Surface and nanomolecular catalysis

Using new instrumentation and experimental techniques that allow scientists to observe chemical reactions and molecular properties at the nanoscale, the authors of Surface and Nanomolecular Catalysis reveal new insights into the surface chemistry of catalysts and the reaction mechanisms that actually occur at a molecular level during catalysis. While each chapter contains the necessary background and explanations to stand alone, the diverse collection of chapters shows how developments from various fields each contributed to our current understanding of nanomolecular catalysis as a whole. The book describes how the size and shape of materials at the nanoscale can change their chemical and physical properties and promote more efficient reactions with fewer by-products. First it highlights the preparation, characterization, and applications of heterogeneous and supported metal catalysts. Then it covers the engineering of catalytic processes, structure and reaction control, and texturological properties of catalytic systems. The authors explain how surface science can elucidate reaction mechanisms and discuss the growing role of high-throughput experimentation and combinatorial approaches in catalysis. From fundamental concepts to future directions, Surface and Nanomolecular Catalysis offers a well-rounded compilation of noteworthy developments which will continue to expand and transform our understanding of catalysis, particularly in the context of clean energy and environmental applications such as fuel cells. FM dk3277fm 1 SURFACE AND NANOMOLECULAR CATALYSIS 1 Dedication 3 Preface 4 The Editor 6 Contributors 7 Contents 9 DK3277ch1 11 Table of Contents -1 CHAPTER 1: Characterization of Heterogeneous Catalysts 11 CONTENTS 11 1.1 INTRODUCTION 12 1.2 STRUCTURAL TECHNIQUES 12 1.2.1 X-Ray Diffraction 12 1.2.2 X-Ray Absorption Spectroscopy 13 1.2.3 Electron Microscopy 15 1.3 ADSORPTION–DESORPTION AND THERMAL TECHNIQUES 17 1.3.1 Surface Area and Pore Structure 17 1.3.2 Temperature-Programmed Desorption and Reaction 18 1.3.3 Thermogravimetry and Thermal Analysis 19 1.3.4 Microcalorimetry 20 1.4 OPTICAL SPECTROSCOPIES 22 1.4.1 Infrared Spectroscopy 22 1.4.2 Raman Spectroscopy 23 1.4.3 Ultraviolet–Visible Spectroscopy 25 1.4.4 Nuclear Magnetic Resonance 26 1.4.5 Electron Spin Resonance 28 1.5 SURFACE-SENSITIVE SPECTROSCOPIES 29 1.5.1 X-Ray and Ultraviolet Photoelectron Spectroscopies 29 1.5.2 Auger Electron Spectroscopy 30 1.5.3 Low-Energy Ion Scattering 31 1.5.4 Secondary-Ion Mass Spectroscopy 31 1.6 MODEL CATALYSTS 32 1.7 CONCLUDING REMARKS 35 REFERENCES 36 CHAPTER 1 QUESTIONS 42 Question 1 42 Question 2 42 Question 3 42 Question 4 43 Question 5 43 Question 6 44 Question 7 44 Question 8 45 Question 9 45 Question 10 46 Question 11 46 Question 12 47 DK3277ch2 48 Table of Contents -1 CHAPTER 2: Catalysis by Metal Oxides 48 CONTENTS 48 2.1 INTRODUCTION 49 2.2 PROPERTIES OF METAL OXIDES 49 2.2.1 The Periodic Table as Metal Oxides 50 2.2.2 Insulators (Highly Ionic) 50 2.2.3 Semiconductors (Ionic–Covalent Bonding) 51 2.2.4 Crystal Structures 51 2.3 SURFACE STRUCTURES 53 2.3.1 Surface Reconstruction 53 2.3.2 Defect Sites 55 2.3.3 Hydroxyl Groups 57 2.4 SOLID ACIDS AND BASES 57 2.4.1 Metal Cations as Lewis Acids 58 2.4.2 Oxygen Anions as Lewis Bases 58 2.4.3 Hydroxyl Groups as Bronsted Acids and Lewis Bases 59 2.4.4 Spectroscopic Methods of Detecting Lewis Acidity/Basicity and Bronsted Acidity/Basicity 59 2.5 EXAMPLES OF CATALYSIS 60 2.5.1 Examples of Solid Acids and Bases 60 2.5.1.1 Hydrogen –Deuterium Exchange Reaction 60 2.5.1.2 Hydrogenation (1,3-Butadiene + D2) 61 2.5.1.3 Dehydration and Dehydrogenation 62 2.5.1.4 Dehydrochlorination 62 2.5.1.5 Benzylation 62 2.5.1.6 Claisen–Schmidt Condensation-Asymmetric Epoxidation 63 2.5.2 Oxidation Catalysis 63 2.5.2.1 Oxidative Dehydrogenation — Vanadia 63 2.5.2.2 Oxidative Coupling of Methane 64 2.5.3 Chloride–Oxide Exchange Catalysis 65 2.5.3.1 Chlorocarbons 65 2.5.3.2 Freons 65 2.6 CONCLUSIONS 66 REFERENCES 66 CHAPTER 2 QUESTIONS 70 Question 1 70 Question 2 70 Question 3 70 Question 4 70 Question 5 70 Question 6 70 Question 7 70 Question 8 70 DK3277ch3 71 Table of Contents -1 CHAPTER 3: Colloidal Nanoparticles in Catalysis 71 CONTENTS 71 3.1 INTRODUCTION 71 3.2 MECHANISM OF STABLE PARTICLE FORMATION 72 3.3 MODES OF STABILIZATION 72 3.4 REDUCTION METHODS 74 3.5 APPLICATIONS IN CATALYSIS 82 3.5.1 Quasi-Homogeneous Reactions 82 3.5.2 Heterogeneous Reactions 82 3.5.2.1 Precursor Concept 82 3.5.2.2 Conditioning: A Key Step in Generating Active Catalysts 83 3.5.2.3 Heterogeneous Catalysts in Catalysis 84 3.5.2.4 Fuel Cell Catalysts 91 3.6 CONCLUSION 93 REFERENCES 94 CHAPTER 3 QUESTIONS 102 Question 1 102 Question 2 102 Question 3 102 Question 4 102 Question 5 102 DK3277ch4 103 Table of Contents -1 CHAPTER 4: Microporous and Mesoporous Catalysts 103 CONTENTS 103 4.1 SETTING THE SCENE 104 4.2 POROUS CATALYSTS 105 4.3 MICROPOROUS CATALYSTS: ZEOLITES 105 4.3.1 What Are Zeolites? 