The in situ study of surface species and structures of oxide-derived copper catalysts for electrochemical CO(2) reduction

Oxide-derived copper (OD-Cu) has been discovered to be an effective catalyst for the electroreduction of CO(2) to C2+ products. The structure of OD-Cu and its surface species during the reaction process are interesting topics, which have not yet been clearly discussed. Herein, in situ surface-enhanced Raman spectroscopy (SERS), operando X-ray absorption spectroscopy (XAS), and (18)O isotope labeling experiments were employed to investigate the surface species and structures of OD-Cu catalysts during CO(2) electroreduction. It was found that the OD-Cu catalysts were reduced to metallic Cu(0) in the reaction. CuO(x) species existed on the catalyst surfaces during the CO(2)RR, which resulted from the adsorption of preliminary intermediates (such as *CO(2) and *OCO(−)) on Cu instead of on the active sites of the catalyst. It was also found that abundant interfaces can be produced on OD-Cu, which can provide heterogeneous CO adsorption sites (strong binding sites and weak binding sites), leading to outstanding performance for obtaining C2+ products. The Faradaic efficiency (FE) for C2+ products reached as high as 83.8% with a current density of 341.5 mA cm(−2) at −0.9 V vs. RHE.