Bioinspired Metal-Organic Framework Catalysts for Selective Methane Oxidation to Methanol
Bioinspired Metal-Organic Framework Catalysts for Selective Methane Oxidation to Methanol
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DOI：
10.1021/jacs.8b11525
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发表时间：
2018-12-26
影响因子：
15
通讯作者：
Yaghi, Omar M.
中科院分区：
文献类型：
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作者：
Baek, Jayeon;Rungtaweevoranit, Bunyarat;Yaghi, Omar M.
颗粒甲烷单加氧酶（pMMO）是一种高活性、高选择性的甲烷氧化酶。在将生物学相关配体用于在合成系统中形成这种活性位点方面已经取得了有限的成功。在这里，我们报告的设计和合成的金属有机框架（MOF）催化剂的灵感来自pMMO的选择性甲烷氧化为甲醇。通过明智地选择具有适当拓扑结构和化学官能度的骨架，M0 F-808用于合成后安装带有咪唑单元的配体，用于随后在分子氧存在下与Cu（I）金属化。该催化剂在150 ℃的等温条件下对甲烷氧化为甲醇表现出高选择性。结合光谱和密度泛函理论计算表明，双（μ-氧代）二铜物种作为催化剂的可能的活性中心。
Particulate methane monooxygenase (pMMO) is an enzyme that oxidizes methane to methanol with high activity and selectivity. Limited success has been achieved in incorporating biologically relevant ligands for the formation of such active site in a synthetic system. Here, we report the design and synthesis of metal-organic framework (MOF) catalysts inspired by pMMO for selective methane oxidation to methanol. By judicious selection of a framework with appropriate topology and chemical functionality, MOF-808 was used to postsynthetically install ligands bearing imidazole units for subsequent metalation with Cu(I) in the presence of dioxygen. The catalysts show high selectivity for methane oxidation to methanol under isothermal conditions at 150 degrees C. Combined spectroscopies and density functional theory calculations suggest bis(mu-oxo) dicopper species as probable active site of the catalysts.