Tailoring Oxygen Vacancies with Atomically Dispersed Cu Sites for Stable and Efficient Photothermal CO ₂ Conversion

Abstract Photothermal catalysis under mild conditions represents a promising and sustainable approach for CO 2 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 a challenge. Here, we present a single‐atom doping strategy for oxygen vacancy engineering to facilitate efficient CO 2 conversion. Specifically, an In 2 O 3 ‐based catalyst with abundant oxygen vacancies induced by homogeneously dispersed Cu single atoms is constructed, exhibiting a competent CO 2 reduction performance in photothermal reverse water‐gas shift reaction. The optimal Cu‐In 2 O 3 catalyst achieves a CO yield rate of 46.17 mol g Cu −1 h −1 with near‐unity selectivity (>99%) and demonstrates stability over 450 h 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 H 2 dissociation and CO 2 activation under photoexcitation. This work provides insights into the design of photothermal catalysts, emphasizing the transformative potential of atomic‐site engineering for efficient CO 2 conversion and sustainable energy technologies.