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

J Phys Chem Lett. 2021 Sep 2;12(34):8363-8369. doi: 10.1021/acs.jpclett.1c02167. Epub 2021 Aug 25.

Abstract

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 Ti5c 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.