Cu–O geometric coordination induced facet evolution of derived Cu catalysts for efficient CO2 electroreduction

• • The OD-Cu t catalyst with dominant Cu(200) facets achieves 75.1% FEC2+ at −187.8 mA cm−2, surpassing the (111)-dominated OD-Cu o by a factor of 1.8 in C2+ selectivity, directly addressing the industrial need for high-current-density CO2 electrolyzers. • • In situ XRD and Raman spectroscopy demonstrate that tetrahedral Cu–O coordination in the precursor leads to a (200)/(111) facet ratio of 3.2, while octahedral coordination yields a ratio of 0.4, providing a deterministic handle for facet engineering. • • Theoretical calculations reveal that the C–C coupling barrier on Cu(200) is 0.68 eV, compared to 0.82 eV on Cu(111), explaining the 22% higher C2+ production rate and offering a mechanistic basis for catalyst design. • • The framework-dissolution strategy enables precise control over the reconstruction pathway, with inert element incorporation (e.g., Al) stabilizing the tetrahedral coordination, resulting in a 95% retention of the initial FEC2+ after 12 hours of operation at −200 mA cm−2.