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Promotion of ceria catalysts by precious metals: changes in nature of the interaction under reducing and oxidizing conditions

Acerbi, Nadia, Golunski, Stanislaw E., Tsang, Shik Chi, Daly, Helen, Hardacre, Chris, Smith, Richard and Collier, Paul 2012. Promotion of ceria catalysts by precious metals: changes in nature of the interaction under reducing and oxidizing conditions. The Journal of Physical Chemistry C 116 (25) , pp. 13569-13583. 10.1021/jp212233u

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By depositing ceria over supported precious metal (PM) catalysts and characterizing them with in situ diffuse reflectance UV (DR UV) and in situ Raman spectroscopy, we have been able to prove a direct correlation between a decrease in ceria band gap and the work function of the metal under reducing conditions. The PM–ceria interaction results in changes on the ceria side of the metal–ceria interface, such that the degree of oxygen vacancy formation on the ceria surface also correlates with the precious metal work function. Nevertheless, conclusive evidence for a purely electronic interaction could not be provided by X-ray photoelectron spectroscopy (XPS) analysis. On the contrary, the results highlight the complexity of the PM–ceria interaction by supporting a spillover mechanism resulting from the electronic interaction under reducing conditions. Under oxidizing conditions, another effect has been observed, namely, a structural modification of ceria induced by the presence of PM cations. In particular, we have been able to demonstrate by in situ Raman spectroscopy that, depending on the PM ionic radius, it is possible to create PM–ceria solid solutions. We observed that this structural modification prevails under an oxidizing atmosphere, whereas electronic and chemical interactions take place under reducing conditions.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Subjects: Q Science > QD Chemistry
Publisher: ACS Publications
ISSN: 1932-7447
Last Modified: 08 Jan 2020 03:44

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