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

Journal Article · · Communications Chemistry
 [1];  [1];  [1];  [1];  [2];  [2];  [3];  [1];  [4];  [2];  [3];  [5];  [1]
  1. Emory Univ., Atlanta, GA (United States)
  2. US Army Combat Capabilities Development Command Chemical Biological Center, Aberdeen, MD (United States)
  3. Stony Brook Univ., NY (United States)
  4. Emory Univ., Atlanta, GA (United States). Cherry L. Emerson Center for Scientific Computation
  5. Emory Univ., Atlanta, GA (United States); Emory Univ., Atlanta, GA (United States). Cherry L. Emerson Center for Scientific Computation
+ Show Author Affiliations
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.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
National Science Foundation (NSF); US Army Research Office (ARO); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1773117
Alternate ID(s):
OSTI ID: 1783744
Report Number(s):
BNL-221221-2021--JAAM
Journal Information:
Communications Chemistry, Journal Name: Communications Chemistry Journal Issue: 1 Vol. 4; ISSN 2399-3669
Publisher:
Springer NatureCopyright Statement
Country of Publication:
United States
Language:
English

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