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

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 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 CO₂RR reaction pathway.