Stabilization of Cu2O catalyst via strong electronic interaction for selective electrocatalytic CO2 reduction to ethanol

[Display omitted] •Ni3+/Co3+ extracts electrons around Cu+ to protect Cu2O from being reduced to Cu.•The durability of Cu2O stabilized by a NiCo2O4 interlayer exceeds 200% that of NF@Cu2O.•NF@NiCo2O4@Cu2O catalyzed conversion of CO2 to ethanol with a high FE of 56.9%•The NiCo2O4@Cu2O heterostructure greatly reduces the ΔG of C-C coupling. While cuprous oxide (Cu2O) remains the most efficient and viable electrocatalyst for the electrochemical conversion of CO2 to ethanol, its reduction to Cu during the catalytic CO2RR process poses a barrier to its industrial application. To address this challenge, we have reported a highly stable Cu2O-based catalyst by introducing pseudo-capacitive NiCo2O4 intermediate layers. The current densities observed on the surface of the prepared NF@NiCo2O4@Cu2O remained consistent over a 15-hour stability test, demonstrating excellent durability that exceeds that of the NF@Cu2O electrode by more than 200 %. Experimental characterization and DFT analysis indicate that the exceptional stability is primarily attributed to the pseudo-capacitive NiCo2O4 interlayer with cyclic charge–discharge properties, where NiCo2O4 can capture and eliminate accumulated reduced electrons around Cu2O under strong electronic interactions and release electrons through catalytic reduction to produce hydrogen. Furthermore, the NiCo2O4@Cu2O (111) heterostructure significantly reduces the Gibbs free energy (ΔG) required for C-C coupling of *CO intermediates compared to Cu2O (111). This mechanism establishes a cyclic charge–discharge process in order to prevent reduction of Cu2O into copper monomers. As a result, NF@NiCo2O4@Cu2O demonstrates a C2H5OH faradaic efficiency of 56.9 % at −0.5 V vs. RHE, surpassing many other Cu-based catalytic electrodes. This work provides new insights into studying strong electronic interaction structures to eliminate electron enrichment at the catalytic site for stabilizing catalysts and also offers an effective strategy for designing catalysts that maintain long-term stability in industrial applications.