Light‐Driven Charge Redistribution of Pt Cluster/CeO 2 Realizing Dual‐Path Synergistic Catalysis for Low‐Temperature Reverse Water‐Gas Shift

ABSTRACT Solar‐driven low‐temperature reverse water‐gas shift offers a sustainable route for CO 2 conversion yet suffers from insufficient efficiency and unclear reaction mechanisms. Herein, we demonstrate that light drives the surface charge redistribution of a Pt cluster/CeO 2 catalyst, unlocking synergistic dual pathways for enhanced CO production. Using light as the sole energy input (2.27 W/cm 2 ), the catalyst surface reaches a localized temperature of ∼309°C while the reactor environment remains at only ∼54°C. In a continuous‐flow system with cold inlet gases, this catalyst achieves a CO production rate of 846.9 mmol g cat −1 h −1 , outperforming conventional thermal systems. Remarkably, comparable performance is achieved using natural sunlight alone, even under outdoor ambient temperature of −21°C. Mechanistic studies reveal that light‐driven interfacial charge redistribution constructs the nonequilibrium Pt δ+ ‐O V ‐Ce 3+ structure, which promotes CO 2 activation, triggering the carboxylate pathway and enhancing the formate route, giving rise to a cooperative effect that significantly accelerates the overall reaction. This stands in stark contrast to the single formate route that dominates conventional thermal catalysis. This work establishes light as a dynamic regulator for engineering catalytic sites, offering a promising strategy for efficient solar energy conversion.