105 4.3.2 Types of Zeolites Used in Catalytic Processes 109 4.3.2.1 Zeolite X and Zeolite Y 109 4.3.2.2 ZSM-5 110 4.3.2.3 Mordenite 110 4.3.2.4 Zeolite A 111 4.3.3 Production of Zeolites 111 4.3.4 Post-Synthesis Treatment of Zeolites and Modification of Zeolites 113 4.3.4.1 Protonation of Zeolites 113 4.3.4.2 Dealumination of Zeolites 114 4.3.4.3 Metals and Metal Complexes in Zeolites 114 4.3.5 Catalytic Application of Zeolites 115 4.3.5.1 Zeolite Catalysts in Petrochemical Processes 117 4.3.5.1.1 Fluid Catalytic Cracking 118 4.3.5.1.2 Hydrocracking 121 4.3.5.1.3 Isomerization of n-Paraffins 122 4.3.5.1.4 Catalytic Dewaxing 124 4.3.5.1.5 Aromatization of Liquefied Petrol Gases 124 4.3.5.2 Methanol to Gasoline and Methanol to Olefins 125 4.4 MESOPOROUS CATALYSTS 126 4.4.1 Ordered Mesoporous Silica Materials 126 4.4.1.1 Surface Modifications of Ordered Mesoporous Silica Materials 130 4.4.1.2 Catalysis with Ordered Mesoporous Silica Materials 131 4.4.2 Nonsiliceous Ordered Mesoporous Materials 133 4.5 CHARACTERIZATION OF MICROPOROUS AND MESOPOROUS MATERIALS 134 4.5.1 X-Ray Diffraction 135 4.5.2 Physisorption Analysis 136 4.5.3 Electron Microscopy 138 4.5.4 Nuclear Magnetic Resonance Spectroscopy 138 4.5.5 Infrared Spectroscopy 140 APPENDIX 142 Terms and Abbreviations 142 Further Reading 143 REFERENCES 143 CHAPTER 4 PROBLEMS 146 Problem 1 146 Problem 2 146 Problem 3 146 Problem 4 147 Problem 5 147 Problem 6 147 Problem 7 147 DK3277ch5 148 Table of Contents -1 CHAPTER 5: Skeletal Catalysts 148 CONTENTS 148 5.1 INTRODUCTION 148 5.2 HISTORY 148 5.3 PREPARATION 149 5.3.1 Leaching Kinetics 151 5.3.2 Promoters 152 5.4 STRUCTURES 154 5.5 DEACTIVATION / AGING 156 5.6 APPLICATIONS 158 5.7 ADVANTAGES / DISADVANTAGES 160 5.8 FUTURE 161 ACKNOWLEDGMENT 161 REFERENCES 161 CHAPTER 5 QUESTIONS 166 Question 1 166 Question 2 166 Question 3 166 Question 4 166 Question 5 166 Question 6 166 Question 7 166 DK3277ch6 167 Table of Contents -1 CHAPTER 6: A Scientific Method to Prepare Supported Metal Catalysts 167 CONTENTS 167 6.1 INTRODUCTION 167 6.2 EARLY PIONEERING WORK 168 6.3 DEVELOPMENT OF THE REVISED PHYSICAL ADSORPTION MODEL 172 6.3.1 Qualitative Discrimination of Mechanisms 172 6.3.2 pH Shift Modeling 174 6.3.3 Metal Adsorption Modeling 180 6.4 CASE STUDY: Pt TETRAAMMINE ADSORPTION OVER SILICA 183 6.4.1 Survey of Pt/Silica Preparation Methods 183 6.4.2 Measurement of Oxide Point of Zero Charge 185 6.4.3 Uptake–pH Survey to Identify Optimal pH 185 6.4.4 Tuning Finishing Conditions to Retain High Dispersion 188 6.5 THE EXTENSION OF STRONG ELECTROSTATIC ADSORPTION TO ALUMINA AND CARBON 191 6.6 FURTHER APPLICATIONS: OTHER OXIDES, BIMETALLICS 193 6.7 SUMMARY 196 REFERENCES 196 CHAPTER 6 QUESTIONS 198 Question 1 198 Question 2 198 Question 3 198 Question 4 198 Question 5 198 Question 6 198 Question 7 198 Question 8 199 Question 9 199 Question 10 199 Question 11 199 Question 12 199 DK3277ch7 200 Table of Contents -1 CHAPTER 7: Catalysis and Chemical Reaction Engineering 200 CONTENTS 200 ANNOTATIONS 200 Greek Letters 201 Subscripts 201 7.1 INTRODUCTION 201 7.2 OVERVIEW OF HETEROGENEOUS CATALYSIS AND CHEMICAL REACTION ENGINEERING 202 7.3 HYDROGEN PRODUCTION AND CLEANING: CATALYSIS AND REACTION ENGINEERING 204 7.3.1 Conventional Processes and Catalysts for Hydrogen Generation and Their Limitations in Low-Temperature Fuel Cells Technology 205 7.3.1.1 Fuel Reforming 205 7.3.1.2 Water-Gas Shift Reaction 207 7.3.1.3 Preferential Oxidation of Carbon Monoxide 207 7.3.2 Fuel Cells and Primary Fuel Processing for Low-Temperature Fuel Cells 209 7.3.2.1 Catalytic Processes of Hydrogen Production for Proton-Exchange Membrane Fuel Cell 210 7.3.2.1.1 Water-Gas Shift Reaction in Excess of H2 Over the Nanostructured CuxCe1-xO2-y Catalyst 211 7.3.2.1.2 Selective CO Oxidation in Excess of H2 (PrOX) over the Nanostructured CuxCe1-xO2-y Catalyst 219 7.4 CONCLUSIONS 229 ACKNOWLEDGMENTS 229 REFERENCES 230 CHAPTER 7 QUESTIONS 232 Question 1 232 Question 2 232 Question 3 232 Question 4 232 Question 5 