A Versatile Self‐Detoxifying Material Based on Immobilized Polyoxoniobate for Decontamination of Chemical Warfare Agent Simulants

• Published in: Chemistry : a European journal 2018-12, Vol.24 (72), p.19208-19215
• Main Authors: Dong, Jing, Lv, Hongjin, Sun, Xiangrong, Wang, Yin, Ni, Yuanman, Zou, Bo, Zhang, Nan, Yin, Anxiang, Chi, Yingnan, Hu, Changwen
• Format: Article
• Language: English
• Subjects: Biological & chemical weapons; Catalysis; Catalytic activity; Chemical warfare; chemical warfare agents; Chemistry; Construction materials; Decontamination; heterogeneous catalysis; Hydrogen peroxide; Hydroxides; Immobilization; Mustard gas; Nerve agents; niobium; Organic chemistry; Oxidation; polyoxometalates; Selectivity; self-detoxifying material; Sulfide; Sulfur; Tabun; Textiles
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201804523

A decontaminating composite, Mg3Al‐LDH‐Nb6, has been successfully prepared by immobilizing Lindqvist [H3Nb6O19]5− (Nb6) into a Mg3Al‐based layered double hydroxide (Mg3Al‐LDH). To our knowledge, this represents the first successful approach to the immobilization of polyoxoniobate. As a versatile catalyst, Mg3Al‐LDH‐Nb6 can effectively catalyze the degradation of both vesicant and nerve agent simulants by multiple pathways under mild conditions. Specifically, the sulfur mustard simulant, 2‐chloroethyl ethyl sulfide (CEES), is converted into the corresponding nontoxic 2‐chloroethyl ethyl sulfoxide (CEESO) by selective oxidation, whereas the Tabun (G‐type nerve agent) simulant, diethyl cyanophosphonate (DECP), and the VX (V‐type nerve agent) simulant, O,S‐diethyl methylphosphonothioate (OSDEMP), are detoxified through hydrolysis and perhydrolysis, respectively. A possible mechanism is proposed on the basis of control experiments and spectroscopic studies. The Mg3Al‐LDH‐Nb6 composite exhibits remarkable robustness and can be readily reused for up to ten cycles with negligible loss of its catalytic activity. More importantly, a protective “self‐detoxifying” material has easily been constructed by integrating Mg3Al‐LDH‐Nb6 into textiles. In this way, the flexible and permeable properties of textiles have been combined with the catalytic activity of polyoxoniobate to remove 94 % of CEES in 1 h by using nearly stoichiometric dilute H2O2 (3 %) as oxidant with 96 % selectivity. Detox done well! A novel decontaminating material, Mg3Al‐LDH‐Nb6, has been prepared by immobilizing hexaniobate into a layered double hydroxide (LDH). As a versatile catalyst, Mg3Al‐LDH‐Nb6 effectively degrades a sulfur mustard simulant by selective oxidation and a G‐ and V‐type nerve agent simulant by hydrolysis and perhydrolysis, respectively (see figure). Furthermore, this catalyst can be integrated into textiles to construct portable and permeable self‐detoxifying clothing.