Constructing Cu−C Bonds in a Graphdiyne‐Regulated Cu Single‐Atom Electrocatalyst for CO<sub>2</sub> Reduction to CH<sub>4</sub>
Guodong Shi, Yunlong Xie, Lili Du, Xinliang Fu, Xiaojie Chen, Wangjing Xie, Tong‐Bu Lu, Mingjian Yuan, Mei Wang
Abstract
Abstract Regulating intermediates through elaborate catalyst design to control the reaction direction is crucial for promoting the selectivity of electrocatalytic CO 2 ‐to‐CH 4 . M−C (M=metal) bonds are particularly important for tuning the multi‐electron reaction; however, its construction in nanomaterials is challenging. Here, via rational design of in situ anchoring of Cu SAs (single atoms) on the unique platform graphdiyne, we firstly realize the construction of a chemical bond Cu−C (GDY). In situ Raman spectroelectrochemistry and DFT calculations confirm that due to the fabrication of the Cu−C bond, during CO 2 reduction, the formation of *OCHO intermediates is dominant rather than *COOH on Cu atoms, facilitating the formation of CH 4 . Therefore, we find that constructing the Cu−C bond in Cu SAs/GDY can supply an efficient charge transfer channel, but most importantly control the reaction intermediates and guide a more facile reaction pathway to CH 4 , thereby significantly boosting its catalytic performance. This work provides new insights on enhancing the selectivity for CO 2 RR at the atomic level.