Adsorbed intermediate structure, selectivity effect

We have shown how the band structure of photoexcited semiconductor particles makes them effective oxidation catalysts. Because of the heterogeneous nature of the photoactivation, selective chemistry can ensue from preferential adsorption, from directed reactivity between adsorbed reactive intermediates, and from the restriction of ECE processes to one electron routes. The extension of these experiments to catalyze chemical reductions and to address heterogeneous redox reactions of biologically important molecules should be straightforward. In fact, the use of surface-modified powders coated with chiral polymers has recently been reputed to cause asymmetric induction at prochiral redox centers. As more semiconductor powders become routinely available, the importance of these photocatalysts to organic chemistry is bound to increase. 

Experimental results showed that carbonmineral composites are much better than others adsorbents, for example, the mineral one. A good selectivity of carbon materials made us to assume that it is a carbon substance is responsible both for selectivity and synergistic effect of adsorption too. From our point of view one of the reason of such a behavior could be specially organized carbon structures such as intermediate complexes (clusters), which possess peculiar electron properties only to them. Probably similariy toxic substances are adsorbed, such as phenols, cresols, quaiacol, aldehydes, polyatomic alcohols, ethers etc. (Table 1). 

As most of the acid sites are located in pores of molecular size the rate and the selectivity of catalytic reactions depend not only on the intrinsic properties of the sites but also on the pore structure. A zeolite catalyst selects the reactant or the product by their ability to diffuse to and from the active sites (reactant and product selectivity). Steric constraints in the environment of the sites limit or inhibit the formation of intermediates or transition states (restricted transition state selectivity) [24,25]. The strong polarizing interaction between zeolite crystallites and adsorbed molecules leads to an unusually high concentration of the reactants in the pores. This concentration effect causes an enhancement of the rates of bimolecular reaction steps over monomolecular reaction steps [26]. 

Following deposition of an active metal upon a ceria surface, it is possible to study chemisorption on a surface that models many of the important aspects expected for actual ceria supported catalysts. Surface techniques offer the possibility to identify where the adsorbates are located and to identify intermediates that are formed in their interaction. By comparison of ceria surfaces, with and without metal, the synergisms between metal and support can be deduced. By controlled metal deposition, it is possible to study the effects of loading and particle size. By selected preparation of the ceria substrate it is possible to vary factors which may affect the interaction between the metal particle and the ceria, sueh as structure, defeet concentration or oxidation state of the ceria. The goal of chemisorption studies, summarized below, is to relate all these factors to the interaction of the model catalyst with particular adsorbates. 

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