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Surface and Nanomolecular Catalysis [Kõva köide]

Edited by (Colorado School of Mines, Golden, USA)
  • Formaat: Hardback, 552 pages, kõrgus x laius: 254x178 mm, kaal: 1133 g
  • Ilmumisaeg: 25-May-2006
  • Kirjastus: CRC Press Inc
  • ISBN-10: 1574444816
  • ISBN-13: 9781574444810
  • Formaat: Hardback, 552 pages, kõrgus x laius: 254x178 mm, kaal: 1133 g
  • Ilmumisaeg: 25-May-2006
  • Kirjastus: CRC Press Inc
  • ISBN-10: 1574444816
  • ISBN-13: 9781574444810
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.
Characterization of Heterogeneous Catalysts
1(38)
Zhen Ma
Francisco Zaera
Introduction
2(1)
Structural Techniques
2(5)
X-Ray Diffraction
2(1)
X-Ray Absorption Spectroscopy
3(2)
Electron Microscopy
5(2)
Adsorption--Desorption and Thermal Techniques
7(5)
Surface Area and Pore Structure
7(1)
Temperature-Programmed Desorption and Reaction
8(1)
Thermogravimetry and Thermal Analysis
9(1)
Microcalorimetry
10(2)
Optical Spectroscopies
12(7)
Infrared Spectroscopy
12(1)
Raman Spectroscopy
13(2)
Ultraviolet--Visible Spectroscopy
15(1)
Nuclear Magnetic Resonance
16(2)
Electron Spin Resonance
18(1)
Surface-Sensitive Spectroscopies
19(3)
X-Ray and Ultraviolet Photoelectron Spectroscopies
19(1)
Auger Electron Spectroscopy
20(1)
Low-Energy Ion Scattering
21(1)
Secondary-Ion Mass Spectroscopy
21(1)
Model Catalysts
22(3)
Concluding Remarks
25(14)
References
26(6)
Questions
32(7)
Catalysis by Metal Oxides
39(24)
Ranjit T. Koodali
Kenneth J. Klabunde
Introduction
40(1)
Properties of Metal Oxides
40(4)
The Periodic Table as Metal Oxides
41(1)
Insulators (Highly Ionic)
41(1)
Semiconductors (Ionic--Covalent Bonding)
42(1)
Crystal Structures
42(2)
Surface Structures
44(4)
Surface Reconstruction
44(2)
Defect Sites
46(2)
Hydroxyl Groups
48(1)
Solid Acids and Bases
48(3)
Metal Cations as Lewis Acids
49(1)
Oxygen Anions as Lewis Bases
49(1)
Hydroxyl Groups as Bronsted Acids and Lewis Bases
50(1)
Spectroscopic Methods of Detecting Lewis Acidity/Basicity and Bronsted Acidity/Basicity
50(1)
Examples of Catalysis
51(6)
Examples of Solid Acids and Bases
51(1)
Hydrogen--Deuterium Exchange Reaction
51(1)
Hydrogenation (1,3-Butadiene + D2)
52(1)
Dehydration and Dehydrogenation
53(1)
Dehydrochlorination
53(1)
Benzylation
53(1)
Claisen--Schmidt Condensation-Asymmetric Epoxidation
54(1)
Oxidation Catalysis
54(1)
Oxidative Dehydrogenation --- Vanadia
54(1)
Oxidative Coupling of Methane
55(1)
Chloride--Oxide Exchange Catalysis
56(1)
Chlorocarbons
56(1)
Freons
56(1)
Conclusions
57(6)
References
57(4)
Questions
61(2)
Colloidal Nanoparticles in Catalysis
63(32)
Helmut Bonnemann
K.S. Nagabhushana
Introduction
63(1)
Mechanism of Stable Particle Formation
64(1)
Modes of Stabilization
64(2)
Reduction Methods
66(8)
Applications in Catalysis
74(11)
Quasi-Homogeneous Reactions
74(1)
Heterogeneous Reactions
74(1)
Precursor Concept
74(1)
Conditioning: A Key Step in Generating Active Catalysts
75(1)
Heterogeneous Catalysis in Catalysis
76(7)
Fuel Cell Catalysts
83(2)
Conclusion
85(10)
References
86(8)
Chapter Questions
94(1)
Microporous and Mesoporous Catalysts
95(46)
Wolfgang Schmidt
Setting the Scene
96(1)
Porous Catalysts
97(1)
Microporous Catalysts: Zeolites
97(21)
What Are Zeolites?
