Environmental Science and Pollution Research

, Volume 25, Issue 32, pp 32140–32155 | Cite as

Sonocatalytic removal of methylene blue from water solution by cobalt ferrite/mesoporous graphitic carbon nitride (CoFe2O4/mpg-C3N4) nanocomposites: response surface methodology approach

  • Aydin HassaniEmail author
  • Paria Eghbali
  • Önder MetinEmail author
Research Article


In this study, cobalt ferrite/mesoporous graphitic carbon nitride (CoFe2O4/mpg-C3N4) nanocomposites were successfully synthesized by using a two-step protocol. Firstly, monodispersed CoFe2O4 nanoparticles (NPs) were synthesized via thermal decomposition of metal precursors in a hot surfactant solution and then they were assembled on mpg-C3N4 via a liquid phase self-assembly method. The sonocatalytic performance of as-synthesized CoFe2O4/mpg-C3N4 nanocomposites was evaluated on the methylene blue (MB) removal from water under ultrasonic irradiation. For this purpose, response surface methodology (RSM) based on central composite design (CCD) model was successfully utilized to optimize the MB removal over CoFe2O4/mpg-C3N4 nanocomposites. Analysis of variance (ANOVA) was applied to investigate the significance of the model. The results predicted by the model were obtained to be in reasonable agreement with the experimental data (R2 = 0.969, adjusted R2 = 0.942). Pareto analysis demonstrated that pH of the solution was the most effective parameter on the sonocatalytic removal of MB by CoFe2O4/mpg-C3N4 nanocomposites. The optimum catalyst dose, initial dye concentration, pH, and sonication time were set as 0.25 g L−1, 8 mg L−1, 8, and 45 min, respectively. The high removal efficiency of MB dye (92.81%) was obtained under optimal conditions. The trapping experiments were done by using edetate disodium, tert-butyl alcohol, and benzoquinone. Among the reactive radicals, OH played a more important role than h+ and \( {O}_2^{-\bullet } \) in the MB dye removal process. Moreover, a proposed mechanism was also presented for the removal of MB in the presence of CoFe2O4/mpg-C3N4 nanocomposites under the optimized sonocatalytic conditions. Finally, a reusability test of the nanocomposites revealed a just 9.6% decrease in their removal efficiency after five consecutive runs.


Sonocatalysis Graphitic carbon nitride CoFe2O4 nanoparticles Nanocomposites Response surface methodology Methylene blue Wastewater treatment 



Paria Eghbali gratefully acknowledges the support of Atatürk University as a post-doctoral researcher.


The financial support by the Science Academy in the context of “Young Scientists Award Program (BAGEP)” is highly acknowledged.


