Hydrothermal degradation of adsorbed sulfur mustard on activated carbon

Osovsky, Ruth; Kaplan, Doron; Rotter, H.; Kendler, Shai; Goldvaser, Michael; Zafrani, Yossi; Columbus, Ishay

doi:10.1016/j.carbon.2011.05.028

Cited by 13 publications

(23 citation statements)

References 11 publications

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“…11,13−18 For instance, on activated carbon, the rate of hydrolysis of SM vapor is enhanced by the presence of increasing amounts of water in the micropores of the textile material. 13,14 Similar results have been observed on nanosized metal oxides 15−17 and peroxides 18 used in the decontamination of SM and other CWAs via hydrolysis. In some cases, the absence of water on the metal oxide surfaces resulted in the formation of an alkoxide derivative which remained strongly bound to the surface 16,17 and thus reducing their ability to neutralize the CWA.…”

Section: Introductionsupporting

confidence: 68%

“…The hydrolysis of SM in water is preceded by a relatively slow hydration step but results in the formation of the nontoxic thiodiglycol (TDG) and hydrochloric acid under pseudo-first-order conditions. , Conversely, SM gives rise to relatively toxic polymeric sulfonium products if a limited amount of water is used for the hydrolysis . As well as influencing the toxicity and reactivity of SM, water strongly affects the rate of the SM hydrolysis reaction. ,− For instance, on activated carbon, the rate of hydrolysis of SM vapor is enhanced by the presence of increasing amounts of water in the micropores of the textile material. , Similar results have been observed on nanosized metal oxides − and peroxides used in the decontamination of SM and other CWAs via hydrolysis. In some cases, the absence of water on the metal oxide surfaces resulted in the formation of an alkoxide derivative which remained strongly bound to the surface , and thus reducing their ability to neutralize the CWA.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Study of the Microhydration the Chemical Warfare Agent Sulfur Mustard

2020

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A microhydration study of sulfur mustard (SM) was carried out using M06-2X, B3LYP, B3LYP-D3, and MP2 levels of theory with the 6-311++G(2d,2p) basis set. The changes in energetics, structural parameters and vibrational wavenumbers following the addition of up to three discrete water molecules to SM were analyzed. We observed slight changes in the geometry of SM upon microhydration. The stability of hydrated clusters is due to weak C–H···O–H hydrogen bonds. The free energy change for the formation of the clusters is positive at room temperature and becomes exergonic when the temperature decreases. The infrared stretchings of C–Cl of SM and O–H of water are redshifted upon the addition of water molecules. The findings from this work add to the literature of hydrated SM and can be useful in its detection and subsequent destruction.

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Section: Introductionsupporting

confidence: 68%

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Microhydration the Chemical Warfare Agent Sulfur Mustard

2020

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“…TDG is partially oxidized to TDGsulfoxide (TDG-SO, Figure 1b). 5 Note that the observed reaction products as well as the CWAs themselves are all in the adsorbed state, as shown by the chemical shifts and line widths in the MAS NMR spectra. Typically, adsorption on a microporous AC shifts the MAS NMR resonances by about 5−10 ppm upfield and broadens the lines up to a δν 1/2 of 300− 1000 Hz.…”

Section: ■ Results and Discussionmentioning

confidence: 95%

Decontamination of Adsorbed Chemical Warfare Agents on Activated Carbon Using Hydrogen Peroxide Solutions

Osovsky

Kaplan

Nir

et al. 2014

Environ. Sci. Technol.

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Mild treatment with hydrogen peroxide solutions (3-30%) efficiently decomposes adsorbed chemical warfare agents (CWAs) on microporous activated carbons used in protective garments and air filters. Better than 95% decomposition of adsorbed sulfur mustard (HD), sarin, and VX was achieved at ambient temperatures within 1-24 h, depending on the H2O2 concentration. HD was oxidized to the nontoxic HD-sulfoxide. The nerve agents were perhydrolyzed to the respective nontoxic methylphosphonic acids. The relative rapidity of the oxidation and perhydrolysis under these conditions is attributed to the microenvironment of the micropores. Apparently, the reactions are favored due to basic sites on the carbon surface. Our findings suggest a potential environmentally friendly route for decontamination of adsorbed CWAs, using H2O2 without the need of cosolvents or activators.

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“…While these methods are highly effective at sequestering toxins, they present a challenge for final disposal of protective gear. Under normal environmental conditions, CWAs adsorbed to activated carbon surfaces have demonstrated persistence for weeks following initial exposure and consequently require additional detoxifying treatments to prevent the media from becoming secondary emitters . Furthermore, a decontamination approach based on adsorption alone exhibits finite capacity that is dependent on the available adsorption sites in the material.…”

Section: Introductionmentioning

confidence: 99%

“…Under normal environmental conditions, CWAs adsorbed to activated carbon surfaces have demonstrated persistence for weeks following initial exposure and consequently require additional detoxifying treatments to prevent the media from becoming secondary emitters. [4,[6][7][8] Furthermore, a decontamination approach based on adsorption alone exhibits finite capacity that is dependent on the available adsorption sites in the material. Therefore, materials that reduce CWA toxicity via sequestration and reactivity would be highly valuable for next generation force-protection.…”

mentioning

confidence: 99%

Air Activated Self‐Decontaminating Polydicyclopentadiene PolyHIPE Foams for Rapid Decontamination of Chemical Warfare Agents

McGann

Daniels

Giles

et al. 2018

Macromol. Rapid Commun.

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The threat of chemical warfare agents (CWA) compels research into novel self-decontaminating materials (SDM) for the continued safety of first-responders, civilians, and active service personnel. The capacity to actively detoxify, as opposed to merely sequester, offending agents under typical environmental conditions defines the added value of SDMs in comparison to traditional adsorptive materials. Porous polymers, synthesized via the high internal phase emulsion (HIPE) templating, provide a facile fabrication method for materials with permeable open cellular structures that may serve in air filtration applications. PolyHIPEs comprising polydicyclopentadiene (polyDCPD) networks form stable hydroperoxide species following activation in air under ambient conditions. The hydroperoxide-containing polyDCPD materials react quickly with CWA simulants, Demeton-S and 2-chloroethyl ethyl sulfide, forming oxidation products as confirmed via gas chromatography mass spectrometry. The simplicity of the detoxification chemistry paired with the porous foam form factor presents an exciting opportunity for the development of self-decontaminating filter media.

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Hydrothermal degradation of adsorbed sulfur mustard on activated carbon

Cited by 13 publications

References 11 publications

Theoretical Study of the Microhydration the Chemical Warfare Agent Sulfur Mustard

Theoretical Study of the Microhydration the Chemical Warfare Agent Sulfur Mustard

Decontamination of Adsorbed Chemical Warfare Agents on Activated Carbon Using Hydrogen Peroxide Solutions

Air Activated Self‐Decontaminating Polydicyclopentadiene PolyHIPE Foams for Rapid Decontamination of Chemical Warfare Agents

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