Atypical Oxygen-Bearing Copper Boosts Ethylene Selectivity toward Electrocatalytic CO_2 Reduction

摘要

Oxygen-bearing copper (OBC) has been widely studied for enabling the C-C coupling of the electrocatalytic CO_2 reduction reaction (CO_2RR) since this is a distinctive hallmark of strongly correlated OBC systems and may benefit many other Cu-based catalytic processes. Unresolved problems, however, include the instability of and limited knowledge regarding OBC under realistic operating conditions, raising doubts about its role in CO_2RR. Here, an atypical and stable OBC catalyst with a hierarchical pore and nanograin- boundary structure was constructed and was found to exhibit efficient CO_2RR for the production of ethylene with a Faradaic efficiency of 45% at a partial current density of 44.7 mA cm~(-2) in neutral media, and the ethylene partial current density is nearly 26 and 116 times that of oxygen-free copper (OFC) and commercial Cu foam, respectively. More importantly, the structure-activity relationship in CO_2RR was explored through a comprehensive analysis of experimental data and computational techniques, thus increasing the fundamental understanding of CO_2RR. A systematic characterization analysis suggests that atypical OBC (Cu_4O) was formed and that it is stable even at -1.00 Ⅴ [(vs the reversible hydrogen electrode (RHE)]. Density functional theory calculations show that the atypical OBC enables control over CO adsorption and dimerization, making it possible to implement a preference for the electrosynthesis of ethylene (C_2) products. These results provide insight into the synthesis and structural characteristics of OBC as well as its interplay with ethylene selectivity.