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1.1 Importance of Catalysis . 1. . I 1.1.1 Additional Suggested Textbooks on Heterogeneous Catalysis . 3 1.2 Molecular Description of Heterogeneous Catalysis . . . . 4 1.3 Outline of the Book . . . . . . . . . . 8 1.4 Theoretical and Simulation Methods . . . . . 11 2 Principles of Molecular Heterogeneous Catalysis 2.1 General Introduction . . 19 2.1.1 The Catalytic Cycle . . . . . . 20 2.1.1.1 The Sabatier Principle . . . . .. . 20 2.1.1.2 Reaction Cycles; Intermediate Reagents . . . . . 25 2.2 Physical Chemistry of Intrinsic Reaction Rates . . . . 7 2.2.1 Introduction . . . . . .. ... 27 22.2.2 The Transition-State Theory Definition of the Reaction Rate Constant: Loose and Tight Transition States . . . . . . . 28 2.2.3 T.he Bronsted-Evans--Polanyi Reaction Rate Expression Relations 3. 2 2.3 The Reaciive Surface--Adsorbate Complex and the influence of the Reaction Environment . . , , , , . , . . 35 2.i3, Introduction . . . . . . . . . .. 35 2.132 The Material- and Pressure-Gap Problem in Heterogeneous Catalysis . 39 2.3.3 Ensemble Effects and Defect Sites . . . 2.3.4 Cluster Size Effects and Metal-Support Interaction . . . . . 47 2.3.4.1 Metal--Siupport Effects and Promotion: Relation to Catalyst Synthesis 47 2.3. 4.2 Cluster Size Dependence . . . . . . . 49 2.3.,4. Gold Catalysts; an Example of Coordination, Particle Size and Support Effects . . 53 2.3,4.4 Structural Effects 54. . 2.3.4.5 Quantum Size Effects . . . . . . . . 57 2.3,4.6 Support Effects . . . . . . .. . 56 2.3.4.7 Elucidating Mechanisms and the Nature of Active Sites . . . 57 2.3.4.8 Electron Transfer Effects . . . . . . . 57 2.3.4.9 Neutral Au Clusters 58. 2.3.4.10 Negatively Charged Au clusters . . . . . 59 2.3.4.11 Positively Charged Au Clusters . . . .. . . . 60 2.3.5 Cooperativity . . . . . . . . . 61 2.3.6 Surface Moderation by Coadsorption of Organic Molecules . . . 63 2.3.7 Stereochemistry of Homogeneous Catalysts. Anti-Lock and Key Concept 65 2.4 Surface Kinematics . . . . . . . . 68 2.4.1 Surface Reconstruction . . . . . . . . 68 2.4.2 Transient Reaction intermediates in Oxidation Catalysis . . 73 2.5 Summary; Concepts in Catalysis 75. . . . . 3 The Reactivity of Transition-Metal Surfaces 3.1 General Introduction . . . .83 3.2 Quantum Chemistry of the Chemical Bond in Molecules . 83 3.3 Chemical Bonding to Transition-Metal Surfaces . . 89 3.3.1 Bonding in Transition-Metal Complexes . . . 101 3.4 Chemisorption of Atoms: Periodic Trends . . . . . 105 3.5 Elementary Quantum Chemistry of the Surface Chemical Bond . . 113 3.5.1 Molecular Orbital View of Chemisorption. A Sumary . . . 118 3.6 Elementary Reaction Steps on Transition-Metal Surfaces. Trends with Position of a, Meta, in the Periodic Table . . 119 3.6. General Considerations . . . . . 19 3.6.2 Activation of CO and Other Diatomics . . . . 121 3.6.3 Association Reactions: Carbon- Carbon Bond Formation . . . 126 3.7 Organometallic Chemistry of the Hydroformiulation Reaction . 127 3.8 Activation of CH4, NH3 and H20 . . . . . . 