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 CO2. Herein, we demonstrate that the pathways of the electrocatalytic CO2 reduction reaction (CO2RR) can be rationally altered toward C1 or C2+ products by simply optimizing the coordination of Cu with O-containing organic species (squaric acid (H2C4O4) and cyclohexanehexaone (C6O6)). 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 CO2RR. Specifically, the C6O6−Cu catalysts made up from organized nanodomains shows a dominant C1 pathway with a total Faradaic efficiency (FE) of 63.7 % at −0.6 V (versus reversible hydrogen electrode, RHE). In comparison, the C4O4−Cu with an about perfect crystalline structure results in uniformly dispersed Cu-atoms, showing a notable FE of 65.8 % for C2+ 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 VRHE, 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 CO2RR reaction pathway.