232 Question 6 232 Question 7 232 Question 8 232 Question 9 233 Question 10 233 DK3277ch8 234 Table of Contents -1 CHAPTER 8: Structure and Reaction Control at Catalyst Surfaces 234 CONTENTS 234 8.1 INTRODUCTION 234 8.2 REGULATION OF CATALYSIS BY COADSORBED MOLECULES 236 8.2.1 Self-Assisted Dehydrogenation of Ethanol on an Nb/SiO2 Catalyst 236 8.2.2 Reactant-Promoted Water-Gas-Shift Reactions 238 8.2.2.1 WGS Reactions on ZnO 239 8.2.2.2 WGS Reactions on Rh/CeO2 240 8.2.3 Regulation of Selective Oxidation of Methanol on a Modified Mo (112) Surface 241 8.2.3.1 Reaction Aspect of Methanol Oxidation 241 8.2.3.2 Reaction Scheme of Methanol Oxidation in TPR 245 8.2.3.3 Reaction Kinetics of the Steady-State Methanol Oxidation 247 8.2.3.4 Regulation of the Methanol Oxidation by Extra Oxygen Atoms 247 8.3 REGULATION OF CATALYSIS BY DESIGN OF ACTIVE STRUCTURES 249 8.3.1 Chemical Tuning of Active Sites 249 8.3.2 ReOx Clusters Produced in Situ 251 8.4 DESIGN OF REACTION INTERMEDIATE AND TRANSITION-STATE ANALOGUE FOR A TARGET REACTION ON OXIDE SURFACES 253 8.4.1 Reaction Regulation by Molecular Imprinting 253 8.4.2 Design of a Reaction Intermediate on Catalyst Surface 257 8.5 CONCLUSION 259 REFERENCES 259 CHAPTER 8 PROBLEMS 261 Problem 1 261 Problem 2 261 Problem 3 261 Problem 4 261 DK3277ch9 262 Table of Contents -1 CHAPTER 9: Texturology 262 CONTENTS 262 9.1 INTRODUCTION 263 9.2 BASIC PRINCIPLES OF PHYSICAL CHEMISTRY OF DISPERSED SYSTEMS 266 9.2.1 Gibbsian Classical Thermodynamic Theory 266 9.2.2 Flat Interface 267 9.2.3 Curved Interface 269 9.2.4 Surface Curvature 270 9.2.5 The Limits of the Classic Thermodynamic Theory 271 9.2.6 Typical Mechanisms and Processes of Texture Genesis Derived from the Laws of Surface-Capillary Phenomena 272 9.2.6.1 Fundamental Mechanisms of Texture Genesis 272 9.2.6.2 Fundamental Processes of Texture Genesis 274 9.3 ADSORPTION AS A PRIMARY INSTRUMENT FOR TEXTURE CHARACTERIZATION 279 9.4 MORPHO-INDEPENDENT TEXTURAL PARAMETERS 285 9.4.1 Density and Porosity 285 9.4.2 Experimental Techniques of Measurements of True, Apparent, and Bulk Density 288 9.4.3 The Properties of Porosity 289 9.4.4 The Specific Surface Area 294 9.5 MORPHO-DEPENDENT TEXTURAL PARAMETERS: MEAN SIZES OF PARTICLES AND PORES 295 9.6 GENERAL PROBLEMS OF POROUS SOLIDS TEXTURE MODELING 298 9.6.1 Morphology of Porous Solids and Problems with Modeling 298 9.6.2 Classification of Porous Systems and Texture Modeling 299 9.6.3 Generalized Models and Systematic Sets of Models 304 9.7 MODELING PARTICLES AND PORES IN A LOCAL ARRANGEMENT 306 9.7.1 Voronoi–Delaunay Method for Description of Corpuscular and Sponge-Like Porous Solids 306 9.7.2 Ordered Packings 311 9.7.3 Disordered Packings 316 9.8 MODELING THE ENSEMBLES (CLUSTERS) OF PARTICLES AND PORES ON THE BASIS OF A FRACTAL APPROACH 319 9.9 LATERAL AND STATISTICAL MODELS OF PORES AND PARTICLES ARRANGEMENT 325 9.9.1 Percolation Theory 325 9.9.1.1 Problem of Bonds 326 9.9.1.2 Problem of Sites 327 9.9.2 The Stochastic and other Statistical Models of Long-Range Order 329 9.10 CONCLUSIONS 332 REFERENCES 333 CHAPTER 9 PROBLEMS 340 Problem 1 340 Problem 2 340 Problem 3 340 Problem 4 340 Problem 5 340 Problem 6 340 Problem 7 341 Problem 8 341 Problem 9 341 Problem 10 341 Problem 11 341 DK3277ch10 342 Table of Contents -1 CHAPTER 10: Understanding Catalytic Reaction Mechanisms: Surface Science Studies of Heterogeneous Catalysts 342 CONTENTS 342 10.1 INTRODUCTION 342 10.1.1 Studies of CO Hydrogenation on Single-Crystal Surfaces 343 10.1.1.1 Effects of Poisons and Promoters on CO Methanation 344 10.1.2 CO Oxidation on Single-Crystal Surfaces 345 10.1.3 Bimetallic Surfaces 345 10.1.4 Experimental Techniques 349 10.2 MODEL CATALYSTS 349 10.2.1 Thin-Film Growth 350 10.2.1.1 TiO2 Thin Films 350 10.2.1.2 Amorphous SiO2 Films 350 10.2.1.3 Crystalline SiO2 Films 353 10.2.1.4 Highly Defective TiOx Films 353 10.2.2 Supported Metal Clusters (Au as an Example) 354 10.3 IN SITU STUDIES 360 10.3.1 Vibrational Spectroscopy 360 10.3.2 In Situ STM 368 10.3.3 Elevated Pressure XPS 368 10.4 CONCLUSIONS 373 ACKNOWLEDGMENTS 373 REFERENCES 373 CHAPTER 10 QUESTIONS 377 Question 1 377 Question 2 377 Question 3 377 Question 4 377 Question 5 377 Question 6 377 Question 7 377 Question 8 377 Question 9 377 Question 10 377 DK3277ch11 378 Table of Contents -1 CHAPTER 11: High-Throughput Experimentation and Combinatorial Approaches in Catalysis 378 CONTENTS 378 11.1 HIGH-THROUGHPUT EXPERIMENTATION AND COMBINATORIAL CATALYSIS — DEFINITION AND SCOPE 379 11.2 