Adsorption of Au atoms on stoichiometric and reduced TiO2(110) rutile surfaces:: a first principles study

Using ab initio quantum mechanical methods (DFT-GGA/LDA, pseudopotentials) we have investigated the adsorption properties of Au atoms on stoichiometric and reduced TiO2(1 1 0) rutile surfaces. This study predicts that the most stable adsorption site for the Au atom on the stoichiometric surface is on the fourfold hollow position over the fivefold-coordinated Ti and in-plane and bridging O atoms, indicated as the H2 site. At the H2 site, it is likely that the covalent and ionic bonding interactions with the fivefold-coordinated Ti and the bridging O, respectively, contribute synergistically to the Au adsorption. For Au adsorption over a neutral F-s(0) center on the reduced surface, there is rather strong ionic bonding between the Au and surrounding sixfold-coordinated Ti atoms. The An adsorption energy at the defect site is affected significantly by the presence of oxygen vacancies nearby along the [0 0 1] direction. Our DFT-GGA results clearly show that the binding of An to an oxygen vacancy site is substantially stronger than to the stoichiometric surface. (C) 2003 Elsevier B.V. All rights reserved.