Comprehensive Insight into Construction of Active Sites toward Steering Photocatalytic CO₂ Conversion

Abstract Photoreduction of CO₂ into hydrocarbon fuels is a promising avenue for achieving a sustainable alternative to the artificial carbon cycle. Photocatalytic CO₂ conversion is the chemical transformation of photogenerated carriers and adsorbed CO₂ at active sites of catalysts. Active sites can regulate the kinetic process of carriers, control the adsorption of CO₂ and intermediates, lower activation barriers, and promote C‐C coupling. This review mainly concentrates on the efficiency and selectivity regulation of the target products through construction of active sites. First, the principles of CO₂ photoreduction, such as the influencing factors and specific pathways for monocarbon and multicarbon (C₂₊) formation, are discussed. Then, leading works focusing on improving catalytic efficiency and regulating product selectivity through the introduction of active sites are highlighted, concerning the underlying mechanism of the performance, especially for C₂₊ generation. Subsequently, an overview of the currently available in situ techniques and theoretical calculation for identifying the active sites are provided. Finally, the challenges of emerging strategies to achieve carbon recycling from scientific, technical, and economic perspectives are considered. This review offers deep insight into the construction of active site with atomic precision to achieve efficient photocatalytic CO₂ conversion and the generation of C₂₊ in high selectivity.