Selective Oxidation of 2-Chloroethyl Ethyl Sulfide in Aqueous Media Catalyzed by {Mo<sub>72</sub>M<sub>30</sub>} Nano-polyoxometalate Clusters Differentiating the Catalytic Activity of Nodal Metals
Jianbo Yin, Chengcheng Huang, Yunshan Zhou, Lijuan Zhang, Nan Li, Ran Sun
Abstract
Using green and economical H2O as a solvent and H2O2 as an oxidant, the catalytic degradation of the 2-chloroethyl ethyl sulfide (CEES) simulant for sulfur mustard was studied by using four kinds of isostructural heteronode nano-polyoxometalate clusters {Mo72M30} (M = V, Cr, Fe, and Mo) under different reaction conditions. The experimental results showed that by controlling the molar ratio of H2O2 and CEES, CEES was converted into the corresponding nontoxic 2-chloroethyl ethyl sulfoxide by selective oxidation. All other degradation conditions being equal, the catalytic degradation processes of CEES all conformed to first-order reaction kinetics, and the kinetic constant of the reactions was 0.56, 0.53, 0.47, and 0.44 min–1, respectively. That is, the activities of the four catalysts {Mo72M30} (M = V, Cr, Fe, and Mo) for the degradation of CEES were in the order of V > Cr > Fe > Mo. After 5 min of the reaction, the degradation rates of {Mo72M30} (M = V, Cr, Fe, and Mo) were 97.01, 90.56, 90.26, and 90.56%, respectively. After five cycles, their conversion rates were found to be slightly decreased, being 93.41, 90.50, 90.13, and 89.70%, respectively, and the selectivity of the four catalysts remained above 99%.