Light-Driven Charge Redistribution of Pt Cluster/CeO₂ Realizing Dual-Path Synergistic Catalysis for Low-Temperature...

Solar-driven low-temperature reverse water-gas shift offers a sustainable route for CO₂ conversion yet suffers from insufficient efficiency and unclear reaction mechanisms. Herein, we demonstrate that light drives the surface charge redistribution of a Pt cluster/CeO₂ catalyst, unlocking synergistic dual pathways for enhanced CO production. Using light as the sole energy input (2.27 W/cm²), 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-Ce³⁺ structure, which promotes CO₂ 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.