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Photocatalytic Destruction of a Thiosulfonate

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This paper presents experimental and quantum chemical consideration of photocatalytic and photochemical transformations in acetonitrile of CH3C6H4S(O2)SCH2CH2N(iPr)2 (diisopropylaminoethyl 4-methylbenzenethiosulfonate, DAMT), an imitant of chemical agent VX with close structural properties and ionization energy. Diisopropylaminoethyl disulfide and 4-methylbenzenesulfonic acid were detected as major products of photocatalytic and photochemical degradation. Photocatalytic degradation stopped at about 60% DAMT conversion due to acidification of the system. Photochemical degradation proceeded slower but to a higher conversion since DAMT protonation did not stop photolysis completely. DAMT· + forms at the first step of photocatalytic degradation, then it splits into CH3C6H4SO 2 · and SCH2CH2N+(iPr)2. The former fragment transforms into sulfonic acid and the latter decomposes into SCH2 and CH2N+(iPr)2 in the absence of TiO2, the route observed in mass spectrometry. However it is stable in adsorbed state on the TiO2 surface and after reduction with photogenerated electron recombines to produce the disulfide product. The results suggest that photocatalytic and photolytic detoxification of VX is possible provided conditions are adjusted for its complete conversion.

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Correspondence to Alexander V. Vorontsov.

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Vorontsov, A.V., Charvy, C. & Lion, C. Photocatalytic Destruction of a Thiosulfonate. Top Catal 35, 245–253 (2005). https://doi.org/10.1007/s11244-005-3831-3

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Keywords

  • photocatalysis
  • TiO2
  • mechanism
  • thiyl
  • sulfonyl
  • surface cation radical