Heterogeneous Catalysis of Mixed Oxides Perovskite and Heteropoly Catalysts 1st Edition by Makoto Misono – Ebook PDF Instant Download/Delivery: 044453833X, 9780444538338
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ISBN 10: 044453833X
ISBN 13: 9780444538338
Author: Makoto Misono
Mixed oxides are the most widely used catalyst materials for industrial catalytic processes. The principal objective of this book is to describe systematically the mixed oxide catalysts, from their fundamentals through their practical applications. After describing concisely general items concerning mixed oxide and mixed oxide catalysts, two important mixed oxide catalyst materials, namely, heteropolyacids and perovskites, are taken as typical examples and discussed in detail.
These two materials have several advantages: 1. They are, respectively, typical examples of salts of oxoacids and double oxide, that is, the two main categories of mixed oxides in solid state chemistry. 2. Both exhibit excellent catalytic performance in nearly crystalline state and are used in several industrial applications. 3. They have studied for many years.
In addition, metal oxides functioning as a catalyst support (carrier) are included. Although the supports are very important in practical applications, and tremendous progress has been made in the past decades, few systematic reviews exist. It is notable that heteropolyacids and perovskite exhibit unique performance when used as a support.
Fundamental catalytic science and technology and solid state chemistry necessary is presented for the proper understanding of mixed oxide catalysts as well as for R&D. For the latter, the concept of design of practical catalysts is very important. This is considered throughout the book.
- Systematically describes design principles of mixed oxide catalysts
- Shows how catalysis and solid-state chemistry of metal oxides are inter-related
- Covers all useful basic concepts of mixed oxide catalysis
Table of contents:
Chapter 1: Basis of Heterogeneous Catalysis
1.1. Catalyst and Catalysis
1.1.1. Rate and Equilibrium of Chemical Reaction and Role of Catalyst
1.1.2. Three Essential Functions of Catalyst
1.1.3. Essence of Catalytic Functions Based on Reaction Mechanism
1.1.4. A Short History of Industrial Catalysts
1.1.5. Classification of Catalysts
1.1.6. Practical Applications of Catalysts
1.1.7. Components and Shape of Industrial Catalysts
1.2. Rate of Catalytic Reaction and Reaction Mechanism
1.2.1. Reaction Rate
1.2.2. Adsorption on Solid Surface; Rate and Isotherm
1.2.3. Rate Equation of Catalytic Reaction
1.2.3.1. Reaction of A+BC; L-H and E-R Mechanisms
1.2.3.2. Other Mechanisms
1.2.4. Reactor Type and Rate Expression
1.2.5. Elucidation of Reaction Mechanism
1.2.5.1. Rate Equation and Stoichiometry of Reaction
1.2.5.2. Uses of Isotopes
1.2.5.3. Direct Spectroscopic Observation of Reaction Intermediates Adsorbed on Catalyst
1.2.5.4. Linear Free Energy Relationship (LFER)
1.2.5.5. Stereochemistry of Reaction
1.2.5.6. Measurement of Rates of Reduction and Reoxidation of Catalyst
1.2.6. Mass and Heat Transfer
1.2.6.1. Effectiveness Factor
1.2.6.2. Temperature Control
1.2.7. Deactivation of Catalyst
1.2.8. Comparison of Heterogeneous, Homogeneous and Biocatalysis
1.3. Catalyst Design
1.4. Preparation and Characterization of Catalysts
References
Chapter 2: Chemistry and Catalysis of Mixed Oxides
2.1. Chemistry of Binary Oxides
2.1.1. Structure of Binary Oxides (or Single Metal Oxides)
