TY - JOUR
T1 - Pathways of photocatalytic gas phase destruction of HD simulant 2-chloroethyl ethyl sulfide
AU - Vorontsov, Alexandre V.
AU - Lion, Claude
AU - Savinov, Evgueni N.
AU - Smirniotis, Panagiotis G.
N1 - Funding Information:
We gratefully acknowledge the support of the US Department of Army Young Investigator Program under Grant DAAD 19-00-1-0399, and NATO Science for Peace Programme Grant SfP 974209. We also acknowledge funding from the Ohio Board of Regents (OBR) that provided matching funds for equipment to the NSF CTS-9619392 grant through the OBR Action Fund No. 333. A.V.V. is grateful to INTAS for support via fellowship YSF 2002-55.
PY - 2003/12/10
Y1 - 2003/12/10
N2 - Photocatalytic oxidation of HD simulant, 2-chloroethyl ethyl sulfide (CEES), was studied in a specially designed coil and flow photocatalytic reactor by means of GC-MS and FTIR techniques. TiO2 Hombikat UV 100 photocatalyst was deactivated after a few hours of operation, which was signaled by the appearance of incomplete oxidation products in the reactor effluent and accumulation of incomplete oxidation products on the TiO 2 surface. Complete reactivation of the photocatalyst was achieved by washing the photocatalyst with water. Compared to diethyl sulfide, CEES showed lower reactivity in photocatalytic oxidation and was accumulated on the TiO2 surface after catalyst deactivation. Without UV irradiation, hydrolysis of CEES proceeded on the TiO2 surface. Major gaseous products of CEES incomplete photocatalytic oxidation are acetaldehyde, chloroacetaldehyde, SO2, diethyl disulfide, and chloroethylene. Surface products extracted from the TiO2 surface with acetonitrile and water include mainly 2-chloroethyl ethyl sulfoxide and ethanesulfinic and ethanesulfonic acids, as well as diethyl di-, tri-, and tetrasulfides mono and disubstituted in the β position with a chlorine or hydroxyl group. While surface monodentate sulfates can be removed upon washing, surface bidentate species stayed on the surface and possibly contribute to the permanent catalyst deactivation.
AB - Photocatalytic oxidation of HD simulant, 2-chloroethyl ethyl sulfide (CEES), was studied in a specially designed coil and flow photocatalytic reactor by means of GC-MS and FTIR techniques. TiO2 Hombikat UV 100 photocatalyst was deactivated after a few hours of operation, which was signaled by the appearance of incomplete oxidation products in the reactor effluent and accumulation of incomplete oxidation products on the TiO 2 surface. Complete reactivation of the photocatalyst was achieved by washing the photocatalyst with water. Compared to diethyl sulfide, CEES showed lower reactivity in photocatalytic oxidation and was accumulated on the TiO2 surface after catalyst deactivation. Without UV irradiation, hydrolysis of CEES proceeded on the TiO2 surface. Major gaseous products of CEES incomplete photocatalytic oxidation are acetaldehyde, chloroacetaldehyde, SO2, diethyl disulfide, and chloroethylene. Surface products extracted from the TiO2 surface with acetonitrile and water include mainly 2-chloroethyl ethyl sulfoxide and ethanesulfinic and ethanesulfonic acids, as well as diethyl di-, tri-, and tetrasulfides mono and disubstituted in the β position with a chlorine or hydroxyl group. While surface monodentate sulfates can be removed upon washing, surface bidentate species stayed on the surface and possibly contribute to the permanent catalyst deactivation.
KW - Catalyst deactivation
KW - Chemical warfare agents
KW - Coil reactor
KW - Mechanism
KW - Photocatalysis
KW - Products
KW - Reactivation
UR - http://www.scopus.com/inward/record.url?scp=0242558340&partnerID=8YFLogxK
U2 - 10.1016/S0021-9517(03)00293-8
DO - 10.1016/S0021-9517(03)00293-8
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AN - SCOPUS:0242558340
SN - 0021-9517
VL - 220
SP - 414
EP - 423
JO - Journal of Catalysis
JF - Journal of Catalysis
IS - 2
ER -