Size and Shape Dependence of the Electronic Structure of Gold Nanoclusters on TiO₂

Understanding the mechanism behind the superior catalytic power of single- or few-atom heterogeneous catalysts has become an important topic in surface chemistry. This is particularly the case for gold, with TiO₂ being an efficient support. Here we use scanning tunneling microscopy/spectroscopy with theoretical calculations to investigate the adsorption geometry and local electronic structure of several-atom Au clusters on rutile TiO₂(110), with the clusters fabricated by controlled manipulation of single atoms. Our study confirms that Au₁ and Au₂ clusters prefer adsorption at surface O vacancies. Au₃ clusters adsorb at O vacancies in a linear-chain configuration parallel to the surface; in the absence of O vacancies they adsorb at Ti_5c sites with a structure of a vertically pointing upright triangle. We find that both the electronic structure and cluster-substrate charge transfer depend critically on the cluster size, bonding configuration, and local environment. This suggests the possibility of engineering cluster selectivity for specific catalytic reactions.