Modern Heterogeneous Catalysis

Rutger Anthony van Santen is professor at the Institute of Molecular Complexity at Eindhoven Technical University (TU/e, The Netherlands). He received his doctorate as theoretical chemist from Leiden University in 1971. After his initial stay at Shell Research (Amsterdam, The Netherlands), he became professor in Catalysis at the Technical University Eindhoven (The Netherlands) in 1986. In 1993, van Santen was the founding director of the Netherlands Institute of Catalysis and from 2001 to 2005 he was Rector Magnificus of TU/e. He is a member of the Royal Netherlands Academy of Arts and Sciences and a Knight in the order of the Dutch Lion. His research interests are in the field of the molecular aspects of heterogeneous catalysis with the following three main themes: computational studies of surface-chemical reactivity, mechanism in heterogeneous catalysis and physical chemistry of catalyst synthesis.

• Preface xvAcknowledgments xixArrangement of This Book xxiPart I Physical Chemistry and Kinetics 11 Heterogeneous Catalysis 31.1 What is Heterogeneous Catalysis? 31.2 Early Developments 41.2.1 Early Nineteenth Century Discoveries 51.2.2 Later Nineteenth Century Discoveries 71.3 The Three Basic Laws of Catalysis 71.3.1 Berzelius’ Catalysis Law 71.3.2 Ostwald’s Catalysis Law 81.3.3 Sabatier’s Catalysis Law 10References 122 Heterogeneous Catalytic Processes 152.1 Introduction 152.2 Important Heterogeneous Catalytic Reactions and Processes 192.2.1 Hydrogenation and Dehydrogenation Reactions 192.2.1.1 Hydrogenation Reactions: Transition Metal Catalysts 192.2.2 Hydrocarbon Transformation Reactions 222.2.2.1 Brønsted Acid Catalysis 222.2.3 Oligomerization and Polymerization Catalysis 272.2.3.1 Methanol to Ethylene and Aromatics: The Aufbau Reaction 272.2.3.2 Fischer–Tropsch Catalysis 292.2.3.3 Disproportionation and Metathesis Reaction: Single Site Catalysis 322.2.3.4 Polymerization: Surface Coordination Complex Catalyst 352.2.4 Hydrodesulfurization and Related Hydrotreating Reactions 362.2.4.1 Hydrodesulfurization 362.2.4.2 The Biomass Refinery 372.2.5 Oxidation and Reduction Reactions 382.2.5.1 Steam Reforming 382.2.5.2 Nh 3 to No X Oxidation 392.2.5.3 NO Reduction Catalysis 452.3 Summary 48References 513 Physical Chemistry, Elementary Kinetics 593.1 Introduction 593.2 Catalyst Characterization 633.2.1 Langmuir Adsorption Isotherm 643.2.2 Measurement of Pore Volume 653.2.3 Porosity 663.2.4 Temperature-Programmed Reactivity Measurements 673.2.5 Spectroscopic Techniques 683.3 Elementary Kinetics 683.3.1 Lumped Kinetics Expressions: Kinetic Determination of Key Reaction Intermediates 683.3.1.1 The Rate Constant of an Elementary Reaction 683.3.1.2 Elementary Catalytic Reaction Kinetics 713.3.2 Sabatier Principle and Volcano Curves: Brønsted–Evans–Polanyi Relations 783.3.2.1 Brønsted–Evans–Polanyi Relations of Elementary Surface Reaction Rate Constants 793.3.2.2 The Sabatier Volcano Curve 843.3.2.3 The Reaction Energy Diagram of the Catalytic Reaction Cycle 903.3.2.4 Electrocatalysis and Sabatier Principle Optimum 943.3.2.5 Temperature Dependence of Catalytic Reaction Rate 963.3.2.6 Summary: The Order of Reaction Rate 1013.4 Transient Kinetics: The Determination of Site Concentration 1043.5 Diffusion 1063.5.1 Concentration Profiles 1063.5.2 Effectiveness Factor 1073.5.3 Diffusion in Zeolitic Micropores 110References 1144 The State of the Working Catalyst 1174.1 Introduction 1174.2 Surface Reconstruction 1194.3 Compound Formation: Activation and Deactivation 1234.4 Supported Small Metal Particles 1244.4.1 Nature of the Support Material 1254.4.2 Reactivity and Stability 1274.4.3 Summary 1284.5 Structure Sensitivity of Transition Metal Particle Catalysts 1294.5.1 Particle Size and Structure Dependence of Heterogeneous Catalytic Reactions 1294.5.2 