Concepts of Modern Catalysis and Kinetics

Ib Chorkendorff is Professor in Heterogeneous Catalysis and Director of the Danish National Research Foundation CINF (Center for Individual Nanoparticle Functionality), consulting Professor at SLAC, Stanford University and Director of The Villum Center for Science of Sustainable Fuels and Chemicals. He has been author and coauthor of close to 300 scientific papers and 16 patents. Hans Niemantsverdriet is Emeritus Professor of Physical Chemistry of Surfaces of Eindhoven University of Technology (1989-2015, The Netherlands) and Honorary Distinguished Professor at Cardiff University (UK). Presently he is Director of the Research Institute SynCat@Beijing of Synfuels China Technology, Co., Ltd and his own Dutch research enterprise Syngaschem BV in Eindhoven. He coauthored almost 300 scientific papers and three books, and has served as Editor of the Journal of Catalysis (1996-2015).

• Preface xiiiList of Acronyms xvii1 Introduction to Catalysis 11.1 What Is Catalysis? 21.2 Catalysts Can Be Atoms,Molecules, Enzymes, and Solid Surfaces 41.2.1 Homogeneous Catalysis 51.2.2 Biocatalysis 51.2.3 Heterogeneous Catalysis 61.3 Why Is Catalysis Important? 91.3.1 Catalysis and Green Chemistry 91.3.2 Atom Efficiency, E Factors, and Environmental Friendliness 101.3.3 The Chemical Industry 111.4 Catalysis as a Multidisciplinary Science 161.4.1 The Many Length Scales of a “Catalyst” 161.4.2 Time Scales in Catalysis 171.5 The Scope of this Book 181.6 Appendix: Catalysis in Journals 18References 222 Kinetics 232.1 Introduction 232.2 The Rate Equation and Power Rate Laws 252.3 Reactions and Thermodynamic Equilibrium 282.3.1 Example of Chemical Equilibrium: The Ammonia Synthesis 312.3.2 Chemical Equilibrium for a Nonideal Gas 332.4 The Temperature Dependence of the Rate 352.5 Integrated Rate Equations: Time Dependence of Concentrations in Reactions of Different Orders 382.6 Coupled Reactions in Flow Reactors: The Steady State Approximation 412.7 Coupled Reactions in Batch Reactors 452.8 Catalytic Reactions 482.8.1 The Mean-Field Approximation 522.9 Langmuir Adsorption Isotherms 532.9.1 Associative Adsorption 532.9.2 Dissociative Adsorption 542.9.3 Competitive Adsorption 552.10 Reaction Mechanisms 552.10.1 Langmuir–Hinshelwood or Eley–Rideal Mechanisms 562.10.2 Langmuir–Hinshelwood Kinetics 562.10.3 The Complete Solution 572.10.4 The Steady State Approximation 582.10.5 The Quasi-Equilibrium Approximation 592.10.6 Steps with Similar Rates 602.10.7 Irreversible Step Approximation 612.10.8 TheMARI Approximation 612.10.9 The Nearly Empty Surface 622.10.10 The Reaction Order 632.10.11 The Apparent Activation Energy 632.11 Entropy, Entropy Production, Auto Catalysis, and Oscillating Reactions 672.12 Kinetics of Enzyme-Catalyzed Reactions 73References 773 Reaction Rate Theory 793.1 Introduction 793.2 The Boltzmann Distribution and the Partition Function 803.3 Partition Functions of Atoms andMolecules 833.3.1 The Boltzmann Distribution 833.3.2 Maxwell–Boltzmann Distribution of Velocities 863.3.3 Total Partition Function of a System 873.4 Molecules in Equilibrium 933.5 Collision Theory 1003.5.1 Reaction Probability 1043.5.2 Fundamental Objection against Collision Theory 1053.6 Activation of Reacting Molecules by Collisions: The Lindemann Theory 1063.7 Transition State Theory 1073.8 Transition State Theory of Surface Reactions 1133.8.1 Adsorption of Atoms 1133.8.2 Adsorption ofMolecules 1183.8.3 Reaction between Adsorbates 1213.8.4 Desorption ofMolecules 1233.9 Summary 124References 1274 Catalyst Characterization 1294.1 Introduction 1294.2 X-ray Diffraction (XRD) 1314.3 X-ray Photoelectron Spectroscopy (XPS) 1344.4 X-ray Absorption Spectroscopy (EXAFS and XANES) 1394.4.1 Extended X-ray Absorption Fine Structure (EXAFS) 1394.4.2 X-ray Absorption Near-Edge Spectroscopy (XANES) 