenation 953.4.1 Background and Scope 953.4.2 H2 DihydrideMechanism:Wilkinson’s Catalyst 963.4.3 H2 Monohydride Mechanism and Heterolytic Cleavage 973.4.4 Asymmetric Homogeneous Hydrogenation 983.4.5 Transfer Hydrogenation with 2-Propanol 1003.4.6 Other Alkene Addition Reactions 1023.5 Hydroformylation 1043.5.1 Scope and Importance of the Reaction and Its Products 1043.5.2 Cobalt-Catalyzed Hydroformylation 1053.5.3 Rhodium-Catalyzed Hydroformylation 1073.5.4 Asymmetric Hydroformylation 1103.6 Oligomerization and Polymerization of Alkenes 1123.6.1 Scope and Importance of Oligomerization and Polymerization 1123.6.2 Oligomerization of Ethene (Ni, Cr) 1133.6.3 Stereochemistry and Mechanism of Propene Polymerization 1153.6.4 Metallocene Catalysis 1173.6.5 Polymerization with Non-Metallocenes (Pd, Ni, Fe, Co) 1183.7 Miscellaneous Homogeneously Catalyzed Reactions 1183.7.1 Cross-Coupling Reactions: Pd-Catalyzed C–C Bond Formation 1183.7.2 Metathesis Reactions 120Question 1 (total 20 points) 122Question 2 (total 20 points) 122References 123Further Reading 1244 Biocatalysis 127Guzman Torrelo, Frank Hollmann, and Ulf Hanefeld4.1 Introduction 1274.2 Why Are Enzymes So Huge? 1294.3 Classification of Enzymes 1374.3.1 Oxidoreductases (EC 1) 1394.3.2 Transferases (EC 2) 1474.3.3 Hydrolases (EC 3) 1474.3.4 Lyases (EC 4) 1574.4 Concepts and Methods 1574.4.1 Cofactor Regeneration Systems 1584.4.2 Methods to Shift Unfavorable Equilibria 1594.4.3 Two-Liquid-Phase Systems (and Related) 1644.4.4 (Dynamic) Kinetic Resolutions and Desymmetrization 1644.4.5 Enantiomeric Ratio E 1684.5 Applications and Case Studies 1694.5.1 Oxidoreductases (E.C. 1) 1694.5.2 Transferases (EC 2) 1774.5.3 Hydrolases (EC 3) 1794.5.3.1 Lipases and Esterases (EC 3.1.1) 1794.5.4 Lyases (EC 4) 181Question 1 186Question 2 186Question 3 187Question 4 188Further Reading 1885 Chemical Kinetics of Catalyzed Reactions 191Freek Kapteijn, Jorge Gascon, and T. Alexander Nijhuis5.1 Introduction 1915.2 Rate Expressions – Quasi-Steady-State Approximation and Quasi-Equilibrium Assumption 1935.3 Adsorption Isotherms 1985.3.1 One-Component Adsorption 1985.3.2 Multicomponent Adsorption 1995.3.3 Dissociative Adsorption 2005.4 Rate Expressions – Other Models and Generalizations 2005.5 Limiting Cases – Reactant and Product Concentrations 2025.6 Temperature and Pressure Dependence 2065.6.1 Transition-StateTheory 2075.6.2 Forward Reaction – Temperature and Pressure Dependence 2085.6.3 Forward Reaction – Limiting Cases 2095.7 Sabatier Principle – Volcano Plot 2135.8 Concluding Remarks 214Notation 216Greek 217Subscripts 217Superscripts 217Question 1 217Question 2 218Question 3 218References 2196 Catalytic Reaction Engineering 221Freek Kapteijn, Jorge Gascon, and T. Alexander Nijhuis6.1 Introduction 2216.2 Chemical Reactors 2226.2.1 Balance and Definitions 2226.2.2 Batch Reactor 2246.2.2.1 Multiple Reactions 2266.2.3 Continuous Flow Stirred Tank Reactor (CSTR) 2286.2.4 Plug-Flow Reactor (PFR) 2316.2.5 Comparison between Plug-flow and CSTR reactor 2336.3 Reaction and Mass Transport 2366.3.1 External Mass Transfer 2376.3.2 Internal Mass Transport 2426.3.3 Gas–Liquid Mass Transfer 2486.3.4 Heat Transfer 2546.4 Criteria to Check for Transport Limitations 2576.4.1 Numerical Checks 2576.4.2 Experimental Checks 260Notation 264Greek symbols 265Subscripts 265Question 1 265Question 2 266Question 3 267References 2697 Characterization of Catalysts 271Guido Mul, Frank de Groot, Barbara Mojet-Mol, and Moniek Tromp7.1 Introduction 2717.1.1 Importance of Characterization of Catalysts 2717.1.2 Overview of the Various Techniques 2717.2 Techniques Based on Probe Molecules 2737.2.1 Temperature-Programmed Techniques 2737.2.2 Physisorption and Chemisorption 2757.3 Electron Microscopy Techniques 2807.4 Techniques from Ultraviolet up to Infrared Radiation 2837.4.1 UV/Vis Spectroscopy 2837.4.2 Infrared Spectroscopy 2867.4.3 Raman Spectroscopy 2897.5 Techniques Based on X-Rays 2917.5.1 Introduction 2917.5.2 Interaction of X-Rays with Matter 2937.5.3 X-Ray Photoelectron Spectroscopy (XPS) 2947.5.4 X-ray Absorption Spectroscopy (XAS) 2957.5.5 X-Ray Scattering 2997.5.6 X-Ray Microscopy 3027.6 Ion Spectroscopies 3037.7 Magnetic Resonance Spectroscopy Techniques 3047.7.1 NMR 3047.7.2 EPR 3067.8 Summary 310Question 1 310Question 2 311Question 3 312References 3138 Synthesis of Solid Supports and Catalysts 315Petra de Jongh and Krijn de Jong8.1 Introduction 3158.2 Support Materials 3178.2.1 Mesoporous Metal Oxides 3188.2.2 Ordered Microporous Materials 3268.2.3 Carbon Materials 3318.2.4 Shaping 3338.3 Synthesis of Supported Catalysts 3338.3.1 Colloidal Synthesis Routes 3348.3.2 Chemical Vapor Deposition 3358.3.3 Ion Adsorption 3388.3.4 Deposition Precipitation 3418.3.5 Co-Precipitation 3458.3.6 Impregnation and Drying 349Question 1 357Question 2 357Question 3 358References 358Index 361

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