Critical Role of Cu Nanoparticle-Loaded Cu(100) Surface Structures on Structured Copper-Based Catalysts in Boosting Ethanol Generation in CO₂ Electroreduction

Presently, realizing high ethanol selectivity in CO 2 electroreduction remains challenging due to difficult C–C coupling and fierce product competition. In this work, we report an innovative approach for improving the efficiency of Cu-based electrocatalysts in ethanol generation from electrocatalytic CO 2 reduction using a crystal plane modification strategy. These novel Cu-based electrocatalysts were fabricated by electrochemically activating three-dimensional (3D) flower-like CuO micro/nanostructures grown in situ on copper foils and modifying with surfactants. It was demonstrated that the fabricated Cu-based electrocatalyst featured a predominantly exposed Cu(100) surface loaded with high-density Cu nanoparticles (NPs). The optimal Cu-based electrocatalyst displayed considerably improved CO 2 electroreduction performance, with a Faraday efficiency of 37.9% for ethanol and a maximum Faraday efficiency of 68.0% for C 2+ products at −1.4 V vs RHE in an H-cell, accompanied by a high current density of 69.9 mA·cm –2, much better than the particulate Cu-based electrocatalyst. It was unveiled that the Cu(100)-rich surface of nanoscale petals with abundant under-coordinated copper atoms from CuNPs was conducive to the formation and stabilization of key *CH 3 CHO and *OC 2 H 5 intermediates, thereby promoting ethanol generation. This study highlighted the critical role of CuNP-loaded Cu(100) surface structures on structured Cu-based electrocatalysts in enhancing ethanol production for the CO 2 electroreduction process.