A Polyoxoniobate-Polyoxovanadate Double-Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants
A Polyoxoniobate-Polyoxovanadate Double-Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants
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用于同时氧化和水解净化化学战剂模拟物的多铌酸盐-多钒酸盐双阴离子催化剂
DOI：
10.1002/anie.201700159
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发表时间：
2017-04-10
影响因子：
16.6
通讯作者：
Hu, Changwen
中科院分区：
文献类型：
--
作者：
Dong, Jing;Hu, Jufang;Hu, Changwen
合成了一种新的双阴离子配合物H-13[（CH 3）（4）N]（12-）[PNb 12 O 40（（VO）-O-V）（2）中心点（（V4 O 12）-O-IV）（2）]中心点22 H（2）O（1），并通过常规方法进行了表征，并将其用于化学战剂的催化去污。在温和条件下，1催化神经毒剂模拟物氰基膦酸二乙酯（DECP）的水解和硫芥模拟物2-氯乙基乙基硫醚（CEES）的选择性氧化。在氧化去污系统中，用接近化学计量比的3%H2O2水溶液，100%CEES选择性地转化为无毒的2-氯乙基乙基亚砜和乙烯基乙基亚砜，转化频率（TOF）为16000 h（-1）。重要的是，即使在10次循环后仍保持催化活性，并且CEES在3分钟内完全去污而不形成高毒性砜副产物。提出了三步氧化机理。
A novel double-anion complex, H-13[(CH3)(4)N](12-)[PNb12O40((VO)-O-V)(2)center dot((V4O12)-O-IV)(2)]center dot 22H(2)O (1), based on bicapped polyoxoniobate and tetranuclear polyoxovanadate was synthesized, characterized by routine techniques and used in the catalytic decontamination of chemical warfare agents. Under mild conditions, 1 catalyzes both hydrolysis of the nerve agent simulant, diethyl cyanophosphonate (DECP) and selective oxidation of the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). In the oxidative decontamination system 100% CEES was transformed selectively to nontoxic 2-chloroethyl ethyl sulfoxide and vinyl ethyl sulfoxide using nearly stoichiometric 3% aqueous H2O2 with a turnover frequency (TOF) of 16 000 h(-1). Importantly, the catalytic activity is maintained even after ten recycles and CEES is completely decontaminated in 3 mins without formation of the highly toxic sulfone by-product. A three-step oxidative mechanism is proposed.