Light-induced electronic structure modulation in perovskite ferrite for efficient photothermal dry reforming of methane.

Solar-driven dry reforming of methane (DRM) offers a sustainable pathway to convert CH4 and CO2 into valuable syngas feedstock, yet the efficiency is hindered by the sluggish lattice oxygen (LO) migration of the catalyst and the incomplete understanding of light-enhanced redox cycling. Here, we demonstrate that Ru/LaFeO3 functions as a highly efficient and durable photothermal catalyst for DRM. The incorporation of Ru not only serves as an electron trap but also modulates the catalyst's electronic structure. Notably, under light irradiation, photoinduced charge redistribution further intensifies this electronic modulation, leading to electron enrichment at Ru, La, and Fe sites, and hole accumulation at LO sites. This interfacial charge dynamics weakens La-O and Fe-O bonds and facilitates LO migration, enabling efficient CH4 activation and oxidation at Ru sites, accompanied by the generation of oxygen vacancies (OVs). Simultaneously, the in situ generated OVs promote CO2 adsorption and activation, facilitating its cleavage into CO and replenishing the OVs, thereby sustaining the redox cycle for continuous catalysis. This study provides key mechanistic insights into photoinduced LO dynamics driven by charge redistribution, and offers valuable guidance for the rational design of advanced photothermal systems that leverage both thermal and photonic effects of solar energy for enhanced catalysis via the LO-mediated pathways.