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Nerve Agent Degradation Using Polyoxoniobates Public Deposited

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https://ir.library.oregonstate.edu/concern/articles/k35696173

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  • Polyoxoniobates are exceptional amongst polyoxometalates in that they can potentially perform base catalysis in water, a process in which a proton is bonded to an oxo ligand, and a hydroxyl is released. Catalytic decomposition of chemical warfare agents such as organofluorophosphates that were used recently in the infamous civilian attacks in Syria is one opportunity to employ this process. Upon evaluation of the polyoxoniobate Lindqvist ion, [Nb₆O₁₉]⁸⁻ fast neutralization kinetics was discovered for the breakdown of the nerve agent simulant diisopropyl fluorophosphate (DFP). Further testing of the polyoxoniobates against nerve agents Sarin (GB), and Soman (GD) was also performed. It was determined that different Lindqvist countercations (Li, K, or Cs) affect the rate of decomposition of the organophosphate compounds in both aqueous media (homogeneous reaction), and in the solid-state (heterogeneous reaction). Small-angle X-ray scattering of solutions of the Li, K, and Cs [Nb₆O₁₉]⁸⁻ salts at concentrations which the experiments were performed revealed distinct differences that could be linked to their relative reaction rates. This study represents the first demonstration of exploiting the unique alkaline reactivity of polyoxoniobates for nerve agent decontamination.
  • This is an author's peer-reviewed final manuscript, as accepted by the publisher. The published article is copyrighted by Wiley-VCH and can be found at: http://onlinelibrary.wiley.com/doi/10.1002/ejic.201400016/full.
  • Keywords: Nerve agents, Small-angle X-ray scattering, Kinetics, Polyoxometalates, Ion pairs
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  • Kinnan, M. K., Creasy, W. R., Fullmer, L. B., Schreuder-Gibson, H. L. and Nyman, M. (2014), Nerve Agent Degradation with Polyoxoniobates. European Journal of Inorganic Chemistry, 2014: 2361–2367. doi: 10.1002/ejic.201400016
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  • 2014
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  • MK acknowledges Sandia National Laboratories internal funding for support. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under Contract DE-AC04- 94AL85000. Additional funding was provided by the Defense Threat Reduction Agency for live agent testing at ECBC by Science Applications International Corporation (SAIC) under contracts DAAD13-03-D-0017 and W911SR-11-C-0047.
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