Asymmetric‐Coordinated Indium Single Atoms for Highly Selective Photocatalytic CO ₂ Reduction

ABSTRACT Photocatalytic CO ₂ reduction involves multiple proton‐coupled and multi‐electron transfers, leading to a plethora of reaction pathways and consequently unpredictable products. The unique electronic structure and unsaturated coordination environment of single‐atom photocatalysts can influence the reaction pathways of CO ₂ photoreduction, enhancing the yield of a target product. Herein, we rationally design the In single‐atom photocatalyst (In‐NTO) containing isolated In ^δ+ –N ₃ O ₂ atomic interface sites for highly efficient and selective CO ₂ ‐to‐CO photoreduction. This distinctive atomic configuration not only reduces the overall activation energy barrier but also transforms the key *CO desorption step from an endoergic to an exoergic one, thereby altering the reaction pathway to selectively produce CO rather than CH ₄ . Consequently, the 0.25 wt% In‐NTO exhibits high selectivity (95.9%) for photocatalytic CO ₂ ‐to‐CO conversion, with a rate of 6.34 µmol g ⁻¹ h ⁻¹ . This work offers a novel strategy for modulating the reactivity and product selectivity of photocatalytic CO ₂ reduction toward desired products by constructing single‐atom sites with heteroatomic coordination.