In Situ Monitoring of the Spatial Distribution of Oxygen Vacancies and Enhanced Photocatalytic Performance at the Single-Particle Level.

Oxygen vacancies (OVs) on specific sites/facets can strengthen the interaction between reactants and oxide surfaces, facilitating interfacial charge transfer. However, precise monitoring of the spatial distribution of OVs remains a grand challenge. We report here that a single-particle spectroscopy technique addresses this challenge by establishing a positive correlation relationship between defects and bound exciton luminescence across different facets. Taking monoclinic BiVO4 as an example, on the basis of theoretical guidance, by in situ tracking the PL lifetimes and PL spectra of different facets on single particles before and after hydrogen treatment, we provide evidence that the PL emission originates from the OV state and determine that OVs is more inclined to be generated at the {010} facets. This anisotropic defect engineering significantly prolongs the lifetime of carriers and accelerates the activation of molecular oxygen. These findings not only verify preference rules of OVs in metal oxides but also provide a time-space-resolved monitoring method.