EXPERIMENTAL PLANNING AND DATA HANDLING 381 11.2.1 Descriptor-Driven Approaches 381 11.2.2 Approaches Based on Classical Statistical Designs 382 11.2.3 Other Techniques for Finding Local Optima 383 11.3 STAGE I AND STAGE II SCREENING 385 11.4 ANALYTICAL TECHNIQUES FOR SCREENING 387 11.5 SYNTHETIC APPROACHES FOR HIGH-THROUGHPUT EXPERIMENTATION AND COMBINATORIAL CHEMISTRY 390 11.5.1 Synthetic Approaches for Molecular Catalysts 391 11.5.2 Synthetic Approaches for Solid-State Inorganic Catalysts 392 11.5.3 Combinatorial Synthetic Approaches for Solid-State Inorganic and Molecular Catalysts 394 11.6 TESTING OF CATALYSTS IN GAS-PHASE REACTIONS 395 11.6.1 Stage I Testing of Catalysts for Gas-Phase Reactions 401 11.6.1.1 General Considerations 401 11.6.1.2 Reactant Distribution for Stage I Screening Systems 401 11.6.1.3 Single-Bead Reactors 403 11.6.1.4 Optimal Use of Stage I in Screening Programs 406 11.6.2 Stage II Testing in Gas-Phase Applications 407 11.6.2.1 The Epoxidation of 1,3-Butadiene with Ag-Based Catalysts 410 11.6.2.2 Dynamic Experiments in Stage II Screening for Automotive Applications 412 11.6.2.3 Refinery Catalysis Applications in High-Throughput Experimentation 414 11.6.2.3.1 Pressure Flow and Pressure Control 415 11.6.2.3.2 Liquid–Gas Separation 416 11.7 TESTING OF CATALYSTS IN LIQUID–LIQUID, GAS–LIQUID, AND GAS–LIQUID–SOLID REACTIONS 416 11.7.1 Stage I Screening for Liquid-Phase Catalysis 418 11.7.1.1 Alternative Stage I Screening Concepts 422 11.7.2 Stage II Screening for Liquid-Phase Catalysis 423 11.8 SUMMARY AND OUTLOOK 425 REFERENCES 426 CHAPTER 11 QUESTIONS 430 Question 1 430 Question 2 430 Question 3 430 Question 4 430 Question 5 430 Question 6 430 Question 7 430 Question 8 431 Question 9 431 Question 10 431 Question 11 431 DK3277ch12 432 Table of Contents -1 CHAPTER 12: Heterogeneous Photocatalysis 432 CONTENTS 432 12.1 INTRODUCTION 433 12.2 PHOTOCATALYSIS 434 12.2.1 General Principles 435 12.2.2 TiO2 Photocatalysts 438 12.2.2.1 Preparation Procedures 440 12.2.3 Modified Titania Photocatalysts 443 12.2.4 Mixed Oxide and Composites Containing Titania 446 12.2.5 Noble Metal Deposited on Titania Surfaces 446 12.2.6 Monoliths Containing Titania 448 12.2.7 ZnO 448 12.2.8 Other Oxide Semiconductors 449 12.2.9 Calcium Hydroxyapatite Modified with Ti(IV) 449 12.2.10 Polyoxometalates 449 12.2.11 Heterogeneous Fenton-Type Catalysts 450 12.3 KINETIC STUDIES 450 12.4 COMBINATORIAL APPROACHES IN PREPARATION AND TESTING PHOTOCATALYSTS 451 12.5 EXAMPLE OF REACTIONS UNDER PHOTOCATALYTIC CONDITIONS 453 12.5.1 Photoinduced Deposition of Various Metals onto Semiconductor 454 12.5.2 Energy Storage 455 12.6 SOLAR PHOTOCATALYSIS 455 12.7 SONOPHOTOCATALYSIS 455 12.8 PHOTOCATALYSIS ASSOCIATED TO MICROWAVE RADIATION 457 12.9 PHOTOCATALYST DEACTIVATION 457 12.10 CONCLUSIONS 457 REFERENCES 458 CHAPTER 12 QUESTIONS 466 Question 1 466 Question 2 466 Question 3 466 Question 4 466 Question 5 466 Question 6 466 Question 7 466 Question 8 466 Question 9 466 Question 10 466 DK3277ch13 467 Table of Contents -1 CHAPTER 13: Liquid-Phase Oxidations Catalyzed by Polyoxometalates 467 CONTENTS 467 13.1 INTRODUCTION 467 13.2 HOMOGENEOUS CATALYSTS WITH POLYOXOMETALATE-BASED COMPOUNDS 469 13.2.1 Mixed-Addenda Polyoxometalates 469 13.2.2 Transition-Metal-Substituted Polyoxometalates 469 13.2.3 Peroxometalates 476 13.2.4 Lacunary Polyoxometalates 478 13.3 HETEROGENEOUS CATALYSTS WITH POLYOXOMETALATE-BASED COMPOUNDS 478 13.3.1 Dispersion onto Inert Supports 479 13.3.1.1 Active Carbon 479 13.3.1.2 Silica and MCM-41 481 13.3.1.3 Others 482 13.3.2 Formation of Insoluble Solid Ionic Materials 482 13.3.2.1 Metal Ions 482 13.3.2.2 Alkylammonium Ions 482 13.3.2.3 Crosslinking of Copolymer with POM 483 13.3.3 Intercalation into Anion-Exchange Materials 484 13.3.4 Immobilization on Surface-Modified Supports 486 13.3.4.1 Anion–Cation Pairing 486 13.3.4.2 Covalent Bond Formation 488 13.3.4.3 Others 488 13.4 CONCLUSIONS AND FUTURE OPPORTUNITIES 489 ACKNOWLEDGMENTS 491 REFERENCES 491 CHAPTER 13 QUESTIONS 496 Question 1 496 Question 2 496 Question 3 496 Question 4 496 Question 5 496 Question 6 496 DK3277ch14 497 Table of Contents -1 CHAPTER 14: Asymmetric Catalysis by Heterogeneous Catalysts 497 CONTENTS 497 14.1 INTRODUCTION 497 14.2 PRINCIPLES OF STEREODIFFERENTIATION AND ASYMMETRIC CATALYSIS 500 14.3 HISTORICAL DEVELOPMENTS 503 14.4 TARTARIC ACID-MODIFIED ME/SUPPORT HYDROGENATION CATALYSTS AND RELATED SYSTEMS 506 14.4.1 Catalyst Preparation Process 506 14.4.2 The Modification