The photocatalytic conversion of methane (CH4) into high-value multicarbon (C2+) merchandise underneath ambient circumstances offers a extremely promising strategy for transformation of power construction and environmental safety. Nevertheless, the excessive C−H bond dissociation power of CH4 and the overoxidation of methyl radical (·CH3) intermediates enormously restrict the conversion of CH4 to C2+ merchandise. Herein, we show a metal-organic framework (MOF) crystal engineering technique to synthesize MOF-derived PdO/TiO2 nanocomposite for photocatalytic nonoxidative coupling of methane (NOCM), attaining excessive selectivity and exercise within the conversion of CH4 to ethane (C2H6). Mechanistic investigations reveal that the spatially separated energetic websites for C−H bond cleavage and C−C coupling contribute to the environment friendly conversion of CH4 to C2H6. Particularly, the lattice oxygen captures the photogenerated holes, resulting in the formation of oxygen radical anions (·O−), which activate the C−H bond and generate ·CH3 intermediates. PdO stabilizes ·CH3 intermediates, successfully inhibiting the overoxidation of ·CH3, and thereby selling the C−C coupling course of. This work opens a brand new avenue for the rational design of environment friendly MOF-derived photocatalysts for NOCM.