1434.5 Electron Microscopy 1444.6 Mossbauer Spectroscopy 1484.7 Ion Spectroscopy: SIMS, LEIS, RBS 1514.8 Temperature-Programmed Reduction, Oxidation, and Sulfidation 1554.9 Infrared Spectroscopy 1584.10 Surface Science Techniques 1604.10.1 Low Electron Energy Diffraction (LEED) 1614.10.2 Scanning ProbeMicroscopy 1644.11 Concluding Remarks 169References 1705 SolidCatalysts 1735.1 Requirements of a Successful Catalyst 1735.2 The Structure ofMetals, Oxides, and Sulfides and Their Surfaces 1755.2.1 Metal Structures 1755.2.2 Surface Crystallography of Metals 1765.2.3 Oxides and Sulfides 1825.2.4 Surface Free Energy 1855.3 Characteristics of Small Particles and Porous Material 1875.3.1 The Wulff Construction 1875.3.2 The Pore System 1905.3.3 The Surface Area 1915.4 Catalyst Supports 1975.4.1 Silica 1975.4.2 Alumina 1995.4.3 Carbon 2015.4.4 Shaping of Catalyst Supports 2015.5 Preparation of Supported Catalysts 2035.5.1 Coprecipitation 2035.5.2 Impregnation, Adsorption, and Ion Exchange 2035.5.3 Deposition Precipitation 2055.6 Unsupported Catalysts 2065.7 Zeolites 2065.7.1 Structure of a Zeolite 2075.7.2 Compensating Cations and Acidity 2085.7.3 Applications of Zeolites 2095.8 Catalyst Testing 2105.8.1 Ten Commandments for Testing Catalysts 2115.8.2 Activity Measurements 213References 2236 Surface Reactivity 2256.1 Introduction 2256.2 Physisorption 2266.2.1 The Van derWaals Interaction 2266.2.2 Including the Repulsive Part 2276.3 Chemical Bonding 2286.3.1 Bonding in Molecules 2296.3.2 The Solid Surface 2336.4 Chemisorption 2466.4.1 The Newns–Anderson Model 2466.4.2 Summary of the Newns–Anderson Approximation in Qualitative Terms 2526.4.3 Electrostatic Effects in Atomic Adsorbates on Jellium 2546.5 Important Trends in Surface Reactivity 2566.5.1 Trend in Atomic Chemisorption Energies 2576.5.2 Trends in Molecular Chemisorption 2616.5.3 Trends in Surface Reactivity 2656.5.4 Universality in Heterogeneous Catalysis 2746.5.5 Scaling Relations 2766.5.6 Appendix: Density Functional Theory (DFT) 278References 2807 Kinetics of Reactions on Surfaces 2837.1 Elementary Surface Reactions 2837.1.1 Adsorption and Sticking 2837.1.2 Desorption 2897.1.3 Lateral Interactions in Surface Reactions 2957.1.4 Dissociation Reactions on Surfaces 2977.1.5 Intermediates in Surface Reactions 3017.1.6 Association Reactions 3017.2 Kinetic Parameters from Fitting Langmuir–Hinshelwood Models 3047.3 Microkinetic Modeling 3067.3.1 Reaction Scheme and Rate Expressions 3077.3.2 Activation Energy and Reaction Orders 3107.3.3 Ammonia Synthesis Catalyst underWorking Conditions 313References 3158 Catalysis in Practice: Synthesis Gas and Hydrogen 3198.1 Introduction 3198.2 Synthesis Gas and Hydrogen 3198.2.1 Steam Reforming: Basic Concepts of the Process 3218.2.2 Mechanistic Detail of Steam Reforming 3238.2.3 Challenges in the Steam Reforming Process 3268.2.4 The SPARG Process: Selective Poisoning by Sulfur 3288.2.5 Gold–Nickel Alloy Catalyst for Steam Reforming 3298.2.6 Direct Uses of Methane 3308.3 Reaction of Synthesis Gas 3328.3.1 Methanol Synthesis 3328.3.2 Fischer–Tropsch Process 3438.4 Water–Gas Shift Reaction 3518.5 Synthesis of Ammonia 3538.5.1 History of Ammonia Synthesis 3538.5.2 Ammonia Synthesis Plant 3558.5.3 Operating the Reactor 3568.5.4 Scientific Rationale for Improving Catalysts 3598.6 Promoters and Inhibitors 3618.7 The “Hydrogen Society” 3648.7.1 The Need for Sustainable Energy 3648.7.2 Sustainable Energy Sources 3668.7.3 Energy Storage 3688.7.4 Hydrogen Fuel Cells 377References 3859 Oil Refining and Petrochemistry 3919.1 Crude Oil 3919.2 Hydrotreating 3949.2.1 Heteroatoms and Undesired Compounds 3959.2.2 Hydrotreating Catalysts 3979.2.3 Hydrodesulfurization Reaction Mechanisms 3999.3 Gasoline Production 4029.3.1 Fluidized Catalytic Cracking 4049.3.2 Reforming and Bifunctional Catalysis 4069.3.3 Alkylation 