Process 507 14.4.3 Substrate and Hydrogenation Parameters 507 14.4.4 Mechanistic Investigations and Hypotheses for Enantioselection 508 14.4.5 Proposed Mechanisms 511 14.5 CHIRAL-MODIFIED PLATINUM HYDROGENATION CATALYSTS AND RELATED SYSTEMS 514 14.5.1 Kinetic Models 516 14.5.2 Mechanistic Investigations 516 14.6 HETEROGENEIZED HOMOGENEOUS CATALYSTS 521 14.7 ORGANIC POLYMERS 523 14.8 DIASTEREOSELECTIVE CATALYSIS 523 14.9 CONCLUSIONS 527 REFERENCES 527 CHAPTER 14 QUESTIONS 535 Question 1 535 Question 2 535 Question 3 535 Question 4 535 Question 5 535 Question 6 535 Question 7 535 Question 8 535 Question 9 535 Question 10 535 SURFACE AND NANOMOLECULAR CATALYSIS......Page 1 Dedication......Page 3 Preface......Page 4 The Editor......Page 6 Contributors......Page 7 Contents......Page 9 CONTENTS......Page 11 Table of Contents......Page 0 1.2.1 X-Ray Diffraction......Page 12 1.2.2 X-Ray Absorption Spectroscopy......Page 13 1.2.3 Electron Microscopy......Page 15 1.3.1 Surface Area and Pore Structure......Page 17 1.3.2 Temperature-Programmed Desorption and Reaction......Page 18 1.3.3 Thermogravimetry and Thermal Analysis......Page 19 1.3.4 Microcalorimetry......Page 20 1.4.1 Infrared Spectroscopy......Page 22 1.4.2 Raman Spectroscopy......Page 23 1.4.3 Ultraviolet–Visible Spectroscopy......Page 25 1.4.4 Nuclear Magnetic Resonance......Page 26 1.4.5 Electron Spin Resonance......Page 28 1.5.1 X-Ray and Ultraviolet Photoelectron Spectroscopies......Page 29 1.5.2 Auger Electron Spectroscopy......Page 30 1.5.4 Secondary-Ion Mass Spectroscopy......Page 31 1.6 MODEL CATALYSTS......Page 32 1.7 CONCLUDING REMARKS......Page 35 REFERENCES......Page 36 Question 3......Page 42 Question 5......Page 43 Question 7......Page 44 Question 9......Page 45 Question 11......Page 46 Question 12......Page 47 CONTENTS......Page 48 2.2 PROPERTIES OF METAL OXIDES......Page 49 2.2.2 Insulators (Highly Ionic)......Page 50 2.2.4 Crystal Structures......Page 51 2.3.1 Surface Reconstruction......Page 53 2.3.2 Defect Sites......Page 55 2.4 SOLID ACIDS AND BASES......Page 57 2.4.2 Oxygen Anions as Lewis Bases......Page 58 2.4.4 Spectroscopic Methods of Detecting Lewis Acidity/Basicity and Bronsted Acidity/Basicity......Page 59 2.5.1.1 Hydrogen –Deuterium Exchange Reaction......Page 60 2.5.1.2 Hydrogenation (1,3-Butadiene + D2)......Page 61 2.5.1.5 Benzylation......Page 62 2.5.2.1 Oxidative Dehydrogenation — Vanadia......Page 63 2.5.2.2 Oxidative Coupling of Methane......Page 64 2.5.3.2 Freons......Page 65 REFERENCES......Page 66 Question 8......Page 70 3.1 INTRODUCTION......Page 71 3.3 MODES OF STABILIZATION......Page 72 3.4 REDUCTION METHODS......Page 74 3.5.2.1 Precursor Concept......Page 82 3.5.2.2 Conditioning: A Key Step in Generating Active Catalysts......Page 83 3.5.2.3 Heterogeneous Catalysts in Catalysis......Page 84 3.5.2.4 Fuel Cell Catalysts......Page 91 3.6 CONCLUSION......Page 93 REFERENCES......Page 94 Question 5......Page 102 CONTENTS......Page 103 4.1 SETTING THE SCENE......Page 104 4.3.1 What Are Zeolites?......Page 105 4.3.2.1 Zeolite X and Zeolite Y......Page 109 4.3.2.3 Mordenite......Page 110 4.3.3 Production of Zeolites......Page 111 4.3.4.1 Protonation of Zeolites......Page 113 4.3.4.3 Metals and Metal Complexes in Zeolites......Page 114 4.3.5 Catalytic Application of Zeolites......Page 115 4.3.5.1 Zeolite Catalysts in Petrochemical Processes......Page 117 4.3.5.1.1 Fluid Catalytic Cracking......Page 118 4.3.5.1.2 Hydrocracking......Page 121 4.3.5.1.3 Isomerization of n-Paraffins......Page 122 4.3.5.1.5 Aromatization of Liquefied Petrol Gases......Page 124 4.3.5.2 Methanol to Gasoline and Methanol to Olefins......Page 125 4.4.1 Ordered Mesoporous Silica Materials......Page 126 4.4.1.1 Surface Modifications of Ordered Mesoporous Silica Materials......Page 130 4.4.1.2 Catalysis with Ordered Mesoporous Silica Materials......Page 131 4.4.2 Nonsiliceous Ordered Mesoporous Materials......Page 133 4.5 CHARACTERIZATION OF MICROPOROUS AND MESOPOROUS MATERIALS......Page 134 4.5.1 X-Ray Diffraction......Page 135 4.5.2 Physisorption Analysis......Page 136 4.5.4 Nuclear Magnetic Resonance Spectroscopy......Page 138 4.5.5 Infrared Spectroscopy......Page 140 Terms and Abbreviations......Page 142 REFERENCES......Page 143 Problem 3......Page 146 Problem 7......Page 147 5.2 HISTORY......Page 148 5.3 PREPARATION......Page 149 5.3.1 Leaching Kinetics......Page 151 5.3.2 Promoters......Page 152 5.4 STRUCTURES......Page 154 5.5 DEACTIVATION / AGING......Page 156 5.6 APPLICATIONS......Page 