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Craig L. Hill, Email: chill@emory.edu

D.C.W. along with K.P.S. and C.L.H. wrote the manuscript with contributions from all authors. D.C.W. along with K.P.S. and V.G.S. designed and carried out the majority of simulant experiments. Y.V.G. was responsible for a number of the stopped-flow studies. W.O.G. and A.B. conducted the live agent HD studies. Y.T. and A.I.F. performed the XAFS experiments. R.M.S. carried out a number of simulant experiments. C.L.H., Y.V.G., A.I.F., A.L.K., D.G.M., C.J.K. and W.O.G. provided critical guidance throughout the project. C.L.H. supervised the research.

We thank DTRA (grant number W911NF-15-2-0107 through ARO) and CCDC through ARO grant number W911NF-18-2-0089 for support of this work. We also gratefully acknowledge DTRA program CB3587. This research used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory (BNL) under Contract No. DE-SC0012704. We thank Dr. Lu Ma for collecting Cu K-edge data at the QAS beamline.

The work with CEES at BNL Chemistry Division was made possible due to the Program Development fund to A.I.F. The Bruker 600 MHz NMR used for this work was funded by NSF grant no. CHE1531620. Finally, we thank John Mahle for his assistance with the HD GC-MS experiments.

The authors declare no competing interests.



  • Science & Technology
  • Physical Sciences
  • Chemistry, Multidisciplinary
  • Chemistry

A solvent-free solid catalyst for the selective and color-indicating ambient-air removal of sulfur mustard

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Journal Title:



Volume 4, Number 1


, Pages 33-33

Type of Work:

Article | Final Publisher PDF


Bis(2-chloroethyl) sulfide or sulfur mustard (HD) is one of the highest-tonnage chemical warfare agents and one that is highly persistent in the environment. For decontamination, selective oxidation of HD to the substantially less toxic sulfoxide is crucial. We report here a solvent-free, solid, robust catalyst comprising hydrophobic salts of tribromide and nitrate, copper(II) nitrate hydrate, and a solid acid (NafionTM) for selective sulfoxidation using only ambient air at room temperature. This system rapidly removes HD as a neat liquid or a vapor. The mechanisms of these aerobic decontamination reactions are complex, and studies confirm reversible formation of a key intermediate, the bromosulfonium ion, and the role of Cu(II). The latter increases the rate four-fold by increasing the equilibrium concentration of bromosulfonium during turnover. Cu(II) also provides a colorimetric detection capability. Without HD, the solid is green, and with HD, it is brown. Bromine K-edge XANES and EXAFS studies confirm regeneration of tribromide under catalytic conditions. Diffuse reflectance infrared Fourier transform spectroscopy shows absorption of HD vapor and selective conversion to the desired sulfoxide, HDO, at the gas–solid interface.

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© The Author(s) 2021

This is an Open Access work distributed under the terms of the Creative Commons Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0/).
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