Selective CO 2 photoreduction to hydrocarbon fuels such as CH 4 is promising and sustainable for carbonneutral future. However, lack of proper binding strengths with reaction intermediates makes it still a challenge for photocatalytic CO 2 methanation with both high activity and selectivity. Here, low-coordination single Au atoms (Au 1 -S 2 ) on ultrathin ZnIn 2 S 4 nanosheets was synthesized by a complex-exchange route, enabling exceptional photocatalytic CO 2 reduction performance. Under visible light irradiation, Au 1 /ZnIn 2 S 4 catalyst exhibits a CH 4 yield of 275 μmol g À 1 h À 1 with a selectivity as high as 77 %. As revealed by detailed characterizations and density functional theory calculations, Au 1 / ZnIn 2 S 4 with Au 1 -S 2 structure not only display fast carrier transfer to underpin its superior activity, but also greatly reduce the energy barrier for protonation of *CO and stabilize the *CH 3 intermediate, thereby leading to the selective CH 4 generation from CO 2 photoreduction.

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Single-atom catalysts (SACs) have recently emerged as promising photocatalysts for CO 2 reduction; however, understanding their interplay between the local electronic structure and the overall performance at an atomic level still remains elusive. Here, we construct two Ni-SACs at different sites of WO 2.72 nanowires, i.e., bulk doping of single Ni atoms in WO 2.72 (B-Ni 1 /WO 2.72 ) and surface anchoring of single Ni atoms on WO 2.72 (S-Ni 1 /WO 2.72 ), to unravel the electronic structure manipulation for boosting CO 2 photoreduction. Impressively, B-Ni 1 /WO 2.72 displays superior photocatalytic CO 2 reduction performance to S-Ni 1 /WO 2.72 , reaching a CO yield of 80.5 mmol g −1 h −1 with a selectivity of 98.7%. Experimental results and computational calculations reveal that compared to S-Ni 1 /WO 2.72 , B-Ni 1 /WO 2.72 is endowed with improved charge transfer and a more upshifted d-band center, thereby leading to CO production with concurrent high activity and selectivity. This work provides deeper insights into the exploration of efficient SACs for artificial photosynthesis to targeted products by optimization of their site-related electronic structures.