Decomposition Of Nerve Agents Research Articles

Multimodal Characterization of Materials and Decontamination Processes for Chemical Warfare Protection.

This Review summarizes the recent progress made in the field of chemical threat reduction by utilizing new in situ analytical techniques and combinations thereof to study multifunctional materials designed for capture and decomposition of nerve gases and their simulants. The emphasis is on the use of in situ experiments that simulate realistic operating conditions (solid-gas interface, ambient pressures and temperatures, time-resolved measurements) and advanced synchrotron methods, such as in situ X-ray absorption and scattering methods, a combination thereof with other complementary measurements (e.g., XPS, Raman, DRIFTS, NMR), and theoretical modeling. The examples presented in this Review range from studies of the adsorption and decomposition of nerve agents and their simulants on Zr-based metal organic frameworks to Nb and Zr-based polyoxometalates and metal (hydro)oxide materials. The approaches employed in these studies ultimately demonstrate how advanced synchrotron-based in situ X-ray absorption spectroscopy and diffraction can be exploited to develop an atomic- level understanding of interfacial binding and reaction of chemical warfare agents, which impacts the development of novel filtration media and other protective materials.

Impact of ambient gases on the mechanism of [Cs8Nb6O19]-promoted nerve-agent decomposition.

The impact of ambient gas molecules (X), NO2, CO2 and SO2 on the structure, stability and decontamination activity of Cs8Nb6O19 polyoxometalate was studied computationally and experimentally. It was found that Cs8Nb6O19 absorbs these molecules more strongly than it adsorbs water and Sarin (GB) and that these interactions hinder nerve agent decontamination. The impacts of diamagnetic CO2 and SO2 molecules on polyoxoniobate Cs8Nb6O19 were fundamentally different from that of NO2 radical. At ambient temperatures, weak coordination of the first NO2 radical to Cs8Nb6O19 conferred partial radical character on the polyoxoniobate and promoted stronger coordination of the second NO2 adsorbent to form a stable diamagnetic Cs8Nb6O19/(NO2)2 species. Moreover, at low temperatures, NO2 radicals formed stable dinitrogen tetraoxide (N2O4) that weakly interacted with Cs8Nb6O19. It was found that both in the absence and presence of ambient gas molecules, GB decontamination by the Cs8Nb6O19 species proceeds via general base hydrolysis involving: (a) the adsorption of water and the nerve agent on Cs8Nb6O19/(X), (b) concerted hydrolysis of a water molecule on a basic oxygen atom of the polyoxoniobate and nucleophilic addition of the nascent OH group to the phosphorus center of Sarin, and (c) rapid reorganization of the formed pentacoordinated-phosphorus intermediate, followed by dissociation of either HF or isopropanol and formation of POM-bound isopropyl methyl phosphonic acid (i-MPA) or methyl phosphonofluoridic acid (MPFA), respectively. The presence of the ambient gas molecules increases the energy of the intermediate stationary points relative to the asymptote of the reactants and slightly increases the hydrolysis barrier. These changes closely correlate with the Cs8Nb6O19-X complexation energy. The most energetically stable intermediates of the GB hydrolysis and decontamination reaction were found to be Cs8Nb6O19/X-MPFA-(i-POH) and Cs8Nb6O19/X-(i-MPA)-HF both in the absence and presence of ambient gas molecules. The high stability of these intermediates is due to, in part, the strong hydrogen bonding between the adsorbates and the protonated [Cs8Nb6O19/X/H]+-core. Desorption of HF or/and (i-POH) and regeneration of the catalyst required deprotonation of the [Cs8Nb6O19/X/H]+-core and protonation of the phosphonic acids i-MPA and MPFA. This catalyst regeneration is shown to be a highly endothermic process, which is the rate-limiting step of the GB hydrolysis and decontamination reaction both in the absence and presence of ambient gas molecules.

Recent Advancements On Warfare Agents/metal Oxides Surface Chemistry And Their Simulation Study

Chemical warfare agents (CWA) have been used in the World Wars and in terrorist attacks, and hence there is an urgent need to find means of their decontamination. Metal oxides offer a rapid means of their disposal, since they contain reactive Lewis acid and basic sites, on which adsorption of the CWA, and subsequent hydrolysis, can take place. Destructive adsorption of CWA on metal oxides yields non-toxic products. Nanoscale metal oxides display enhanced reactive properties toward warfare agents due to their high surface area, large number of highly reactive edges, corner defect sites, unusual lattice planes and high surface to volume ratio. Both experimental and theoretical studies have established that decomposition of nerve agents is facilitated on nanoscale Al2O3, MgO, CaO, TiO2, ZnO and small edge and corner clay mineral fragments. Compared to sulfur mustard, nerve agents are more potent. We first briefly describe their mode of action. Many experimental and theoretical studies have been performed to study their decomposition on various metal oxide surfaces, such as MgO, CaO, Al2O3, TiO2, V2O5, and clay minerals. The results of these studies are reviewed here. Photochemical degradation on TiO2 nanosurfaces has also yielded promising results. Because of the toxicity and risk involved, experimental studies have been mostly confined to the benign simulants, whereas theoretical studies have attempted to compare the real agents with their mimics. These studies establish a qualitative correlation between the G-agents and their simulant DMMP, and, hence, decomposition on metal oxide surfaces can be analyzed by observing the surface chemistry of DMMP on a wide variety of metal oxide surfaces. This review attempts to compile the literature concerning CWA and their simulants. Copyright © 2013 VBRI press.