Journal of Materials Science

, Volume 51, Issue 10, pp 4928–4941 | Cite as

Thermodynamics of dye adsorption on electrochemically exfoliated graphene

  • Zhishuang Xue
  • Shanlin Zhao
  • Zenghua Zhao
  • Ping Li
  • Jianhui Gao
Original Paper


Graphene sheets prepared by electrochemical exfoliation have been used for the adsorption of methylene blue (MB), a cationic dye from aqueous solution. The maximum adsorbed amount of MB on exfoliated graphene (EG) reaches 511.7 mg g−1 when the initial concentration of MB is 500 mg L−1, with EG whose dosage is 10 mg. Further study on the adsorption mechanism of EG includes isothermal adsorption equilibrium, thermodynamics, and kinetics. The study on isothermal adsorption equilibrium shows that the adsorption follows the Langmuir isotherm. Various thermodynamic parameters such as Gibbs free energy (∆G 0), enthalpy (∆H 0), and entropy (∆S 0) change were also evaluated. It indicates that the adsorption is a spontaneous, endothermic, and physical adsorption process. The kinetic data reveals that the adsorption process of MB fits well with the pseudo second-order model. The Weber’s intra-particle diffusion model demonstrates that the adsorption rate is controlled by both external diffusion and intra-particle diffusion. EG as a cationic dye scavenger displays high speed and efficiency.


Adsorption Capacity Graphene Oxide Methylene Blue Adsorption Process Adsorbent Dosage 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



This study was funded by Science and Technology Department of Liaoning Province (Grant number 2011223011).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10853_2016_9798_MOESM1_ESM.docx (443 kb)
Supplementary material 1 (DOCX 443 kb)


