Study of visible-light photocatalytic degradation of 2,4-dichlorophenoxy acetic acid in batch and circulated-mode photoreactors

  • Sorur Safa
  • Majid Mirzaei
  • Foad KazemiEmail author
  • Mohammad Taghi Ghaneian
  • Babak Kaboudin
Research Article



The consumption of pesticides and chemical fertilizers is one of the major environmental and health problems. In this report, 2,4-dichlorophenoxyacetic acid (2,4-D) was chosen to evaluate the impact of photodegradation using LED (Light-emitting diode) (400 and 365 nm) sources in batch and programmable circulated-mode photoreactors respectively.


A β-cyclodextrin (β-CD) grafted titanium dioxide P25 (P25/β-CD) and complexation of 2,4-D and β-CD were synthesized via photoinduced and spray-drying methods, respectively. The structures were characterized. Moreover, we investigated the effects of the amount of catalyst, the β-CD amount on bed catalyst, irradiation time, kind of photoreactor on the photocatalytic degradation efficiency.


Based on the results of experiments in batch reactor, the optimum amount of TiO2, β-CD grafted by catalyst were 1 and 0.1 g/L, respectively. In batch-mode the photodegradation efficiency of 2,4-D after 5 h with P25, P25/β-CD as a photocatalyst and 2,4-D/β-CD complex with P25 photocatalyst were approximately 81, 85 and 95% respectively. After 8 h of irradiation in circulated-mode reactor, degradation yields with P25, P25/β-CD and 2,4-D/β-CD complex along with P25 were 89, 91 and 96% respectively. On the other hand, the circulated-mode photoreactor with high efficiency was appropriate to degradation of the high concentration of 2,4-D solution (200 mg/L). After 5 successive cycles with 25 h of irradiation, P25 and P25/β-CD maintained as high 2,4-D removal efficiency as 82.6, 84% respectively, with excellent stability and reusability.


The photodegradation method can be used as an effective and environmental friendly process in the degradation of organic compound.


2,4-Dichlorophenoxyacetic acid (2,4-D) Light-emitting diode (LED) 2,4-D/β-CD complex Batch-mode photoreactor Circulated-mode photoreactor 



The authors acknowledge the support by Shahid Sadoughi University of Medical Sciences and Institute for Advanced Studies in Basic Sciences (IASBS) Research Council of this work.


The present work was financially supported by Shahid Sadoughi University of Medical Sciences.

Compliance with ethical standards

Conflicts of interest

The authors confirm no conflicts of interest associated with this publication.

Consent for publication

All authors agreed to publish this article.

Ethics approval and consent to participate

There was no human participation in this study.


