Charge‐Directed Photothermal Methane Dry Reforming Enabled by Interfacial TiO <i> _x </i> Nanodomains

Abstract

ABSTRACT Photothermal dry reforming of methane (DRM) enables solar‐driven upgrading of CH 4 and CO 2 , 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 *OCH 3 formation, the potential‐determining step, thus suppressing *CH 3 over‐dehydrogenation and mitigating carbon formation. Concurrently, CO 2 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 , H 2 : 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.