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

Achieving efficient hydrogenation of CO 2 at low temperatures remains a fundamental challenge in catalytic science. Herein, we report a Cu/CeO 2 catalyst with highly dispersed Cu nanoparticles. The construction of an electronic structure at the Cu/CeO 2 interface enables the catalyst to achieve 100% CO selectivity and a CO production rate of 359.9 mmol g cat –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 CeO 2 surface serving as the primary active site for CO 2 activation. While Cu itself does not directly participate in the CO 2 hydrogenation reaction, Cu nanoparticles serve as H 2 dissociation sites, continuously supplying reactive H atoms to the CeO 2 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/CeO 2 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 CO 2 catalysis and demonstrate a powerful strategy for designing high-performance systems for low-temperature carbon conversion.