Low‐Coordination Single Au Atoms on Ultrathin ZnIn2S4 Nanosheets for Selective Photocatalytic CO2 Reduction towards CH4.

Selective CO2 photoreduction to hydrocarbon fuels such as CH4 is promising and sustainable for carbon‐neutral future. However, lack of proper binding strengths with reaction intermediates makes it still a challenge for photocatalytic CO2 methanation with both high activity and selectivity. Here, low‐coordination single Au atoms (Au1‐S2) on ultrathin ZnIn2S4 nanosheets was synthesized by a complex‐exchange route, enabling exceptional photocatalytic CO2 reduction performance. Under visible light irradiation, Au1/ZnIn2S4 catalyst exhibits a CH4 yield of 275 μmol g−1 h−1 with a selectivity as high as 77 %. As revealed by detailed characterizations and density functional theory calculations, Au1/ZnIn2S4 with Au1‐S2 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 *CH3 intermediate, thereby leading to the selective CH4 generation from CO2 photoreduction. [ABSTRACT FROM AUTHOR]