Lattice-Plane-Dependent Distribution of Ce³⁺ at Pt and CeO₂ Interfaces for Pt/CeO₂ Catalysts

The interaction between a metal and a support, which is known as the metal-support interaction, often plays a determining role in the catalytic properties of supported metal catalysts. Herein, we have developed model Pt/CeO₂ catalysts, which enabled us to investigate the interface atomic and electronic structures between Pt and the {001}, {011}, and {111} planes of CeO₂ using scanning transmission electron microscopy and electron energy-loss spectroscopy. We found that the number of Ce³⁺ ions around the Pt nanoparticles followed the order {001} > {011} > {111}, which was the opposite order of the generally accepted stability of low index surfaces of CeO₂. Systematic first-principles calculations revealed that the presence of Pt nanoparticles facilitated the formation of oxygen vacancies and that the appearance of the Pt^δ+ state was preferred when Pt nanoparticles were in contact with CeO₂ {001} planes due to direct charge transfer from Pt to CeO₂. These results provide important insights into the nature of the metal-support interaction for a comprehensive understanding of the properties of supported metal catalysts.