128 3.9 Carbon-Carbon Bond Cleavage and Formation Reactions, a Comparison with CO Oxidation . . . . . . .. 138 3.10 Lateral Interactions . . . . 143 3.10.1 Introduction . . . . .. . . . 143 3.10.2 Lateral Interaction Models . . . 4 . . . . 144 3.10.3 Hydrogenation of Ethylene; the importance of Lateral Interactions 146 3.10.4 Lateral interactions: the Simulation of Overall Surface Reaction Rates 148 3.11 Addendum; Hybridization . . 1. . . . . 55 4 Shape Selective-Microporous Catalysts, the Zeolites 4.1 Zeolite Catalysis, an Introduction . . . 1 . 6 1 4.1.1 Zeolite Structural Features . . . . . 161 4.2 Activation of Reactant Molecules . 165 4.2.1 Proton-Activated Reactivity . . . 165 4.2.2 Transition-State Selectivity. Alkylation of Toluene by Methanol Catalyzed by Mordenite . . . . . . 177 4.2.3 Lewis Acid Catalvysis . . . . . 178 4.2.3.1 Lewis Acidity in Zeolites; Cations Compared with Oxy-Cations . 178 4.3 Redox Catalvsis . . 187 4.3.1 Selective Oxidation of Alkanes Using the Reducible M.1Ali_ PO4 Zeolitic Polymorphs .. . . . . 187 4.3.2 Photo Catalytic Oxidation . . . . . . . . 189 4.3.3 The N20 Decomposition Reaction; Self-Organization in Zeolite Catalysis 190 4.3.4 Oxidation of Benzene by N20, the Panov Reaction . . . . 193 4.4 The Zeolite Catalytic Cycle. Adsorption and Catalysis in Zeolites: the Principle of Least Optimum Fit . . . . . . . 195 4.5 Adsorption Equilibria and Catalytic Selectivity . . . 205 "4.6 Diffusion in Zeoltes .. . 207 5 Catalysis by Oxides and Sulfides 5.1 General Introduction . . . . 213 5.2 Elementary Theory of Reactivity and Stability of Ionic Surfaces 214 5.3 The Contribution of Covalency to the Ionic Surface Chemical Bond . 223 o.3.1 CO Oxidatio:n by BuO2 223 5.3.2 Atomic Orbital H ybridization at Surfaces; Hydration Energies . 226 54 Medium Effects on Bronsted Acidity . . . . . 230 5.5 Aciditv of Heteropolyacids . . . . .. . 234 5.6 Oxidation Catalysis . . . . 238 5.6.1 Introduction . . . . . . 238 5.6.2 Lessons Learned from Surface Science . . . . 243 5.6.3 Redox Considerations . . . . . . . 244 5.6.4 3ifunctional Systems . . . . 246 5.6.5 Butane Oxidation to Maleic Anhydride . . . 246 .5.6 Methanol Oxidation . . . . .. 248 5.6.7 Isobutyric Acid Oxidative Dehydrogenation . . . 249 5.6.8 Oxidative Dehydrogenation of Propane . .. 249 5.6,9 Chemical Reactivity of Reducible Oxides . . . 250 5.6.10 Selective Catalytic Reduction of NO with NH . . . 251 5.6.11 Oxidation by Non-Reducible Oxides . . . . . . 253 5.7 Heterogeneous Sulfide Catalysts . . . . 255 5.7.1 Introduction . . . . .. . . 255 S57.2 The Sulfide Surface . . 256 .7.3 Promoted Sulfide Catalysts . . . .. . 259 5.8 Suunmary . . . . . . 262 6 Mechanisms for Aqueous Phase Heterogeneous Catalysis and Electrocatalysis. A Comparison with Heterogeneous Catalytic Reactions 6.1 General Introduction . . . . . . . . 267 S.2 The Chenistry of Water on Transition-Metal Surfaces . . . 268 6.2.1 Reactions in Solutions . . . . . . 268 6.2.2 The Adsorption of Water on Metal Surfaces . . .. 268 6.2.3 Influence of Potential . . . . . . . . . 