☆ 4.7 Article

A bifunctional composite H5PV2Mo10O40@MOF-808(Ce): Preparation, characterization, and performance in the decontamination of chemical warfare agent surrogates CEES and DMNP

MICROPOROUS AND MESOPOROUS MATERIALS (2021)

Journal

MICROPOROUS AND MESOPOROUS MATERIALS

Volume 322, Issue -, Pages -

Publisher

ELSEVIER

DOI: 10.1016/j.micromeso.2021.111163

Keywords

Composite; Chemical warfare agent; Detoxification; Hydrolysis; Oxidation

Funding

Natural Science Foundation of China

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Abstract

In this study, a composite with different loadings of an alpha-Keggin-type polyoxometalate H5PV2Mo10O40 in MOF-808(Ce) was prepared using an immersion method. The optimized conditions for decontamination of the erosive agent surrogate, 2-chloroethyl ethyl sulfide (CEES), and the nerve agent surrogate, methyl paraoxon (DMNP), were determined. The composite exhibited good decontamination performance by following first-order reaction kinetics for both CEES and DMNP, showing its effectiveness as a bifunctional catalyst for the selective oxidation and hydrolysis of chemical warfare agent surrogates.

In this study, an alpha-Keggin-type polyoxometalate H5PV2Mo10O40 was loaded into the adamantane cage (18 & Aring;) of MOF-808(Ce) by an immersion method to obtain composites with different polyoxometalate loadings. The effects of the H5PV2Mo10O40 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 mu L CEES reached 93.91% in 120 min using 40 mg of optimized composite, and the decontamination rate of 160 mu L 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 (t1/2) 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.

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Demonstration of High Detoxification Efficiency of Glassy Polymer-Metal Hydroxide Composites toward Chemical Warfare Agent Simulants

Peter O. O. Aina, Sukanta K. K. Mondal, Joshua Costain, Ali A. A. Rownaghi, Fateme Rezaei

Summary: The design and development of polymeric composites that can effectively capture and destruct toxic chemicals with a fast detoxification rate is of high importance. Zr(OH)(4)-incorporated Ultem, Matrimid, and PIM-1 composites were synthesized and assessed for detoxification of DMNP. Increasing Zr(OH)(4) loading enhances the hydrolysis rate and the amount of DMNP converted for all three polymers. 30%-Zr(OH)(4)@PIM-1 exhibits the best performance with a hydrolysis rate of 5.5 x 10(-3) μmol/s at room temperature and achieves 100% conversion in 2 hours.

ACS APPLIED POLYMER MATERIALS (2023)