Oxo dicopper anchored on carbon nitride for selective oxidation of methane

Selective conversion of methane (CH(4)) into value-added chemicals represents a grand challenge for the efficient utilization of rising hydrocarbon sources. We report here dimeric copper centers supported on graphitic carbon nitride (denoted as Cu(2)@C(3)N(4)) as advanced catalysts for CH(4) partial oxidation. The copper-dimer catalysts demonstrate high selectivity for partial oxidation of methane under both thermo- and photocatalytic reaction conditions, with hydrogen peroxide (H(2)O(2)) and oxygen (O(2)) being used as the oxidizer, respectively. In particular, the photocatalytic oxidation of CH(4) with O(2) achieves >10% conversion, and >98% selectivity toward methyl oxygenates and a mass-specific activity of 1399.3 mmol g Cu(−1)h(−1). Mechanistic studies reveal that the high reactivity of Cu(2)@C(3)N(4) can be ascribed to symphonic mechanisms among the bridging oxygen, the two copper sites and the semiconducting C(3)N(4) substrate, which do not only facilitate the heterolytic scission of C-H bond, but also promotes H(2)O(2) and O(2) activation in thermo- and photocatalysis, respectively.