Systematic Characterization of Electronic Metal-Support Interactions in Ceria-Supported Pt Particles

Electronic metal-support interactions affect the chemical and catalytic properties of metal particles supported on reducible metal oxides, but their characterization is challenging due to the complexity of the electronic structure of these systems. These interactions often involve different states with varying numbers and positions of strongly correlated d or f electrons and the corresponding polarons. In this work, we present an approach to characterize electronic metal-support interactions by means of computationally efficient density functional calculations within the projector augmented wave method. We describe Ce³⁺ cations with potentials that include a Ce4f electron in the frozen core, overcoming prevalent convergence and 4f electron localization issues. We systematically explore the stability and chemical properties of different electronic states for a Pt₈/CeO₂(111) model system, revealing the predominant effect of electronic metal-support interactions on Pt atoms located directly at the metal-oxide interface. Adsorption energies and the reactivity of these interface Pt atoms vary significantly upon donation of electrons to the oxide support, pointing to a strategy to selectively activate interfacial sites of metal particles supported on reducible metal oxides.