Separation of MnWOx and NaWSiOx Phases Boosts Oxidative Coupling of Methane

The oxidative coupling of methane (OCM) is an attractive approach for methane transformations, but achieving a satisfactory combination of activity and selectivity remains challenging, even with the promising Mn‐Na2WO4/SiO2 catalyst. Herein, we demonstrate that nanoscale separation of Mn‐based and Na2WO4‐based phases results in a highly efficient catalyst, achieving a remarkable 79% selectivity for C2‐C3 hydrocarbons at a 32% CH4 conversion at 775 oC, outperforming most previously reported catalysts. Our studies reveal that MnWOx phases with adjustable surface Mn/W ratios and redox activities are more effective for the selective activation of O2, thereby enhancing the OCM of CH4. The assembly of MnWOx and Na2WO4/SiO2 components in nanoscale proximity significantly promotes the formation of C2‐C3 hydrocarbons by suppressing deep oxidation. We propose a bifunctional mechanism involving the transfer of active oxygen species from MnWOx to Na2WO4/SiO2, which induces selective activation and coupling of CH4 on the Na2WO4/SiO2 surface.