  1. 1.
    López-Granada G, Barceinas-Sanchez JDO, López R, Gómez R. High temperature stability of anatase in titania–alumina semiconductors with enhanced photodegradation of 2, 4-dichlorophenoxyacetic acid. J Hazard Mater. 2013;263:84–92.CrossRefGoogle Scholar
  2. 2.
    Kundu S, Pal A, Dikshit AK. UV induced degradation of herbicide 2,4-D: kinetics, mechanism and effect of various conditions on the degradation. Sep Purif Technol. 2005;44(2):121–9.CrossRefGoogle Scholar
  3. 3.
    Ova D, Ovez B. 2, 4-Dichlorophenoxyacetic acid removal from aqueous solutions via adsorption in the presence of biological contamination. J Environ Chem Eng. 2013;1(4):813–21.CrossRefGoogle Scholar
  4. 4.
    Ji R, Bian X, Chen J. Degradation of 2,4-Dichlorophenoxyacetic acid (2,4-D) by novel photocatalytic material of tourmaline-coated TiO2 nanoparticles&58; kinetic study and model. Materials. 2013;6(4):1530–42.CrossRefGoogle Scholar
  5. 5.
    Pignatello JJ. Dark and photoassisted iron (3+)-catalyzed degradation of chlorophenoxy herbicides by hydrogen peroxide. Environ Sci Technol. 1992;26(5):944–51.CrossRefGoogle Scholar
  6. 6.
    Schenone AV, Conte LO, Botta MA, Alfano OM. Modeling and optimization of photo-Fenton degradation of 2,4-D using ferrioxalate complex and response surface methodology (RSM). J Environ Manag. 2015;155:177–83.CrossRefGoogle Scholar
  7. 7.
    Murcia M, Vershinin N, Briantceva N, Gomez M, Gomez E, Cascales E, et al. Development of a kinetic model for the UV/H2O2 photodegradation of 2,4-dichlorophenoxiacetic acid. Chem Eng J. 2015;266:356–67.CrossRefGoogle Scholar
  8. 8.
    Rivera-Utrilla J, Sánchez-Polo M, Ocampo-Pérez R. Role of activated carbon in the photocatalytic degradation of 2, 4-dichlorophenoxyacetic acid by the UV/TiO2/activated carbon system. Appl Catal B Environ. 2012;126:100–7.CrossRefGoogle Scholar
  9. 9.
    Kanakaraju D, Glass BD, Oelgemöller M. Titanium dioxide photocatalysis for pharmaceutical wastewater treatment. Environ Chem Lett. 2014;12(1):27–47.CrossRefGoogle Scholar
  10. 10.
    Liang N, Zai J, Xu M, Zhu Q, Wei X, Qian X. Novel Bi2S3/Bi2O2CO3 heterojunction photocatalysts with enhanced visible light responsive activity and wastewater treatment. J Mater Chem A. 2014;2(12):4208–16.CrossRefGoogle Scholar
  11. 11.
    Zand Z, Kazemi F, Hosseini S. Development of chemoselective photoreduction of nitro compounds under solar light and blue LED irradiation. Tetrahedron Lett. 2014;55(2):338–41.CrossRefGoogle Scholar
  12. 12.
    Wang H, Zhang L, Chen Z, Hu J, Li S, Wang Z, et al. Semiconductor heterojunction photocatalysts: design, construction, and photocatalytic performances. Chem Soc Rev. 2014;43(15):5234–44.CrossRefGoogle Scholar
  13. 13.
    Li R, Weng Y, Zhou X, Wang X, Mi Y, Chong R, et al. Achieving overall water splitting using titanium dioxide-based photocatalysts of different phases. Energy Environ Sci. 2015;8(8):2377–82.CrossRefGoogle Scholar
  14. 14.
    López R, Gómez R. Band-gap energy estimation from diffuse reflectance measurements on sol–gel and commercial TiO2: a comparative study. J Sol-Gel Sci Technol. 2012;61(1):1–7.CrossRefGoogle Scholar
  15. 15.
    Chalasani R, Vasudevan S. Cyclodextrin-functionalized Fe3O4@TiO2: reusable, magnetic nanoparticles for photocatalytic degradation of endocrine-disrupting chemicals in water supplies. ACS Nano. 2013;7(5):4093–104.CrossRefGoogle Scholar
  16. 16.
    Landy D, Mallard I, Ponchel A, Monflier E, Fourmentin S. Remediation technologies using cyclodextrins: an overview. Environ Chem Lett. 2012;10(3):225–37.CrossRefGoogle Scholar
  17. 17.
    Kakroudi MA, Kazemi F, Kaboudin B. β-Cyclodextrin–TiO2: green Nest for reduction of nitroaromatic compounds. RSC Adv. 2014;4(95):52762–9.CrossRefGoogle Scholar
  18. 18.
    Yu L, Achari G, Langford CH. LED-based photocatalytic treatment of pesticides and chlorophenols. J Environ Eng. 2013;139(9):1146–51.CrossRefGoogle Scholar
  19. 19.
    Jo W-K, Tayade RJ. New generation energy-efficient light source for photocatalysis: LEDs for environmental applications. Ind Eng Chem Res. 2014;53(6):2073–84.CrossRefGoogle Scholar
  20. 20.
    Ramdar M, Kazemi F, Kaboudin B, Taran Z, Partovi A. Visible light active CdS nanorods: one-pot synthesis of aldonitrones. New J Chem. 2016;40(11):9257–62.CrossRefGoogle Scholar
  21. 21.
    Ramdar M, Kazemi F, Kaboudin B. A photocatalytic green system for chemoselective reduction of nitroarenes. Chem Pap. 2017;71(6):1155–63.CrossRefGoogle Scholar
  22. 22.
    Ginés JM, Pérez-Martínez JI, Arias MJ, Moyano J, Morillo E, Ruiz-Conde A, et al. Inclusion of the herbicide 2, 4-dichlorophenoxyacetic acid (2,4-D) with β-cyclodextrin by different processing methods. Chemosphere. 1996;33(2):321–34.CrossRefGoogle Scholar