  1. Abdessalem AK, Oturan N, Bellakhal N, Dachraoui M, Oturan MA (2008) Experimental design methodology applied to electro-Fenton treatment for degradation of herbicide chlortoluron. Appl Catal, B 78:334–341. CrossRefGoogle Scholar
  2. Areerob Y, Cho JY, Jang WK, Oh W-C (2018) Enhanced sonocatalytic degradation of organic dyes from aqueous solutions by novel synthesis of mesoporous Fe3O4-graphene/ZnO@SiO2 nanocomposites. Ultrason Sonochem 41:267–278. CrossRefGoogle Scholar
  3. Chadi NE, Merouani S, Hamdaoui O, Bouhelassa M (2018) New aspect of the effect of liquid temperature on sonochemical degradation of nonvolatile organic pollutants in aqueous media. Sep Purif Technol 200:68–74. CrossRefGoogle Scholar
  4. Chen X, Dai J, Shi G, Li L, Wang G, Yang H (2016) Sonocatalytic degradation of rhodamine B catalyzed by β-Bi2O3 particles under ultrasonic irradiation. Ultrason Sonochem 29:172–177. CrossRefGoogle Scholar
  5. Darvishi Cheshmeh Soltani R, Jorfi S, Safari M, Rajaei M-S (2016) Enhanced sonocatalysis of textile wastewater using bentonite-supported ZnO nanoparticles: response surface methodological approach. J Environ Manag 179:47–57. CrossRefGoogle Scholar
  6. Dong G, Zhang Y, Pan Q, Qiu J (2014) A fantastic graphitic carbon nitride (g-C3N4) material: electronic structure, photocatalytic and photoelectronic properties. J Photochem Photobiol C 20:33–50. CrossRefGoogle Scholar
  7. Dükkancı M (2018) Sono-photo-Fenton oxidation of bisphenol-A over a LaFeO3 perovskite catalyst. Ultrason Sonochem 40:110–116. CrossRefGoogle Scholar
  8. Erdogan DA, Sevim M, Kısa E, Emiroglu DB, Karatok M, Vovk EI, Bjerring M, Akbey Ü, Metin Ö, Ozensoy E (2016) Photocatalytic activity of mesoporous graphitic carbon nitride (mpg-C3N4) towards organic chromophores under UV and VIS light illumination. Top Catal 59:1305–1318. CrossRefGoogle Scholar
  9. Eskandarloo H, Badiei A, Behnajady MA, Tavakoli A, Ziarani GM (2016) Ultrasonic-assisted synthesis of Ce doped cubic–hexagonal ZnTiO3 with highly efficient sonocatalytic activity. Ultrason Sonochem 29:258–269. CrossRefGoogle Scholar
  10. Farhadi S, Siadatnasab F, Khataee A (2017) Ultrasound-assisted degradation of organic dyes over magnetic CoFe2O4@ZnS core-shell nanocomposite. Ultrason Sonochem 37:298–309. CrossRefGoogle Scholar
  11. Gholivand MB, Yamini Y, Dayeni M, Seidi S, Tahmasebi E (2015) Adsorptive removal of alizarin red-S and alizarin yellow GG from aqueous solutions using polypyrrole-coated magnetic nanoparticles. J Environ Chem Eng 3:529–540. CrossRefGoogle Scholar
  12. Grčić I, Vujević D, Žižek K, Koprivanac N (2013) Treatment of organic pollutants in water using TiO2 powders: photocatalysis versus sonocatalysis. React Kinet Mech Catal 109:335–354. CrossRefGoogle Scholar
  13. Guo S, Sun S (2012) FePt nanoparticles assembled on graphene as enhanced catalyst for oxygen reduction reaction. J Am Chem Soc 134:2492–2495. CrossRefGoogle Scholar
  14. Gürses A, Hassani A, Kıranşan M, Açışlı Ö, Karaca S (2014) Removal of methylene blue from aqueous solution using by untreated lignite as potential low-cost adsorbent: kinetic, thermodynamic and equilibrium approach. J Water Process Eng 2:10–21. CrossRefGoogle Scholar
  15. Hapeshi E, Fotiou I, Fatta-Kassinos D (2013) Sonophotocatalytic treatment of ofloxacin in secondary treated effluent and elucidation of its transformation products. Chem Eng J 224:96–105. CrossRefGoogle Scholar
  16. Hassani A, Alidokht L, Khataee AR, Karaca S (2014) Optimization of comparative removal of two structurally different basic dyes using coal as a low-cost and available adsorbent. J Taiwan Inst Chem Eng 45:1597–1607. CrossRefGoogle Scholar
