Collaborative Innovation Center of Chemical Science and Engineering, Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300354, China
Surface engineering and Cu valence regulation are essential factors in improving the C2 selectivity during the electrochemical reduction of CO2. Herein, we present a sea urchin-like CuO/Cu2O catalyst derived from rhombic dodecahedra Cu2O through one-step oxidation/etching method where the mixed Cu+/Cu0 states are formed via in situ reduction during electrocatalysis. The combined effects of the morphology and the mixed Cu+/Cu0 states on C–C coupling are evaluated by the Faradaic efficiency of C2 and the C2/C1 ratio obtained in an H-cell. R-CuO/Cu2O exhibited 49.5% Faradaic efficiency of C2 with a C2/C1 ratio of 3.1 at −1.4 V vs. reversible hydrogen electrode, which are 1.5 and 3.2 times higher than those of R-Cu2O, respectively. Using a flow-cell, 68.0% Faradaic efficiency of C2 is achieved at a current density of 500 mA·cm−2. The formation of the mixed Cu+/Cu0 states was confirmed by in situ Raman spectra. Additionally, the sea urchin-like structure provides more active sites and enables faster electron transfer. As a result, the excellent C2 production on R-CuO/Cu2O is primarily attributed to the synergistic effects of the sea urchin-like structure and the stable mixed Cu+/Cu0 states. Therefore, this work presents an integrated strategy for developing Cu-based electrocatalysts for C2 production through electrochemical CO2 reduction.
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