  23. 23.
    Sasikala R, Shirole A, Sudarsan V, Sudakar C, Naik R, Rao R, et al. Enhanced photocatalytic activity of indium and nitrogen co-doped TiO2–Pd nanocomposites for hydrogen generation. Appl Catal A Gen. 2010;377(1–2):47–54.CrossRefGoogle Scholar
  24. 24.
    Velusamy P, Pitchaimuthu S, Rajalakshmi S, Kannan N. Modification of the photocatalytic activity of TiO2 by β-Cyclodextrin in decoloration of ethyl violet dye. J Adv Res. 2014;5(1):19–25.CrossRefGoogle Scholar
  25. 25.
    Montazer M, Pakdel E. Functionality of nano titanium dioxide on textiles with future aspects: focus on wool. J Photochem Photobiol C: Photochem Rev. 2011;12(4):293–303.CrossRefGoogle Scholar
  26. 26.
    Pitchaimuthu S, Lakshmi G, Velusamy P. Enhanced photocatalytic activity of TiO2 using β-Cyclodextrin on solar light assisted decoloration of azocarmine G dye. J adv Chem Sci. 2014:9–14.Google Scholar
  27. 27.
    Zhang X, Wu F, Deng N. Efficient photodegradation of dyes using light-induced self assembly TiO2/β-cyclodextrin hybrid nanoparticles under visible light irradiation. J Hazard Mater. 2011;185(1):117–23.CrossRefGoogle Scholar
  28. 28.
    Hu Q-D, Tang G-P, Chu PK. Cyclodextrin-based host–guest supramolecular nanoparticles for delivery: from design to applications. Acc Chem Res. 2014;47(7):2017–25.CrossRefGoogle Scholar
  29. 29.
    Pitchaimuthu S, Rajalakshmi S, Kannan N, Velusamy P. Enhanced photocatalytic activity of titanium dioxide by β-cyclodextrin in decoloration of acid yellow 99 dye. Desalin Water Treat. 2014;52(16–18):3392–402.CrossRefGoogle Scholar
  30. 30.
    Zhang X, Wu F, Wang Z, Guo Y, Deng N. Photocatalytic degradation of 4, 4′-biphenol in TiO2 suspension in the presence of cyclodextrins: a trinity integrated mechanism. J Mol Catal A Chem. 2009;301(1–2):134–9.CrossRefGoogle Scholar
  31. 31.
    Yang Z, Zhang X, Cui J. Self-assembly of bioinspired catecholic cyclodextrin TiO2 heterosupramolecule with high adsorption capacity and efficient visible-light photoactivity. Appl Catal B Environ. 2014;148:243–9.CrossRefGoogle Scholar
  32. 32.
    Sakthivel P, Velusamy P. Modification of the photocatalytic performance of various metal oxides by the addition of β-cyclodextrin under visible light irradiation. Journal of water process engineering. 2017;16:329–37.CrossRefGoogle Scholar
  33. 33.
    Lu S, Sun N, Wang T. Research on photocatalytic degradation of methyl orange by a β-Cyclodextrin/Titanium dioxide composite. General Chemistry. 2017;3(3):164–9.CrossRefGoogle Scholar
  34. 34.
    Attarchi N, Montazer M, Toliyat T. Ag/TiO2/β-CD nano composite: preparation and photo catalytic properties for methylene blue degradation. Appl Catal A Gen. 2013;467:107–16.CrossRefGoogle Scholar
  35. 35.
    Zhang X, Li X, Deng N. Enhanced and selective degradation of pollutants over cyclodextrin/TiO2 under visible light irradiation. Ind Eng Chem Res. 2011;51(2):704–9.CrossRefGoogle Scholar
  36. 36.
    Lu P, Wu F, Deng N. Enhancement of TiO2 photocatalytic redox ability by β-cyclodextrin in suspended solutions. Appl Catal B Environ. 2004;53(2):87–93.CrossRefGoogle Scholar
  37. 37.
    Pereira R, Anconi C, Nascimento C, De Almeida W, Dos Santos H. Stability and spatial arrangement of the 2, 4-dichlorophenoxyacetic acid and beta-cyclodextrin inclusion compound: a theoretical study. Chem Phys Lett. 2015;633:158–62.CrossRefGoogle Scholar
  38. 38.
    Behnajady M, Modirshahla N, Daneshvar N, Rabbani M. Photocatalytic degradation of an azo dye in a tubular continuous-flow photoreactor with immobilized TiO2 on glass plates. Chem Eng J. 2007;127(1–3):167–76.CrossRefGoogle Scholar
  39. 39.
    García-Martínez M, Canoira L, Blázquez G, Da Riva I, Alcántara R, Llamas J. Continuous photodegradation of naphthalene in water catalyzed by TiO2 supported on glass Raschig rings. Chem Eng J. 2005;110(1–3):123–8.CrossRefGoogle Scholar

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© Springer Nature Switzerland AG 2019

Authors and Affiliations

  • Sorur Safa
    • 1
  • Majid Mirzaei
    • 2
  • Foad Kazemi
    • 3
    Email author
  • Mohammad Taghi Ghaneian
    • 4
  • Babak Kaboudin
    • 3
  1. 1.Department of Environmental Health EngineeringInternational Campus of Shahid Sadoughi University of Medical SciencesYazdIran
  2. 2.Department of PhysicsInstitute for Advanced Studies in Basic Sciences (IASBS)ZanjanIran
  3. 3.Department of ChemistryInstitute for Advanced Studies in Basic Sciences (IASBS)ZanjanIran
  4. 4.Department of Environmental Health EngineeringShahid Sadoughi University of Medical SciencesYazdIran

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