Dynamic Surface Reconstruction of Amphoteric Metal (Zn, Al) Doped Cu2O for Efficient Electrochemical CO2 Reduction to C2+ Products

Abstract The recognition of the surface reconstruction of the catalysts during electrochemical CO 2 reduction (CO2RR) is essential for exploring and comprehending active sites. Although the superior performance of Cu–Zn bimetallic sites toward multicarbon C 2+ products has been established, the dynamic surface reconstruction has not been fully understood. Herein, Zn‐doped Cu 2 O nano‐octahedrons are used to investigate the effect of the dynamic stability by the leaching and redeposition on CO2RR. Correlative characterizations confirm the Zn leaching from Zn‐doped Cu 2 O, which is redeposited at the surface of the catalysts, leading to dynamic stability and abundant Cu–Zn bimetallic sites at the surface. The reconstructed Zn‐doped Cu 2 O catalysts achieve a high Faradaic efficiency (FE) of C 2+ products (77% at –1.1 V versus reversible hydrogen electrode (RHE)). Additionally, similar dynamic stability is also discovered in Al‐doped Cu 2 O for CO2RR, proving its universality in amphoteric metal‐doped catalysts. Mechanism analyses reveal that the OHC–CHO pathway can be the C–C coupling processes on bare Cu 2 O and Zn‐doped Cu 2 O, and the introduction of Zn to Cu can efficiently lower the energy barrier for CO2RR to C 2 H 4 . This research provides profound insight into unraveling surface dynamic reconstruction of amphoteric metal‐containing electrocatalysts and can guide rational design of the high‐performance electrocatalysts for CO2RR.