Unraveling the Oxygen Vacancy–Performance Relationship in Perovskite Oxides at Atomic Precision via Precise Synthesis

Understanding the fundamental effect of the oxygen vacancy atomic structure in perovskite oxides on catalytic properties remains challenging due to diverse facets, surface sites, defects, etc. in traditional powder catalysts and the inherent structural complexity. Through quantitative synthesis of tetrahedral (LaCoO_2.5-T), pyramidal (LaCoO_2.5-P), and octahedral (LaCoO₃) epitaxial thin films as model catalysts, we demonstrate the reactivity orders of active-site geometrical configurations in oxygen-deficient perovskites during the CO oxidation model reaction: CoO₄ tetrahedron > CoO₆ octahedron > CoO₅ pyramid. Ambient-pressure Co L-edge and O K-edge XAS spectra clarify the dynamic evolutions of active-site electronic structures during realistic catalytic processes and highlight the important roles of defect geometrical structures. In addition, in situ XAS and resonant inelastic X-ray scattering spectra and density functional theory calculations directly reveal the nature of high reactivity for CoO₄ sites and that the derived shallow-acceptor defect levels in the band structure facilitate the adsorption and activation of reactive gases, resulting in more than 23-fold enhancement for catalytic reaction rates than CoO₅ sites.