A Polyoxoniobate-Polyoxovanadate Double-Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants.
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 H2O2with 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.
Department of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, P.R. China.
Jing
J
Dong
Department of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, P.R. China.
Jufang
J
Hu
Department of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, P.R. China.
Yingnan
Y
Chi
Department of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, P.R. China.
Zhengguo
Z
Lin
Department of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, P.R. China.
Bo
B
Zou
Department of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, P.R. China.
Song
S
Yang
Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, GA, 30322, USA.
Craig L
CL
Hill
Department of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, P.R. China.
Changwen
C
Hu
chemical warfare agents; decontamination; double anions; niobium; polyoxometalates