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List of Contributors XVII Preface XXI Part I Basic Concepts 1 1 Catalysis in Perspective: Historic Review 3 Rutger van Santen 1.1 History of Catalysis Science 3 1.2 The Development of Catalytic Processes: History and Future 11 1.3 Fundamental Catalysis in Practice 13 1.4 Catalyst Selection 13 1.5 Reactor Choice 16 1.6 Process Choice 17 References 19 Further Reading 19 2 Kinetics of Heterogeneous Catalytic Reactions 20 Rutger van Santen 2.1 Physical chemical principles 20 2.2 The Lock and Key Model, the Role of Adsorption Entropy 27 2.3 Equivalence of Electrocatalysis and Chemocatalysis 30 2.4 Microkinetics; the Rate–Determining Step 32 2.5 Elementary Rate Constant Expressions for Surface Reactions 34 2.6 The Pressure Gap 36 2.7 The Materials Gap 39 2.8 Coupling of Catalytic Reaction and Inorganic Solid Chemistry 42 2.9 In situ Generation of Organo–Catalyst 42 2.10 The Compensation Effect 44 References 46 3 Kinetics in Homogeneous Catalysis 48 Detlef Heller 3.1 Principles of a Catalyst and Kinetic Description 48 3.2 Catalyst Activity 54 3.3 Catalyst Activation and Deactivation 58 References 64 4 Catalytic Reaction Engineering Principles 67 Albert Renken and Lioubov Kiwi–Minsker 4.1 Preface 67 4.2 Formal Kinetics of Catalytic Reactions 68 4.3 Mass and Heat Transfer Effects 77 4.4 Homogenous Catalysis in Biphasic Fluid/Fluid Systems 103 References 108 Part II The Chemistry of Catalytic Reactivity 111 5 Heterogeneous Catalysis 113 Rutger van Santen 5.1 General Introduction 113 5.2 Transition Metal Catalysis 114 5.3 Solid Acids and Bases 132 5.4 Reducible Oxides 143 References 150 6 Homogeneous Catalysis 152 Matthias Beller, Serafino Gladiali, and Detlef Heller 6.1 General Features 152 References 169 7 Biocatalysis 171 Uwe Bornscheuer 7.1 Introduction 171 7.2 Examples 176 7.3 Summary/Conclusions 194 References 194 8 Electrocatalysis 201 Timo Jacob 8.1 Introduction 201 8.2 Theory 203 8.3 Application to the Oxygen Reduction Reaction (ORR) on Pt(111) 207 8.4 Summary 212 References 213 9 Heterogeneous Photocatalysis 216 Guido Mul 9.1 Introduction 216 9.2 Applications of Photocatalysis 219 9.3 Case Studies 220 9.4 Concluding Remarks 228 References 228 Part III Industrial Catalytic Conversions 231 10 Carbonylation Reactions 233 Matthias Beller 10.1 General Aspects 233 10.2 Hydroformylation 234 10.3 Other Carbonylations of Olefins and Alkynes 238 10.4 Carbonylations of Alcohols and Aryl Halides 244 References 246 11 Biocatalytic Processes 250 Uwe Bornscheuer 11.1 Introduction 250 11.2 Examples 253 11.2.1 General Applications 253 11.3 Case Study: Synthesis of Lipitor Building Blocks 257 11.4 Conclusions 259 References 259 12 Polymerization 261 Vincenzo Busico 12.1 Introduction 261 12.2 Polyolefins in Brief 262 12.3 Olefin Polymerization Catalysts 264 12.4 Olefin Polymerization Process Technology 273 12.5 The Latest Breakthroughs 280 References 285 13 Ammonia Synthesis 289 Jens Rostrup–Nielsen 13.1 Ammonia Plant 289 13.2 Synthesis 291 13.3 Steam Reforming 295 13.4 Conclusions 299 Abbreviations 299 References 299 14 Fischer–Tropsch Synthesis in a Modern Perspective 301 Hans Schulz 14.1 Introduction 301 14.2 Stoichiometry and Thermodynamic Aspects 304 14.3 Processes and Product Composition 308 14.4 Catalysts, General 311 14.5 Reaction Fundamentals 313 14.6 Concluding Remarks 323 References 323 15 Zeolite Catalysis 325 Rutger van Santen 15.1 Introduction 325 15.2 The Hydrocracking Reaction; Acid Catalysis 325 15.3 Lewis Acid–Lewis Base Catalysis; Hydrocarbon Activation 332 15.4 Selective Oxidation; Redox Catalysis 333 15.5 Framework–Substituted Redox Ions 335 References 339 16 Catalytic Selective Oxidation –Fundamentals, Consolidated Technologies, and Directions for Innovation 341 Fabrizio Cavani 16.1 Catalytic Selective Oxidation: Main Features 341 16.2 Catalytic Selective Oxidation: What Makes the Development of an Industrial Process More Challenging (and Troublesome) than Other Reactions 353 16.3 Catalytic Selective Oxidation: the Forefront in the Continuous Development of More–Sustainable Industrial Technologies 355 16.4 The Main Issue in Catalytic Oxidation: the Control of Selectivity 356 16.5 Dream Reactions in Catalytic Selective Oxidation: a Few Examples (Some Sustainable, Some Not Sustainable) 359 16.6 A New Golden Age for Catalytic Selective Oxidation? 