276 6.2.4 Electrochemical Activation of Water . . . . . . . 282 6.3 The Synthesis of Vinyl Acetate via the Acetoxylation of Ethylene . 286 6.3. Homogeneous Catalyzed Vinyl Acetate Synthesis . . . 288 6.3.2 Element ary Reaction Steps of Vinyl Acetate in the Liquid Phase . 289 G.3.3 VAM Synthesis: Homogeneous or Heterogeneous? . . . . 293 6.4 Low- Temperatu r Ammonia Oxidation . . . . . 294 6.4. 1 Ammonia Oxidation with Pt2± Ion-Exchanged Zeolite Catalysts; Catalysis Through Coordination Chemistry . . . . . 300 6.4.2 Electrocatalytic NH3 Oxidation . . . . . 303 6.5 Electrochemical NO Reducton . . . .. 305 6.6 Electrocatalytic Oxidation of CO . . .306 . 7 Summar . . . . . 307 Addendumd: The Tafel Slope and Reaction Mechanism in Electrocatalysis 308 7 Mechanisms in Biocatalysis; Relationship with Chemocatalysis 7.1 General Introduction . . .. . . . . 313 .2 The Mechanism of Enzvme Action: the Induced Fit Model 315 7 3 AIT-Synthase Mechanism.; a Rotating Carousel with Multiple Catalytic Sites . 320 7.4 Carbonic Anhydrase . . . . . . .. 322 7.5 Biominicking of Enzyme Catalysis . . . . . 323 7.6 Bio-Electrocatalytic and Chemocatalytic Reduction Reactions 326 7.6.1 Oxidation Catalysis . . . . . . . 326 7.7 Reduction Catalysis . . . . . . 330 7.8 Enzyme Mechanistic Action Summarized 334 8 Self Organization and Self Assembly of Catalytic Systems 8.1 General Introduction . . .. . . . 337 8.2 Self Repair in Chemocatalysis . . . . 338 8.3 Synchroniza ion of R.eaction enters . .. . . 341 8.4 The Physical Chemistry of Self Organization . . . 344 8.5 Size Dependence and Cooperative Behavior 349 8.6 Immunoresponse and Evolutionary Catalysis . . . 351 8.7 Inorganic Self Assembly Processes: Zeolite Synthesis . . . 35 8.7.1 General Aspects . . . .. . 354 8.7.2 Mechanism of Zeolite Synthesis . 355 8.8 Evolutionary Computational Methods . . 358 8.9 Summary . . . . . 36 . 363 9 Heterogeneous Catalysis and the Origin of Life. Biornineralization 9.1 General Introduction . . . . . 367 9.2 The Origin of Chirality . . . 373 9.3 Artificial Catalytic Chemistry . . . . 374 9.3.1 Graded Autocatalysis Replication Domain Model . . 375 9.4 Control Parameters and the Emergence of Artificial Life . . . 379 9.4.1 The Logistic Map . . . . . . 379 9.4.2 Life at the Edge of Chaos . . . 382 9.5 Different Levels of Self Organization in Catalysis: a sunmmary . 385 9.6 Biomineralization, the Synthesis of Mesoporous Silicas . . . 386 9.6.1 Biomimetic Approaches for Amorphous Silica Synthesis . . . 88 9.6.2 Micro-Emulsion Mediated Silica Formation . . . 390 9.7 Aging of Silica Gels . . . . .. 394 9.7.1 Silica Gel Synthesis . . . . . 394 9.7.2 Fractals . .. . . . 396 "9.7.3 Sinmulation of Aggregation Processes . 398 9. Expressions for Aging of Fractal Systems 4 . . . 02 9.9 In Conclusion; Self Organization and Self Assembly . 403 10 Postscript . . . . . 409 Appendices: Computational Methods Introduction . . . 423 A: ELECTRONIC STRUCTURE METHODS . . .. 424 B: ATOMIC/MOLECULAR SIMAULATION . . . . 447 C: SIMULATING KINETICS . 456