Investigation into geometric configurations and electronic properties of CeO₂-supported gold clusters

Abstract A detailed understanding of the geometric structure and electronic properties of gold nanoparticles on the ceria surface is crucial for comprehending their unique catalytic activity. Using the first-principles method based on density functional theory, the adsorption of Au x (x = 1–4) clusters on the CeO 2 (111) surface was studied. It was discovered that the standing configurations of Au 2 and Au 3 , as well as the tetrahedral structure of Au 4 , are the most stable adsorption structures. The stability of these configurations is jointly determined by the number and strength of Au-Au bonds, the Au-O bonding energy, and the interaction dynamics between the clusters and the substrate. The analysis of Bader charge, difference charge density and density of states suggested that lattice relaxation and electronic localization occur in the reduced Ce 3+ . The reduced amount and location of Ce 3+ are significantly influenced by the position and charge transfer amount of Au x cluster. The adsorption of CO on Au 4 /CeO 2 (111) indicated that stronger Au-C bonding energy due to the hybridization of Au-5d and C-2p, thereby enhancing the catalytic activity for CO oxidation reactions.