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

Abstract

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.