Abstract
The stability of atomically dispersed Pt2+ species on the surface of nanostructured CeO2 films during the reaction with methanol has been investigated by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy. The isolated Pt2+ species were prepared at low Pt concentration in Pt–CeO2 film. Additionally, Pt2+ species coexisting with metallic Pt particles were prepared at high Pt concentration. We found that adsorption of methanol yields similar decomposition products regardless of Pt concentration in Pt–CeO2 films. A small number of oxygen vacancies formed during the methanol decomposition can be replenished in the Pt–CeO2 film with low Pt concentration by diffusion of oxygen from the bulk. In the presence of supported Pt particles, a higher number of oxygen vacancies leads to a partial reduction of the Pt2+ species. The isolated Pt2+ species are reduced under rather strongly reducing conditions only, i.e. during annealing under continuous exposure to methanol. Reduction of isolated Pt2+ species results in the formation of ultra-small Pt particles containing around 25 atoms per particle or less. Such ultra-small Pt particles demonstrate excellent stability against sintering during annealing of Pt–CeO2 film with low Pt concentration under reducing conditions.
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