361 16.7 Conclusions: Several Opportunities for More Sustainable Oxidation Processes 363 References 363 17 High–Temperature Catalysis: Role of Heterogeneous, Homogeneous, and Radical Chemistry 365 Olaf Deutschmann 17.1 Introduction 365 17.2 Fundamentals 366 17.3 Applications 372 17.4 Hydrogen Production from Logistic Fuels by High–Temperature Catalysis 378 17.5 High–Temperature Catalysis in Solid Oxide Fuel Cells 380 References 385 18 Hydrodesulfurization 390 Roel Prins 18.1 Introduction 390 18.2 Hydrodesulfurization 391 18.3 The C–X Bond–Breaking Mechanism 393 18.4 Structure of the Sulfidic Catalyst 393 18.5 Hydrodenitrogenation 397 18.6 Determination of Surface Sites 398 References 398 Part IV Catalyst Synthesis and Materials 399 19 Molecularly Defined Systems in Heterogeneous Catalysis 401 Fernando Rasc´on and Christophe Cop´eret 19.1 Introduction 401 19.2 Single Sites: On the Border between Homogeneous and Heterogeneous Catalysis 402 19.3 Conclusion and Perspectives 415 References 415 20 Preparation of Supported Catalysts 420 Krijn P. de Jong 20.1 Introduction 420 20.2 Support Surface Chemistry 422 20.3 Ion Adsorption 423 20.4 Impregnation and Drying 425 20.5 Deposition Precipitation 427 20.6 Thermal Treatment 428 References 429 21 Porous Materials as Catalysts and Catalyst Supports 431 Petra de Jongh 21.1 General Characteristics 431 21.2 Sol–gel and Fumed Silica 433 21.3 Alumina and Other Oxides 436 21.4 Carbon Materials 438 21.5 Zeolites 440 21.6 Ordered Mesoporous Materials 442 21.7 Metal–Organic Frameworks 442 21.8 Shaping 443 References 444 22 Development of Catalytic Materials 445 Manfred Baerns 22.1 Introduction 445 22.2 Fundamental Aspects 446 22.3 Micro–Kinetics and Solid–State Properties as a Knowledge Source in Catalyst Development 448 22.4 Combinatorial Approaches and High–Throughput Technologies in the Development of Solid Catalysts 453 References 459 Part V Characterization Methods 463 23 In–situ Techniques for Homogeneous Catalysis 465 Detlef Selent and Detlef Heller 23.1 Introduction 465 23.2 In–situ Techniques for Homogeneous Catalysis 466 23.3 Gas Consumption and Gas Formation 467 23.4 NMR Spectroscopy 470 23.5 IR–Spectroscopy 481 23.6 UV/Vis Spectroscopy 486 23.7 Summary 490 References 490 24 In–situ Characterization of Heterogeneous Catalysts 493 Bert Weckhuysen 24.1 Introduction 493 24.2 Some History, Recent Developments, and Applications 495 24.3 In situ Characterization of a Reactor Loaded with a Catalytic Solid 497 24.4 In situ Characterization at a Single Catalyst Particle Level 501 24.5 Concluding Remarks 511 Acknowledgments 511 References 511 25 Adsorption Methods for Characterization of Porous Materials 514 Evgeny Pidko and Emiel Hensen 25.1 Introduction 514 25.2 Physical Adsorption 514 25.3 Classification of Porous Materials 517 25.4 Adsorption Isotherms 517 25.5 The Application of Adsorption Methods 518 25.6 Theoretical Description of Adsorption 519 25.7 Characterization of Microporous Materials 524 25.8 Characterization of Mesoporous Materials 527 25.9 Mercury Porosimetry 533 25.10 Xenon Porosimetry 533 References 534 26 A Critical Review of Some ‘‘Classical’’ Guidelines for Catalyst Testing 536 Frits Dautzenberg 26.1 Introduction 536 26.2 Encouraging Effectiveness 536 26.3 Ensuring Efficiency 537 26.4 Concluding Remarks 552 Appendix A: Three–Phase Trickle–Bed Reactors 552 List of Symbols and Abbreviations 558 References 559 Part VI Catalytic Reactor Engineering 561 27 Catalytic Reactor Engineering 563 Albert Renken and Madhvanand N. Kashid 27.1 Introduction 563 27.2 Types of Catalytic Reactors 564 27.3 Ideal Reactor Modeling/Heat Management 575 27.4 Residence Time Distribution 587 27.5 Microreaction Engineering 602 References 625 Index 629