158 5.7 ADVANTAGES / DISADVANTAGES......Page 160 REFERENCES......Page 161 Question 7......Page 166 6.1 INTRODUCTION......Page 167 6.2 EARLY PIONEERING WORK......Page 168 6.3.1 Qualitative Discrimination of Mechanisms......Page 172 6.3.2 pH Shift Modeling......Page 174 6.3.3 Metal Adsorption Modeling......Page 180 6.4.1 Survey of Pt/Silica Preparation Methods......Page 183 6.4.3 Uptake–pH Survey to Identify Optimal pH......Page 185 6.4.4 Tuning Finishing Conditions to Retain High Dispersion......Page 188 6.5 THE EXTENSION OF STRONG ELECTROSTATIC ADSORPTION TO ALUMINA AND CARBON......Page 191 6.6 FURTHER APPLICATIONS: OTHER OXIDES, BIMETALLICS......Page 193 REFERENCES......Page 196 Question 7......Page 198 Question 12......Page 199 ANNOTATIONS......Page 200 7.1 INTRODUCTION......Page 201 7.2 OVERVIEW OF HETEROGENEOUS CATALYSIS AND CHEMICAL REACTION ENGINEERING......Page 202 7.3 HYDROGEN PRODUCTION AND CLEANING: CATALYSIS AND REACTION ENGINEERING......Page 204 7.3.1.1 Fuel Reforming......Page 205 7.3.1.3 Preferential Oxidation of Carbon Monoxide......Page 207 7.3.2 Fuel Cells and Primary Fuel Processing for Low-Temperature Fuel Cells......Page 209 7.3.2.1 Catalytic Processes of Hydrogen Production for Proton-Exchange Membrane Fuel Cell......Page 210 7.3.2.1.1 Water-Gas Shift Reaction in Excess of H2 Over the Nanostructured CuxCe1-xO2-y Catalyst......Page 211 7.3.2.1.2 Selective CO Oxidation in Excess of H2 (PrOX) over the Nanostructured CuxCe1-xO2-y Catalyst......Page 219 ACKNOWLEDGMENTS......Page 229 REFERENCES......Page 230 Question 8......Page 232 Question 10......Page 233 8.1 INTRODUCTION......Page 234 8.2.1 Self-Assisted Dehydrogenation of Ethanol on an Nb/SiO2 Catalyst......Page 236 8.2.2 Reactant-Promoted Water-Gas-Shift Reactions......Page 238 8.2.2.1 WGS Reactions on ZnO......Page 239 8.2.2.2 WGS Reactions on Rh/CeO2......Page 240 8.2.3.1 Reaction Aspect of Methanol Oxidation......Page 241 8.2.3.2 Reaction Scheme of Methanol Oxidation in TPR......Page 245 8.2.3.4 Regulation of the Methanol Oxidation by Extra Oxygen Atoms......Page 247 8.3.1 Chemical Tuning of Active Sites......Page 249 8.3.2 ReOx Clusters Produced in Situ......Page 251 8.4.1 Reaction Regulation by Molecular Imprinting......Page 253 8.4.2 Design of a Reaction Intermediate on Catalyst Surface......Page 257 REFERENCES......Page 259 Problem 4......Page 261 CONTENTS......Page 262 9.1 INTRODUCTION......Page 263 9.2.1 Gibbsian Classical Thermodynamic Theory......Page 266 9.2.2 Flat Interface......Page 267 9.2.3 Curved Interface......Page 269 9.2.4 Surface Curvature......Page 270 9.2.5 The Limits of the Classic Thermodynamic Theory......Page 271 9.2.6.1 Fundamental Mechanisms of Texture Genesis......Page 272 9.2.6.2 Fundamental Processes of Texture Genesis......Page 274 9.3 ADSORPTION AS A PRIMARY INSTRUMENT FOR TEXTURE CHARACTERIZATION......Page 279 9.4.1 Density and Porosity......Page 285 9.4.2 Experimental Techniques of Measurements of True, Apparent, and Bulk Density......Page 288 9.4.3 The Properties of Porosity......Page 289 9.4.4 The Specific Surface Area......Page 294 9.5 MORPHO-DEPENDENT TEXTURAL PARAMETERS: MEAN SIZES OF PARTICLES AND PORES......Page 295 9.6.1 Morphology of Porous Solids and Problems with Modeling......Page 298 9.6.2 Classification of Porous Systems and Texture Modeling......Page 299 9.6.3 Generalized Models and Systematic Sets of Models......Page 304 9.7.1 Voronoi–Delaunay Method for Description of Corpuscular and Sponge-Like Porous Solids......Page 306 9.7.2 Ordered Packings......Page 311 9.7.3 Disordered Packings......Page 316 9.8 MODELING THE ENSEMBLES (CLUSTERS) OF PARTICLES AND PORES ON THE BASIS OF A FRACTAL APPROACH......Page 319 9.9.1 Percolation Theory......Page 325 9.9.1.1 Problem of Bonds......Page 326 9.9.1.2 Problem of Sites......Page 327 9.9.2 The Stochastic and other Statistical Models of Long-Range Order......Page 329 9.10 CONCLUSIONS......Page 332 REFERENCES......Page 333 Problem 6......Page 340 Problem 11......Page 341 10.1 INTRODUCTION......Page 342 10.1.1 Studies of CO Hydrogenation on Single-Crystal Surfaces......Page 343 10.1.1.1 Effects of Poisons and Promoters on CO Methanation......Page 344 10.1.3 Bimetallic Surfaces......Page 345 10.2 MODEL CATALYSTS......Page 349 10.2.1.2 Amorphous SiO2 Films......Page 350 10.2.1.4 Highly Defective TiOx Films......Page 353 10.2.2 Supported Metal Clusters (Au as an Example)......Page 354 10.3.1 Vibrational Spectroscopy......Page 360 10.3.3 Elevated Pressure XPS......Page 368 REFERENCES......Page 