Unveiling the Power of Cu Species: Cu–O–Ce Interfacial Sites Fueling Photothermal RWGS and Ce Redox Boost

Achieving efficient hydrogenation of CO2 at low temperatures remains a fundamental challenge in catalytic science. Herein, we report a Cu/CeO2 catalyst with highly dispersed Cu nanoparticles. The construction of an electronic structure at the Cu/CeO2 interface enables the catalyst to achieve 100% CO selectivity and a CO production rate of 359.9 mmol gcat–1 h–1 under1.5 W cm ̵2 light irradiation, which is 6.7 times higher than that obtained in the dark at the same catalyst surface temperature of 320.6 °C. Operando spectroscopies and density functional theory reveal a redox-driven mechanism, with Ce species on the CeO2 surface serving as the primary active site for CO2 activation. While Cu itself does not directly participate in the CO2 hydrogenation reaction, Cu nanoparticles serve as H2 dissociation sites, continuously supplying reactive H atoms to the CeO2 surface for oxygen vacancy (□) regeneration. In addition, the localized surface plasmon resonance (LSPR) effect of Cu nanoparticles significantly increases the local temperature of the catalyst surface, while the photogenerated LSPR electrons generated on Cu nanoparticles are transferred across the Cu/CeO2 interface, promoting the redox behavior of Ce sites’ redox behavior. These combined effects collectively result in significantly enhanced CO formation performance. Our findings provide mechanistic insights into light-assisted CO2 catalysis and demonstrate a powerful strategy for designing high-performance systems for low-temperature carbon conversion.