Abstract
This review substantiates the molecular approach to the study of the catalytic action of various systems, which consists in the comparative study of the nature and reactivity of adsorbed species and considering the problems of pressure and material gaps. The pressure gap problem can be solved by a continuous increase in the pressure of the reaction mixture, including carrying out in situ studies. The solution to the problem of material gap is possible when one passes from bulk to dispersed samples, which model real supported catalysts. As the last step that can build a bridge between surface science and catalysis, the study of nanoparticle reactivity toward the reactants of a catalytic reaction with varying sizes of nanoparticles is proposed. The scope of such an approach is demonstrated by the study of silver catalysts of ethylene epoxidation. It was found that the catalytic action of silver in the process of ethylene oxide synthesis is determined by the possibility of formation of electrophilic adsorbed atomic oxygen. Its formation is more efficient under the action of reaction mixtures at high pressures and on the surfaces of silver species with sizes smaller than 50 nm. It is shown that the reaction center should also contain the nucleophilic form of Oads, which itself is only active in the complete oxidation of ethylene but creates the Ag1+ sites for ethylene adsorption. The disappearance of Onucl with a decrease in the size of silver particles below 50 nm leads to a drastic decrease in the rate of ethylene epoxidation. The reaction mechanism made it possible to propose systems with an abnormally high value of selectivity to ethylene oxide (>90%).
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Bukhtiyarov, V.I. The Study of the Nature of Adsorbed Species to Build a Bridge between Surface Science and Catalysis: Problems of Pressure and Material Gap. Kinetics and Catalysis 44, 420–431 (2003). https://doi.org/10.1023/A:1024407321481
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DOI: https://doi.org/10.1023/A:1024407321481