373 Question 10......Page 377 CONTENTS......Page 378 11.1 HIGH-THROUGHPUT EXPERIMENTATION AND COMBINATORIAL CATALYSIS — DEFINITION AND SCOPE......Page 379 11.2.1 Descriptor-Driven Approaches......Page 381 11.2.2 Approaches Based on Classical Statistical Designs......Page 382 11.2.3 Other Techniques for Finding Local Optima......Page 383 11.3 STAGE I AND STAGE II SCREENING......Page 385 11.4 ANALYTICAL TECHNIQUES FOR SCREENING......Page 387 11.5 SYNTHETIC APPROACHES FOR HIGH-THROUGHPUT EXPERIMENTATION AND COMBINATORIAL CHEMISTRY......Page 390 11.5.1 Synthetic Approaches for Molecular Catalysts......Page 391 11.5.2 Synthetic Approaches for Solid-State Inorganic Catalysts......Page 392 11.5.3 Combinatorial Synthetic Approaches for Solid-State Inorganic and Molecular Catalysts......Page 394 11.6 TESTING OF CATALYSTS IN GAS-PHASE REACTIONS......Page 395 11.6.1.2 Reactant Distribution for Stage I Screening Systems......Page 401 11.6.1.3 Single-Bead Reactors......Page 403 11.6.1.4 Optimal Use of Stage I in Screening Programs......Page 406 11.6.2 Stage II Testing in Gas-Phase Applications......Page 407 11.6.2.1 The Epoxidation of 1,3-Butadiene with Ag-Based Catalysts......Page 410 11.6.2.2 Dynamic Experiments in Stage II Screening for Automotive Applications......Page 412 11.6.2.3 Refinery Catalysis Applications in High-Throughput Experimentation......Page 414 11.6.2.3.1 Pressure Flow and Pressure Control......Page 415 11.7 TESTING OF CATALYSTS IN LIQUID–LIQUID, GAS–LIQUID, AND GAS–LIQUID–SOLID REACTIONS......Page 416 11.7.1 Stage I Screening for Liquid-Phase Catalysis......Page 418 11.7.1.1 Alternative Stage I Screening Concepts......Page 422 11.7.2 Stage II Screening for Liquid-Phase Catalysis......Page 423 11.8 SUMMARY AND OUTLOOK......Page 425 REFERENCES......Page 426 Question 7......Page 430 Question 11......Page 431 CONTENTS......Page 432 12.1 INTRODUCTION......Page 433 12.2 PHOTOCATALYSIS......Page 434 12.2.1 General Principles......Page 435 12.2.2 TiO2 Photocatalysts......Page 438 12.2.2.1 Preparation Procedures......Page 440 12.2.3 Modified Titania Photocatalysts......Page 443 12.2.5 Noble Metal Deposited on Titania Surfaces......Page 446 12.2.7 ZnO......Page 448 12.2.10 Polyoxometalates......Page 449 12.3 KINETIC STUDIES......Page 450 12.4 COMBINATORIAL APPROACHES IN PREPARATION AND TESTING PHOTOCATALYSTS......Page 451 12.5 EXAMPLE OF REACTIONS UNDER PHOTOCATALYTIC CONDITIONS......Page 453 12.5.1 Photoinduced Deposition of Various Metals onto Semiconductor......Page 454 12.7 SONOPHOTOCATALYSIS......Page 455 12.10 CONCLUSIONS......Page 457 REFERENCES......Page 458 Question 10......Page 466 13.1 INTRODUCTION......Page 467 13.2.2 Transition-Metal-Substituted Polyoxometalates......Page 469 13.2.3 Peroxometalates......Page 476 13.3 HETEROGENEOUS CATALYSTS WITH POLYOXOMETALATE-BASED COMPOUNDS......Page 478 13.3.1.1 Active Carbon......Page 479 13.3.1.2 Silica and MCM-41......Page 481 13.3.2.2 Alkylammonium Ions......Page 482 13.3.2.3 Crosslinking of Copolymer with POM......Page 483 13.3.3 Intercalation into Anion-Exchange Materials......Page 484 13.3.4.1 Anion–Cation Pairing......Page 486 13.3.4.3 Others......Page 488 13.4 CONCLUSIONS AND FUTURE OPPORTUNITIES......Page 489 REFERENCES......Page 491 Question 6......Page 496 14.1 INTRODUCTION......Page 497 14.2 PRINCIPLES OF STEREODIFFERENTIATION AND ASYMMETRIC CATALYSIS......Page 500 14.3 HISTORICAL DEVELOPMENTS......Page 503 14.4.1 Catalyst Preparation Process......Page 506 14.4.3 Substrate and Hydrogenation Parameters......Page 507 14.4.4 Mechanistic Investigations and Hypotheses for Enantioselection......Page 508 14.4.5 Proposed Mechanisms......Page 511 14.5 CHIRAL-MODIFIED PLATINUM HYDROGENATION CATALYSTS AND RELATED SYSTEMS......Page 514 14.5.2 Mechanistic Investigations......Page 516 14.6 HETEROGENEIZED HOMOGENEOUS CATALYSTS......Page 521 14.8 DIASTEREOSELECTIVE CATALYSIS......Page 523 REFERENCES......Page 527 Question 10......Page 535

Sports Injuries of the Knee discusses 32 key surgical treatments for managing the most common problems and sports-related injuries to the knee.

Doody Review Services

Reviewer:Neeru A. Jayanthi, MD(Loyola University Medical Center)
Description:This is an updated summary of surgical approaches to the spectrum of sports-related injuries to the knee. Information is presented regarding simple meniscal repairs to transplantation, articular cartilage procedures, and more complicated fractures as well as more routine ACL reconstruction with different grafts.