Site Generation 1334.6 Alloys and Other Promotors 1334.7 The Working Zeolite Catalysts 1364.8 The State of the Mixed Oxide Surface 1394.9 Summary 139References 1405 Advanced Kinetics: Breakdown of Mean Field Approximation 1455.1 Introduction 1455.2 The Kinetic Monte Carlo Method: RuO 2 Catalyzed Oxidation 1465.3 Single Molecule Spectroscopy 1495.4 Catalytic Self-Organizing Systems 1535.4.1 Introduction 1535.4.2 Heterogeneous Catalytic Self-Organizing Systems 1545.4.2.1 Alternation Between Two Different Surface Phases: Spiral Wave Formation 1555.4.2.2 Competitive Reactive Steps Prevent Reactive Phase Formation 165References 165Part II Molecular Heterogeneous Catalysis 167Introduction 167References 1716 Basic Quantum-Chemical Concepts, The Chemical Bond Revisited (Jointly Written with I. Tranca) 1736.1 Introduction 1736.2 The Definitions of Partial Density of States and Bond Order Overlap Population 1746.3 Diatomic Molecules that Have σ Bonds 1766.4 Diatomic Molecules with π Bonds 1826.5 Comparison of the Electronic Structure of Molecules and Solids 1866.6 Chemical Bonding in Transition Metals 1906.6.1 The Electronic Structure of the Transition Metals 1906.6.2 The Relative Stability of Transition Metal Structures 199Appendix 205References 2057 Chemical Bonding and Reactivity of Transition Metal Surfaces 2097.1 Introduction 2097.2 TheNatureoftheSurfaceChemicalBond 2107.2.1 The Electronic Structure of the Transition Metal Surface 2107.2.2 Chemisorption of Atoms and Molecules (This Section has been Jointly Written with I. Tranca.) 2137.2.2.1 The H Adatom: The Covalent Surface Bond 2147.2.2.2 Adsorption of the Carbon Atom: The Surface Molecular Complex 2207.2.2.3 The Oxygen Adatom: The Polar Surface Bond 2287.2.3 Adsorption Site Preference as a Function of Accessible Free Valence 2337.2.3.1 Chemisorption of Molecular Fragments Ch X ,nh X ,andoh X Species: Coordination Preference as a Function of Accessible Free Valence 2337.2.3.2 CH 3 and NH 3 Chemisorption: The Agostic Interaction 2357.2.4 Adsorption as a Function of Coordinative Unsaturation of Surface Atoms: Relation with d Valence Band Energy Shift 2437.2.5 Chemisorption of CO: Donative and Backdonative Interactions 2497.2.6 Lateral Interactions 2587.2.7 Scaling Laws 2597.2.8 In Summary: The Adsorbate Chemical Bond 2627.3 The Transition States of Elementary Surface Reactions 2647.3.1 Adsorbate σ-Bond Activation 2657.3.1.1 Activation of Methane 2657.3.1.2 The Oxidative Addition and Reductive Elimination Model 2687.3.1.3 The Umbrella Effect 2697.3.1.4 Activation Entropy 2707.3.1.5 σ-Bond Activation of Molecules that Bind Through their Lone Pair Orbital 2707.3.2 Dissociation of Diatomic Molecules with π-Bonds 2737.3.2.1 Principle of Non-Shared Bonding with the Same Surface Metal Atom 2747.4 Reactivity of Surfaces at High Coverage 2747.4.1 Decreased Surface Reactivity and Site Blocking 2757.4.2 Adatom Co-Assisted Activation 2767.4.2.1 Hydrogen Activated Dissociation 2767.4.2.2 Oxygen Assisted X–H Bond Cleavage 2777.4.2.3 Reactivity of the Oxide Overlayers 281References 2868 Mechanisms of Transition Metal Catalyzed Reactions 2938.1 Introduction 2938.2 Hydrogenation Reactions 2938.2.1 Ammonia Synthesis 2938.2.1.1 Heterogeneous Catalytic Reaction 2938.2.1.2 Enzyme Catalysis 2968.2.2 Synthesis Gas Conversion to Methane and Liquid Hydrocarbons 2978.2.3 Hydroconversion of Hydrocarbons 3068.2.3.1 Ethylene 3068.2.3.2 Acetylene 3098.2.3.3 Hydrogenolysis and Isomerization 3108.2.4 NH 3 and CH 4 to HCN 3148.2.5 Electrocatalysis; H 2 Evolution 3168.3 Oxidation Reactions 3218.3.1 Synthesis Gas from Methane 3218.3.1.1 Steam Reforming 3218.3.1.2 Methane Oxidation 3228.3.1.3 NH 3 Oxidation to NO and N 2 3238.3.1.4 Selective Oxidation of Ethylene 3258.4 Uniqueness of a Metal for a Particular Selective Reaction 337References 3389 