Atomic-level insights into surface engineering of semiconductors for photocatalytic CO2 reduction

Abstract Photocatalytic conversion of CO2 into solar fuels provides a bright route for the green and sustainable development of human society. However, the realization of efficient photocatalytic CO2 reduction reaction (CO2RR) is still challenging owing to the sluggish kinetics or unfavorable thermodynamics for basic chemical processes of CO2RR, such as adsorption, activation, conversion and product desorption. To overcome these shortcomings, recent works have demonstrated that surface engineering of semiconductors, such as introducing surface vacancy, surface doping, and cocatalyst loading, serves as effective or promising strategies for improved photocatalytic CO2RR with high activity and selectivity. The essential reason lies in the activation and reaction pathways can be optimized and regulated through the reconstruction of surface atomic and electronic structures. Herein, in this review, we focus on recent research advances about rational design of semiconductor surface for photocatalytic CO2RR. The surface engineering strategies for improved CO2 adsorption, activation, and product selectivity will be reviewed. In addition, theoretical calculations along with in situ characterization techniques will be in the spotlight to clarify the kinetics and thermodynamics of the reaction process. The aim of this review is to provide deep understanding and rational guidance on semiconductors for photocatalytic CO2RR.