Construction of the sp-C–O–V interface for selective conversion of methane to methyl hydroperoxide under mild conditions†

The catalytic conversion of methane into high-value-added products under mild and environmentally friendly conditions is a promising route towards sustainable industrial applications; but still limited by their low selectivity and activity issues, developments in new high-performance catalysts are needed. Herein, a two-dimensional heterostructured V₂O₅/graphdiyne nanosheet with electron-rich sp-C–O–V interfaces is constructed by the growth of a layer of V₂O₅ on the surface of graphdiyne. Such well-defined interface structure provides large numbers of new active sites with high selectivity and activity for CH₄ oxidation, exhibiting a high yield of 18.04 mmol g_cat⁻¹ h⁻¹ at 70 °C and a selectivity of up to 85%, efficiently suppressing the formation of undesired by-products such as CO and CO₂. In situ infrared spectroscopy and kinetic studies revealed that the highly ordered V₂O₅ structure on the GDY surface significantly enhanced CH₄ adsorption, reducing the coupling energy barriers for the *CH₃ and *OOH species. The activation of CH₄ by *OOH or *OH facilitated the formation of *CH₃, which subsequently underwent coupling to yield CH₃OOH. Our results show that graphdiyne provides a good opportunity for synthesizing new materials with high-performance for the direct conversion of CH₄ to targeted high-value-added products, offering valuable insights for the design of efficient methane conversion systems.