Surface Local Polarization Induced by Bismuth‐Oxygen Vacancy Pairs Tuning Non‐Covalent Interaction for CO₂ Photoreduction

Abstract

Abstract The inefficient charge separation and lack of active sites have been regarded as the main obstacles limiting the CO 2 photoreduction efficiency. It is highly desirable but challenging to create a local polarization field to accelerate charge separation and build reactive sites for CO 2 reduction dynamics. Herein, atomic level bismuth‐oxygen vacancy pairs are engineered into Bi 24 O 31 Br 10 (BOB) atomic layers to create a local polarization field. It facilitates photogenerated electrons to migrate from BOB to vacancy pair sites and favors the activation of CO 2 molecules. Simultaneously, it works as reactive sites to tune the non‐covalent interaction of intermediates and optimizes the reaction process. The vacancy pairs tuned surface atomic structures enable the formation of a highly stable Bi−C−O−Bi intermediate state and consecutive Bi−C−O intermediate, thus changing the rate‐determining step from CO* formation to COOH* formation. Benefiting from these features, the V BiO ‐BOB delivers a 20.9‐fold CO 2 photoreduction activity enhancement relative to highly crystalline BOB in pure water with highly stability. This work provides new insights for the design of a vacancy pair to create local polarization and tune the non‐covalent interaction.