97(4)
Types of Zeolites Used in Catalytic Processes
101(1)
Zeolite X and Zeolite Y
101(1)
ZSM-5
102(1)
Mordenite
102(1)
Zeolite A
103(1)
Production of Zeolites
103(2)
Post-Synthesis Treatment of Zeolites and Modification of Zeolites
105(1)
Protonation of Zeolites
105(1)
Dealumination of Zeolites
106(1)
Metals and Metal Complexes in Zeolites
106(1)
Catalytic Application of Zeolites
107(2)
Zeolite Catalysts in Petrochemical Processes
109(8)
Methanol to Gasoline and Methanol to Olefins
117(1)
Mesoporous Catalysts
118(8)
Ordered Mesoporous Silica Materials
118(4)
Surface Modifications of Ordered Mesoporous Silica Materials
122(1)
Catalysis with Ordered Mesoporous Silica Materials
123(2)
Nonsiliceous Ordered Mesoporous Materials
125(1)
Characterization of Microporous and Mesoporous Materials
126(15)
X-Ray Diffraction
127(1)
Physisorption Analysis
128(2)
Electron Microscopy
130(1)
Nuclear Magnetic Resonance Spectroscopy
130(2)
Infrared Spectroscopy
132(2)
Appendix
134(1)
Terms and Abbreviations
134(1)
Further Reading
135(1)
References
135(3)
Chapter 4 Problems
138(3)
Skeletal Catalysts
141(20)
Andrew J. Smith
Introduction
141(1)
History
141(1)
Preparation
142(5)
Leaching Kinetics
144(1)
Promoters
145(2)
Structures
147(2)
Deactivation/Aging
149(2)
Applications
151(2)
Advantages/Disadvantages
153(1)
Future
154(7)
Acknowledgment
154(1)
References
154(5)
Chapter 5 Questions
159(2)
A Scientific Method to Prepare Supported Metal Catalysts
161(34)
John R. Regalbuto
Introduction
161(1)
Early Pioneering Work
162(4)
Development of the Revised Physical Adsorption Model
166(11)
Qualitative Discrimination of Mechanisms
166(2)
pH Shift Modeling
168(6)
Metal Adsorption Modeling
174(3)
Case Study: Pt Tetraammine Adsorption over Silica
177(8)
Survey of Pt/Silica Preparation Methods
177(2)
Measurement of Oxide Point of Zero Charge
179(1)
Uptake-pH Survey to Identify Optimal pH
179(3)
Tuning Finishing Conditions to Retain High Dispersion
182(3)
The Extension of Strong Electrostatic Adsorption to Alumina and Carbon
185(2)
Further Applications: Other Oxides, Bimetallics
187(3)
Summary
190(5)
References
190(2)
Chapter 6 Questions
192(3)
Catalysis and Chemical Reaction Engineering
195(34)
Stanko Hocevar
Annotations
195(1)
Greek Letters
196(1)
Subscripts
196(1)
Introduction
196(1)
Overview of Heterogeneous Catalysis and Chemical Reaction Engineering
197(2)
Hydrogen Production and Cleaning: Catalysis and Reaction Engineering
199(25)
Conventional Processes and Catalysts for Hydrogen Generation and Their Limitations in Low-Temperature Fuel Cells Technology
200(1)
Fuel Reforming
200(2)
Water-Gas Shift Reaction
202(1)
Preferential Oxidation of Carbon Monoxide
202(2)
Fuel Cells and Primary Fuel Processing for Low-Temperature Fuel Cells
204(1)
Catalytic Processes of Hydrogen Production for Proton-Exchange Membrane Fuel Cell
205(19)
Conclusions
224(5)
Acknowledgments
224(1)
References
225(2)
Chapter 7 Questions
227(2)
Structure and Reaction Control at Catalyst Surfaces
229(28)
Mizuki Tada
Yasuhiro Iwasawa
Introduction
229(2)
Regulation of Catalysis by Coadsorbed Molecules
231(13)
Self-Assisted Dehydrogenation of Ethanol on an Nb/SiO2 Catalyst
231(2)
Reactant-Promoted Water-Gas-Shift Reactions
233(1)
WGS Reactions on ZnO
234(1)
WGS Reactions on Rh/CeO2
235(1)
Regulation of Selective Oxidation of Methanol on a Modified Mo(112) Surface
236(1)
Reaction Aspect of Methanol Oxidation
236(4)
Reaction Scheme of Methanol Oxidation in TPR
240(2)
Reaction Kinetics of the Steady-State Methanol Oxidation
242(1)
Regulation of the Methanol Oxidation by Extra Oxygen Atoms
242(2)
Regulation of Catalysis by Design of Active Structures
244(4)
