Journal of Sol-Gel Science and Technology

, Volume 88, Issue 1, pp 211–219 | Cite as

Polyethylene glycol-assisted sol-gel synthesis of magnetic CoFe2O4 powder as photo-Fenton catalysts in the presence of oxalic acid

  • Tuong Phuc Hoang Ngo
  • Tien Khoa LeEmail author
Original Paper: Sol-gel and hybrid materials for catalytic, photoelectrochemical and sensor applications


The aim of the study was to prepare magnetic photo-Fenton catalysts based on CoFe2O4 by polyethylene glycol-assisted sol-gel method for the degradation of methylene blue under UVA and visible light irradiation with H2C2O4 as a radical producing source. The catalysts were synthesized at different annealing temperatures in order to investigate the influence of annealing temperature on their crystal structure, morphology, surface functional groups, magnetic properties, and their photo-Fenton catalytic activity. According to the results, when the annealing temperature increased from 600 to 800 °C, the content of CoFe2O4 cubic spinel phase was significantly enhanced, the amount of Fe3+ ions in the tetrahedral sites also increased on the surface of samples, which improved the magnetic properties as well as the photo-Fenton catalytic performance under both UVA and visible light. However, at the annealing temperature of 900 °C, the photo-Fenton activity was declined, which can be attributed to the growth of catalytic particles and the decrease of Fe3+ ions on their surface.


  • Preparation of CoFe2O4 catalysts by polyethylene glycol-assisted sol-gel method.

  • Increasing of annealing temperature improves the CoFe2O4 phase content.

  • The Fe3+ ions in surface tetrahedral sites increases with annealing temperature.

  • Enhanced CoFe2O4 phase and surface Fe3+ contents improve the photo-Fenton activity.

  • H2C2O4 plays as an efficient radical source for the photo-Fenton catalysis.


Polyethylene glycol-assisted sol-gel method CoFe2O4 Magnetic powder Photo-Fenton catalysis H2C2O4 


Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Zepp RG, Faust BC, Hoigné J (1992) Hydroxyl radical formation in aqueous reactions (pH 3–8) of iron(II) with hydrogen peroxide: the photo-Fenton reaction. Environ Sci Technol 26:313–319CrossRefGoogle Scholar
  2. 2.
    Lofrano G, Rizzo L, Grassi M, Belgiorno V (2009) Advanced oxidation of catechol: a comparison among photocatalysis, Fenton photo Fenton processes. Desalination 249:878–883CrossRefGoogle Scholar
  3. 3.
    Pignatello JJ, Oliveros E, MacKay A (2006) Advanced oxidation processes for organic contaminant destruction based on the Fenton reaction and related chemistry. Crit Rev Environ Sci Technol 36:1–84CrossRefGoogle Scholar
  4. 4.
    Haber F, Weiss J (1934) The catalytic decomposition of hydrogen peroxide by iron salts. Proc Math Phys Eng Sci 147:332–351CrossRefGoogle Scholar
  5. 5.
    Metelitsa DI (1971) Mechanisms of the hydroxylation of aromatic compounds. Russ Chem Rev 40:563–580CrossRefGoogle Scholar
  6. 6.
    Valdés-Solís TP, Valle-Vigón P, Álvarez S, Marbán G, Fuertes AB (2007) Manganese ferrite nanoparticles synthesized through a nanocasting route as a highly active Fenton catalyst. Catal Commun 8:2037–2042CrossRefGoogle Scholar
  7. 7.
    Herney-Ramirez J, Vicente MA, Madeira LM (2010) Heterogeneous photo-Fenton oxidation with pillared clay-based catalysts for wastewater treatment: a review. Appl Catal B 98:10–26CrossRefGoogle Scholar
  8. 8.
    Blanco M, Martinez A, Marcaide A, Aranzabe E, Aranzabe A (2014) Heterogeneous Fenton catalyst for the efficient removal of azo dyes in water. Am J Anal Chem 5:490–499CrossRefGoogle Scholar
  9. 9.
    Tekbas M, Yatmaz HC, Bektas N (2008) Heterogeneous photo-Fenton oxidation of reactive azo dye solutions using iron exchanged zeolite as a catalyst Microporous Mesoporous Mater 115:594–602CrossRefGoogle Scholar
  10. 10.
    Xu T, Zhu R, Zhu G, Zhu J, Liang X, Zhu Y, He H (2017) Mechanisms for the enhanced photo-Fenton activity of ferrihydrite modified with BiVO4 at neutral pH. Appl Catal B 212:50–58CrossRefGoogle Scholar
  11. 11.
    Sharma R, Bansal S, Singhal S (2015) Tailoring the photo-Fenton activity of spinel ferrites (MFe2O4) by incorporating different cations (M=Cu, Zn, Ni and Co) in the structure. RSC Adv 5:6006–6018CrossRefGoogle Scholar
  12. 12.
    Houshiar M, Zebhi F, Razi ZJ, Alidoust A, Askari Z (2014) Synthesis of cobalt ferrite (CoFe2O4) nanoparticles using combustion, coprecipitation, and precipitation methods: a comparison study of size, structural, and magnetic properties. J Magn Magn Mater 371:43–48CrossRefGoogle Scholar
  13. 13.
    Yuan HL, Wang YQ, Zhou SM, Liu LS, Chen XL, Lou SY, Yuan RJ, Hao YM, Li N (2010) Low-temperature preparation of superparamagnetic CoFe2O4 microspheres with high saturation magnetization. Nanoscale Res Lett 5:1817–1821CrossRefGoogle Scholar
  14. 14.
    Liu SQ, Feng LR, Xu N, Chen ZG, Wang XM (2012) Magnetic nickel ferrite as a heterogeneous photo-Fenton catalyst for the degradation of rhodamine B in the presence of oxalic acid. Chem Eng J 203:432–439CrossRefGoogle Scholar
  15. 15.
    Anchieta CG, Severo EC, Rigo C, Mazutti MA, Kuhn RC, Muller EI, Flores EMM, Moreira RFPM, Foletto EL (2015) Rapid and facile preparation of zinc ferrite (ZnFe2O4) oxide by microwave-solvothermal technique and its catalytic activity in heterogeneous photo-Fenton reaction. Mater Chem Phys 160:141–147CrossRefGoogle Scholar
  16. 16.
    Guo X, Wang K, Li D, Qin J (2017) Heterogeneous photo-Fenton processes using graphite carbon coating hollow CuFe2O4 spheres for the degradation of methylene blue. Appl Surf Sci 420:792–801CrossRefGoogle Scholar
  17. 17.
    Gharagozlou M (2009) Synthesis, characterization and influence of calcination temperature on magnetic properties of nanocrystalline spinel Co-ferrite prepared by polymeric precursor method. J Alloy Compd 486:660–665CrossRefGoogle Scholar
  18. 18.
    Dang HT, Le TK (2016) Precursor chain length dependence of polymeric precursor method for the preparation of magnetic Fenton-like CuFe2O4-based catalysts. J Sol-Gel Sci Technol 80:160–167CrossRefGoogle Scholar
  19. 19.
    Yan S, Geng J, Yin L, Zhou E (2004) Preparation of nanocrystalline NiZnCu ferrite particles by sol–gel method and their magnetic properties. J Magn Magn Mater 277:84–89CrossRefGoogle Scholar