  17. Hassani A, Çelikdağ G, Eghbali P, Sevim M, Karaca S, Metin Ö (2018a) Heterogeneous sono-Fenton-like process using magnetic cobalt ferrite-reduced graphene oxide (CoFe2O4-rGO) nanocomposite for the removal of organic dyes from aqueous solution. Ultrason Sonochem 40:841–852. CrossRefGoogle Scholar
  18. Hassani A, Darvishi Cheshmeh Soltani R, Kıranşan M, Karaca S, Karaca C, Khataee A (2016) Ultrasound-assisted adsorption of textile dyes using modified nanoclay: central composite design optimization. Korean J Chem Eng 33:178–188. CrossRefGoogle Scholar
  19. Hassani A, Eghbali P, Ekicibil A, Metin Ö (2018b) Monodisperse cobalt ferrite nanoparticles assembled on mesoporous graphitic carbon nitride (CoFe2O4/mpg-C3N4): a magnetically recoverable nanocomposite for the photocatalytic degradation of organic dyes. J Magn Magn Mater 456:400–412. CrossRefGoogle Scholar
  20. Hassani A, Karaca C, Karaca S, Khataee A, Açışlı Ö, Yılmaz B (2018c) Enhanced removal of basic violet 10 by heterogeneous sono-Fenton process using magnetite nanoparticles. Ultrason Sonochem 42:390–402. CrossRefGoogle Scholar
  21. Hassani A, Khataee A, Karaca S, Karaca C, Gholami P (2017) Sonocatalytic degradation of ciprofloxacin using synthesized TiO2 nanoparticles on montmorillonite. Ultrason Sonochem 35:251–262. CrossRefGoogle Scholar
  22. Hassani A, Khataee A, Karaca S, Karaca M, Kıranşan M (2015a) Adsorption of two cationic textile dyes from water with modified nanoclay: a comparative study by using central composite design. J Environ Chem Eng 3:2738–2749. CrossRefGoogle Scholar
  23. Hassani A, Kıranşan M, Soltani RDC, Khataee AR, Karaca S (2015b) Optimization of the adsorption of a textile dye onto nanoclay using a central composite design. Turk J Chem 39:734–749. doi:10.3906/kim-1412-64CrossRefGoogle Scholar
  24. Hassani A, Soltani RDC, Karaca S, Khataee A (2015c) Preparation of montmorillonite–alginate nanobiocomposite for adsorption of a textile dye in aqueous phase: isotherm, kinetic and experimental design approaches. J Ind Eng Chem 21:1197–1207. CrossRefGoogle Scholar
  25. Heidari S, Haghighi M, Shabani M (2018) Ultrasound assisted dispersion of Bi2Sn2O7-C3N4 nanophotocatalyst over various amount of zeolite Y for enhanced solar-light photocatalytic degradation of tetracycline in aqueous solution. Ultrason Sonochem 43:61–72. CrossRefGoogle Scholar
  26. Jiang G, Lan M, Zhang Z, Lv X, Lou Z, Xu X, Dong F, Zhang S (2017) Identification of active hydrogen species on palladium nanoparticles for an enhanced electrocatalytic hydrodechlorination of 2,4-dichlorophenol in water. Environ Sci Technol 51:7599–7605. CrossRefGoogle Scholar
  27. Jiang G, Wang K, Li J, Fu W, Zhang Z, Johnson G, Lv X, Zhang Y, Zhang S, Dong F (2018) Electrocatalytic hydrodechlorination of 2,4-dichlorophenol over palladium nanoparticles and its pH-mediated tug-of-war with hydrogen evolution. Chem Eng J 348:26–34. CrossRefGoogle Scholar
  28. Khataee A, Alidokht L, Hassani A, Karaca S (2013) Response surface analysis of removal of a textile dye by a Turkish coal powder. Adv Environ Res 2:291–308. Scholar
  29. Khataee A, Eghbali P, Irani-Nezhad MH, Hassani A (2018a) Sonochemical synthesis of WS2 nanosheets and its application in sonocatalytic removal of organic dyes from water solution. Ultrason Sonochem 48:329–339. CrossRefGoogle Scholar
  30. Khataee A, Gholami P, Kalderis D, Pachatouridou E, Konsolakis M (2018b) Preparation of novel CeO2-biochar nanocomposite for sonocatalytic degradation of a textile dye. Ultrason Sonochem 41:503–513. CrossRefGoogle Scholar
  31. Khataee A, Hassandoost R, Rahim Pouran S (2018c) Cerium-substituted magnetite: fabrication, characterization and sonocatalytic activity assessment. Ultrason Sonochem 41:626–640. CrossRefGoogle Scholar
