Polyniobate Nanothreads for Decomposition of the Nerve Agent Simulant Dimethyl Chlorophosphate

Abstract

The nanoscale one-dimensional polymeric polyniobate K12[Ti2O2]­[SiNb12O40]·22H2O (KSiNb) rapidly hydrolyzes the gaseous organophosphorus nerve agent simulant dimethyl chlorophosphate (DMCP). A multimodal approach combining X-ray, IR and Raman spectroscopies and computation reveals that this reaction, involving the initial nucleophilic attack of polyoxometalate (POM) oxygen at phosphorus, is greatly modulated by the polyniobate counterions: the most negative and nucleophilic oxygen atoms in KSiNb, the Ti–O–Ti and Ti–O–Nb oxygen atoms, preferentially bind the potassium counterions, compelling the less negative oxygen atoms to become the nucleophiles. This heretofore unnoted paradigm of the POM counterion location and function could well impact a myriad of POM reaction studies.

All-Weather Dry Decontaminant Polymer-H2O2 Complex for HD Degradation

“…9 Pure and high concentrations of H 2 O 2 , however, are unstable and can readily oxidize organic material or decompose in the presence of light. 11,12 Several strategies have been developed and show great promise to circumvent the need for liquid-based decontaminants, notably metal oxides, 2,13,14 metal-organic frameworks, 15,16 polyoxometalates, 17 and reactive polymers. 18,19 However, it would be advantageous to be able to deliver H 2 O 2 in a nonliquid form that retains its efficacy to decontaminate CWA.…”

“…Earlier work has demonstrated the benefits of using aqueous forms of H 2 O 2 for the decontamination of HD that circumvent more conventional yet corrosive methods such as bleach . Pure and high concentrations of H 2 O 2 , however, are unstable and can readily oxidize organic material or decompose in the presence of light. , Several strategies have been developed and show great promise to circumvent the need for liquid-based decontaminants, notably metal oxides, ,, metal-organic frameworks, , polyoxometalates, and reactive polymers. , However, it would be advantageous to be able to deliver H 2 O 2 in a nonliquid form that retains its efficacy to decontaminate CWA. Stable solid complexes of H 2 O 2 , such as urea-H 2 O 2 , can overcome this limitation, but the complex itself can become unstable at temperatures higher than 40 °C, thus limiting its shelf life …”

Immobilization of Brønsted basic hexaniobate on the Lewis acidic zirconia using an emulsion assisted self-assembly strategy for synergistic boosting of nerve agent simulant decontamination

“…[32][33][34][35][36] In addition, PONbs have basic surface oxygen atoms, [37][38][39] which can accelerate the hydrolysis of nerve agents. 40,41 Nyman et al initially demonstrated the hydrolysis of Sarin and Soman using homogeneous Lindqvist [Nb 6 O 19 ] 8− . 42 Then, Hill and Zheng reported that Keggin-type PONb, K 12 [Ti 2 O 2 ][XNb 12 O 40 ] (X = Ge or Si), and copper-containing PONb, H 2 Li 5 Na 5 K 5 [Cu(en) 2 ] 7 [Nb 47 O 128 (OH) 6 (CO 3 ) 2 ]•20H 2 O (en = ethylenediamine), as solid bases can catalyze the hydrolysis of nerve agent simulants, but their sluggish hydrolysis kinetics leaves much room for improvement.…”

Decaniobate: The Fruit Fly of Niobium Polyoxometalate Chemistry

“…Starting in 2002, Nb-POM chemistry has mostly relied on the blind and uninformed process of hydrothermal synthesis for compositional and topological diversification. Yet applications in nerve agent degradation, H 2 evolution, and other catalytic reactions arose from the increased diversification of Nb-POM chemistry. − Reviewed here, the manipulations of Nb 10 to diversify the form and function of Nb-POMs are conducive to studying reaction pathways and embody the principles of sustainable chemistry. All experiments are performed in water at mild pH with minimal electrolytes and at room temperature.…”