Bifang Li, Li Zhang, Bo Su, Jiabin Chen, Kunlong Liu, Chengyang Feng, Xiahui Lin, Yidong Hou, Huabin Zhang, Sibo Wang
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.