Graphene nanosheets as efficient adsorbent for an azo dye removal: kinetic and thermodynamic studies

  • Sara Samiee
  • Elaheh K. GoharshadiEmail author
Research Paper


Graphene nanosheets were synthesized by a cost effective, simple, and environmentally friendly procedure via burning Mg ribbons in dry ice. The graphene nanosheets were characterized by seven methods including X-ray diffraction, transmission electron microscopy (TEM) and high-resolution TEM, scanning electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, and N2 adsorption–desorption technique (BET). The BET analysis confirmed that graphene nanosheets with the average pore diameter of 6.28 nm can be considered as a good adsorbent. The next step was to investigate the potential of graphene nanosheets for adsorption of an azo dye, Reactive Black 5 (RB5). The influence of different parameters including adsorbent dosage, pH, temperature, dye concentration, and ionic strength on the dye removal efficiency was studied. The experimental data were fitted well with the pseudo-second-order kinetic model (R 2 = 0.997). The activation energy of 25.80 kJ mol−1 revealed the physisorption of RB5 on graphene. The adsorption isotherm was described well by Freundlich isotherm. The high value of Freundlich constant (191.9 mg1−1/n  L1/n  g−1) shows the high capacity of graphene for the RB5 adsorption from aqueous solutions. The thermodynamic parameters confirmed that the RB5 adsorption on graphene surface was spontaneous and endothermic. Some significant features of using graphene as an adsorbent for RB5 removal are the fast dye removal process, the low required amount of graphene, and the frequent usage of graphene with no change in its efficiency.


Few-layer graphene nanosheets Dye removal Reactive Black 5 Adsorption Thermodynamic study 



The authors acknowledge Ferdowsi University of Mashhad for supporting of this project (3/23032). Also, the authors gratefully appreciate Mrs. Roksana Pesian for taking TEM image and Mr. Alireza Bakhtiari for taking BET.


