Cu–O geometric coordination induced facet evolution of derived Cu catalysts for efficient CO2 electroreduction
Oxide-derived copper (OD-Cu) catalysts are pivotal for the selective electroreduction of CO2 to multi-carbon (C2+) products, yet the reconstruction pathways that dictate active facet formation remain inadequately resolved. This study introduces a 'framework-dissolution' strategy to modulate the Cu–O geometric coordination in precursor oxides by incorporating inert elements, thereby directing the reconstruction process. In situ X-ray diffraction and Raman spectroscopy reveal that distinct Cu–O coordination environments—specifically tetrahedral versus octahedral—govern the evolution of OD-Cu facets. Tetrahedral coordination yields a dominant Cu(200) facet, whereas octahedral coordination favors Cu(111). The OD-Cu t catalyst, enriched in (200) facets, achieves a Faradaic efficiency for C2+ products (FEC2+) of 75.1% at a partial current density of −187.8 mA cm−2, significantly outperforming its (111)-dominated counterpart. Density functional theory calculations attribute this enhancement to the lower energy barrier for C–C coupling on the (200) surface. These findings establish a direct correlation between precursor coordination geometry and catalytic performance, offering a rational design principle for high-efficiency CO2 reduction catalysts.