Photocatalytic nonoxidative coupling of methane (CH4, NOCM) to ethane (C2H6) is a promising route for CH4 valorization, yet its efficient implementation requires the seamless coordination of CH4 adsorption, C–H bond activation, and C–C coupling. This intrinsic complexity makes it fundamentally challenging for a single type of active site to drive the entire NOCM process efficiently. Herein, we induce the formation of Ce3+ sites on the surface of CeO2 by loading Ag nanoparticles (NPs) for NOCM, and achieve highly efficient and selective conversion of CH4 to C2H6. Mechanistic studies indicate that the Ce3+ sites enhance CH4 adsorption and facilitate C–H bond activation to generate methyl radicals (•CH3). Subsequently, Ag NPs promote the coupling of •CH3, ultimately producing C2H6. This study presents a synergistic catalysis strategy for designing efficient photocatalysts to achieve the selective coupling of CH4 into higher-value chemicals.
