Chengxuan He, Shiqun Wu*, Qixin Li, Mingyang Li, Jiaying Li, Lingzhi Wang, Jinlong Zhang*
wushiqun@ecust.edu.cn (S.W.)
jlzhang@ecust.edu.cn (J.Z.)

Photocatalytic dry reforming of methane (DRM) is a promising green process for converting two greenhouse gases into syngas. Nonetheless, achieving photocatalytic DRM with both high activity and stoichiometric products ratio remains a grand challenge. We report here a Ru single-atom-modified hierarchical porous TiO₂- SiO₂ (Ru-TS) as a photocatalyst for DRM, achieving a remarkable syngas generation rate of 98.52 mmol g_Ru^-1 h^-1 for CO and 96.50 mmol g_Ru^-1 h^-1 for H₂ with extraordinary durability under mild conditions. The local microstructure of Ru-Ov-Ti on catalyst provides matched active sites for CH₄ and CO₂ adsorption and activation through charge redistribution and electronic localization and optimizes CH₄-CO₂ reaction route for inhibiting side reaction and promoting effective C–O coupling. This work provides guidance in the active site construction of robust catalysts for photocatalytic DRM and other multi-molecule synergetic reactions.