Routes of photocatalytic destruction of chemical warfare agent simulants

Selected imitants of chemical warfare agents such as dimethyl methylphosphonate (DMMP), diethyl phosphoramidate (DEPA), pinacolyl methylphosphonate (PMP), butylaminoethanethiol (BAET) were subjected to photocatalytic and sonophotocatalytic treatment in aqueous suspensions of TiO₂. Complete conversion of the same mass of imitants to inorganic products was obtained within 600 min for DMMP, DEPA, PMP, but required a longer time for BAET. Sonolysis accelerated photodegradation of DMMP. No degradation was observed without ultraviolet illumination. Final products of degradation were PO₄^3-, CO₂ for DMMP and PMP, PO₄^3-, NO₃^- (25%), NH₄⁺ (75%), CO₂ for DEPA, and SO₄^2-, NH₄⁺, CO₂ for BAET. The number of main detected intermediate products increases in the order DMMP (7), DEPA (9), PMP (21), and exceeds 34 for BAET. Degradation of DMMP mainly proceeds through consecutive oxidation of methoxy groups and then the methyl group. Dimethyl hydroxymethylphosphonate and dimethylphosphate testify to the parallel oxidation of the methyl group. Destruction of DEPA mainly starts with cleavage of the P-NH₂ bond to form diethyl phosphate, which transforms further into ethyl phosphate. Oxidation of α and β carbons of ethoxy groups to form ethylphosphonoamidate, hydroxyethyl ethylphosphonoamidate and other products also contributes to the destruction. Photocatalytic degradation of PMP mainly starts with oxidation of the pinacolyl fragment, methylphosphonic acid and acetone being the major products. Oxidation of BAET begins with dark dimerization to disulfide, which undergoes oxidation of sulfur forming sulfinic and sulfonic acids as well as oxidation of carbons to form butanal, aminobutane, etc., and cyclic products such as 2-propylthiazole. A scheme of degradation was proposed for DMMP and DEPA, and starting routes for PMP and BAET. Quantum efficiencies of complete mineralization calculated as reaction rate to photon flux ratio approximate 10^-3%.