Tailoring Ni Clusters in Ordered Macroporous CeO2 for Efficient Photothermal Reverse Water Gas Shift Reaction

• • Achieved CO production rate of 63.36 mmol g−1 h−1 with 93% CO selectivity under 2.6 W cm−2 simulated solar irradiation, demonstrating industrially relevant throughput for solar-driven CO2 conversion. • • The 3DOM CeO2 architecture with (Niδ+)n clusters enhances light absorption across UV-vis-NIR, enabling efficient photothermal heating that accelerates reaction kinetics without external heat input. • • Positively charged Ni clusters modulate CeO2 local structure, promoting CO2 adsorption and activation while providing active sites for H2 dissociation, as confirmed by theoretical calculations showing reduced energy barrier for *COOH formation. • • The catalyst design integrates light harvesting and catalytic active sites in a single architecture, offering a scalable platform for solar-to-fuel production with potential for cost-effective carbon recycling.