Oxygen-modulated engineering of Cu0–Cu+ interfaces for CO2-to-C2H4 photoreduction

CO2-to-hydrocarbon fuel conversion via artificial photosynthesis is limited by catalyst poisoning under high O2 partial pressures and sluggish C2-product formation. Herein, Ru0.6Cu1(Cu0–Cu1+)/CeO2 catalysts with adaptive O2 tolerance are prepared by O2-mediated dynamic interfacial reconstruction. Single-atom Ru doping at Ce lattice sites creates a trigonal prismatic coordination configuration, enabling proton-coupled electron transfer and accelerating H2O dissociation. Photothermal effect promotes O2-driven self-assembly of Cu0–Cu1+ charge-gradient interfaces within Ru/Cu alloy clusters, thereby optimizing the adsorption behavior of *CHOCO intermediates and restructuring the C–C coupling pathway. Interfacial charge cascade transfer and geometric site synergy thermodynamically shift the product selectivity from C1 to C2, as determined by operando spectroscopy and electronic structure analysis. Under concentrated solar irradiation, the catalyst produces 549 ± 20 μmol·g−1 C2H4 with 74.3% selectivity and 0.5% solar-to-chemical energy conversion efficiency—25-fold higher than that in non-concentrated systems. Dynamic interfacial regulation facilitates precise carbon chain synthesis in complex reaction networks. Ru0.6Cu1(Cu0–Cu1+)/CeO2 catalyst converts CO2-to-fuels via artificial photosynthesis, overcoming O2 poisoning and sluggish C2 yield through photothermal interface reconstruction. It achieves 74.3% selectivity for C2H4 with 0.5% solar efficiency.