Photocatalytic oxidation of oxalic acid by oxygen and ozone in aqueous solution

封面

如何引用文章

全文:

开放存取 开放存取
受限制的访问 ##reader.subscriptionAccessGranted##
受限制的访问 订阅存取

详细

Experimental study of mineralization of oxalic acid Н2С2О4 and some other oxidation-resistant organic compounds in an aqueous solution under the action of oxygen, ozone, and ultraviolet radiation is performed. It is found that in acidic solutions Н2С2О4 is not oxidized under the action of ozone or UV-irradiation in the presence of oxygen; under simultaneous action of O3 + UV, oxidation with low rate is observed. The possibility of photocatalysis of mineralization process by ions Mn2+, MnO4–, Fe3+, Со2+, BrO3–, or IO3– is studied. Fe3+ ions are the most effective photocatalyst as there is a rather fast oxidation of oxalic acid to CO2 in their presence and under UV-irradiation both under the action of O3 and O2. The conditions of maximum ozone conversion at oxalic acid photomineralization are found. The possibility of oxidative destruction of more oxidation-resistant substrate - acetic acid - at ozonation and UV-irradiation of solutions with Fe(III) and Н2С2О4 additives is shown.

全文:

受限制的访问

作者简介

A. Levanov

M. V. Lomonosov Moscow State University

编辑信件的主要联系方式.
Email: levanovav@my.msu.ru

Department of Chemistry

俄罗斯联邦, Moscow

A. Lapina

Branch of M. V. Lomonosov Moscow State University in Baku

Email: levanovav@my.msu.ru
阿塞拜疆, Baku

O. Isaikina

M. V. Lomonosov Moscow State University

Email: levanovav@my.msu.ru

Department of Chemistry

俄罗斯联邦, Moscow

参考

  1. Baird C., Cann M. Environmental Chemistry. 5 ed. New York: W.H. Freeman & Co., 2012.
  2. Beltran F.J. Ozone Reaction Kinetics for Water and Wastewater Systems. Boca Raton (Florida, USA): Lewis Publishers, CRC Press LLC, 2004.
  3. Lim S., Shi J.L., Von Gunten U., Mccurry D.L. // Water Res. 2022. V. 213. P. 118053.
  4. Marcì G., García-López E., Palmisano L. // J. Appl. Electrochem. 2008. V. 38. № 7. P. 1029.
  5. Bangun J., Adesina A.A. // Applied Catalysis A: General. 1998. V. 175. № 1. P. 221.
  6. Michael K.M., Rizvi G.H., Mathur J.N., Ramanujam A. // J. Radioanalyt. Nucl. Chem. 2000. V. 246. № 2. P. 355.
  7. Ganesh S., Desigan N., Chinnusamy A., Pandey N.K. // Ibid. 2021. V. 328. № 3. P. 857.
  8. Ананьев А.В., Тананаев И.Г., Шилов В.П. // Успехи химии. 2005. Т. 74. № 11. С. 1132. [Ananiev A.V., Tananaev I.G., Shilov V.P. // Russ. Chem. Rev. 2005. V. 74. № 11. P. 1039.]
  9. Von Sonntag C., Von Gunten U. Chemistry of Ozone in Water and Wastewater Treatment. From Basic Principles to Applications. London: IWA Publishing, 2012.
  10. Hoigné J., Bader H. // Water Res. 1983. V. 17. № 2. P. 185.
  11. Kuhn H.J., Braslavsky S.E., Schmidt R. // Pure Appl. Chem. 2004. V. 76. № 12. P. 2105.
  12. Parker C.A., Bowen E.J. // Proc. Roy. Soc. London A. 1953. V. 220. № 1140. P. 104.
  13. Hatchard C.G., Parker C.A., Bowen E.J. // Proc. Roy. Soc. London A. 1956. V. 235. № 1203. P. 518.
  14. Rabani J., Mamane H., Pousty D., Bolton J.R. // Photochem. Photobiol. 2021. V. 97. № 5. P. 873–902.
