金属-有机骨架双铜中心协同催化化学战剂模拟物的高效解毒,Journal of the American Chemical Society

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金属-有机骨架双铜中心协同催化化学战剂模拟物的高效解毒
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2022-10-31 , DOI: 10.1021/jacs.2c05176
Qian-You Wang ₁ , Zhi-Bing Sun ₁ , Meng Zhang ₁ , Shu-Na Zhao ₁ , Peng Luo ₂ , Chun-Hua Gong ₁ , Wen-Xiao Liu ₁ , Shuang-Quan Zang ₁

Affiliation

化学战剂 (CWA) 是人类已知的最致命的化学品之一。因此，开发用于高效解毒各种CWAs的多功能催化剂具有重要意义。在这项工作中，我们开发了一种坚固的四唑酸铜金属有机骨架 (MOF) 催化剂，该催化剂包含一个双铜单元，类似于天然磷酸酶和酪氨酸酶活性位点的配位几何结构。该催化剂有助于磷酸酯键水解和过氧化氢分解，最终实现对半衰期为 3.5 分钟的神经毒剂模拟物（二乙氧基磷酰氰化物 (DECP)）和硫芥模拟物（2-氯乙基）的高解毒效率乙基硫醚 (CEES)），半衰期为 4.5 分钟，使其与其他报道的材料相比具有竞争力。ZZU-282 中的双铜位点提供了多种与底物的结合模式，从而促进底物的活化并提高催化效率。结合后修饰金属交换控制实验、密度泛函理论计算和催化评估证实双 Cu 位点是促进催化反应的活性中心。本研究为实现 CWA 解毒的高级催化剂提供了新的设计视角。

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Cooperative Catalysis between Dual Copper Centers in a Metal–Organic Framework for Efficient Detoxification of Chemical Warfare Agent Simulants

Chemical warfare agents (CWAs) are among the most lethal chemicals known to humans. Thus, developing multifunctional catalysts for highly efficient detoxification of various CWAs is of great importance. In this work, we developed a robust copper tetrazolate metal–organic framework (MOF) catalyst containing a dicopper unit similar to the coordination geometry of the active sites of natural phosphatase and tyrosinase enzymes. This catalyst aided in phosphate ester bond hydrolysis and hydrogen peroxide decomposition, ultimately achieving high detoxification efficiency against both a nerve agent simulant (diethoxy-phosphoryl cyanide (DECP)) with a half-life of 3.5 min and a sulfur mustard simulant (2-chloroethyl ethyl sulfide (CEES)) with a half-life of 4.5 min, making it competitive with other reported materials. The dicopper sites in ZZU-282 provide versatile binding modes with the substrates, thereby promoting the activation of substrates and enhancing the catalytic efficiency. A combination of postmodified metal exchange control experiments, density functional theory calculations, and catalytic evaluations confirmed that dual Cu sites are the active centers promoting the catalytic reaction. This study offers a new design perspective to achieve advanced catalysts for CWA detoxification.

更新日期：2022-10-31

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