Trends in the Electronic Structure of Extended Gold Compounds: Implications for Use of Gold in Heterogeneous Catalysis

• Published in: Inorganic chemistry 2012-07, Vol.51 (14), p.7569-7578
• Main Authors: Miao, Mao-Sheng, Kurzman, Joshua A, Mammen, Nisha, Narasimhan, Shobhana, Seshadri, Ram
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic3002674

First-principles electronic structure calculations are presented on a variety of Au compounds and speciesencompassing a wide range of formal oxidation states, coordination geometries, and chemical environmentsin order to understand the potentially systematic behavior in the nature and energetics of d states that are implicated in catalytic activity. In particular, we monitor the position of the d-band center, which has been suggested to signal catalytic activity for reactions such as CO oxidation. We find a surprising absence of any kind of correlation between the formal oxidation state of Au and the position of the d-band center. Instead, we find that the center of the d band displays a nearly linear dependence on the degree of its filling, and this is a general relationship for Au irrespective of the chemistry or geometry of the particular Au compound. Across the compounds examined we find that even small calculated changes in the d-band filling result in a relatively large effect on the position of the d-band center. The results presented here have some important implications for the question of the catalytic activity of Au and indicate that the formal oxidation state is not a determining factor.