  15. Goldstein S., Rabani J. // J. Photochem. Photobiol. A. 2008. V. 193. № 1. P. 50.
  16. Леванов А.В., Исайкина О.Я., Грязнов Р.А. // Кинетика и катализ. 2022. Т. 63. № 2. С. 203. [Levanov A.V., Isaikina O.Y., Gryaznov R.A. // Kinetics and Catalysis. 2022. V. 63. № 2. P. 180.]
  17. Леванов А.В., Исайкина О.Я., Гасанова Р.Б., Лунин В.В. // Журн. физ. химии. 2017. Т. 91. № 8. С. 1307. [Levanov A.V., Isaikina O.Y., Gasanova R.B., Lunin V.V. // Russ. J. Phys. Chem. A. 2017. V. 91. № 8. P. 1427.]
  18. Леванов А.В., Кусков И.В., Зосимов А.В. и др. // Журн. аналит. химии. 2003. Т. 58. № 5. С. 496. [Levanov A.V., Kuskov I.V., Zosimov A.V. et al. // J. Anal. Chem. 2003. V. 58. № 5. P. 439.]
  19. Леванов А.В., Исайкина О.Я., Харланов А.Н. // Журн. физ. химии. 2020. Т. 94. № 11. С. 1616. [Levanov A.V., Isaikina O.Y., Kharlanov A.N. // Russ. J. Phys. Chem. A. 2020. V. 94. № 11. P. 2219.]
  20. Mao S., Chen Z., An X., Shen W. // J. Phys. Chem. A. 2011. V. 115. № 22. P. 5560.
  21. Wayne R.P. // Atmospheric Environment. 1987. V. 21. № 8. P. 1683.
  22. Bauer D., D’ottone L., Hynes A.J. // Phys. Chem. Chem. Phys. 2000. V. 2. № 7. P. 1421.
  23. Smith G.D., Molina L.T., Molina M.J. // J. Phys. Chem. A. 2000. V. 104. № 39. P. 8916.
  24. Taniguchi N., Takahashi K., Matsumi Y. // Ibid. 2000. V. 104. № 39. P. 8936.
  25. Wilkinson F., Helman W.P., Ross A.B. // J. Phys. Chem. Ref. Data. 1995. V. 24. № 2. P. 663.
  26. Biedenkapp D., Hartshorn L.G., Bair E.J. // Chem. Phys. Lett. 1970. V. 5. № 6. P. 379.
  27. Reisz E., Schmidt W., Schuchmann H.P., Von Sonntag C. // Env. Sci. Tech. 2003. V. 37. № 9. P. 1941.
  28. Sehested K., Getoff N., Schwoerer F. et al. // J. Phys. Chem. 1971. V. 75. № 6. P. 749.
  29. Ершов Б.Г., Яната Э., Алам М.С., Гордеев А.В. // Изв. Академии наук. Сер. химическая. 2008. № 6. С. 1165. [Ershov B.G., Janata E., Alam M.S., Gordeev A.V. // Russ. Chem. Bull. 2008. V. 57. № 6. P. 1187.]
  30. Ершов Б.Г., Яната Э., Алам М.С., Гордеев А.В. // Химия высоких энергий. 2008. Т. 42. № 1. С. 5. [Ershov B.G., Janata E., Alam M.S., Gordeev A.V. // High Energy Chem. 2008. V. 42. № 1. P. 1.]
  31. Zuo Y., Hoigne J. // Env. Sci. Tech. 1992. V. 26. № 5. P. 1014.
  32. Zuo Y., Hoigné J. // Atmospheric Environment. 1994. V. 28. № 7. P. 1231.
  33. Martell A.E., Smith R.M. Critical Stability Constants. V. 5. First Supplement. New York: Plenum Press, 1982.
  34. Pilz F.H., Lindner J., Vöhringer P. // Phys. Chem. Chem. Phys. 2019. V. 21. № 43. P. 23803.
  35. Pozdnyakov I.P., Kel O.V., Plyusnin V.F. et al. // J. Phys. Chem. A. 2008. V. 112. № 36. P. 8316.

补充文件

附件文件
动作
1. JATS XML
下载
2. Fig. 1. Scheme of the experimental setup.

下载 (399KB)
索引源数据
3. Fig. 2. Dependences of the ferrioxalate concentration in a 0.2 M H2C2O4 and 1.2 × 10–3 M Fe(III) solution on the irradiation time (λ = 254 nm, ℐabs = 2.0 × 10–4 E l–1min–1) when passing gaseous N2 (1) or O2 (2) through the solution.

下载 (165KB)
索引源数据
4. Fig. 3. Change in optical density at 552 nm of the solution in the trap depending on the time of treatment of the solution with 0.2 M H2C2O4. ℐabs = 2 × 10–4 E l–1min–1, Cin(O3) = 28 g/m3.

