Photocatalytic Dry Reforming of Methane Enhanced by “Dual‐Path” Strategy with Excellent Low‐Temperature Catalytic Performance

Abstract Dry reforming of methane (DRM), which involves the activation of inert CH bonds and CO bonds, at mild conditions is a tremendous challenge. The sluggish mobility of oxygen during the reaction is known as a key issue causing low activity and poor stability of catalysts by the coke formation. Herein, a novel Cu‐CNN/Pd‐BDCNN photocatalyst that is made up of “Cu‐nanoparticle‐loaded g‐C₃N₄ nanosheets” and “Pd‐nanoparticle‐loaded boron‐doped nitrogen‐deficient g‐C₃N₄ nanosheets” is reported. The existing dual‐reaction‐sites benefit the reactive oxygen intermediates participate in the reaction directly without distant migration. The in situ characterizations and density functional theory calculations reveal a newly dual reaction pathway through simultaneous dehydrogenation of methoxy and methyl intermediates, and demonstrate the importance of metal loading, which promote the CO₂ and CH₄ activation from both aspects of thermodynamics and kinetics. The optimized Cu‐CNN/Pd‐BDCNN photocatalyst displays an excellent syngas formation rate of over 800 µmol g⁻¹ h⁻¹ with H₂/CO = 1 and splendid stability in continuous flow reaction under 300 mW cm⁻² xenon lamp irradiation at room temperature. The “dual‐site” and “dual‐path” strategy shed light on the design of effective photocatalysts for methane dry reforming.