2.1.2. Lattice Defects and Nonstoichiometry (Berthollide Compounds)
2.1.3. Surface Structure of Single Metal Oxides
2.1.4. Chemical Properties of Single Metal Oxides
2.1.4.1. Acidity and Basicity
2.1.4.2. Redox Properties
2.1.5. Catalysis of Single Metal Oxides
2.1.5.1. Acid-Base Catalysis
2.1.5.2. Catalytic Oxidation and Hydrogenation-Dehydrogenation
2.2. Chemistry of Mixed Oxides
2.2.1. Structure of Mixed Oxides
2.2.1.1. Crystal Structure of Mixed Oxides
2.2.1.2. Surface Structure of Mixed Oxides
2.2.2. Valence and Defects in Mixed Oxides
2.2.3. Acidity and Basicity
2.2.4. Redox Properties
2.2.5. Mixed Oxides for Supports
2.3. Catalysis of Mixed Oxides
2.3.1. Acid and Base Catalysis
2.3.2. Oxidation Catalysis
2.3.2.1. Complete Oxidation
2.3.2.2. Selective Oxidation
2.3.3. Hydrogenation, Dehydrogenation, and Metathesis
2.4. Synergistic Effects in Mixed Oxide Catalysis
2.4.1. Combination of Acid and Base Catalysis
2.4.1.1. Concerted Action of Acid-Base Pair Sites
2.4.1.2. Acidic and Basic Sites Functioning in Different Reaction Steps of Catalysis
2.4.2. Combination of Dual Functions in Selective Oxidation
2.4.2.1. Hydrogen Abstraction and Oxygen Addition Sites
2.4.2.2. Acid and Oxidation Sites
2.4.3. Roles of Catalyst Supports
2.5. Participation of Solid Bulk in Catalysis of Metal Oxides
2.5.1. Surface Layer Hypothesis
2.5.2. Redox Mechanism of Cu-Hydroxyapatite and Catalytic Activity
2.5.3. Iron Oxide; Redox Mechanism and Active Phase for Butene to Butadiene
2.5.4. Two Bulk-Type Catalysis of Solid Heteropoly Catalysts
2.5.5. Concluding Remarks on the Role of Solid Bulk of Catalyst
References
Chapter 3: Catalysis of Perovskite and Related Mixed Oxides
3.1. Structures and Properties of Perovskite Family
3.1.1. Structure
3.1.2. Nonstoichiometry and Vacancies
3.1.3. Thermal and Chemical Stability
3.1.4. Applications Utilizing Electric, Magnetic, and Chemical Properties
3.2. Catalytic Properties of Perovskites
3.3. Design of Perovskites Catalysts
3.3.1. Strategy for Catalyst Design of Perovskite-Type Mixed Oxides
3.3.2. Selection of B-Site Transition Element
3.3.3. Valence Control of B-Site Elements
3.3.3.1. LaCoO3
3.3.3.2. Others
3.3.4. Synergistic Effects of B-Site Elements
3.3.5. Combination of Valence Control and Synergistic Effect
3.3.6. Enhancement of Surface Area
3.4. Catalysis of Valence-Controlled LaCoO3 and La2CuO4
3.4.1. La1-x SrxCoO3
3.4.1.1. Structure and Nonstoichiometry
3.4.1.2. Surface Composition
3.4.1.3. TPD and Adsorption of Oxygen
3.4.1.4. Catalytic Activity for Oxidation
3.4.1.5. Reduction and Reoxidation of La1-xSrxCoO3
3.4.1.6. Isotopic Exchange and Equilibration of Oxygen
3.4.1.7. Oxygen Species Active for Catalytic Oxidation and Reaction Mechanism
3.4.2. La2-xAxCu1-yByO4 (A: Ba, Sr, and Ca; B: Zr and Al)
3.4.2.1. Structural Properties of Catalysts
3.4.2.2. Composition and Oxidation State of Cu on the Surface and Bulk
3.4.2.3. Catalytic Activities for Decomposition of NO and N2O
3.4.2.4. Mechanism of Catalytic NO Decomposition
3.5. Practical Applications of Perovskite Catalysts
3.5.1. Household Appliances
3.5.2. Catalytic Combustion
3.5.3. Automotive Catalysts with High Durability
3.5.4. Removal of Soot and NOx in Exhaust from Diesel Vehicles
3.5.5. Membrane Reactor for Reforming of Hydrocarbons
References
Chapter 4: Catalysis of Heteropoly Compounds (Polyoxometalates)
4.1. General Characteristics of Heteropoly Catalysis
4.2. Chemistry of Heteropoly Compounds in Solution