下载 (156KB)
索引源数据
5. Fig. 4. Carbon dioxide evolution rates during the treatment of a 0.2 M H2C2O4 solution with additives of various ions, oxygen and/or ozone. ℐabs = 2.0 × 10–4 E l–1min–1, Cin(O3) = 27–30 g/m3, concentration of added ions 1 × 10–3 M.

下载 (462KB)
索引源数据
6. Fig. 5. Dependence of the rate of CO2 evolution on the concentration of Fe(III) during UV irradiation of a 0.2 M H2C2O4 solution in an oxygen flow; 1 – ℐabs = 2.0 × 10–4 E l–1min–1, 2 – ℐabs = 1.0 × 10–4 E l–1min–1.

下载 (128KB)
索引源数据
7. Fig. 6. Dependences of the rate of CO2 evolution on the concentration of acetic acid (1, 2), methyl and n-butyl alcohols (3) in the reaction solution under UV irradiation with different intensities: 1 – C(H2C2O4) = 0.2 M, C(Fe(III) = 1.0 × 10–3 M, ℐabs = 2.0 × 10–4 E l–1min–1; 2, 3 – C(H2C2O4) = 0.2 M, C(Fe(III) = 1.5 × 10–3 M, ℐabs = 5.0 × 10–5 E l–1min–1.

下载 (150KB)
索引源数据
8. Fig. 7. Dependences of the rate of CO2 evolution on the ozone concentration in the initial gas mixture at different concentrations of oxalic acid in the solution (C(Fe(III) = 1.5 × 10–3 M; ℐabs = 6.0 × 10–5 E l–1min–1): 1 – C(H2C2O4) = 0.01 M, 2 – C(H2C2O4) = 0.05 M, 3 – C(H2C2O4) = 0.1 M, 4 – C(H2C2O4) = 0.2 M.

下载 (161KB)
索引源数据
9. Fig. 8. Dependence of the rate of CO2 evolution on the ozone concentration in the initial gas mixture at different intensities of UV radiation (C(H2C2O4) = 0.2 M; C(Fe(III) = 1.5 × 10–3 M): 1 – ℐabs = 1 × 10–4 E l–1min–1, 2 – ℐabs = 7 × 10–5 E l–1min–1, 3 – ℐabs = 6 × × 10–5 E l–1min–1.

下载 (125KB)
索引源数据
10. Fig. 9. Dependences of the rate of CO2 evolution on the concentration of oxalic acid in the reaction solution at different ozone concentrations in the initial gas mixture (C(Fe(III) = 1.5 × 10–3 M; ℐabs = 6 × 10–5 E l–1min–1): 1 – Cin(O3) = 0, 2 – Cin(O3) = 9.8 g/m3, 3 – Cin(O3) = 20.5 g/m3, 4 – Cin(O3) = 29.7 g/m3.

下载 (155KB)
索引源数据
11. Fig. 10. Dependences of the ratio (r(CO2) – r(CO2) С(О3)=0) / r(O3) on the concentration of oxalic acid in the reaction solution at different ozone concentrations in the initial gas mixture (C(Fe(III) = 1.5 × 10–3 M; ℐabs = 6 × 10–5 E l–1min–1): 1 – Cin(O3) = 9.8 g/m3, 2 – Cin(O3) = 20.5 g/m3, 3 – Cin(O3) = 29.7 g/m3.

下载 (155KB)
索引源数据
12. Fig. 11. Dependences of the rate of CO2 evolution on the concentration of acetic acid in the reaction solution during ozonation and UV irradiation with different intensities: 1 – C(H2C2O4) = 0.2 M, C(Fe(III) = 1.0 × 10–3 M; ℐabs = 2 × 10–4 E l–1min–1, Cin(O3) = 27.5 g/m3; 2 – C(H2C2O4) = 0.2 M, C(Fe(III) = 1.5 × 10–3 M; ℐabs = 6 × 10–5 E l–1min–1, Cin(O3) = 29.7 g/m3.

下载 (107KB)
索引源数据
13. Fig. 12. The amount of carbon dioxide formed during treatment with ozone (Cin(O3) = 30.0 g/m3) and UV radiation (ℐabs = 6 × 10–5 E l–1min–1) of 395 ml of a solution with concentrations of C(Н2С2О4) = 0.01 M, C(СН3СООН) = 0.13 M, C(Fe(III) = 1.5 × 10–3 M.

下载 (85KB)
索引源数据

版权所有 © Russian Academy of Sciences, 2025