Zirconium-based metal–organic frameworks (Zr-MOFs) have been considered as prospective materials for the degradation of nerve chemical warfare agents (CWAs) but show poor catalytic performance toward blister agents. Moreover, the powder issues and the poor adsorption capability also remain as the major challenges for the application of Zr-MOFs in practical CWA detoxification. Herein, a series of defected granular UiO-66-NH2 metal–organic gels are synthesized via adjusting the amount of added concentrated hydrochloric acid for the decontamination of 2-chloroethyl ethyl sulfide (2-CEES), a sulfur mustard simulant. The half-life of 2-CEES decontaminated by defected granular UiO-66-NH2 metal–organic gels can be shortened to 7.6 min, which is the highest reported value for MOFs under ambient conditions. The mechanism of decontamination is that the amino group on the linkers in UiO-66-NH2 MOGs undergoes a substitution reaction with 2-CEES to yield 2-(2-(ethylthio)­ethylamino)­terephthalic acid, which is less toxic and fixed in the frameworks. The recycling test corroborates that the granular UiO-66-NH2 xerogels possess good stability and reusability. Static adsorption and desorption tests show that UiO-66-NH2 xerogels possess a high 2-CEES vapor adsorption capacity of 802 mg/g after exposure for 1 d and only 28 wt % desorption capacity after air exposure for 7 d. The dual function of ultrafast degradation and high adsorption capability provide a firm foundation for using UiO-66-NH2 xerogels as a future protection media.

Chemical protective clothing (CPC) is major equipment to protect human skin from hazardous chemical warfare agents (CWAs), especially nerve agents and blister agents. CPC performance is mainly dominated by the chemical protective material, which needs to meet various requirements, such as mechanical robustness, protective properties, physiological comfort, cost-effectiveness, and dimensional stability. In this study, polyvinylidene fluoride (PVDF) based sodium sulfonate membranes with different ion exchange capacities (IECs) are prepared simply from low-cost materials. Their mechanical properties, contact angles, permeations, and selectivities have been tested and compared with each other. Results show that membranes with IEC in the range of 1.5–2 mmol g−1 have high selectivities of water vapor permeation over CWA simulant vapor permeation and good mechanical properties. Therefore, PVDF-based sodium sulfonate membranes are potential materials for CPC applications.

In this paper, the hydrophobic effect or hydration of hydrophobe was firstly introduced into the mechanism of polystyrene particles formation. Negatively charged surface of hydration shell was proposed due to the ordered structure of water molecules. Consequentially the concentration of hydrophobic chains depended on pH because protons destroyed the hydration shell, thereby extruded hydrophobic chains from the H-bonds networks. The soap-free emulsion polymerization of styrene by using AIBN (azodiisobutyronitrile) and KPS (Potassium Persulfate), respectively was performed at various pHs. It was proved that protons played a crucial role on the formation of PSt (polystyrene) particles. By using AIBN, particles were not prepared at pH 2.0 (HAc), pH 4.0 (HCl) and pH 2.0 (HCl), whereas by using KPS, particles were obtained regardless to pH. It indicated that anions of sulfate greatly enhanced the tolerance of hydration shell to the suffering from protons. Meanwhile, the roles of polymerization in the monomer phase, aqueous phase and growing particles were elucidated. By using AIBN, ca. 30 % PSt with M n (Numeral average molecular weight) = 300-1500 formed in the monomer phase at pH 6.8, which dissolved in water at pH 8.0 and pH 10.0. By using KPS, ca. 20 % and 30 % conversion of St were found in the aqueous phase at pH 2.0 (HCl) and pH 10.0 (NaOH), respectively. At pH 2.0 (HCl), oligomers generated in the aqueous phase were protonated, whereas at pH 10.0 (NaOH), they were soluble due to the seriously suppressed dissociation of water. At other pHs, oligomers captured protons, thereby relieved particles and interface from the suffering of protons. As the concentration of oligomers increased, oligomers precipitated to form clusters due to the increase of average number of protons on the surface of oligomers hydration shell, which successively incorporated into the growing particles, thus enlarged PDI (Polydispersity index) of MW (Weight-average molecular weight) distribution in particles. By using AIBN, owing to the limited partition of AIBN in the interfacial layer of St phase, the flat-roof peaks of GPC curves were observed, namely that the weight fraction of M i was constant. It implies that the freeradicals are living in the growing particles.

For the first time, we report hierarchically porous monolithic UiO-66-X xerogels for ultra-fast destruction of chemical warfare agents. The half-lives of the vesicant agent sulfur mustard (HD) and of the nerve agent VX are as short as 14.4 min and 1.5 min, respectively.