Constructing Cu−C Bonds in a Graphdiyne‐Regulated Cu Single‐Atom Electrocatalyst for CO2 Reduction to CH4

Regulating intermediates through elaborate catalyst design to control the reaction direction is crucial for promoting the selectivity of electrocatalytic CO2‐to‐CH4. 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 CO2 reduction, the formation of *OCHO intermediates is dominant rather than *COOH on Cu atoms, facilitating the formation of CH4. 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 CH4, thereby significantly boosting its catalytic performance. This work provides new insights on enhancing the selectivity for CO2RR at the atomic level. The interfacial chemical Cu−C bond is successfully constructed through in situ anchoring Cu SAs (single atoms) on the unique platform graphdiyne. Experimental results and theoretical calculations demonstrate that due to the existence of the Cu−C bond, the formation of *OCHO intermediates dominates and promotes the production of CH4.