Chemical Tuning of Active Sites
244(2)
ReOx Clusters Produced in Situ
246(2)
Design of Reaction Intermediate and Transition-State Analogue for a Target Reaction on Oxide Surfaces
248(6)
Reaction Regulation by Molecular Imprinting
248(4)
Design of a Reaction Intermediate on Catalyst Surface
252(2)
Conclusion
254(3)
References
254(2)
Chapter 8 Problems
256(1)
Texturology
257(80)
Vladimir B. Fenelonov
Maxim S. Mel'gunov
Introduction
258(3)
Basic Principles of Physical Chemistry of Dispersed Systems
261(13)
Gibbsian Classical Thermodynamic Theory
261(1)
Flat Interface
262(2)
Curved Interface
264(1)
Surface Curvature
265(1)
The Limits of the Classical Thermodynamic Theory
266(1)
Typical Mechanisms and Processes of Texture Genesis Derived from the Laws of Surface-Capillary Phenomena
267(1)
Fundamental Mechanisms of Texture Genesis
267(2)
Fundamental Processes of Texture Genesis
269(5)
Adsorption as a Primary Instrument for Texture Characterization
274(6)
Morpho-Independent Textural Parameters
280(10)
Density and Porosity
280(3)
Experimental Techniques of Measurements of True, Apparent, and Bulk Density
283(1)
The Properties of Porosity
284(5)
The Specific Surface Area
289(1)
Morpho-Dependent Textural Parameters: Mean Sizes of Particles and Pores
290(3)
General Problems of Porous Solids Texture Modeling
293(8)
Morphology of Porous Solids and Problems with Modeling
293(1)
Classification of Porous Systems and Texture Modeling
294(5)
Generalized Models and Systematic Sets of Models
299(2)
Modeling Particles and Pores in a Local Arrangement
301(13)
Voronoi--Delaunay Method for Description of Corpuscular and Sponge-Like Porous Solids
301(5)
Ordered Packings
306(5)
Disordered Packings
311(3)
Modeling the Ensembles (Clusters) of Particles and Pores on the Basis of a Fractal Approach
314(6)
Lateral and Statistical Models of Pores and Particles Arrangement
320(7)
Percolation Theory
320(1)
Problem of Bonds
321(1)
Problem of Sites
322(2)
The Stochastic and other Statistical Models of Long-Range Order
324(3)
Conclusions
327(10)
References
328(7)
Chapter 9 Problems
335(2)
Understanding Catalytic Reaction Mechanisms: Surface Science Studies of Heterogeneous Catalysts
337(36)
W.T. Wallace
D. Wayne Goodman
Introduction
337(7)
Studies of CO Hydrogenation on Single-Crystal Surfaces
338(1)
Effects of Poisons and Promoters on CO Methanation
339(1)
CO Oxidation on Single-Crystal Surfaces
340(1)
Bimetallic Surfaces
340(4)
Experimental Techniques
344(1)
Model Catalysts
344(11)
Thin-Film Growth
345(1)
TiO2 Thin Films
345(1)
Amorphous SiO2 Films
345(3)
Crystalline SiO2 Films
348(1)
Highly Defective TiOx Films
348(1)
Supported Metal Clusters (Au as an Example)
349(6)
In Situ Studies
355(13)
Vibrational Spectroscopy
355(8)
In Situ STM
363(1)
Elevated Pressure XPS
363(5)
Conclusions
368(5)
Acknowledgments
368(1)
References
368(4)
Chapter 10 Questions
372(1)
High-Throughput Experimentation and Combinatorial Approaches in Catalysis
373(54)
Stephan Andreas Schunk
Oliver Busch
Dirk G. Demuth
Olga Gerlach
Alfred Haas
Jens Klein
Torsten Zech
High-Throughput Experimentation and Combinatorial Catalysis --- Definition and Scope
374(2)
Experimental Planning and Data Handling
376(4)
Descriptor-Driven Approaches
376(1)
Approaches Based on Classical Statistical Designs
377(1)
Other Techniques for Finding Local Optima
378(2)
Stage I and Stage II Screening
380(2)
Analytical Techniques for Screening
382(3)
Synthetic Approaches for High-Throughput Experimentation and Combinatorial Chemistry
385(5)
Synthetic Approaches for Molecular Catalysts
386(1)
Synthetic Approaches for Solid-State Inorganic Catalysts
387(2)
Combinatorial Synthetic Approaches for Solid-State Inorganic and Molecular Catalysts
