Effective degradation of sulfur mustard simulant using novel sulfur-doped mesoporous zinc oxide under ambient conditions

Abstract

Sulfur doped metal oxides were synthesized using a two-step precipitation method. When reacted against neat 2-CEES (2-chloroethyl-ethyl sulfide, a mustard gas simulant) under ambient conditions, sulfur doped mesoporous zinc oxide (MS-Zn) showed higher catalytic activity than the other metal oxides with 92.7% overall conversion in 24 h for a 2.5 μL neat 2-CEES droplet added on top of 2 × 2 cm large 400 mg catalyst layer. The reaction proceeded mainly by hydrolysis and further solvolysis reaction also occurred depending on the extracting solvents. Cyclic sulfonium ion intermediate reaction was thought to be involved in this reaction, and metal oxide surfaces were thought to facilitate the formation of sulfonium ions from adsorbed 2-CEES. All other by-products were also found to form via sulfonium ions, reconfirming the well-known importance of this intermediate species for the degradation reaction to proceed. The sulfur content for MS-Zn was varied and tested for degradation of neat 2-CEES. This modification showed that there is an optimal amount of sulfur content for the peak catalytic activity of MS-Zn for 2-CEES degradation. Adsorption energy of a 2-CEES molecule was calculated on model sulfur doped and non doped zinc oxide surfaces and the different adsorption energy levels were correlated with the catalytic activity of sulfur doped zinc oxide.

Keywords: 2-CEES; Adsorption energy; Hydrolysis, solvolysis; Sulfur mustard; Sulfur-doped metal oxide.