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

Jing Dong; Jufang Hu; Yingnan Chi; Zhengguo Lin; Bo Zou; Song Yang; Craig L. Hill; Changwen Hu

doi:10.1002/anie.201700159

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

Jing Dong, Jufang Hu, Yingnan Chi^*, Zhengguo Lin, Bo Zou, Song Yang, Craig L. Hill, Changwen Hu

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

Research output: Contribution to journal › Article › peer-review

199 Citations (Scopus)

Abstract

A novel double-anion complex, H₁₃[(CH₃)₄N]₁₂[PNb₁₂O₄₀(V^VO)₂⋅(V^IV₄O₁₂)₂]⋅22 H₂O (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 2-chloroethyl ethyl sulfoxide and vinyl ethyl sulfoxide using nearly stoichiometric 3 % aqueous H₂O₂ with a turnover frequency (TOF) of 16 000 h⁻¹. 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.

Original language	English
Pages (from-to)	4473-4477
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	16
DOIs	https://doi.org/10.1002/anie.201700159
Publication status	Published - 10 Apr 2017

Keywords

chemical warfare agents
decontamination
double anions
niobium
polyoxometalates

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title = "A Polyoxoniobate–Polyoxovanadate Double-Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants",

abstract = "A novel double-anion complex, H13[(CH3)4N]12[PNb12O40(VVO)2⋅(VIV4O12)2]⋅22 H2O (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 2-chloroethyl ethyl sulfoxide and vinyl ethyl sulfoxide using nearly stoichiometric 3 % aqueous H2O2 with a turnover frequency (TOF) of 16 000 h−1. 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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author = "Jing Dong and Jufang Hu and Yingnan Chi and Zhengguo Lin and Bo Zou and Song Yang and Hill, {Craig L.} and Changwen Hu",

note = "Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2017",

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AU - Chi, Yingnan

AU - Lin, Zhengguo

AU - Zou, Bo

AU - Yang, Song

AU - Hill, Craig L.

AU - Hu, Changwen

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N2 - A novel double-anion complex, H13[(CH3)4N]12[PNb12O40(VVO)2⋅(VIV4O12)2]⋅22 H2O (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 2-chloroethyl ethyl sulfoxide and vinyl ethyl sulfoxide using nearly stoichiometric 3 % aqueous H2O2 with a turnover frequency (TOF) of 16 000 h−1. 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.

AB - A novel double-anion complex, H13[(CH3)4N]12[PNb12O40(VVO)2⋅(VIV4O12)2]⋅22 H2O (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 2-chloroethyl ethyl sulfoxide and vinyl ethyl sulfoxide using nearly stoichiometric 3 % aqueous H2O2 with a turnover frequency (TOF) of 16 000 h−1. 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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KW - polyoxometalates

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

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