In-situ detoxification of schedule-I chemical warfare agents utilizing Zr(OH)4@W-ACF functional material for the development of next generation NBC protective gears

Abstract

Chemical warfare agents (CWAs) have become a pivotal concern for the global community and spurred a wide spectrum of research for the development of new generation protective materials. Herein, a highly effective self-detoxifying filter consisting of in-situ immobilized Zirconium hydroxide [Zr(OH)4] over woven activated carbon fabric [Zr(OH)4@W-ACF] is presented for the removal of CWAs. It was prepared to harness the synergistic effect of high surface area of W-ACF, leads to high dispersion of CWAs and high phosphilicity and reactivity of [Zr(OH)4]. The synthesized materials were characterized by ATR-FTIR, EDX, SEM, TEM, XPS, TGA, and BET surface area analyzer. The kinetics of in-situ degradation of CWAs over Zr(OH)4@W-ACF were studied and found to be following the first-order reaction kinetics. The rate constant was found to be 0.244 min−1 and 2.31 × 10−2 min−1 for sarin and soman, respectively over Zr(OH)4@W-ACF. The potential practical applicability of this work was established by fabricating Zr(OH)4@W-ACF as reactive adsorbent layer for protective suit, and found to be meeting the specified criteria in terms of air permeability, tearing strength and nerve agent permeation as per TOP-08-2-501A:2013 and IS-17380:2020. The degradation products of CWAs were analyzed with NMR and GC–MS. The combined properties of dual functional textile with reactive material are expected to open up new exciting avenues in the field of CWAs protective clothing and thus find diverse application in defence and environmental sector.

Oxime-Functionalized, Nonwoven Nanofabrics for Rapid, Inexpensive Decontamination of a Nerve Agent Simulant

“…Research by Wilson et al explained that the unexpected side product of M4NP is formed via nucleophilic attack of softer amine bases onto electrophilic, methoxy methyl groups rather than central phosphorus atoms. 36 These researchers exhaustively studied the various byproducts formed in these reactions using mass spectrometry and NMR (including 1 H, 13 C, and 31 P NMR), which were used to confirm their formation in the present study. This side product cannot be observed via UV−Vis spectroscopy, emphasizing the significance of 31 P NMR analysis in these studies.…”

“…1 H NMR (400 MHz, DMSO-d 6 ) δ 13.15 (s, 1H), 8.97 (d, J = 6.1 Hz, 1H), 8.78 (s, 1H), 8.51 (t, J = 7.9 Hz, 1H), 8.37 (d, J = 8.1 Hz, 1H), 8.06 (t, J = 7.0 Hz, 1H), 4.72 (t, J = 6.9 Hz, 2H), 3.26 (t, J = 6.3 Hz, 2H), 1.82 (t, J = 6.1 Hz, 3H). 13 Oxime Functionalization via P4VP Pendant Quaternization. The outlined procedure is for the synthesis of P4VP-POx 10% but was applied to all P4VP-Ox material syntheses, except with corresponding stoichiometry targeting either 10 or 20% of pyridine pendant groups.…”

“…Even since their widespread prohibition in the 1920s via the Geneva Protocol, the use of highly toxic organophosphorus-based nerve agents has still been documented in several high-profile assassinations of recent years. − Invented in the 1930s for intended applications as broad-spectrum insecticides, these molecules found other uses as CWAs due to their high toxicities and synthetic accessibility, leading to their implementation as “V-series” and “G-series” nerve agents (Figure ). − A plethora of research has been carried out globally with the common goal of developing and designing reactive and cost-effective materials for the degradation of nerve agent CWAs. , The materials currently being investigated for degradation include, but are not limited to, heterogeneous catalysts, , titanium-based nanomaterials, metal–organic frameworks (MOFs), − enzymes, reactive polymers, , coatings, sensors, , and smart fabrics. − …”

“…1 H NMR (400 MHz, DMSO-d 6 ) δ 12.82 (s, 1H), 8.98 (d, J = 6.3 Hz, 2H), 8.39 (s, 1H), 8.20 (d, J = 6.3 Hz, 2H), 4.56 (t, J = 7.1 Hz, 2H), 3.26 (t, J = 6.8 Hz, 2H), 1.95 (p, J = 7.4 Hz, 2H), 1.75 (q, J = 7.3 Hz, 2H). 13 4-Iodobutyl-ortho-oxime Pyridinium (OOx) (2-((Hydroxyimino)methyl)-1-(4-iodobutyl)pyridin-1-ium) Synthesis. To a 250 mL RBF equipped with a reflux condenser, an addition funnel, and a magnetic stirrer, pyridine-2-aldoxime (5.0 g, 40.94 mmol) was added in 100 mL of MEK.…”

Assessing Detoxification Performance of Metal Hydroxide@Polymer Composites Prepared via Matrix-Incorporation and Spray-Coating Techniques

“…The in situ degradation kinetics followed first-order reaction kinetics with rate constants of 0.244 and 0.0231 min −1 for sarin and soman, respectively. 21 In another study, Dwyer et al 22 compared the catalytic performance of Ce(OH) 4 , Zr(OH) 4 , and Ti(OH) 4 toward detoxification of paraoxon methyl and reported Ce(OH) 4 as an outstanding catalyst with a half-life of 183 min.…”