Oxygen Vacancy‐Mediated Exciton Effect in Hierarchical BiOBr Enables Dichotomy of Energy Transfer and Electron Transfer in Photocatalysis

Abstract Using solar energy through green and simple artificial photosynthesis systems are considered as a promising way to solve the energy and environmental crisis. However, one of the important primary steps of photosynthesis, i.e., energy transfer, is long being ignored especially in inorganic semiconducting systems due to the small exciton binding energies. Herein, the simultaneous interrogation of the charge transfer and energy transfer steps in a photoexcitation process is proposed by utilizing few‐layered nanosheet‐assembled hierarchical BiOBr nanotubes with rich oxygen vacancies (OVs) as efficient multifunctional photocatalysts. Benefiting from the integrated 1D/2D structure and abundant OV defects, the excitonic effect strikes a delicate balance in the optimized BiOBr photocatalyst, showing not only improved charge carrier separation and transfer but also enhanced exciton generation. As a result, the hierarchical BiOBr nanotubes exhibit high efficiency toward photocatalytic CO 2 reduction with an impressive CO evolution rate of 135.6 µmol g −1 h −1 without cocatalyst or photosensitizer. The dominant reactive oxygen species of singlet oxygen ( 1 O 2 ) are discriminated for the first time, which originated from an energy transfer process, with electrophilic character, whereas the minor effect of superoxide anion radical ( • O 2 − ) with a nucleophilic rate‐determining step in the photocatalytic aerobic oxidation of sulfides.