Forked Vein Structure W/WO_3−x with Dual Active Sites in W and Oxygen Vacancies to Enhance Methylene Self‐Coupling for Efficient Conversion of Methane to Ethylene

Abstract The directional conversion of methane to ethylene is challenging due to the dissociation of the C─H bond and the self‐coupling of methyl intermediates. Herein, a novel W/WO_3−x catalyst with the fork vein structure consisting of an alternating arrangement of WO_3−x and W is developed. Impressively, the catalyst achieves an unprecedented C₂H₄ yield of 1822.73 µmol g⁻¹ h⁻¹, with a selectivity of 82.49%. The enhanced catalytic activity is ascribed to the multifunctional synergistic effect induced by oxygen vacancies and W sites in W/WO_3−x. Oxygen vacancies provide abundant coordination of unsaturation sites, which promotes the adsorption and activation of CH₄, thus reducing the dissociation energy barrier of the C─H bond. The CH₂ coupling barrier on the metal W surface is significantly lower compared to WO₃, so CH₂ can migrate to the W site for coupling. Importantly, the W/WO_3−x with high periodicity provides multiple ordered local microelectric fields, and CH₂ intermediates with dipole moments undergo orientation polarization and displacement polarization driven by the electric field, thus enabling CH₂ migration. This work opens a new avenue for the structural design and modulation of photocatalysts, and provides new perspectives on the migration of methylene between multiple active sites.