Identifying an O2 supply pathway in CO oxidation on Au/TiO2(110): a density functional theory study on the intrinsic role of water.

Au catalysis has been one of the hottest topics in chemistry in the last 10 years or so. How O2 is supplied and what role water plays in CO oxidation are the two challenging issues in the field at the moment. In this study, using density functional theory we show that these two issues are in fact related to each other. The following observations are revealed: (i) water that can dissociate readily into OH groups can facilitate O2 adsorption on TiO2; (ii) the effect of OH group on the O2 adsorption is surprisingly long-ranged; and (iii) O2 can also diffuse along the channel of Ti (5c) atoms on TiO2(110), and this may well be the rate-limiting step for the CO oxidation. We provide direct evidence that O2 is supplied by O2 adsorption on TiO2 in the presence of OH and can diffuse to the interface of Au/TiO2 to participate in CO oxidation. Furthermore, the physical origin of the water effects on Au catalysis has been identified by electronic structure analyses: There is a charge transfer from TiO2 in the presence of OH to O2, and the O2 adsorption energy depends linearly on the O2 charge. These results are of importance to understand water effects in general in heterogeneous catalysis.