Charge-Directed Photothermal Methane Dry Reforming Enabled by Interfacial TiO_x Nanodomains

Photothermal dry reforming of methane (DRM) enables solar-driven upgrading of CH₄ and CO₂, yet its efficiency and durability are hindered by carbon deposition and poorly defined photochemical contributions. Here, we demonstrate a charge-directed photothermal DRM catalyst composed of Rh nanoparticles supported on TiO_x-functionalized TiC, where interfacial TiO_x domains play a critical role by coupling directional photocarrier flow with adaptive oxygen chemistry. Upon illumination, metallic TiC generates charge carriers that transfer electrons to Rh sites while steering holes to TiO_x surface oxygens. This charge-directed interfacial chemistry selectively lowers the barrier for *OCH₃ formation, the potential-determining step, thus suppressing *CH₃ over-dehydrogenation and mitigating carbon formation. Concurrently, CO₂ activation at oxygen vacancies within TiO_x regions restocks surface oxygens, closing a regenerative photothermal Mars-van Krevelen cycle. As a result, the catalyst delivers high syngas production rates (CO: 17.5 mol g_Rh ^-1 h^-1, H₂: 10.5 mol g_Rh ^-1 h^-1), attains a light-to-chemical energy efficiency of 29%, and operates stably for over 100 h without coking. This work highlights the mechanistic importance of amorphous TiO_x interface in charge-directed photothermal DRM and provides design insights for developing coking-resistant reforming catalysts.