Bismuth Vacancy-Tuned Bismuth Oxybromide Ultrathin Nanosheets toward Photocatalytic CO2 Reduction.

Surface defects in semiconductors have a significant role to tune the photocatalytic reactions. However, the dominant studied defect type is oxygen vacancy, and metal cation vacancies are seldom explored. Herein, bismuth vacancies are engineered into BiOBr through ultrathin structure control and employed to tune photocatalytic CO2 reduction. VBi-BiOBr ultrathin nanosheets deliver a high selective CO generation rate of 20.1 μmol g-1 h-1 in pure water, without any cocatalyst, photosensitizer, and sacrificing reagent, roughly 3.8 times higher than that of BiOBr nanosheets. The increased CO2 reduction activity is ascribed to the tuned electronic structure, optimized CO2 adsorption, activation, and CO desorption process over VBi-BiOBr ultrathin nanosheets. This work offers new opportunities for designing surface metal vacancies to optimize the CO2 photoreduction performances.