  20. 20.
    Nikolić AS, Jović N, Rogan J, Kremenović A, Ristić M, Meden A, Antić B (2013) Carboxylic acids and polyethylene glycol assisted synthesis of nanocrystalline nickel ferrites. Ceram Int 39:6681–6688CrossRefGoogle Scholar
  21. 21.
    Wu X, Wang W, Li F, Khaimanov S, Tsidaeva N, Lahoubi M (2016) PEG-assisted hydrothermal synthesis of CoFe2O4 nanoparticles with enhanced selective adsorption properties for different dyes. Appl Surf Sci 389:1003–1011CrossRefGoogle Scholar
  22. 22.
    Zuo Y, Hoigné J (1992) Formation of hydrogen peroxide and depletion of oxalic acid in atmospheric water by photolysis of iron(III)-oxalato complexes. Environ Sci Technol 26:1014–1022CrossRefGoogle Scholar
  23. 23.
    Duesterberg CK, Cooper WJ, Waite TD (2005) Fenton-mediated oxidation in the presence and absence of oxygen. Environ Sci Technol 39:5052–5058CrossRefGoogle Scholar
  24. 24.
    Kusic H, Koprivanac N, Bozic AL (2011) Treatment of chlorophenols in water matrix by UV/ferri-oxalate system: Part II. Degradation mechanisms and ecological parameters evaluation. Desalination 280:208–216CrossRefGoogle Scholar
  25. 25.
    Huang YH, Huang YJ, Tsai HC, Chen HT (2010) Degradation of phenol using low concentration of ferric ions by the photo-Fenton process. J Taiwan Inst Chem Eng 41:699–704CrossRefGoogle Scholar
  26. 26.
    Dinh TT, Nguyen TQ, Quan GC, Nguyen VDN, Tran HQ, Le TK (2017) Starch-assisted sol–gel synthesis of magnetic CuFe2O4 powder as photo-Fenton catalysts in the presence of oxalic acid. Int J Environ Sci Technol 14:2613–2622CrossRefGoogle Scholar
  27. 27.
    Rodriguez-Carvajal J (2001) Commission of powder diffraction. IUCr Newsl 26:12–19Google Scholar
  28. 28.
    Zaki HM, Dawoud HA (2010) Far-infrared spectra for copper–zinc mixed ferrites. Phys B: Condens Matter 405:4476–4479CrossRefGoogle Scholar
  29. 29.
    Rao KS, Choudary GSVRK, Rao KH, Sujatha C (2015) Structural and magnetic properties of ultrafine CoFe2O4 nanoparticles. Procedia Sci 10:19–27CrossRefGoogle Scholar
  30. 30.
    Aliyan N, Mirkazemi SM, Masoudpanah SM, Akbari S (2017) The effect of post-calcination on cation distributions and magnetic properties of the coprecipitated MgFe2O4 nanoparticles. Appl Phys A 123:446. 2017CrossRefGoogle Scholar
  31. 31.
    Sahoo SK, Agarwal K, Singh AK, Polke BG, Raha KC (2010) Characterization of γ- and α-Fe2O3 nano powders synthesized by emulsion precipitation-calcination route and rheological behaviour of α-Fe2O3. Int J Eng Sci Tech 2:118–126Google Scholar
  32. 32.
    Aochi YO, Farmer WJ (2011) Effects of surface charge and particle morphology on the sorption/desorption behaviour of water on clay minerals. Colloids Surf A Physicochem Eng Asp 374(1–3):22–32CrossRefGoogle Scholar
  33. 33.
    Golsefidi MA, Yazarlou F, Nezamabad MN, Nezamabad BN, Karim M (2016) Effects of capping agent and surfactant on the morphology and size of CoFe2O4 nanostructures and photocatalyst properties. J Nanostruct 6(2):121–126CrossRefGoogle Scholar
  34. 34.
    Šolek P (2009) Techincká Mechanika II, 1st edn. Slovenská technická univerzita v Bratislave, Nakladatel’stvo STU, Bratislava (Technical Mechanics II) in Slovak language.Google Scholar
  35. 35.
    Brown ID, Shannon RD (1973) Empirical bond-strength-bond-length curves for oxides. Acta Cryst A29:266–282CrossRefGoogle Scholar
  36. 36.
    Hatchard CG, Parker CA (1956) A new sensitive chemical actinometer. II. Potassium ferrioxalate as a standard chemical acainometer. Proc R Soc Lond A 235:518–536CrossRefGoogle Scholar
  37. 37.
    Mulazzani QG, D’Angelantonio M, Venturi M, Hoffman MZ, Rodgers MAJ (1986) Interaction of formate and oxalate ions with radiation-generated radicals in aqueous solution. Methylviologen as a mechanistic probe. J Phys Chem 90:5347–5352CrossRefGoogle Scholar
  38. 38.
    Walling C (1975) Fenton’s reagent revisited. Acc Chem Res 8:125–131CrossRefGoogle Scholar
  39. 39.
    Sedlak DL, Hoigné J (1993) The role of copper and oxalate in the redox cycling of iron in atmospheric waters. Atmos Environ 27:2173–2185CrossRefGoogle Scholar
  40. 40.
    Dean JA (1998) Lange’s handbook of chemistry. The McGraw-Hill Companies 15th ed:8.98.Google Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.VNUHCM - University of ScienceHo Chi Minh CityVietnam

Personalised recommendations