Dual Lewis Acid‐Base Sites Regulate Silver‐Copper Bimetallic Oxide Nanowires for Highly Selective Photoreduction of Carbon Dioxide to Methane

Abstract Highly selective photoreduction of CO 2 to valuable hydrocarbons is of great importance to achieving a carbon‐neutral society. Precisely manipulating the formation of the Metal 1 ⋅⋅⋅C=O⋅⋅⋅Metal 2 (M 1 ⋅⋅⋅C=O⋅⋅⋅M 2 ) intermediate on the photocatalyst interface is the most critical step for regulating selectivity, while still a significant challenge. Herein, inspired by the polar electronic structure feature of CO 2 molecule, we propose a strategy whereby the Lewis acid‐base dual sites confined in a bimetallic catalyst surface are conducive to forming a M 1 ⋅⋅⋅C=O⋅⋅⋅M 2 intermediate precisely, which can promote selectivity to hydrocarbon formation. Employing the Ag 2 Cu 2 O 3 nanowires with abundant Cu⋅⋅⋅Ag Lewis acid‐base dual sites on the preferred exposed {110} surface as a model catalyst, 100 % selectivity toward photoreduction of CO 2 into CH 4 has been achieved. Subsequent surface‐quenching experiments and density functional theory (DFT) calculations verify that the Cu⋅⋅⋅Ag Lewis acid‐base dual sites do play a vital role in regulating the M 1 ⋅⋅⋅C=O⋅⋅⋅M 2 intermediate formation that is considered to be prone to convert CO 2 into hydrocarbons. This study reports a highly selective CO 2 photocatalyst, which was designed on the basis of a newly proposed theory for precise regulation of reaction intermediates. Our findings will stimulate further research on dual‐site catalyst design for CO 2 reduction to hydrocarbons.