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

The impact of ambient gas molecules (X), NO, CO and SO on the structure, stability and decontamination activity of CsNbO polyoxometalate was studied computationally and experimentally. It was found that CsNbO absorbs these molecules more strongly than it adsorbs water and Sarin (GB) and that these interactions hinder nerve agent decontamination. The impacts of diamagnetic CO and SO molecules on polyoxoniobate CsNbO were fundamentally different from that of NO radical. At ambient temperatures, weak coordination of the first NO radical to CsNbO conferred partial radical character on the polyoxoniobate and promoted stronger coordination of the second NO adsorbent to form a stable diamagnetic CsNbO/(NO) species. Moreover, at low temperatures, NO radicals formed stable dinitrogen tetraoxide (NO) that weakly interacted with CsNbO. It was found that both in the absence and presence of ambient gas molecules, GB decontamination by the CsNbO species proceeds general base hydrolysis involving: (a) the adsorption of water and the nerve agent on CsNbO/(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 CsNbO-X complexation energy. The most energetically stable intermediates of the GB hydrolysis and decontamination reaction were found to be CsNbO/X-MPFA-(i-POH) and CsNbO/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 [CsNbO/X/H]-core. Desorption of HF or/and (i-POH) and regeneration of the catalyst required deprotonation of the [CsNbO/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.