Photo-assisted enhancement performance for rapid detoxification of chemical warfare agent simulants over versatile ZnIn2S4/UiO-66-NH2 nanocomposite catalysts

Abstract 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 ZnIn2S4/UiO-66-NH2 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-1 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.