Transition metal sulfides surface composition

Solid state chemistry plays an important role in the catalysis by Transition Metal Sulfides however, it is a role that is somewhat different than the role usually assigned to solid state chemistry in catalysis. In catalysis, by sulfides, the chemistry of ternary phases is not now important and thus, the usual role of solid state chemistry in preparing ternary phases and systematically studying the effect on catalytic properties through variation of the composition of these ternary phases is absent. Nevertheless, preparation of the Transition Metal Sulfides is crucial in controlling the properties of the catalysts. Low temperature solid state preparations are the key to obtaining good catalysts in reasonable surface area for catalytic measurements. 

Surface reconstruction is inherent to surface oxidation and sulfidation chemistry. In involves essentially surface corrosion and surface compound formation phenomena. The state of a surface can change from a metallic state to that of a solid oxide, sulfide, carbide or nitride depending upon the reaction environment. The surface of the epoxidation catalyst, discussed earlier, in the absence of Cl or Cs, for example, has a composition similar to AgO in the oxidizing reaction environment of the epoxidation system. The oxidation of CO over Ru can readily lead to the formation of surface RUO2 (see Chapter 5). In desulfurization reactions the transition-metal surface is converted to a sulfide form. The reactivity of the surface in these systems begins to look chemically more similar to that of coordination complexes. This we will illustrate in Chapter 5 for the C0S/M0S2 system. 

Metal oxides belong to a class of widely used catalysts. They exhibit acidic or basic properties, which make them appropriate systems to be used as supports for highly dispersed metal catalysts or as precursors of a metal phase or sulfide, chloride, etc. Simple metal oxides range from essentially ionic compounds with the electropositive elements to covalent compounds with the nonmetals. However, taking into account the large variety of metal oxides, the principal objective of this book is to examine only metal oxides that are more attractive from the catalytic point of view, and most specifically transition metal oxides (TMO). In particular, TMO usually exhibit nonstoichiometry as a consequence of the presence of defective structures. The interaction of TMO with surfaces of the appropriate carriers develop monolayer structures of these oxides. The crystal and electronic structure, stoichiometry and composition, redox properties, acid-base character and cation valence sates are major ingredients of the chemistry investigated in the first part of the book. New approaches to the preparation of ordered TMO with extended structure of texturally well defined systems are also included. 

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