TY - JOUR
T1 - Photocatalytic hydrogen evolution from aqueous solutions of organophosphorous compounds
AU - Kozlova, Ekaterina A.
AU - Vorontsov, Alexander V.
N1 - Funding Information:
We gratefully acknowledge the support of SB RAS integration grants # 36 and 70 as well as RAS presidium grant # 27.56 and Lavrentiev grant for young scientists .
PY - 2010/7
Y1 - 2010/7
N2 - Photocatalytic hydrogen production from water solutions of dimethyl methylphosphonate (DMMP), trimethyl phosphate (TMP), triethyl phosphate (TEP), and radiation protective amine WR 2721, that imitate nerve chemical warfare agents was studied for the first time. Platinized titianium dioxide Degussa P25 was used as catalyst. No significant hydrogen evolution was detected without organic electron donors - sacrificial agents. The hydrogen evolution rate was shown to grow slowly with the rise of initial DMMP concentration. The initial rate vs. DMMP concentration curve is well fitted by Langmuir-Hinshelwood (L-H) equation. The DMMP adsorption constant obtained from the L-H equation fit is markedly higher than that obtained from the Langmuir adsorption isotherm. Reactions of full destruction into inorganic products of the four organophosphorous compounds were conducted. Amounts of evolved hydrogen and carbon dioxide were completely consistent with stoichiometry of proposed reaction. There were no initial compounds and only trace of total organic carbon after the end of the reaction. Complete water purification and production of an amount of valuable hydrogen was achieved. Intermediates of DMMP oxygen-free destruction were identified by means of GC/MS. They were the same as those in the case of DMMP photocatalytic oxidation. A mechanism of hydrogen evolution that explains smaller rates of mineralization compared to photocatalytic oxidation by oxygen was proposed.
AB - Photocatalytic hydrogen production from water solutions of dimethyl methylphosphonate (DMMP), trimethyl phosphate (TMP), triethyl phosphate (TEP), and radiation protective amine WR 2721, that imitate nerve chemical warfare agents was studied for the first time. Platinized titianium dioxide Degussa P25 was used as catalyst. No significant hydrogen evolution was detected without organic electron donors - sacrificial agents. The hydrogen evolution rate was shown to grow slowly with the rise of initial DMMP concentration. The initial rate vs. DMMP concentration curve is well fitted by Langmuir-Hinshelwood (L-H) equation. The DMMP adsorption constant obtained from the L-H equation fit is markedly higher than that obtained from the Langmuir adsorption isotherm. Reactions of full destruction into inorganic products of the four organophosphorous compounds were conducted. Amounts of evolved hydrogen and carbon dioxide were completely consistent with stoichiometry of proposed reaction. There were no initial compounds and only trace of total organic carbon after the end of the reaction. Complete water purification and production of an amount of valuable hydrogen was achieved. Intermediates of DMMP oxygen-free destruction were identified by means of GC/MS. They were the same as those in the case of DMMP photocatalytic oxidation. A mechanism of hydrogen evolution that explains smaller rates of mineralization compared to photocatalytic oxidation by oxygen was proposed.
KW - Hydrogen production
KW - Nerve gases simulants destruction
KW - Organophosphorous compounds
KW - Photocatalysis
UR - http://www.scopus.com/inward/record.url?scp=77953917168&partnerID=8YFLogxK
U2 - 10.1016/j.ijhydene.2010.04.122
DO - 10.1016/j.ijhydene.2010.04.122
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AN - SCOPUS:77953917168
SN - 0360-3199
VL - 35
SP - 7337
EP - 7343
JO - International Journal of Hydrogen Energy
JF - International Journal of Hydrogen Energy
IS - 14
ER -