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Metal-Oxygen Clusters is the first book, providing an overview of the surface chemistry and catalytic properties of heteropoly oxometalates. After a brief look at the early knowledge of heteropoly oxometalates, the book discusses the synthesis, characterization, structure, bulk properties and stability of these materials. The remainder and the largest portion of the book explores the properties of these solids as catalysts in acid-catalyzed and oxidation processes in supported or unsupported forms. The book provides an up-to-date review of the methods for synthesizing heteropoly oxometalates of Keggin structure, techniques from spectroscopic through electrochemical to elemental analysis for their characterization and the current information on their structure, bulk properties and their stabilities at high temperatures and under acid and alkaline conditions. The book discusses the materials employed as supports for the title solid and the results of the examination of the supported materials. Methods for the identification of the nature and source of the two catalytic functions, the acidic and oxidative properties, of the heteropoly oxometalates are reviewed and discussed. The use of both the supported and unsupported heteropoly oxometalates as catalysts in acidity-requisite processes ranging from methanol conversion to hydrocarbons to ring-expansion and contraction processes and in oxidation processes from methane cyclohexane are described and related to the aforementioned properties.
1: A Brief Look at the Early History of Heteropoly Oxometalates. I. History. II. References. 2: Synthesis. I. Introduction. II. The 12-heteropoly acids. III. Various Syntheses. IV. References. 3: Characterization. I. Spectroscopy. II. Electrochemical Methods. III. Elemental Analysis. IV. Other Techniques. V. References. Chapter 4: Structure and Bulk Properties. I. Anions. II. Cations and Crystallographic Structure. III. Langmuir Films. IV. References. 5: Stability. I. Thermal Stability. II. pH Stability. III. Regeneration in the Presence of Water. IV. References. 6: Supported Heteropoly Acids and Their Derivatives. I. Supports. II. Formation of Heteropoly Acids from Oxides Supported on Silica. III. References. 7: Microporosity. I. Introduction. II. Microporosity of Salts prepared from the Monovalent Cations of the Group 1 Alkali Metals and Ammonium and Related Cations. III: A. Microporosity of the Salts Prepared from the Monovalent Cations of the Groups 11 and 13 Elements. B. Stoichiometric and Nonstoichiometric Salts of Groups 11 and 13 and Their Morphological Properties. IV. Pore Structures from 129Xe NMR. V. Sorption and Diffusion in Metal-Oxygen Cluster Compounds. VI: A. Cation Exchange and Microporosity. B. Crystal Structure and Morphology Retention on Ion Exchange. VII. Argon Adsorption. VIII.Divalent Salts. IX. Reactions on the Microporous Salts and Shape Selectivity. X. References. 8: The Two Functions: Acidity and Oxidation-Reduction. I. Acidity. II. Oxidation-Reduction. III. References. 9: Acid-Catalyzed Processes. I. Methanol Conversion to Hydrocarbons. II. Ethanol. III. Propene. IV. Propanol. V. Butane. VI. Butene. VII. Isobutane. VIII. Isobutene. IX. Butanol. X. Alkylation Processes. XI. Friedel-Crafts Reactions. XII. C5-C8 Alkanes. XIII. C6-C8 Alkenes. XIV. Ring-Expansion of Methylcyclopentane and Ring-Contraction of Cyclohexane. XV. References. 10: Oxidation Processes. I. A. Methane. B. The Effect of Gas Phase Additives in the Conversion of Methane on Heteropoly Oxometalates. II. Ethane. III. Propane. IV. Butane. V. Isobutane. VI. Methacrolein. VII. Isobutyric Acid. VIII. Pentane. IX. Butadiene. X. 1-Butene. XI. Cyclohexane. XII. Ammoxidation. XIII. References. 11: Environmentally-Related Processes. I. Conversion of Nitrogen Oxides. II. Hydrodesulphurization. III.Polymerization. IV. References.