Dual Lewis Acid‐Base Sites Regulate Silver‐Copper Bimetallic Oxide Nanowires for Highly Selective Photoreduction of Carbon Dioxide to Methane
Shimao Deng, Ranhao Wang, Xuezhen Feng, Renji Zheng, Shaokuan Gong, Xihan Chen, Yangzi Shangguan, Lili Deng, Huan Tang, Hao Dai, Lele Duan, Chengyuan Liu, Yang Pan, Hong Chen
Abstract
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.