Light‐Induced Redox Looping of a Rhodium/CexWO3 Photocatalyst for Highly Active and Robust Dry Reforming of Methane

Dry reforming of methane (DRM) has provided an effective avenue to convert two greenhouse gases, CH4 and CO2 , into syngas. Here, we design a DRM photocatalyst Rh/Cex WO3 that invokes both photothermal and photoelectric processes, which overcomes the thermodynamic limitation of DRM under conventional conditions. In contrast to plasmonic or UV-response photocatalysts, our photocatalyst produces a superior light-to-chemical energy efficiency (LTCEE) of 4.65 % with a moderate light intensity. We propose that a light-induced metal-to-metal charge transfer plays a crucial role in the DRM reaction, which induces a redox looping between Ce to W species to lower the activation energy. Quantum mechanical studies reveal that a high oxygen mobility of Cex WO3 , accompanied with the formation of oxo-bridge species, results in a substantial elimination of deposited C species during the reaction. Our catalyst design strategy could offer a promising energy-efficient industrial process for DRM.