Metal-oxygen hybridization in Agcluster/TiO2 for selective CO2 photoreduction to CH4

Selective photocatalytic reduction of CO2 to CH4 is one of the most efficient ways to achieve carbon neutralization. However, the formation of methane remains a challenge due to the slow multiple-proton-coupled electron transfer process and the involvement of various C1 intermediates. Herein, an Agcluster/TiO2 catalyst with Ag-O hybridization was synthesized by supporting Ag clusters on anatase phase TiO2 microspheres for photocatalytic CO2 methanation. The Agcluster/TiO2 sample presents an electron selectivity of 86 % for CH4 production with a yield of 25.25 mu mol g-1 h-1. Mechanistic study reveals that Ag clusters accelerate the separation and migration of photogenerated carriers, and enhance the adsorption of CO2. Moreover, the Ag-O hybridization promotes the multiple-proton-electron coupling transfer process by effectively stabilizing intermediates and facilitating *CO hydrogenation to *CHO, resulting in selective CO2 reduction to CH4. This work provides a new insight into the development of selective photocatalytic conversion of CO2 to methane by constructing supported cluster catalysts.