  1. 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
  2. Al-Degs YS, El-Barghouthi MI, El-Sheikh AH, Walker GM (2008) Effect of solution pH, ionic strength, and temperature on adsorption behavior of reactive dyes on activated carbon. Dyes Pigments 77(1):16–23CrossRefGoogle Scholar
  3. Annadurai G, Ling LY, Lee J-F (2008) Adsorption of reactive dye from an aqueous solution by chitosan: isotherm, kinetic and thermodynamic analysis. J Hazard Mater 152(1):337–346CrossRefGoogle Scholar
  4. Chakrabarti A, Lu J, Skrabutenas JC, Xu T, Xiao Z, Maguire JA, Hosmane NS (2011) Conversion of carbon dioxide to few-layer graphene. J Mater Chem 21(26):9491–9493Google Scholar
  5. Chatterjee S, Chatterjee T, Woo SH (2011) Influence of the polyethyleneimine grafting on the adsorption capacity of chitosan beads for Reactive Black 5 from aqueous solutions. Chem Eng J 166(1):168–175CrossRefGoogle Scholar
  6. Cheng X, Kan AT, Tomson MB (2004) Naphthalene adsorption and desorption from aqueous C60 fullerene. J Chem Eng Data 49(3):675–683CrossRefGoogle Scholar
  7. Cheung WH, Szeto YS, McKay G (2007) Intraparticle diffusion processes during acid dye adsorption onto chitosan. Bioresour Technol 98(15):2897–2904CrossRefGoogle Scholar
  8. Combes RD, Haveland-Smith RB (1982) A review of the genotoxicity of food, drug and cosmetic colours and other azo, triphenylmethane and xanthene dyes. Mutat Res 98(2):101–243CrossRefGoogle Scholar
  9. Deng X, Lü L, Li H, Luo F (2010) The adsorption properties of Pb(II) and Cd(II) on functionalized graphene prepared by electrolysis method. J Hazard Mater 183(1–3):923–930CrossRefGoogle Scholar
  10. Dresselhaus MS, Jorio A, Hofmann M, Dresselhaus G, Saito R (2010) Perspectives on carbon nanotubes and graphene Raman spectroscopy. Nano Lett 10(3):751–758CrossRefGoogle Scholar
  11. Eren Z, Acar FN (2007) Equilibrium and kinetic mechanism for Reactive Black 5 sorption onto high lime Soma fly ash. J Hazard Mater 143(1–2):226–232CrossRefGoogle Scholar
  12. Ferrari AC, Robertson J (2000) Interpretation of Raman spectra of disordered and amorphous carbon. Phys Rev B 61(20):14095–14107CrossRefGoogle Scholar
  13. Ferrari AC, Meyer JC, Scardaci V, Casiraghi C, Lazzeri M, Mauri F, Piscanec S, Jiang D, Novoselov KS, Roth S, Geim AK (2006) Raman spectrum of graphene and graphene layers. Phys Rev Lett 97(18):187401CrossRefGoogle Scholar
  14. Forgacs E, Cserháti T, Oros G (2004) Removal of synthetic dyes from wastewaters: a review. Environ Int 30(7):953–971CrossRefGoogle Scholar
  15. Georgakilas V, Otyepka M, Bourlinos AB, Chandra V, Kim N, Kemp KC, Hobza P, Zboril R, Kim KS (2012) Functionalization of graphene: covalent and non-covalent approaches, derivatives and applications. Chem Rev 112(11):6156–6214CrossRefGoogle Scholar
  16. Graf D, Molitor F, Ensslin K, Stampfer C, Jungen A, Hierold C, Wirtz L (2007) Spatially resolved Raman spectroscopy of single- and few-layer graphene. Nano Lett 7(2):238–242CrossRefGoogle Scholar
  17. Gulnaz O, Kaya A, Dincer S (2006) The reuse of dried activated sludge for adsorption of reactive dye. J Hazard Mater 134(1–3):190–196CrossRefGoogle Scholar
  18. Gupta VK, Suhas (2009) Application of low-cost adsorbents for dye removal—a review. J Environ Manage 90(8):2313–2342CrossRefGoogle Scholar
  19. Ho YS, McKay G (1998) The kinetics of sorption of basic dyes from aqueous solution by sphagnum moss peat. Can J Chem Eng 76(4):822–827Google Scholar
  20. Huang X, Yin Z, Wu S, Qi X, He Q, Zhang Q, Yan Q, Boey F, Zhang H (2011) Graphene-based materials: synthesis, characterization, properties, and applications. Small 7(14):1876–1902CrossRefGoogle Scholar
  21. Ip AWM, Barford JP, McKay G (2009) Reactive Black dye adsorption/desorption onto different adsorbents: effect of salt, surface chemistry, pore size and surface area. J Colloid Interface Sci 337(1):32–38CrossRefGoogle Scholar
  22. Joo JB, Park J, Yi J (2009) Preparation of polyelectrolyte-functionalized mesoporous silicas for the selective adsorption of anionic dye in an aqueous solution. J Hazard Mater 168(1):102–107CrossRefGoogle Scholar
  23. Kilpatrick M, Baker LL, McKinney CD (1953) Studies of fast reactions which evolve gases.the reaction of sodium–potassium alloy with water in the presence and absence of oxygen. J Phys Chem 57(4):385–390Google Scholar
  24. Kim H, Abdala AA, Macosko CW (2010) Graphene/polymer nanocomposites. Macromolecules 43(16):6515–6530CrossRefGoogle Scholar
  25. Konicki W, Pełech I, Mijowska E, Jasińska I (2012) Adsorption of anionic dye Direct Red 23 onto magnetic multi-walled carbon nanotubes-Fe3C nanocomposite: kinetics, equilibrium and thermodynamics. Chem Eng J 210:87–95CrossRefGoogle Scholar
  26. Kyzas G, Travlou N, Kalogirou O, Deliyanni E (2013) Magnetic graphene oxide: effect of preparation route on Reactive Black 5 adsorption. Materials 6(4):1360–1376CrossRefGoogle Scholar
  27. Lagergren S (1898) Zur theorie der sogenannten adsorption gelöster stoffe. Kungliga Svenska Vetenskapsakademiens, Handlingar 24:1–39Google Scholar
  28. Langmuir I (1916) The constitution and fundamental properties of solids and liquids. Part I. Solids. J Am Chem Soc 38(11):2221–2295CrossRefGoogle Scholar
  29. Li N, Zheng M, Chang X, Ji G, Lu H, Xue L, Pan L, Cao J (2011) Preparation of magnetic CoFe2O4-functionalized graphene sheets via a facile hydrothermal method and their adsorption properties. J Solid State Chem 184(4):953–958CrossRefGoogle Scholar
