Oxygen-Vacancy-Mediated Exciton Dissociation in BiOBr for Boosting Charge-Carrier-Involved Molecular Oxygen Activation.

Excitonic effects mediated by Coulomb interactions between photogenerated electrons and holes play crucial roles in photoinduced processes of semiconductors. In terms of photocatalysis, however, efforts have seldom been devoted to the relevant aspects. For the catalysts with giant excitonic effects, the coexisting, competitive exciton generation serves as a key obstacle to the yield of free charge carriers, and hence, transformation of excitons into free carriers would be beneficial for optimizing the charge-carrier-involved photocatalytic processes. Herein, by taking bismuth oxybromide (BiOBr) as a prototypical model system, we demonstrate that excitons can be effectively dissociated into charge carriers with the incorporation of oxygen vacancy, leading to excellent performances in charge-carrier-involved photocatalytic reactions such as superoxide generation and selective organic syntheses under visible-light illumination. This work not only establishes an in-depth understanding of defective structures in photocatalysts but also paves the way for excitonic regulation via defect engineering.