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 nodes of UiO-66, while the organic terephthalic acid (H 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 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 h with 97.9 % selectivity, circa 8 times higher than those modulated with AA. 6 2 6 cat −1 −1