Yupeng Zhai,Jialin Yu,Lijuan Zhang,Yunshan Zhou,Yuxu Zhong,Ying Yang,Yong’An Wang
In this study, an α-Keggin-type polyoxometalate H 5 PV 2 Mo 10 O 40 was loaded into the adamantane cage (18 Å) of MOF-808(Ce) by an immersion method to obtain composites with different polyoxometalate loadings. The effects of the H 5 PV 2 Mo 10 O 40 loading in the composite, the reaction time, and the quantity of the composite during the decontamination of the erosive agent surrogate, 2-chloroethyl ethyl sulfide (CEES) were investigated, and the optimized catalytic conditions for CEES were determined. The decontamination rate of 4 μL CEES reached 93.91% in 120 min using 40 mg of optimized composite, and the decontamination rate of 160 μL of the nerve agent surrogate, methyl paraoxon (DMNP) reached 100% in 25 min using 5 mg of the composite. Decontamination of CEES and DMNP by the composite followed first-order reaction kinetics. The half-life ( t 1/2 ) and kinetic rate constant ( k ) of these two reactions were 27.77 min and −0.02496 min −1 and 1.895 min and −0.36569 min −1 , respectively. The composite exhibited good decontamination performance after four replicate experiments. The results showed that CEES was oxidized to CEESO, while DMNP was hydrolyzed to p -nitrophenol and dimethyl phosphonate in the presence of the composite, showing that the proposed composite is an effective bifunctional catalyst for the selective oxidation and hydrolysis of chemical warfare agent surrogates.
Xuejiao Wang,Jing Yang,Ming Zhang,Qian Hu,Bai-Xue Li,Jin Qu,Zhong-Zhen Yu,Dongzhi Yang
We design a spontaneously super-hygroscopic alkaline microreactor by photoinduced integration of Zr-MOF catalyst and alkaline poly(dimethylaminoethyl acrylate) onto LiCl-salinized poly(N-isopropylacrylamide) gel, generating a microenvironment with non-volatile polymeric base and non-bulk water for detoxification of a typical nerve agent simulant, dimethyl 4-nitrophenyl phosphate (DMNP), in atmospheric environments. The super-hygroscopic gel with directional microchannels facilitates the absorption, transport and storage of water under different humidities, and exhibits fast hygroscopic efficiency with a high moisture absorption capacity of 6.4 g g −1 . The integrated microreactor achieves simultaneous water uptake and catalytic hydrolysis of DMNP in an atmospheric environment with an initial half-life of ∼1.9 h and a final conversion of 95.5%, which is attributed to the synergistic catalytic microenvironment of the exposed Zr-MOF catalyst, the polymeric base, and the water from moist air. This work provides a feasible strategy for designing spontaneously hygroscopic microreactors for detoxifying nerve agent simulants in atmospheric environments.
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