Catalysis

PREFACE

PART I: Basic Concepts

CATALYSIS IN PERSPECTIVE: HISTORIC REVIEW
History of Catalysis Science
The Development of Catalytic Processes: History and Future
Fundamental Catalysis in Practice
Catalyst Selection
Reactor Choice
Process Choice

KINETICS OF HETEROGENEOUS CATALYTIC REACTIONS
Physical chemical principles
The Lock and Key Model, the Role of Adsorption Entropy
Equivalence of Electrocatalysis and Chemocatalysis
Microkinetics; the Rate-Determining Step
Elementary Rate Constant Expressions for Surface Reactions
The Pressure Gap
The Materials Gap
Coupling of Catalytic Reaction and Inorganic Solid Chemistry
In situ Generation of Organo-Catalyst
The Compensation Effect

KINETICS IN HOMOGENEOUS CATALYSIS
Principles of a Catalyst and Kinetic Description
Catalyst Activity
Catalyst Activation and Deactivation

CATALYTIC REACTION ENGINEERING PRINCIPLES
Preface
Formal Kinetics of Catalytic Reactions
Mass and Heat Transfer Effects
Homogenous Catalysis in Biphasic Fluid/Fluid Systems

PART II: The Chemistry of Catalytic Reactivity

HETEROGENEOUS CATALYSIS
General Introduction
Transition Metal Catalysis
Solid Acids and Bases
Reducible Oxides

HOMOGENEOUS CATALYSIS
General Features

BIOCATALYSIS
Introduction
Examples
Summary/Conclusions

ELECTROCATALYSIS
Introduction
Theory
Application to the Oxygen Reduction Reaction (ORR) on Pt(111)
Summary

HETEROGENEOUS PHOTOCATALYSIS
Introduction
Applications of Photocatalysis
Case Studies
Concluding Remarks

PART III: Industrial Catalytic Conversions

CARBONYLATION REACTIONS
General Aspects
Hydroformylation
Other Carbonylations of Olefins and Alkynes
Carbonylations of Alcohols and Aryl Halides

BIOCATALYTIC PROCESSES
Introduction
Examples
Case Study: Synthesis of Lipitor Building Blocks
Conclusions

POLYMERIZATION
Introduction
Polyolefins in Brief
Olefin Polymerization Catalysts
Olefin Polymerization Process Technology
The Latest Breakthroughs

AMMONIA SYNTHESIS
Ammonia Plant
Synthesis
Steam Reforming
Conclusions

FISCHER-TROPSCH SYNTHESIS IN A MODERN PERSPECTIVE
Introduction
Stoichiometry and Thermodynamic Aspects
Processes and Product Composition
Catalysts, General
Reaction Fundamentals
Concluding Remarks

ZEOLITE CATALYSIS
Introduction
The Hydrocracking Reaction; Acid Catalysis
Lewis Acid - Lewis Base Catalysis; Hydrocarbon Activation
Selective Oxidation; Redox Catalysis
Framework-Substituted Redox Ions

CATALYTIC SELECTIVE OXIDATION - FUNDAMENTALS, CONSOLIDATED TECHNOLOGIES, AND DIRECTIONS FOR INNOVATION
Catalytic Selective Oxidation: Main Features
Catalytic Selective Oxidation: What Makes the Development of an Industrial Process More Challenging (and Troublesome) than Other Reactions
Catalytic Selective Oxidation: the Forefront in the Continuous Development of More-Sustainable Industrial Technologies
The Main Issue in Catalytic Oxidation: the Control of Selectivity
Dream Reactions in Catalytic Selective Oxidation: a Few Examples (Some Sustainable, Some Not Sustainable)
A New Golden Age for Catalytic Selective Oxidation?
Conclusions: Several Opportunities for More Sustainable Oxidation Processes

HIGH-TEMPERATURE CATALYSIS: ROLE OF HETEROGENEOUS, HOMOGENEOUS, AND RADICAL CHEMISTRY

Introduction
Fundamentals
Applications
Hydrogen Production from Logistic Fuels by High-Temperature Catalysis
High-Temperature Catalysis in Solid Oxide Fuel Cells

HYDRODESULFURIZATION
Introduction
Hydrodesulfurization
The C-X Bond-Breaking Mechanism
Structure of the Sulfidic Catalyst
Hydrodenitrogenation
Determination of Surface Sites

PART IV: Catalyst Synthesis and Materials

MOLECULARLY DEFINED SYSTEMS IN HETEROGENEOUS CATALYSIS
Introduction
Single Sites: On the Border between Homogeneous and Heterogeneous Catalysis
Conclusion and Perspectives

PREPARATION OF SUPPORTED CATALYSTS
Introduction
Support Surface Chemistry
Ion Adsorption
Impregnation and Drying
Deposition Precipitation
Thermal Treatment

POROUS MATERIALS AS CATALYSTS AND CATALYST SUPPORTS
General Characteristics
Sol-gel and Fumed Silica
Alumina and Other Oxides
Carbon Materials
Zeolites
Ordered Mesoporous Materials
Metal-Organic Frameworks
Shaping

DEVELOPMENT OF CATALYTIC MATERIALS
Introduction
Fundamental Aspects
Micro-Kinetics and Solid-State Properties as a Knowledge Source in Catalyst Development
Combinatorial Approaches and High-Throughput Technologies in the Development of Solid Catalysts

PART V: Characterization Methods

IN-SITU TECHNIQUES FOR HOMOGENEOUS CATALYSIS
Introduction
In-situ Techniques for Homogeneous Catalysis
Gas Consumption and Gas Formation
NMR Spectroscopy
IR-Spectroscopy
UV/Vis Spectroscopy
Summary

IN-SITU CHARACTERIZATION OF HETEROGENEOUS CATALYSTS
Introduction
Some History, Recent Developments, and Applications
In situ Characterization of a Reactor Loaded with a Catalytic Solid
In situ Characterization at a Single Catalyst Particle Level
Concluding Remarks


ADSORPTION METHODS FOR CHARACTERIZATION OF POROUS MATERIALS
Introduction
Physical Adsorption
Classification of Porous Materials
Adsorption Isotherms
The Application of Adsorption Methods
Theoretical Description of Adsorption
Characterization of Microporous Materials
Characterization of Mesoporous Materials
Mercury Porosimetry
Xenon Porosimetry

A CRITICAL REVIEW OF SOME "CLASSICAL" GUIDELINES FOR CATALYST TESTING
Introduction
Encouraging Effectiveness
Ensuring Efficiency
Concluding Remarks

APPENDIX A: THREE-PHASE TRICKLE-BED REACTORS

PART VI: Catalytic Reactor Engineering

CATALYTIC REACTOR ENGINEERING
Introduction
Types of Catalytic Reactors
Ideal Reactor Modeling/Heat Management
Residence Time Distribution
Micro Reaction Engineering