4109.4 Petrochemistry: Reactions of Small Olefins 4129.4.1 Ethylene Epoxidation 4129.4.2 Partial Oxidation and Ammoxidation of Propylene 4139.4.3 Polymerization Catalysis 415References 41810 Environmental Catalysis 42110.1 Introduction 42110.2 Air Pollution by Automotive Exhaust 42210.2.1 The Three-Way Catalyst 42310.2.2 Catalytic Reactions in the Three-Way Catalyst: Mechanism and Kinetics 42910.2.3 Concluding Remarks on Automotive Catalysts 43610.3 Air Pollution by Large Stationary Sources 43710.3.1 Selective Catalytic Reduction: The SCR Process 43710.3.2 The SCR Process for Mobile Units 443References 444Appendix 447Questions and Exercises 449Index 497

From Reviews of former editions:'... such an enterprise will be of great value to the community, to professionals as well as graduate and undergraduate students attempting to move into the field of modern catalysis and kinetics. I strongly recommend you publish this book based on the proposal.' - Prof. Dr. G. A. Samorjai, University of California 'Both authors are well respected specialists, with a very long record of original top-quality work and an international reputation. A book from these authors will be considered an authoritative piece of work, I definitely support this project and I am looking forward to use the book when published.' - Prof. Dr. D. E. Resasco, University of Oklahoma 'I wholly support the proposed project. The authors are very competent young colleagues and there is a real need for such a textbook' - Prof. Dr. G. Ertl, Fritz-Haber-Institut, Max-Planck-Gesellschaft, Berlin "I am impressed by the coverage of the book and it is a valuable addition to the catalysis literature and I highly recommend purchase"Energy Sources "The book's structure is based on academic courses taught over the years by the two authors. Questions and exercises are offered at the end of the book. Highly recommended." Choice "...this excellent book is highly recommended to students at technical universities, but also entrants in chemical industry. Furthermore, this informative handbook is also a must for all professionals in the community."AFS "The text is well written and easy to follow, with references provided for the reader who wants to know more. The text is enlivened by snippets of information and comment... If you are looking for a good textbook on heterogeneous catalysis, "Concepts of Modern Catalysis and Kinetics" is well worth considering. It is certainly a book I would have liked to have read when I started in catalysis research."Platinum Metals Review "The authors are experienced experts, who have a fundamental understanding of catalysis - from its theoretical-chemical and physical-chemical basics right up to applications in process technology. I wholeheartedly recommend this book to anyone seeking a solid basis in the field of catalysis."Chemie Ingenieur Technik "In summary "Concepts of Modern Catalysis and Kinetics" is a valuable guide to enter and travel the sometimes rather labyrinthine trails in heterogeneous catalysis. "ChemPhysChem "The book is well written and richly illustrated with instructive black and white diagrams. Students, especially those at Eindhoven and Lyngby, will have to read it from cover to cover. More mature readers, such as myself, have the privilege to skip the dry bits on kinetics and focus on the catalysis parts for the sheer excitement of the facts... The book does catalysis justice as a central concept of chemistry."Chemistry & Industry "This book is a thorough and comprehensive introduction to the science and application of heterogeneous catalysis."Applied Organometallic Chemistry "This book will be a valuable addition to many chemistry libraries... For the specialist in heterogeneous catalysis, the book provides a wealth of information regarding both fundamentals and applications."Synthesis