  32. Khataee AR, Naseri A, Zarei M, Safarpour M, Moradkhannejhad L (2012) Chemometrics approach for determination and optimization of simultaneous photooxidative decolourization of a mixture of three textile dyes. Environ Technol 33:2305–2317. CrossRefGoogle Scholar
  33. Khataee AR, Zarei M, Fathinia M, Jafari MK (2011a) Photocatalytic degradation of an anthraquinone dye on immobilized TiO2 nanoparticles in a rectangular reactor: destruction pathway and response surface approach. Desalination 268:126–133. CrossRefGoogle Scholar
  34. Khataee AR, Zarei M, Ordikhani-Seyedlar R (2011b) Heterogeneous photocatalysis of a dye solution using supported TiO2 nanoparticles combined with homogeneous photoelectrochemical process: molecular degradation products. J Mol Catal A Chem 338:84–91. CrossRefGoogle Scholar
  35. Li T, Song L, Zhang S (2018) A novel WO3 sonocatalyst for treatment of rhodamine B under ultrasonic irradiation. Environ Sci Pollut Res 25:7937–7945. CrossRefGoogle Scholar
  36. Mannan S, Fakhru'l-Razi A, Alam MZ (2007) Optimization of process parameters for the bioconversion of activated sludge by Penicillium corylophilum, using response surface methodology. J Environ Sci 19:23–28. CrossRefGoogle Scholar
  37. Meijide J, Rosales E, Pazos M, Sanromán MA (2017) p-Nitrophenol degradation by electro-Fenton process: pathway, kinetic model and optimization using central composite design. Chemosphere 185:726–736. CrossRefGoogle Scholar
  38. Merouani S, Hamdaoui O, Rezgui Y, Guemini M (2015) Sensitivity of free radicals production in acoustically driven bubble to the ultrasonic frequency and nature of dissolved gases. Ultrason Sonochem 22:41–50. CrossRefGoogle Scholar
  39. Modirshahla N, Behnajady MA, Rahbarfam R, Hassani A (2012) Effects of operational parameters on decolorization of C. I. acid red 88 by UV/H2O2 process: evaluation of electrical energy consumption. CLEAN–Soil, Air, Water 40:298–302. CrossRefGoogle Scholar
  40. Moura JM, Gründmann DDR, Cadaval TRS, Dotto GL, Pinto LAA (2016) Comparison of chitosan with different physical forms to remove reactive black 5 from aqueous solutions. J Environ Chem Eng 4:2259–2267. CrossRefGoogle Scholar
  41. Rasoulifard MH, Dorraji MSS, Taherkhani S (2016) Photocatalytic activity of zinc stannate: preparation and modeling. J Taiwan Inst Chem Eng 58:324–332. CrossRefGoogle Scholar
  42. Sabri NA, Nawi MA, Abu Bakar NHH (2018) Recyclable immobilized carbon coated nitrogen doped TiO2 for photocatalytic degradation of quinclorac under UV–vis and visible light. J Environ Chem Eng 6:898–905. CrossRefGoogle Scholar
  43. Saharan P, Chaudhary GR, Lata S, Mehta SK, Mor S (2015) Ultra fast and effective treatment of dyes from water with the synergistic effect of Ni doped ZnO nanoparticles and ultrasonication. Ultrason Sonochem 22:317–325. CrossRefGoogle Scholar
  44. Sajjadi S, Khataee A, Kamali M (2017) Sonocatalytic degradation of methylene blue by a novel graphene quantum dots anchored CdSe nanocatalyst. Ultrason Sonochem 39:676–685. CrossRefGoogle Scholar
  45. Shankaraiah G, Saritha P, Pedamalla NV, Bhagawan D, Himabindu V (2014) Degradation of Rabeprazole-N-oxide in aqueous solution using sonication as an advanced oxidation process. J Environ Chem Eng 2:510–515. CrossRefGoogle Scholar
  46. Song L, Li Y, Zhang S (2018) Sonocatalytic degradation of rhodamine B in presence of CdS. Environ Sci Pollut Res 25:10714–10719. CrossRefGoogle Scholar
  47. Song L, Zhang S, Wu X, Wei Q (2012) A metal-free and graphitic carbon nitride sonocatalyst with high sonocatalytic activity for degradation methylene blue. Chem Eng J 184:256–260. CrossRefGoogle Scholar
