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Fe‐O Clusters Anchored on Nodes of Metal–Organic Frameworks for Direct Methane Oxidation
Author(s) -
Zhao Wenshi,
Shi Yanan,
Jiang Yuheng,
Zhang Xiaofei,
Long Chang,
An Pengfei,
Zhu Yanfei,
Shao Shengxian,
Yan Zhuang,
Li Guodong,
Tang Zhiyong
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202013807
Subject(s) - oxygenate , metal organic framework , chemistry , trifluoroacetic acid , terephthalic acid , methane , acetic acid , oxidation state , catalysis , inorganic chemistry , photochemistry , organic chemistry , adsorption , polyester
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.