Insights into Catalytic Hydrolysis of Organophosphate Warfare Agents by Metal-Organic Framework NU-1000
Insights into Catalytic Hydrolysis of Organophosphate Warfare Agents by Metal-Organic Framework NU-1000
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DOI：
10.1021/acs.jpcc.8b03641
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发表时间：
2018-06-14
影响因子：
3.7
通讯作者：
Snurr, Randall Q.
中科院分区：
文献类型：
--
作者：
Chen, Haoyuan;Liao, Peilin;Snurr, Randall Q.
金属有机骨架（MOFs）由于其模块化设计和可调谐性而被报道为多用途催化剂。最近，一系列锆基MOFs已被用于催化水解破坏含有磷酸酯键的化学战剂（CWA）。本文采用密度泛函理论计算方法研究了CWA模拟物甲基对氧磷在Zr基MOF NU-1000上的水解反应。我们计算的能垒与以前的实验动力学数据定量一致。非催化水解和MOF催化反应之间的比较揭示了NU-1000的催化作用的起源，并显示类似的酶催化类似的反应。节点扭曲的催化机制上的效果也检查，结果与实验结果是一致的，其中NU- 1000的扭曲的节点显示甲基对氧磷水解的速率增加相比，完全水合的正规形式的NU-1000。
Metal organic frameworks (MOFs) have been reported to be versatile catalysts because of their amenability to modular design and tunability. Recently, a series of zirconium-based MOFs have been used to catalyze the hydrolytic destruction of chemical warfare agents (CWAs) that contain phosphate ester bonds. Here, we adopt density functional theory calculations to study the hydrolysis of the CWA simulant methylparaoxon on the Zr-based MOF NU-1000. Our calculated energy barriers are in quantitative agreement with previous experimental kinetics data. Comparison between uncatalyzed aqueous hydrolysis and the MOF-catalyzed reaction reveals the origin of the catalytic effects of NU-1000 and shows a resemblance to enzymatic catalysis of similar reactions. The effect of node distortion on the catalytic mechanism is also examined, and the results are consistent with experimental findings, where the distorted node of NU- 1000 shows an increase in the rate of methylparaoxon hydrolysis compared to the completely hydrated regular form of NU-1000.