Tailoring Oxygen Vacancies with Atomically Dispersed Cu Sites for Stable and Efficient Photothermal CO2 Conversion

Photothermal catalysis under mild conditions represents a promising and sustainable approach for CO2 conversion into high‐value chemicals, thereby enabling efficient carbon recycling. However, precise manipulation of active sites and their coordination environments at the atomic level to enhance catalyst performance still remains challenging. Here, we present a single‐atom doping strategy for oxygen vacancy engineering to facilitate efficient CO2 conversion. Specifically, an In2O3‐based catalyst with abundant oxygen vacancies induced by homogeneously dispersed Cu single atoms is constructed, exhibiting a competent CO2 reduction performance in photothermal reverse water‐gas shift reaction. The optimal Cu‐In2O3 catalyst achieves a CO yield rate of 46.17 mol·gCu‐1·h‐1 with near‐unity selectivity (>99%) and demonstrates stability over 450 hours under 3 W·cm‐2 full‐spectrum light illumination. Comprehensive spectroscopic characterization and computational simulations elucidate that the Cu single atoms synergistically interact with oxygen vacancies to promote H2 dissociation and CO2 activation under photoexcitation. This work provides insights into the design of photothermal catalysts, emphasizing the transformative potential of atomic‐site engineering for efficient CO2 conversion and sustainable energy technologies.