Charge-Directed Photothermal Methane Dry Reforming Enabled by Interfacial TiOx 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 TiOx-functionalized TiC, where interfacial TiOx 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 TiOx 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 TiOx 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 gRh -1 h-1, H2: 10.5 mol gRh -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 TiOx interface in charge-directed photothermal DRM and provides design insights for developing coking-resistant reforming catalysts.