  48. Sun S, Zeng H, Robinson DB, Raoux S, Rice PM, Wang SX, Li G (2004) Monodisperse MFe2O4 (M = Fe, Co, Mn) Nanoparticles. J Am Chem Soc 126:273–279. CrossRefGoogle Scholar
  49. Taherian S, Entezari MH, Ghows N (2013) Sono-catalytic degradation and fast mineralization of p-chlorophenol: La0.7Sr0.3MnO3 as a nano-magnetic green catalyst. Ultrason Sonochem 20:1419–1427. CrossRefGoogle Scholar
  50. Vinoth R, Karthik P, Devan K, Neppolian B, Ashokkumar M (2017) TiO2–NiO p–n nanocomposite with enhanced sonophotocatalytic activity under diffused sunlight. Ultrason Sonochem 35:655–663. CrossRefGoogle Scholar
  51. Wang J, Jiang Y, Zhang Z, Zhao G, Zhang G, Ma T, Sun W (2007) Investigation on the sonocatalytic degradation of Congo red catalyzed by nanometer rutile TiO2 powder and various influencing factors. Desalination 216:196–208. CrossRefGoogle Scholar
  52. Wang J, Jiang Z, Zhang L, Kang P, Xie Y, Lv Y, Xu R, Zhang X (2009) Sonocatalytic degradation of some dyestuffs and comparison of catalytic activities of nano-sized TiO2, nano-sized ZnO and composite TiO2/ZnO powders under ultrasonic irradiation. Ultrason Sonochem 16:225–231. CrossRefGoogle Scholar
  53. Wang J, Lv Y, Zhang L, Liu B, Jiang R, Han G, Xu R, Zhang X (2010) Sonocatalytic degradation of organic dyes and comparison of catalytic activities of CeO2/TiO2, SnO2/TiO2 and ZrO2/TiO2 composites under ultrasonic irradiation. Ultrason Sonochem 17:642–648. CrossRefGoogle Scholar
  54. Weng C-H, Huang V (2015) Application of Fe0 aggregate in ultrasound enhanced advanced Fenton process for decolorization of methylene blue. J Ind Eng Chem 28:153–160. CrossRefGoogle Scholar
  55. Xu J, Wu H-T, Wang X, Xue B, Li Y-X, Cao Y (2013) A new and environmentally benign precursor for the synthesis of mesoporous g-C3N4 with tunable surface area. Phys Chem Chem Phys 15:4510–4517. CrossRefGoogle Scholar
  56. Yao Y, Lu F, Zhu Y, Wei F, Liu X, Lian C, Wang S (2015) Magnetic core–shell CuFe2O4@C3N4 hybrids for visible light photocatalysis of Orange II. J Hazard Mater 297:224–233. CrossRefGoogle Scholar
  57. Yao Y, Wu G, Lu F, Wang S, Hu Y, Zhang J, Huang W, Wei F (2016) Enhanced photo-Fenton-like process over Z-scheme CoFe2O4/g-C3N4 heterostructures under natural indoor light. Environ Sci Pollut Res 23:21833–21845. CrossRefGoogle Scholar
  58. Zhang H, Wei C, Huang Y, Wang J (2016) Preparation of cube micrometer potassium niobate (KNbO3) by hydrothermal method and sonocatalytic degradation of organic dye. Ultrason Sonochem 30:61–69. CrossRefGoogle Scholar
  59. Zhang S, Li J, Zeng M, Zhao G, Xu J, Hu W, Wang X (2013) In situ synthesis of water-soluble magnetic graphitic carbon nitride photocatalyst and its synergistic catalytic performance. ACS Appl Mater Interfaces 5:12735–12743. CrossRefGoogle Scholar
  60. Zhou M, Yang H, Xian T, Li RS, Zhang HM, Wang XX (2015) Sonocatalytic degradation of RhB over LuFeO3 particles under ultrasonic irradiation. J Hazard Mater 289:149–157. CrossRefGoogle Scholar
  61. Zhu J, Xiao P, Li H, Carabineiro SAC (2014) Graphitic carbon nitride: synthesis, properties, and applications in catalysis. ACS Appl Mater Interfaces 6:16449–16465. CrossRefGoogle Scholar
  62. Zolgharnein J, Bagtash M, Asanjarani N (2014) Hybrid central composite design approach for simultaneous optimization of removal of alizarin red S and indigo carmine dyes using cetyltrimethylammonium bromide-modified TiO2 nanoparticles. J Environ Chem Eng 2:988–1000. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Materials Science and Nanotechnology Engineering, Faculty of EngineeringNear East UniversityNicosiaTurkey
  2. 2.Department of Chemistry, Faculty of ScienceAtatürk UniversityErzurumTurkey
  3. 3.Department of ChemistryKoç UniversitySariyer, IstanbulTurkey

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