389(1)
Testing of Catalysts in Gas-Phase Reactions
390(21)
Stage I Testing of Catalysts for Gas-Phase Reactions
396(1)
General Considerations
396(1)
Reactant Distribution for Stage Screening Systems
396(2)
Single-Bead Reactors
398(3)
Optimal Use of Stage I in Screening Programs
401(1)
Stage II Testing in Gas-Phase Applications
402(3)
The Epoxidation of 1.3-Butadiene with Ag-Based Catalysts
405(2)
Dynamic Experiments in Stage If Screening for Automotive Applications
407(2)
Refinery Catalysis Applications in High-Throughput Experimentation
409(2)
Testing of Catalysts in Liquid--Liquid. Gas--Liquid, and Gas--Liquid--Solid Reactions
411(9)
Stage I Screening for Liquid-Phase Catalysis
413(4)
Alternative Stage I Screening Concepts
417(1)
Stage II Screening for Liquid-Phase Catalysis
418(2)
Summary and Outlook
420(7)
References
421(4)
Chapter 11 Questions
425(2)
Heterogeneous Photocatalysis
427(36)
Vasile I. Parvulescu
Victor Marcu
Introduction
428(1)
Photocatalysis
429(16)
General Principles
430(3)
TiO2 Photocatalysts
433(2)
Preparation Procedures
435(3)
Modified Titania Photocatalysts
438(3)
Mixed Oxide and Composites Containing Titania
441(1)
Noble Metal Deposited on Titania Surfaces
441(2)
Monoliths Containing Titania
443(1)
ZnO
443(1)
Other Oxide Semiconductors
444(1)
Calcium Hydroxyapatite Modified with Ti(IV)
444(1)
Polyoxometalates
444(1)
Heterogeneous Fenton-Type Catalysts
445(1)
Kinetic Studies
445(1)
Combinatorial Approaches in Preparation and Testing Photocatalysts
446(2)
Example of Reactions under Photocatalytic Conditions
448(2)
Photoinduced Deposition of Various Metals onto Semiconductor
449(1)
Energy Storage
450(1)
Solar Photocatalysis
450(1)
Sonophotocatalysis
450(2)
Photocatalysis Associated to Microwave Radiation
452(1)
Photocatalyst Deactivation
452(1)
Conclusions
452(11)
References
453(8)
Chapter 12 Questions
461(2)
Liquid-Phase Oxidations Catalyzed by Polyoxometalates
463(30)
Noritaka Mizuno
Keigo Kamata
Kazuya Yamaguchi
Introduction
463(2)
Homogeneous Catalysts with Polyoxometalate-Based Compounds
465(9)
Mixed-Addenda Polyoxometalates
465(1)
Transition-Metal-Substituted Polyoxometalates
465(7)
Peroxometalates
472(2)
Lacunary Polyoxometalates
474(1)
Heterogeneous Catalysts with Polyoxometalate-Based Compounds
474(11)
Dispersion onto Inert Supports
475(1)
Active Carbon
475(2)
Silica and MCM-41
477(1)
Others
478(1)
Formation of Insoluble Solid Ionic Materials
478(1)
Metal Ions
478(1)
Alky lammonium Ions
478(1)
Crosslinking of Copolymer with POM
479(1)
Intercalation into Anion-Exchange Materials
480(2)
Immobilization on Surface-Modified Supports
482(1)
Anion-Cation Pairing
482(2)
Covalent Bond Formation
484(1)
Others
484(1)
Conclusions and Future Opportunities
485(8)
Acknowledgments
487(1)
References
487(5)
Chapter 13 Questions
492(1)
Asymmetric Catalysis by Heterogeneous Catalysts
493(40)
Simona M. Coman
Georges Poncelet
Vasile I. Parvulescu
Introduction
493(3)
Principles of Stereodifferentiation and Asymmetric Catalysis
496(3)
Historical Developments
499(3)
Tartaric Acid-Modified Me/Support Hydrogenation Catalysts and Related Systems
502(8)
Catalyst Preparation Process
502(1)
The Modification Process
503(1)
Substrate and Hydrogenation Parameters
503(1)
Mechanistic Investigations and Hypotheses for Enantioselection
504(3)
Proposed Mechanisms
507(3)
Chiral-Modified Platinum Hydrogenation Catalysts and Related Systems
510(7)
Kinetic Models
512(1)
Mechanistic Investigations
512(5)
Heterogeneized Homogeneous Catalysts
517(2)
Organic Polymers
519(1)
Diastereoselective Catalysis
519(4)
Conclusions
523(10)
References
523(8)
Questions
531(2)
Index 533


Ryan Richards