Altering the CO2 Electroreduction Pathways Towards C1 or C2+ Products via Engineering the Strength of Interfacial Cu−O Bond

Abstract Copper (Cu)‐based catalysts have established their unique capability for yielding wide value‐added products from CO 2 . Herein, we demonstrate that the pathways of the electrocatalytic CO 2 reduction reaction (CO 2 RR) can be rationally altered toward C 1 or C 2+ products by simply optimizing the coordination of Cu with O‐containing organic species (squaric acid (H 2 C 4 O 4 ) and cyclohexanehexaone (C 6 O 6 )). It is revealed that the strength of Cu−O bonds can significantly affect the morphologies and electronic structures of derived Cu catalysts, resulting in the distinct behaviors during CO 2 RR. Specifically, the C 6 O 6 −Cu catalysts made up from organized nanodomains shows a dominant C 1 pathway with a total Faradaic efficiency (FE) of 63.7 % at −0.6 V (versus reversible hydrogen electrode, RHE). In comparison, the C 4 O 4 −Cu with an about perfect crystalline structure results in uniformly dispersed Cu‐atoms, showing a notable FE of 65.8 % for C 2+ products with enhanced capability of C−C coupling. The latter system also shows stable operation over at least 10 h with a high current density of 205.1 mA cm −2 at −1.0 V RHE , i.e., is already at the boarder of practical relevance. This study sheds light on the rational design of Cu‐based catalysts for directing the CO 2 RR reaction pathway.