  30. Lin Y-F, Chen H-W, Chien P-S, Chiou C-S, Liu C–C (2011) Application of bifunctional magnetic adsorbent to adsorb metal cations and anionic dyes in aqueous solution. J Hazard Mater 185(2–3):1124–1130CrossRefGoogle Scholar
  31. Lucas MS, Peres JA (2006) Decolorization of the azo dye Reactive Black 5 by Fenton and photo-Fenton oxidation. Dyes Pigments 71(3):236–244CrossRefGoogle Scholar
  32. Luo X, Zhang L (2009) High effective adsorption of organic dyes on magnetic cellulose beads entrapping activated carbon. J Hazard Mater 171(1–3):340–347CrossRefGoogle Scholar
  33. Madrakian T, Afkhami A, Ahmadi M, Bagheri H (2011) Removal of some cationic dyes from aqueous solutions using magnetic-modified multi-walled carbon nanotubes. J Hazard Mater 196:109–114CrossRefGoogle Scholar
  34. McMullan G, Meehan C, Conneely A, Kirby N, Robinson T, Nigam P, Banat I, Marchant R, Smyth W (2001) Microbial decolourisation and degradation of textile dyes. Appl Microbiol Biotechnol 56(1–2):81–87CrossRefGoogle Scholar
  35. Moghaddam MB, Goharshadi EK, Entezari MH, Nancarrow P (2013) Preparation, characterization, and rheological properties of graphene–glycerol nanofluids. Chem Eng J 231:365–372CrossRefGoogle Scholar
  36. Nguyen TA, Juang R-S (2013) Treatment of waters and wastewaters containing sulfur dyes: a review. Chem Eng J 219:109–117CrossRefGoogle Scholar
  37. Nollet H, Roels M, Lutgen P, Van der Meeren P, Verstraete W (2003) Removal of PCBs from wastewater using fly ash. Chemosphere 53(6):655–665CrossRefGoogle Scholar
  38. Oh W-C, Chen M, Cho K, Kim C, Meng Z, Zhu L (2011) Synthesis of graphene-CdSe composite by a simple hydrothermal method and its photocatalytic degradation of organic dyes. Chin J Catal 32(9–10):1577–1583CrossRefGoogle Scholar
  39. Otero R, Fernández JM, González MA, Pavlovic I, Ulibarri MA (2013) Pesticides adsorption–desorption on Mg–Al mixed oxides. Kinetic modeling, competing factors and recyclability. Chem Eng J 221:214–221CrossRefGoogle Scholar
  40. Ozdemir O, Armagan B, Turan M, Çelik MS (2004) Comparison of the adsorption characteristics of azo-reactive dyes on mezoporous minerals. Dyes Pigments 62(1):49–60CrossRefGoogle Scholar
  41. Patel R, Suresh S (2008) Kinetic and equilibrium studies on the biosorption of Reactive Black 5 dye by Aspergillus foetidus. Bioresour Technol 99(1):51–58CrossRefGoogle Scholar
  42. Ramesha GK, Vijaya Kumara A, Muralidhara HB, Sampath S (2011) Graphene and graphene oxide as effective adsorbents toward anionic and cationic dyes. J Colloid Int Sci 361(1):270–277CrossRefGoogle Scholar
  43. Robinson T, McMullan G, Marchant R, Nigam P (2001) Remediation of dyes in textile effluent: a critical review on current treatment technologies with a proposed alternative. Bioresour Technol 77(3):247–255CrossRefGoogle Scholar
  44. Sakintuna B, Yürüm Y, Çetinkaya S (2004) Evolution of carbon microstructures during the pyrolysis of Turkish elbistan lignite in the temperature range 700–1000 °C. Energy Fuels 18(3):883–888CrossRefGoogle Scholar
  45. Salleh MAM, Mahmoud DK, Karim WAWA, Idris A (2011) Cationic and anionic dye adsorption by agricultural solid wastes: a comprehensive review. Desalination 280(1–3):1–13CrossRefGoogle Scholar
  46. Travlou NA, Kyzas GZ, Lazaridis NK, Deliyanni EA (2013) Graphite oxide/chitosan composite for reactive dye removal. Chem Eng J 217:256–265CrossRefGoogle Scholar
  47. Vandevivere PC, Bianchi R, Verstraete W (1998) Review: treatment and reuse of wastewater from the textile wet-processing industry: review of emerging technologies. J Chem Technol Biotechnol 72(4):289–302CrossRefGoogle Scholar
  48. Wang B, Chang Y-h, Zhi L-j (2011) High yield production of graphene and its improved property in detecting heavy metal ions. New Carbon Mater 26(1):31–35CrossRefGoogle Scholar
  49. Webi TW, Chakravort RK (1974) Pore and solid diffusion models for fixed-bed adsorbers. AlChE J 20(2):228–238CrossRefGoogle Scholar
  50. Wu T, Cai X, Tan S, Li H, Liu J, Yang W (2011) Adsorption characteristics of acrylonitrile, p-toluenesulfonic acid, 1-naphthalenesulfonic acid and methyl blue on graphene in aqueous solutions. Chem Eng J 173(1):144–149CrossRefGoogle Scholar
  51. Xue Y, Hou H, Zhu S (2009) Adsorption removal of reactive dyes from aqueous solution by modified basic oxygen furnace slag: isotherm and kinetic study. Chem Eng J 147(2–3):272–279CrossRefGoogle Scholar
  52. Yang X, Yang S, Yang S, Hu J, Tan X, Wang X (2011) Effect of pH, ionic strength and temperature on sorption of Pb(II) on NKF-6 zeolite studied by batch technique. Chem Eng J 168(1):86–93CrossRefGoogle Scholar
  53. Yang L, Yee WA, Phua SL, Kong J, Ding H, Cheah JW, Lu X (2012) A high throughput method for preparation of highly conductive functionalized graphene and conductive polymer nanocomposites. RSC Adv 2(6):2208–2210CrossRefGoogle Scholar
  54. Zhang J, Zhang Y, Quan X, Li Y, Chen S, Zhao H, Wang D (2012) An anaerobic reactor packed with a pair of Fe-graphite plate electrodes for bioaugmentation of azo dye wastewater treatment. Biochem Eng J 63:31–37CrossRefGoogle Scholar
  55. Zong E, Wei D, Wan H, Zheng S, Xu Z, Zhu D (2013) Adsorptive removal of phosphate ions from aqueous solution using zirconia-functionalized graphite oxide. Chem Eng J 221:193–203CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2014

Authors and Affiliations

  1. 1.Department of ChemistryFerdowsi University of MashhadMashhadIran
  2. 2.Center of Nano ResearchFerdowsi University of MashhadMashhadIran

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