The Structure, Oxidation States, and Energetics of Co Nanoparticles on CeO₂(111): An STM and DFT Study

Co nanoparticles (NPs) dispersed on ceria have been widely studied as active catalytic materials for many industrially relevant reactions. The detailed nature of such particles and the factors affecting their interaction with ceria remain to be better understood. In this study, a very low coverage (∼0.02 ML) of Co is deposited on a model CeO₂(111) thin-film surface and is examined using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). The Co NPs that nucleate on terrace sites grow with coverage in this range to a maximum size of ca. 40 Co atoms, with an average diameter and height of 16.1 and 1.1 Å, respectively. Global minimization of the structures of Co NPs consisting of up to 23 Co atoms on CeO₂(111) is performed based on the minima hopping algorithm and density functional theory (DFT) calculations, and the energetic and chemical properties of the resulting NPs are analyzed. While the theoretical findings are consistent with the STM observations on the strong Co-ceria interactions and the prevalence of oxidic Co species, some notable discrepancies are identified, including inconsistent aspect ratios and the existence of a low oxidation state Co^δ+ species. The combined experimental and theoretical findings provide new insights into Co NPs formed on ceria and identify areas requiring further investigation.