Probing the intermediates in the MO + CH4 ↔ M + CH3OH reactions by matrix isolation infrared spectroscopy
Probing the intermediates in the MO + CH4 ↔ M + CH3OH reactions by matrix isolation infrared spectroscopy
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DOI：
10.1080/01442350701685946
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发表时间：
2008-01
影响因子：
6.1
通讯作者：
Guanjun Wang;Mingfei Zhou
中科院分区：
文献类型：
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作者：
Guanjun Wang;Mingfei Zhou
在这篇综述中，我们介绍了MO + CH4和M + CH3OH模型反应（M =过渡金属）的最新研究，以提供有关催化甲烷转化为甲醇过程机理的定量信息。采用基质隔离红外吸收光谱法对反应中间体进行了捕获和探测。通过MO + CH4和M + CH3OH反应的同位素取代实验，确定了早期和晚期过渡金属的OM（CH4）、M（CH3OH）、CH3MOH、CH3M(O)H和CH3OMH等重要中间体。根据观察到的反应中间体，提出了一些前所未有的反应途径。互补量子化学计算支持中间鉴定，有助于深入了解反应机制和周期趋势。
In this review, we present our recent studies on the MO + CH4 and M + CH3OH model reactions (M = transition metals) in order to provide quantitative information regarding the mechanisms for the catalytic methane-to-methanol conversion process. The reaction intermediates were trapped and probed by matrix isolation infrared absorption spectroscopy. Various important intermediates including OM(CH4), M(CH3OH), CH3MOH, CH3M(O)H and CH3OMH are identified via isotopic substitution experiments in the MO + CH4 and M + CH3OH reactions for selected early and late transition metals. Based on the observed reaction intermediates, some unprecedented reaction pathways are proposed. Complementary quantum chemical calculations support the intermediate identification and help to gain insight into the reaction mechanisms and periodic trends.