4.2.1. Formation and Stability of Heteropolyanions
4.2.2. Acidic Properties in Solution
4.2.3. Redox Properties in Solution
4.3. Structure of Heteropoly Compounds in the Solid State
4.3.1. Hierarchical Structure of Solid Heteropoly Compounds
4.3.2. Primary Structures
4.3.2.1. Keggin Structure, XM12O40n-
4.3.2.2. Dawson Structure, X2M18O62
4.3.3. Secondary Structures
4.3.3.1. Group A and B Salts of H3PMo12O40 and H3PW12O40
4.3.3.2. Protons in H3PW12O40
4.3.3.3. Cs and H in CsxH3-xPW12O40 (CsX)
4.3.4. Tertiary Structure; Particle Size, Surface Area, and Pore Structure
4.3.4.1. Particle Size and Surface Area
4.3.4.2. Pore Structure
4.3.4.3. Control of Pore Size and Shape-Selective Adsorption
4.3.4.4. Epitaxial Assembly of NH4 and Cs Salts of H3PW12O40
4.3.5. Stability
4.3.5.1. Thermal Stability
4.3.5.2. Chemical Stability
4.4. Chemical Properties of Heteropoly Compounds in the Solid State
4.4.1. Pseudoliquid Behavior
4.4.1.1. Pseudoliquid
4.4.1.2. Absorption in Pseudoliquid
4.4.1.3. Evidence of Catalysis in Pseudoliquid Phase
4.4.1.4. Spectroscopic Study of Reactions in Pseudoliquid
4.4.1.5. Phase Transition of Pseudoliquid Phase
4.4.2. Acidic Properties
4.4.2.1. Bulk and Surface Acidity
4.4.2.2. Origins of Acidity of Solid Heteropoly Compounds
4.4.2.3. Acidic Properties of Acid Forms and Salts
4.4.2.3.1. Acid Forms
4.4.2.3.2. Metallic Salts
4.4.3. Reduction and Oxidation (Redox) Properties
4.4.3.1. Two-Step Reduction of H3PMo12O40
4.4.3.2. Surface and Bulk Redox Properties
4.4.3.3. Oxidizing Ability
4.4.3.3.1. Acid Forms
4.4.3.3.2. Metallic Salts
4.4.3.3.3. H2-D2 Reactions over H3PW12O40 and H3PMo12O40
4.5. Catalysis of Heteropoly Compounds
4.5.1. Three Types of Catalysis in the Solid State
4.5.2. Acid Catalysis
4.5.2.1. Overview
4.5.2.2. Catalytic Activity; Surface- and Bulk-Type (Pseudoliquid Phase) Catalyses
4.5.2.3. Selectivity
4.5.2.4. Shape Selectivity
4.5.2.5. Remarks on Heteropoly Catalysts for Practical Application as Solid Acids
4.5.3. Oxidation Catalysis
4.5.3.1. Overview
4.5.3.2. Redox Mechanisms; Surface-Type and Bulk-Type II Catalyses
4.5.3.3. Oxidation of Methacrolein to Methacrylic Acid
4.5.3.4. VPO Catalysts for the Oxidation of n-Butane to Maleic Anhydride
4.5.4. Bifunctional Catalysis
4.5.4.1. Hydroisomerization
4.5.4.2. Wacker-Type Oxidation
4.5.4.3. Shape-Selective Oxidation and Hydrogenation
4.6. Supported Heteropoly Catalysts
4.6.1. Necessity of Supported Heteropoly Catalysts
4.6.2. Heteropoly Compounds Supported on SiO2
4.6.3. Industrial Production of Ethyl Acetate from Ethylene and Acetic Acid
References
Chapter 5: Mixed Oxides as Catalyst Supports
5.1. Roles of Catalyst Supports
5.1.1. Improvement of the Catalytically Active Component Itself
5.1.2. Improvement of the Catalyst as a Whole
5.2. Perovskites as Catalyst Supports
5.2.1. Perovskites Supports
5.2.2. Perovskite Supports for Automotive Catalysts
5.3. Ceria-Zirconia and Related Mixed Oxides
5.3.1. Storage Effect for Oxygen and Nitrogen Oxide
5.3.2. Mixed Oxide Supports for Noble Metals of Automotive Catalysts
5.4. Heteropolyacids (Polyoxometalates) as Catalyst Supports
5.5. Zeolites as Catalyst Support
5.5.1. Dispersion of Metal Ions by Ion Exchange
5.5.1.1. Metal-Ion Exchange
5.5.2. Pd Supported on ZSM-5 for NOCH4O2 Reaction
5.5.2.1. Reaction Mechanism
5.5.2.2. States of Pd Active and Selective for NOCH4O2 Reaction
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Tags: Makoto Misono, Heterogeneous, Catalysis, Oxides