Fe‐O Clusters Anchored on Nodes of Metal–Organic Frameworks for Direct Methane Oxidation

Direct methane oxidation into value‐added organic oxygenates with high productivity under mild condition remains a great challenge. We show Fe‐O clusters on nodes of metal–organic frameworks (MOFs) with tunable electronic state for direct methane oxidation into C1 organic oxygenates at 50 °C. The Fe‐O clusters are grafted onto inorganic Zr 6 nodes of UiO‐66, while the organic terephthalic acid (H 2 BDC) ligands of UiO‐66 are partially substituted with monocarboxylic modulators of acetic acid (AA) or trifluoroacetic acid (TFA). Experiments and theoretical calculation disclose that the TFA group coordinated with Zr 6 node of UiO‐66 enhances the oxidation state of adjacent Fe‐O cluster due to its electron‐withdrawing ability, promotes the activation of C−H bond of methane, and increases its selective conversion, thus leading to the extraordinarily high C1 oxygenate yield of 4799 μmol g cat −1  h −1 with 97.9 % selectivity, circa 8 times higher than those modulated with AA.