Constructing Dynamic Rhδ+–Ov–Ti Interfacial Sites for Highly Efficient and Stable Photothermal Catalytic Methane Dry Reforming

Abstract

Photothermal catalytic dry reforming of methane (DRM) is a promising process for converting two greenhouse gases into syngas. However, it still suffers from poor reactivity and coke-induced instability. Here, we report a Rh-embedded SrTiO₃ with stable interfacial sites (Rh^δ+–O_v–Ti) induced by strong electronic metal–support interactions, which enables highly efficient and stable DRM. In situ characterizations and theoretical calculations confirm that these interfacial sites act as intrinsic active centers for the adsorption and activation of CH₄ and CO₂ molecules via the CH₃O* pathway, without coking. Furthermore, the local charge redistribution and oxygen vacancy (O_v) regeneration enable the dynamic evolution of the Rh^δ+–O_v–Ti interfacial sites during DRM. Consequently, a syngas yield of 7.6/9.6 mol g_Rh^–1 h^–1 for H₂/CO production and durability of 100 h were achieved with the Rh/SrTiO₃ catalyst under light irradiation. More importantly, this embedding strategy can be universally applied to synthesize other anticoking catalysts for photothermal DRM and other structure-sensitive reactions.