School of Safety Science and Engineering, Henan Polytechnic University, Jiaozuo 454003, China; Institute of Chemical Safety, Henan Polytechnic University, Jiaozuo 454003, China.
School of Safety Science and Engineering, Henan Polytechnic University, Jiaozuo 454003, China.
J Hazard Mater. 2021 Sep 5;417:126056. doi: 10.1016/j.jhazmat.2021.126056. Epub 2021 May 7.
Constructing versatile materials with self-detoxification properties are highly desired for emergency destruction of chemical warfare agents (CWAs). Herein, we first reported in-situ fabrication of ZnInS/UiO-66-NH nanocomposites (ZnInS/UiO) and their application in catalytic detoxification of two CWA simulants. For nerve agent simulant dimethyl 4-nitrophenyl phosphate (DMNP), the optimal ZnInS/UiO-23.9 displayed 5.9 times increase in hydrolysis rate having the turnover frequency (TOF) of 0.0586 s under simulated solar light (SSL), which is superior to the reported UiO-based catalysts. Photo-assisted enhancement in DMNP detoxification was due to photothermal effect of ZnInS and close interfacial contact in ZnInS/UiO heterostructures, facilitating instantaneous heat transfer from ZnInS to UiO catalytic sites. As for mustard gas surrogate 2-chloroethyl ethyl sulfide (CEES), under SSL irradiation for 15 min, ZnInS/UiO-23.9 can eliminate 96.7% of CEES in droplet experiment, being 4.17 and 3.24 times of ZnInS and UiO accordingly. It was ascribed to spatial separation of photoinduced electron-hole pairs and photothermally-assisted charge transfer in ZnInS/UiO composites, improving catalytic activity for CEES detoxification. Besides, the detected products suggested that CEES conversion underwent reductive dechlorination, radical reactions and hydrolysis. This study can be extended to other multifunctional catalysts based on metal-organic frameworks and provides new opportunities for photoassisted enhanced detoxification of CWAs.
构建具有自我解毒性能的多功能材料是非常需要的，以用于紧急破坏化学战剂（CWA）。在此，我们首次报道了原位合成的 ZnInS/UiO-66-NH 纳米复合材料（ZnInS/UiO）及其在两种 CWA 模拟物的催化解毒中的应用。对于神经毒剂模拟物二甲氧基 4-硝基苯基磷酸酯（DMNP），最佳的 ZnInS/UiO-23.9 在模拟太阳光（SSL）下的水解速率提高了 5.9 倍，其转化频率（TOF）为 0.0586 s，优于已报道的基于 UiO 的催化剂。DMNP 解毒中的光辅助增强归因于 ZnInS 的光热效应和 ZnInS/UiO 异质结构中的紧密界面接触，促进了 ZnInS 到 UiO 催化位点的瞬时热传递。对于芥子气模拟物 2-氯乙基乙基硫醚（CEES），在 SSL 照射 15 分钟后，ZnInS/UiO-23.9 可以在液滴实验中消除 96.7%的 CEES，分别是 ZnInS 和 UiO 的 4.17 倍和 3.24 倍。这归因于 ZnInS/UiO 复合材料中光生电子-空穴对的空间分离和光热辅助电荷转移，提高了 CEES 解毒的催化活性。此外，检测到的产物表明 CEES 转化经历了还原脱氯、自由基反应和水解。本研究可以扩展到其他基于金属-有机骨架的多功能催化剂，并为光辅助增强 CWA 解毒提供新的机会。