Solid Acid Catalysis, Theory and Reaction Mechanisms 3459.1 Introduction 3459.2 Elementary Theory of Surface Acidity and Basicity 3459.2.1 The Pauling Charge Excess 3459.2.2 The Chemistry of the Zeolitic Proton 3519.2.2.1 Vibrational Spectroscopy of the OH Bond 3529.2.2.2 Quantum Chemistry of the Zeolite Acidic OH Chemical Bond 3589.2.2.3 The Proton Transfer Reaction 3649.2.2.4 Chemical Reactivity Probes of Proton Donation Affinity: H/D Exchange Reactions 3679.3 Mechanism of Reactions Catalyzed by Zeolite Protons 3719.3.1 Introduction to Acid-Catalyzed Reactions and Their Mechanism 3719.3.2 Elementary Reactions in Acid Catalysis 3749.3.2.1 Alkene Protonation 3749.3.2.2 Alkane Activation 3789.3.2.3 Alkene Isomerization 3839.3.2.4 n-Butene Isomerization 3869.3.2.5 β-C–C Bond Cleavage 3889.3.2.6 The Hydride Transfer Reaction 3909.3.3 Catalytic Reaction Cycles and Kinetics 3949.3.3.1 Physical Chemistry of Zeolite Catalysis 3949.3.3.2 Catalytic Cracking 3969.3.3.3 Bifunctional Catalysis 4029.3.3.4 Methanol Aufbau Chemistry: Alkylation by Methanol 4139.4 Acid Catalysis and Hydride Transfer by Enzyme Catalysts 420References 42110 Zeolitic Non-Redox and Redox Catalysis, Lewis Acid Catalysis 42910.1 Introduction 42910.2 Non-Reducible Cations; The Electrostatic Field 42910.3 Catalysis with Non-Framework Non-Reducible Cations 43310.3.1 Alkali and Earth Alkali Ions 43310.3.2 Non Redox Oxycationic Clusters 43710.4 Catalysis by Non-Framework Redox Complexes 44010.4.1 NO Reduction Catalysis: Selective Catalytic Reduction 44010.4.2 N 2 O Decomposition Catalysis 44110.4.3 Selective Oxidation of Benzene and Methane: The Panov Reaction 44310.5 Related Homogeneous and Enzyme Oxidation Catalysts 44610.6 Lewis Acid Catalysis by Non-Reducible Cations Located in the Zeolitic Framework 45310.6.1 Bayer–Villiger Oxidation 45410.6.2 Meerwein–Ponndorf–Verley Reduction and Oppenauer Oxidation 45610.6.3 Homogeneous and Biocatalyst Analogs 46110.6.4 Propylene Epoxidation 46110.7 Catalysis by Redox Cations located in the Zeolitic Framework: The Thomas Oxidation Catalysts 46310.7.1 Bayer–Villiger Oxidation with Molecular Oxygen 46410.7.2 Zeolite Catalysts for Caprolactam Synthesis 46410.7.3 Alkane Oxidation 46710.8 Summary of Zeolite Catalysis 468References 46911 Reducible Solid State Catalysts 47511.1 Introduction 47511.2 Chemical Bonding of Transition Metal Oxides and Their Surfaces 47511.2.1 Electronic Structure of the Metal Oxide Chemical Bond 47511.2.2 The Electronic Structure of the Transition Metal Oxides 47811.2.3 The Electronic Structure of the Transition Metal Oxide Surface 48811.2.4 Trends in Adsorption Energies of O Adatoms to Transition Metal Oxide Surfaces 49011.2.5 Reconstruction of Polar Surfaces 49211.3 Mechanism of Oxidation Catalysis by Group V, VI Metal Oxides 49411.3.1 Reactivity Trends 49411.3.2 Selective Oxidation of Propylene and Propane 50011.3.2.1 Propylene to Acrolein Conversion 50011.3.2.2 Propane Ammoxidation 50211.3.3 Methane Conversion to Higher Hydrocarbons 50311.3.3.1 Direct CH 4 Conversion to Aromatics 50311.3.3.2 The Mechanism of Oxidative Methane Coupling, the LiO–MgO System 50411.4 Metathesis and Polymerization Catalysis: Surface Coordination Complexes 50711.4.1 Alkene Disproportionation and Metathesis 50711.4.2 Polymerization of Propylene 51111.4.3 Ziegler–Natta Polymerization versus Metathesis Reaction 51411.5 Sulfide Catalysts 51511.6 Electrocatalysis: The Oxygen Evolution Reaction (OER) 52011.6.1 Trends in OER Reactivity 52011.6.2 Reaction Mechanism of OER Reaction 52211.6.3 Summary Mechanism of OER Reaction 53111.6.4 Comparison with the OER in Enzyme Catalysis 53211.7 Photocatalytic Water Splitting 53811.7.1 Device Considerations 53811.7.2 Mechanism of Photoactivation of Water 540References 545Index 553

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