Directed Inward Migration of S‐Vacancy in Bi2S3 QDs for Selective Photocatalytic CO2 to CH3OH

Abstract The directional migration of S‐vacancy is beneficial to the separation of photogenerated carriers and the transition of electrons in semiconductors. In this study, Bi x /Bi 2−x S y @carboxylic‐cellulose (CC) photocatalyst with bionic chloroplast structure is obtained by electron beam irradiation to induce S‐vacancy in Bi 2 S 3 @CC. The results of CO 2 photoreduction experiments demonstrate that the reduction rate of CO 2 to CH 3 OH by Bi x /Bi 2‒x S 2.89 @CC‐450 samples is 10.74 µmol·g −1 ·h −1 , and the selectivity is 92.82%. The results show that the inward migration behavior of the borderline S‐vacancy (b‐S v ) induces the redistribution of electrons in Bi x /Bi 2−x S y @CC. The Bi° clusters in Bi x /Bi 2−x S y @CC is conducive to adsorb CO 2 , and the internal S‐vacancy (i‐S v ) is conducive to adsorb CH 3 OH, which accelerate the transfer of gas‐phase products to realize the controllable conversion of CO 2 and photoreduction products at the gas–liquid–solid three‐phase interface. This study provides a new idea for the development and utilization of green photocatalysts in clean energy.