Solid-supported surface catalysis, metal complexes

Solid-Supported Surface Catalysis by Metal Complexes. Hong et al. (1987a, b, in press) have prepared a variety of hybrid catalysts between Co(II) phthalocyanine complexes and the surfaces of silica gel, polystyrene-divinylben-zene, and Ti02 and tested these hybrids for catalytic activity with respect to the autoxidation of hydrogen sulfide, sulfur dioxide, 2-mercaptoethanol, cysteine, and hydrazine ... 

The instability of polymeric supports leads to the idea of using inorganic solids for supporting molecular catalytic species. Methods have been developed for functionalizing surfaces of SiOj and other metal oxides with groups such as phosphines . Incorporation of a metal complex is straightforward the methods are like those cited in the preceding section. However, even the least reactive surfaces of oxides—such as that of silica gel— are more reactive then those of hydrocarbon polymers, and complications in catalyst synthesis and in the catalysis itself may be caused by the oxide surface. 

A wide variety of solid materials are used in catalytic processes. Generally, the (surface) structure of metal and supported metal catalysts is relatively simple. For that reason, we will first focus on metal catalysts. Supported metal catalysts are produced in many forms. Often, their preparation involves impregnation or ion exchange, followed by calcination and reduction. Depending on the conditions quite different catalyst systems are produced. When crystalline sizes are not very small, typically > 5 nm, the metal crystals behave like bulk crystals with similar crystal faces. However, in catalysis smaller particles are often used. They are referred to as crystallites , aggregates , or clusters . When the dimensions are not known we will refer to them as particles . In principle, the structure of oxidic catalysts is more complex than that of metal catalysts. The surface often contains different types of active sites a combination of acid and basic sites on one catalyst is quite common. 

Metal oxides represent one of the most important and widely employed classes of solid catalysts, either as active phases or as supports. Metal oxides are used for both their acid-base and redox properties and constitute the largest family of catalysts in heterogeneous catalysis [1-6]. The three key features of metal oxides, which are essential for their application in catalysis, are (i) coordination environment of the surface atoms, (ii) redox properties of the oxide, and (iii) oxidation state of the surface. Surface coordination environment can be controlled by the choice of crystal plane exposed and by the preparation procedures employed however, specification of redox properties is largely a matter of choice of the oxide. The majority of oxide catalysts correspond to more or less complex transition metal oxides containing cations of variable oxidation state. These cations introduce redox properties and, in addition, acid-base properties. The acid-base properties of the oxides are usually interrelated to their redox behavior. Many attempts were made... 

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