Biomimetic Oxidation with Fe-ZSM-5 and H2O2? Identification of an Active, Extra-Framework Binuclear Core and an FeIII-OOH Intermediate with Resonance-Enhanced Raman Spectroscopy
Biomimetic Oxidation with Fe-ZSM-5 and H2O2? Identification of an Active, Extra-Framework Binuclear Core and an FeIII-OOH Intermediate with Resonance-Enhanced Raman Spectroscopy
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DOI：
10.1002/cctc.201402642
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发表时间：
2015-02-01
期刊：
影响因子：
4.5
通讯作者：
Dimitratos, Nikolaos
中科院分区：
文献类型：
--
作者：
Hammond, Ceri;Hermans, Ive;Dimitratos, Nikolaos
开发能够模仿自然选择性氧化惰性CH键的无机材料仍然是一个激烈的科学研究课题。近年来，含铁和/或铜的沸石材料已被证明是一种高活性的非均相催化剂，用于烷烃（包括甲烷）的选择性氧化，以及一系列其他相关的氧化挑战。通过共振增强拉曼光谱，我们证明，经过高温预处理（活化），含铁的ZSM-5具有活性双核核心，并在H2O2活化后形成关键的FeOOH中间体。这两个因素都让人想起生物氧化催化剂，并且可能解释了这种材料在低温下选择性地将甲烷氧化成甲醇的独特能力。
Developing inorganic materials that can mimic nature's ability to selectively oxidise inert CH bonds remains a topic of intense scientific research. In recent years, zeolitic materials containing Fe and/or Cu have been shown to be highly active, heterogeneous catalysts for the selective oxidation of alkanes (including methane), amongst a range of other related oxidation challenges. By using resonance-enhanced Raman spectroscopy, we demonstrate that, following high-temperature pre-treatment (activation), Fe-containing ZSM-5 possesses an active binuclear core, and forms a key FeOOH intermediate upon activation with H2O2. Both factors are reminiscent of biological oxidation catalysts, and may account for the unique ability of this material to selectively oxidise methane to methanol at low temperature.