Effect of reducible oxide–metal cluster charge transfer on the structure and reactivity of adsorbed Au and Pt atoms and clusters on anatase TiO2

Wang, Honghong; An, Taicheng; Selloni, Annabella

doi:10.1063/1.4982933

Title: Effect of reducible oxide–metal cluster charge transfer on the structure and reactivity of adsorbed Au and Pt atoms and clusters on anatase TiO₂

Journal Article · Thu May 11 00:00:00 UTC 2017 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.4982933 · OSTI ID:1465991

Wang, Honghong ^[1]; An, Taicheng ^[2]; Selloni, Annabella ^[3]

Princeton Univ., Princeton, NJ (United States); Chinese Academy of Sciences, Guangzhou (China); Univ. of Chinese Academy of Sciences, Beijing (China); Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA
Chinese Academy of Sciences, Guangzhou (China); Guangdong Univ. of Technology, Guangzhou (China)
Princeton Univ., Princeton, NJ (United States)

We carried out density functional theory calculations to study the influence of oxide–metal charge transfers on the structure, energetics, and reactivity of Au and Pt atoms, dimers, and trimers adsorbed on the (101) surface of reduced anatase TiO₂. Pt clusters interact much more strongly with the TiO₂ support than Au clusters, and, with the exception of single Pt adatoms, generally behave as electron acceptors on reduced TiO₂, whereas Au clusters can both accept and donate charge on the reduced surface. The reactivity of the supported clusters was probed by considering their interaction with CO and co-adsorbed O₂. The effect of surface reduction on the interaction with CO is particularly significant when the CO adsorption site is an interfacial metal atom directly in contact with the TiO₂ surface and/or in the presence of co-adsorbed O₂. Pt clusters interact strongly with co-adsorbed O₂ and form Pt–O₂ complexes that can easily accept electrons from reduced surfaces. In contrast, Au clusters donate charge to co-adsorbed O₂ even in the presence of excess electrons from a reduced support. In conclusion, the computed differences in the properties of the supported Pt and Au clusters are consistent with several experimental observations and highlight the important role of excess surface electrons in the behavior of supported metal catalysts on reducible oxides

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Research Organization:: Princeton Univ., Princeton, NJ (United States). Dept. of Chemistry

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0007347

OSTI ID:: 1465991

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 18 Vol. 146; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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