  1. 1.
    Yu B, Zhang X, Xie J et al (2015) Magnetic graphene sponge for the removal of methylene blue. Appl Surf Sci 351:765–771CrossRefGoogle Scholar
  2. 2.
    Wu T, Cai X, Tan S et al (2011) Adsorption characteristics of acrylonitrile, p-toluenesulfonic acid, 1-naphthalenesulfonic acid and methyl blue on graphene in aqueous solutions. Chem Eng J 173:144–149CrossRefGoogle Scholar
  3. 3.
    Yang S, Chen S, Chang Y et al (2011) Removal of methylene blue from aqueous solution by graphene oxide. J Colloid Interface Sci 359:24–29CrossRefGoogle Scholar
  4. 4.
    Parmar KR, Patel I, Basha S et al (2014) Synthesis of acetone reduced graphene oxide/Fe3O4 composite through simple and efficient chemical reduction of exfoliated graphene oxide for removal of dye from aqueous solution. J Mater Sci 49:6772–6783. doi: 10.1007/s10853-014-8378-x CrossRefGoogle Scholar
  5. 5.
    de Matos JB, Cardoso MJEM, Barcia OE et al (2010) Study of oxygen reduction on copper applied to the peroxidase-mediated oxidation of methylene blue. J Mater Sci 45:1677–1682. doi: 10.1007/s10853-009-4151-y CrossRefGoogle Scholar
  6. 6.
    Chen Z, Chen H, Pan X et al (2015) Investigation of methylene blue biosorption and biodegradation by Bacillus thuringiensis 016. Water Air Soil Pollut 226:146CrossRefGoogle Scholar
  7. 7.
    Lamdab U, Wetchakun K, Phanichphant S et al (2015) Highly efficient visible light-induced photocatalytic degradation of methylene blue over InVO4/BiVO4 composite photocatalyst. J Mater Sci 50:5788–5798. doi: 10.1007/s10853-015-9126-6 CrossRefGoogle Scholar
  8. 8.
    Cui L, Guo X, Wei Q et al (2015) Removal of mercury and methylene blue from aqueous solution by xanthate functionalized magnetic graphene oxide: sorption kinetic and uptake mechanism. J Colloid Interface Sci 439:112–120CrossRefGoogle Scholar
  9. 9.
    Liu X, Zhou Y, Nie W et al (2015) Fabrication of hydrogel of hydroxypropyl cellulose (HPC)composited with graphene oxide and its application for methylene blue removal. J Mater Sci 50:6113–6123. doi: 10.1007/s10853-015-9166-y CrossRefGoogle Scholar
  10. 10.
    Li C, Zhong H, Wang S et al (2015) Removal of basic dye (methylene blue) from aqueous solution using zeolite synthesized from electrolytic manganese residue. J Ind Eng Chem 23:344–352CrossRefGoogle Scholar
  11. 11.
    Elmoubarki R, Mahjoubi FZ, Tounsadi H et al (2015) Adsorption of textile dyes on raw and decanted Moroccan clays: kinetics, equilibrium and thermodynamics. Water Resour Ind 9:16–29CrossRefGoogle Scholar
  12. 12.
    Kumar PS, Palaniyappan M, Priyadharshini M et al (2014) Adsorption of basic dye onto raw and surface-modified agricultural waste. Environ Prog Sustain Energy 33:87–98CrossRefGoogle Scholar
  13. 13.
    Namazi AB, Jia CQ, Allen DG (2010) Production and characterization of lignocellulosic biomass-derived activated carbon. Water Sci Technol 62:2637–2646CrossRefGoogle Scholar
  14. 14.
    Kim H, Kang SO, Park S et al (2015) Adsorption isotherms and kinetics of cationic and anionic dyes on three-dimensional reduced graphene oxide macrostructure. J Ind Eng Chem 21:1191–1196CrossRefGoogle Scholar
  15. 15.
    Moradi O, Gupta VK, Agarwal S et al (2015) Characteristics and electrical conductivity of graphene and graphene oxide for adsorption of cationic dyes from liquids: kinetic and thermodynamic study. J Ind Eng Chem 28:294–301CrossRefGoogle Scholar
  16. 16.
    Namvari M, Namazi H (2015) Preparation of efficient magnetic biosorbents by clicking carbohydrates onto graphene oxide. J Mater Sci 50:5348–5361. doi: 10.1007/s10853-015-9082-1 CrossRefGoogle Scholar
  17. 17.
    Yan H, Tao X, Yang Z et al (2014) Effects of the oxidation degree of graphene oxide on the adsorption of methylene blue. J Hazard Mater 268:191–198CrossRefGoogle Scholar
  18. 18.
    Zamani S, Tabrizi N (2015) Removal of methylene blue from water by graphene oxide aerogel: thermodynamic, kinetic, and equilibrium modeling. Res Chem Intermed 41:7945–7963CrossRefGoogle Scholar
  19. 19.
    Marcano DC, Kosynkin DV, Berlin JM et al (2010) Improved synthesis of graphene oxide. ACS Nano 4:4806–4814CrossRefGoogle Scholar
  20. 20.
    Shen J, Hu Y, Shi M et al (2010) One step synthesis of graphene oxide-magnetic nanoparticle composite. J Phys Chem C 114:1498–1503CrossRefGoogle Scholar
  21. 21.
    Parvez K, Li R, Puniredd SR et al (2013) Electrochemically exfoliated graphene as solution-processable, highly conductive electrodes for organic electronics. ACS Nano 7:3598–3606CrossRefGoogle Scholar
  22. 22.
