Chemical warfare agents, such as nerve agents (GD and VX) and blister agents (HD), have strong toxicities to mankind. In recent years, zirconium-based metal-organic frameworks have been found to be attractive materials for chemical warfare agent degradation. Among them, metal-organic framework-808 (MOF-808) and porous coordination network-222 (PCN-222) were the best. However, few papers pay attention to their practical application. In this work, we prepared MOF-808 and PCN-222 using water phase and organic solvothermal methods, respectively. Their performance for the catalytic degradation of chemical warfare agents under practical decontamination conditions was studied. The results showed that MOF-808 displayed a high potency for catalytic hydrolysis of VX (10,000 mg L−1) in unbuffered solution. PCN-222 exhibited weaker reactivity with a half-life ( t1/2) of 28.8 min. Their different performances might stem from the different connectivity of the Zr6 nodes and framework structures. The results illustrated that the hydrolysis of high-concentration GD required a strong alkaline buffer to neutralize the hydrolysis product of hydrofluoric acid (HF) to avoid catalyst poisoning. When H2O2 was used as the oxidant instead of O2, both zirconium-based metal-organic frameworks performed with effective catalytic potency for HD degradation without any special lighting and so was suitable for practical application, whereas the products obtained from HD, such as HDO2 and V-HDO2, still possessed vesicant toxicity. Overall, MOF-808 prepared via a water-phase synthesis performed with effective catalysis for the degradation of high-concentration VX, GD, and HD with t1/2 of < 0.5, 3.1 and 2.2 min, respectively, exhibiting its potential for practical applications.

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Chemical warfare agents (CWAs) still threaten society and have been used in recent terrorist attacks. Various adsorbents have been developed to remove CWA droplets effectively from contaminated objects to protect against serious injury. In this project, a collection of textiles, zirconium hydroxide (ZH) combined with polyvinyl alcohol (PVA)-polyethylene glycol (PEG) or polyacrylonitrile (PAN), were prepared using electro-spinning. Results of scanning electron microscopy, X-ray diffraction and inductively coupled plasma optical emission spectroscopy indicated that ZH was uniformly distributed and attached in the interstices of the polymer fiber with a high Zr load ratio of >24%. The wetting and absorption of ZH textiles to simulation agents such as 2-chloroethyl ethyl sulfide and dimethyl methylphosphate showed good performance in terms of absorption. The calculation results, where the absorption factor ka of each textile was a constant value, suggested they had excellent capacity of removing CWA droplets, such as bis(2-chloroethyl) sulfide (HD), S-2-(diisopropylamino) ethyl O-ethyl methylphosphonothioate (VX) and pinacolyl methylphosphonofluoridate (GD). The detoxification experiment showed that both textiles of ZH@PAN and PAN had optimum degradation of HD with half-lives of 84.5 min due to its fast natural hydrolysis of HD and good adsorption of HD on textile. For degradation of VX solution, ZH@PVA-PEG presented a strong degradation capability with an almost equal half-life of 64.5 min to ZH. ZH@PVA-PEG could also catalyze GD hydrolysis effectively with a half-life of 55.0 min. This work manifested the possibility for quick absorption of CWAs from contaminated objects with non-powder materials and a strong degradation ability.