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Molecular Spectroscopy of Oxide Catalyst Surfaces



Molecular Spectroscopy of Oxide Catalyst Surfaces

Anatoli Davydov

ISBN: 978-0-471-98731-4 June 2003 690 Pages

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As in the study of transition metal complexes in solution, molecular spectroscopic methods - principally the infrared, ultraviolet/visible and electron spin resonance spectroscopies - have played key roles in establishing the concepts of coordination chemistry occurring at the surfaces of solids. This book describes the development of the principals of coordination chemistry of oxide surfaces using analyses of data obtained by these methods. The nature, properties, concentration of the surface adsorption centers and their influence on the character of interaction with different molecules are investigated.
The book commences with an account of the basic theoretical principles and experimental techniques of the various spectroscopy methods, with special attention devoted to in situ measurements where the oxide or catalyst sample is in contact with the adsorbate or the reactant. A detailed account is presented of the methods for characterizing the oxidation state and degree of coordination of surface cations and oxygen anions by the adsorption of probe molecules. The complexation of many inorganic, organometallic and organic molecules with different oxide systems is critically examined, and a classification of formed surface compounds, based on the interaction with definite type of adsorption centers, is given. Possible mechanisms of numerous catalytic reactions, including the transformation of organic molecules over acidic catalysts via the carboionic mechanism, are discussed using the spectroscopic identifications of reaction intermediates. A comprehensive analysis of the literature on the interpretation of the spectra of surface compounds on oxides is presented.
This highly illustrated and extensively referenced volume is intended for specialists working in the fields of surface physical chemistry, surface and materials sciences, and adsorption phenomena and is essential reading for those involved in the heterogeneous catalysis by transition metal-oxides.

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Symbols and abbreviations.


1. Theoretical fundamentals and experimental considerations of spectroscopic methods used in surface chemistry.

Electronic spectroscopy (ES).

Vibrational spectroscopy.

Electron energy loss spectroscopy (EELS).

Inelastic electron tunneling spectroscopy (IETS).

Inelastic neutron scattering spectroscopy (INS).

Other vibrational spectroscopies.

In situ measurements.

Quantitative measurements.

2. Nature of oxide surface centers.

Systems investigated.

Spectral of oxide surfaces.

Determination of the nature of surface sites and their chemical properties using the adsorption of simple molecules.

Determination of acidic surface properties.

Determination of basic surface properties.

Surface defects.

3. Study of cation states by DRES and FT-IR spectroscopies of the probe molecules.

Copper-containing systems.

Nickel-containing systems.

Co-containing systems.

Iron-containing systems.

Silver-containing systems.

Palladium-containing systems.

Rhenium-, Ruthenium-, and Rhodium-containing systems.

Platinum-containing systems.

Molybdenum-containing systems.

Vanadium-containing systems.

Chromium-containing systems.

Effects of the state of adsorption sites on the stretching frequencies of adsorbed Carbon monoxide and Nitrous oxide and the problem of detecting the states of cations in oxide catalyst surfaces.

4. Interactions of inorganic compounds with oxide surface active sites.

Organometallic complexes.

Metal carbonyls and nitrosyls.

Interaction with simple acids and bases.

Heteropoly compounds Systems.

Thermal stability of molybdenum compounds, decomposition mechanism and the role of modifiers.

Cationic modification.

5. Formation of surface complexes of organic molecule.

Complexation of Alkenes.

Complexation of Aryls and aryl halides.

Complexation of Alkynes.

Complexation of Alkanes.

Complexation of Nitriles.

Complexation of Alcohols.

Complexation of Aldehyde and ketone.

Complexation of Acids.

6. The mechanisms of heterogeneous catalytic reactions.

Reactions involving carbon monoxide.

Reactions with participation of hydrocarbons.

Transformations of aldehydes and ketones.

Transformations of alcohols

Transformations of nitrogen-containing compounds.


"…this comprehensive book is truly indispensable as a reference text for researchers engaged in the surface chemistry of oxide surfaces." (Journal of the American Chemical Society, Vol. 126)