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

TitleA Polyoxoniobate-Polyoxovanadate Double-Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants
Publication TypeJournal Article
Year of Publication2017
AuthorsDong J., Hu J., Chi Y., Lin Z., Zou B., Yang S., Hill C.L, Hu C.
JournalAngew Chem Int Ed Engl
Volume56
Issue16
Pagination4473-4477
Date PublishedApr 10
ISBN Number1433-7851 (Linking)
Accession Number28322483
Keywords*Chemical Warfare Agents, *Decontamination, *double anions, *niobium, *polyoxometalates
Abstract

A novel double-anion complex, H13 [(CH3 )4 N]12 [PNb12 O40 (V(V) O)2 (V(IV)4 O12 )2 ]22 H2 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 2-chloroethyl ethyl sulfoxide and vinyl ethyl sulfoxide using nearly stoichiometric 3 % aqueous H2 O2 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.

URLhttps://www.ncbi.nlm.nih.gov/pubmed/28322483
DOI10.1002/anie.201700159
Short TitleA Polyoxoniobate-Polyoxovanadate Double-Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants

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