    Liu J, Notarianni M, Will G et al (2013) Electrochemically exfoliated graphene for electrode films: effect of graphene flake thickness on the sheet resistance and capacitive properties. Langmuir 29:13307–13314CrossRefGoogle Scholar
  23. 23.
    Parvez K, Wu ZS, Li R et al (2014) Exfoliation of graphite into graphene in aqueous solutions of inorganic salts. J Am Chem Soc 136:6083–6091CrossRefGoogle Scholar
  24. 24.
    Gee CM, Tseng CC, Wu FY et al (2013) Flexible transparent electrodes made of electrochemically exfoliated graphene sheets from low-cost graphite pieces. Displays 34:315–319CrossRefGoogle Scholar
  25. 25.
    Buglione L, Chng ELK, Ambrosi A et al (2012) Graphene materials preparation methods have dramatic influence upon their capacitance. Electrochem Commun 14:5–8CrossRefGoogle Scholar
  26. 26.
    Ferrari AC, Basko DM (2013) Raman spectroscopy as a versatile tool for studying the properties of graphene. Nat Nanotechnol 8:235–246CrossRefGoogle Scholar
  27. 27.
    Zhou M, Tang J, Cheng Q et al (2013) Few-layer graphene obtained by electrochemical exfoliation of graphite cathode. Chem Phys Lett 572:61–65CrossRefGoogle Scholar
  28. 28.
    Abdelkader AM, Kinloch IA, Dryfe RAW (2014) Continuous electrochemical exfoliation of micrometer-Sized graphene using synergistic ion intercalations and organic solvents. ACS Appl Mater Interfaces 6:1632–1639CrossRefGoogle Scholar
  29. 29.
    Sing KSW, Everett DH, Haul RAW et al (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure Appl Chem 57:603–619CrossRefGoogle Scholar
  30. 30.
    Ai L, Jiang J (2012) Removal of methylene blue from aqueous solution with self-assembled cylindrical graphene-carbon nanotube hybrid. Chem Eng J 192:156–163CrossRefGoogle Scholar
  31. 31.
    Zhang W, Zhou C, Zhou W et al (2011) Fast and considerable adsorption of methylene blue dye onto graphene oxide. Bull Environ Contam Toxicol l87:86–90Google Scholar
  32. 32.
    Liu F, Chung S, Oh G et al (2012) Three-Dimensional graphene oxide nanostructure for fast and efficient water-soluble dye removal. ACS Appl Mater Interfaces 4:922–927CrossRefGoogle Scholar
  33. 33.
    Sharma P, Das MR (2013) Removal of a cationic dye from aqueous solution using graphene oxide nanosheets: investigation of adsorption parameters. J Chem Eng Data 58:151–158CrossRefGoogle Scholar
  34. 34.
    Cheng C, Deng J, Lei B et al (2013) Toward 3D graphene oxide gels based adsorbents for high-efficient water treatment via the promotion of biopolymers. J Hazard Mater 263:467–478CrossRefGoogle Scholar
  35. 35.
    Fu J, Chen Z, Wang M et al (2015) Adsorption of methylene blue by a high-efficiency adsorbent (polydopamine microspheres): kinetics, isotherm, thermodynamics and mechanism analysis. Chem Eng J 259:53–61CrossRefGoogle Scholar
  36. 36.
    Bai L, Li Z, Zhang Y et al (2015) Synthesis of water-dispersible graphene-modified magnetic polypyrrole nanocomposite and its ability to efficiently adsorb methylene blue from aqueous solution. Chem Eng J 279:757–766CrossRefGoogle Scholar
  37. 37.
    Kumar YP, King P, Prasad VSRK (2006) Zinc. biosorption on Tectona grandis L.f. leaves biomass: equilibrium and kinetic studies. Chem Eng J 124:63–70CrossRefGoogle Scholar
  38. 38.
    Ma T, Chang PR, Zheng P et al (2014) Fabrication of ultra-light graphene-based gels and their adsorption of methylene blue. Chem Eng J 240:595–600CrossRefGoogle Scholar
  39. 39.
    Aluigi A, Rombaldoni F, Tonetti C et al (2014) Study of Methylene Blue adsorption on keratin nano fibrous membranes. J Hazard Mater 268:156–165CrossRefGoogle Scholar
  40. 40.
    Rahman N, Haseen U (2014) Equilibrium modeling, kinetic, and thermodynamic studies on adsorption of Pb(II) by a hybrid inorganic-organic material: polyacrylamide zirconium(IV) iodate. Ind Eng Chem Res 53:8198–8207CrossRefGoogle Scholar
  41. 41.
    Eskandarian L, Arami M, Pajootan E (2014) Evaluation of adsorption characteristics of multiwalled carbon nanotubes modified by a poly(propylene imine) dendrimer in single and multiple dye solutions: isotherms, kinetics, and thermodynamics. J Chem Eng Data 59:444–454CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  • Zhishuang Xue
    • 1
  • Shanlin Zhao
    • 1
  • Zenghua Zhao
    • 2
  • Ping Li
    • 1
  • Jianhui Gao
    • 1
  1. 1.School of Chemistry, Chemical Engineering and Environmental EngineeringLiaoning Shihua UniversityFushunPeople’s Republic of China
  2. 2.State Key Laboratory of Multiphase Complex Systems, Institute of Process EngineeringChinese Academy of SciencesBeijingPeople’s Republic of China

Personalised recommendations