Purpose:The authors hope to provide a summary of the techniques of the nation's leaders in sports-related knee surgery to serve as a concise and updated reference for the busy or training orthopedic surgeon. This book is unique in its approach, with the level of detail, spectrum of injuries, and specificity to sports injuries. The authors seem to have satisfied their lofty goals.
Audience:The book is written for practicing orthopedic surgeons with detailed surgical information and tips. General orthopedic surgeons in practice would likely find this a helpful reference and adjunct, particularly if not doing certain types of surgeries often. This is also a good reference for residents/fellows in orthopedic surgery. It may serve as a good reference for primary care sports medicine, or nonoperative musculoskeletal specialists who work closely with sports orthopedists. The authors are well known and respected in their field.
Features:The book includes surgical management of degenerative and traumatic meniscal tears as well as repairs. Surgical management of articular cartilage injuries, patellofemoral disorders, ligament reconstruction with particular emphasis on graft selection are also covered. Sports-specific fractures such as tibial plateau tibial spine are also covered as well as surgical repair of the ruptured extensor mechanism. Postoperative rehabilitation is covered in more detail than in typical surgical texts. The diagrams and color photos are of the highest quality. The detail and specificity for each surgical topic makes the book a reliable source for the practicing surgeon. The focus of the book is primarily surgical; there is brief mention of nonoperative approaches as a result.
Assessment:This book will likely be recognized as one of the leading references on sports-related knee injuries requiring surgical intervention. The authors have assembled leaders in the field of sports-related knee surgery and provide sufficient detail with clinical pearls and algorithms for management that can be immediately applied by the practicing physician. The book is still readable for nonsurgeons and those training in the field of orthopedic surgery.

Using new instrumentation and experimental techniques that allow scientists to observe chemical reactions and molecular properties at the nanoscale, the authors of Surface and Nanomolecular Catalysis reveal new insights into the surface chemistry of catalysts and the reaction mechanisms that actually occur at a molecular level during catalysis. While each chapter contains the necessary background and explanations to stand alone, the diverse collection of chapters shows how developments from various fields each contributed to our current understanding of nanomolecular catalysis as a whole.

The book describes how the size and shape of materials at the nanoscale can change their chemical and physical properties and promote more efficient reactions with fewer by-products. First it highlights the preparation, characterization, and applications of heterogeneous and supported metal catalysts. Then it covers the engineering of catalytic processes, structure and reaction control, and texturological properties of catalytic systems. The authors explain how surface science can elucidate reaction mechanisms and discuss the growing role of high-throughput experimentation and combinatorial approaches in catalysis.

From fundamental concepts to future directions, Surface and Nanomolecular Catalysis offers a well-rounded compilation of noteworthy developments which will continue to expand and transform our understanding of catalysis, particularly in the context of clean energy and environmental applications such as fuel cells.

32 surgical treatments for problems of the kneeSports Injuries of the Knee: Surgical Approaches discusses 32 key surgical treatments for managing the most common problems and sports-related injuries to the knee.Each chapter outlines physical examination techniques, diagnosis, differential diagnosis, indications, operative and non-operative treatment options, patient positioning, goals, approaches, surgical techniques, and postoperative considerations. Leading experts offer their perspectives on procedures such as arthroscopic meniscal repair, ligament reconstruction, osteochondritis dissecans treatment, osteotomies about the knee, proximal/distal realignment for patellar instability, tibial spine fractures, and more. Highlights:Features practical tips on how to handle from the experts on handling articular cartilage abnormalities, ligament tears, patellofemoral problems, tendon injuries, fractures and more Includes numerous approaches for osteotomy, ACL reconstruction, and PCL reconstruction Describes the management of difficult multiligament injuries Contains'Pearls'and'Pitfalls'call attention to key points and offer tips for how to avoid complications Supplemented by more than 270 illustrations aid the comprehension of each surgical techniqueAll orthopedic surgeons, sports medicine specialists, fellows in training, and residents treating patients with knee injuries and conditions will appreciate the wealth of information in this reference. Characterization Of Heterogeneous Catalysts / Zhen Ma, Francisco Zaera -- Catalysis By Metal Oxides / Ranjit T. Koodali, Kenneth J. Klabunde -- Colloidal Nanoparticles In Catalysis / Helmut Bönnemann, K.s. Nagabhushana -- Microporous And Mesoporous Catalysts / Wolfgang Schmidt -- Skeletal Catalysts / Andrew J. Smith -- A Scientific Method To Prepare Supported Metal Catalysts / John R. Regalbuto -- Catalysis And Chemical Reaction Engineering / Stanko Hočevar. Structure And Reaction Control At Catalyst Surfaces / Mizuki Tada, Yasuhiro Iwasawa -- Texturology / Vladimir B. Fenelonov, Maxim S. Mel'gunov -- Understanding Catalytic Reaction Mechanisms: Surface Science Studies Of Heterogeneous Catalysts / W.t. Wallace, D. Wayne Goodman -- High-throughput Experimentation And Combinatorial Approaches In Catalysis / Stephan Andreas Schunk [and Others] -- Heterogeneous Photocatalysis / Vasile I. Pârvulescu, Victor Marcu -- Liquid-phase Oxidations Catalyzed By Polyoxometalates / Noritaka Mizuno, Keigo Kamata, Kazuya Yamaguchi -- Asymmetric Catalysis By Heterogeneous Catalysts / Simona M. Coman, Georges Poncelet, Vasile I. Pârvulescu. Edited By Ryan Richards. Includes Bibliographical References And Index. "Sports Injuries of the Knee: Surgical Approaches discusses 32 key surgical treatments for managing the most common problems and sports-related injuries to the knee. Each chapter outlines physical examination techniques, diagnosis, differential diagnosis, indications, operative and non-operative treatment options, patient positioning, goals, approaches, surgical techniques, and postoperative considerations. Leading experts offer their perspectives on procedures such as arthroscopic menisecal repair, ligament reconstruction, osteochondritis dissecans treatment, osteotomies about the knee, proximal/distal realignment for patellar instability, tibial spine fractures, and more."--Publisher's website