A Polyoxoniobate–Polyoxovanadate Double‐Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants

Solid electrolytes are crucial materials for lithium-ion or fuel-cell battery technology due to their structural stability and easiness for handling. Emergence of high conductivity in solid electrolytes requires precise control of the composition and structure. A promising strategy toward highly-conductive solid electrolytes is employing a thermally-stable inorganic component and a structurally-flexible organic moiety to construct inorganic-organic hybrid materials. Ionic liquids as the organic component will be advantageous for the emergence of high conductivity, and polyoxometalate, such as heteropolyacids, are well-known as inorganic proton conductors. Here, newly-designed ionic liquid imidazolium cations, having a polymerizable methacryl group (denoted as MAImC 1 ), were successfully hybridized with heteropolyanions of [PW 12 O 40 ] 3− (PW 12 ) to form inorganic-organic hybrid monomers of MAImC 1 -PW 12 . The synthetic procedure of MAImC 1 -PW 12 was a simple ion-exchange reaction, being generally applicable to several polyoxometalates, in principle. MAImC 1 -PW 12 was obtained as single crystals, and its molecular and crystal structures were clearly revealed. Additionally, the hybrid monomer of MAImC 1 -PW 12 was polymerized by a radical polymerization using AIBN as an initiator. Some of the resulting inorganic-organic hybrid polymers exhibited conductivity of 10 −4 S·cm −1 order under humidified conditions at 313 K.

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“…The PW 12 anion lay on the inversion center, and exhibited a common type of disorder for the Keggin anion noted previously [47,48]. …”

Section: Synthesis and Structure Of Maimc1-pw12 Hybrid Monomermentioning

confidence: 58%

Polymerizable Ionic Liquid Crystals Comprising Polyoxometalate Clusters toward Inorganic-Organic Hybrid Solid Electrolytes

et al. 2017

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“…Vanadium oxide enjoys high coefficient of thermal resistance and has been applied to vanadium redox batteries and various catalysts . Vanadium‐containing polyoxometalates have been used in dye‐sensitized solar cells via as cosensitizers and as precursors for solar conversion photoanode synthesis such as BiVO 4 .…”

Section: Polyoxovanadatementioning

confidence: 99%

Polyoxometalates: Tailoring metal oxides in molecular dimension toward energy applications

Zhang

Chen

2020

Int J Energy Res

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Summary Polyoxometalates could be viewed as the molecular counterpart of the metal oxides, which are essential ingredients for various energy conversion and storage applications. In this manuscript, we review the progress of engineering functional polyoxometalates toward energy applications, focusing on, but not limited to, polyoxotitanate, polyoxotungstate, and polyoxomolybdate. These polyoxometalates are considered to be promising candidates for dye‐sensitized solar cell, perovskite solar cell, lithium‐ion battery, lithium‐sulfur battery, supercapacitor, and water‐splitting system. We believe advanced energy devices with better performance could be derived from further engineering the polyoxometalates owing to their molecular design flexibility.

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“…Nb cyan, V pink, O red, C gray, N blue, P green. [23] Figure 2. a) Hydrolytic decontamination of DECP to DEHP. b) Time profile for the hydrolytic decontamination of DECP using 1.…”

Section: Rapidtransformationofchemicalwarfareagents(cwas)tomentioning

confidence: 99%

A Polyoxoniobate–Polyoxovanadate Double‐Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants

Dong

Chi

et al. 2017

Angewandte Chemie

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A novel double-anion complex, H 13 [(CH 3 ) 4 N] 12 -[PNb 12 O 40 (V V O) 2 ·(V IV 4 O 12 ) 2 ]·22 H 2 O (1), based on bicapped polyoxoniobate and tetranuclear polyoxovanadate was synthesized, characterized by routine techniques and used in the catalytic decontamination of chemical warfare agents. Under mild conditions, 1 catalyzes both hydrolysis of the nerve agent simulant, diethyl cyanophosphonate (DECP) and selective oxidation of the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). In the oxidative decontamination system 100 % CEES was transformed selectively to nontoxic 2chloroethyl ethyl sulfoxide and vinyl ethyl sulfoxide using nearly stoichiometric 3 % aqueous H 2 O 2 with a turnover frequency (TOF) of 16 000 h À1 . Importantly, the catalytic activity is maintained even after ten recycles and CEES is completely decontaminated in 3 mins without formation of the highly toxic sulfone by-product. A three-step oxidative mechanism is proposed.

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A Polyoxoniobate–Polyoxovanadate Double‐Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants

Cited by 194 publications

References 62 publications

Polymerizable Ionic Liquid Crystals Comprising Polyoxometalate Clusters toward Inorganic-Organic Hybrid Solid Electrolytes

Polymerizable Ionic Liquid Crystals Comprising Polyoxometalate Clusters toward Inorganic-Organic Hybrid Solid Electrolytes

Polyoxometalates: Tailoring metal oxides in molecular dimension toward energy applications

A Polyoxoniobate–Polyoxovanadate Double‐Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants

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