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Enhanced adsorptive removal of selected pharmaceutical antibiotics from aqueous solution by activated graphene

Environmental Science and Pollution Research volume 22, pages 4715–4724 (2015)Cite this article

Abstract

Activated graphene adsorbents (G-KOH) were synthesized by a one-step alkali-activated method, with a high specific surface area (SSA) and a large number of micropores. As a result, the SSA of the final product greatly increases to ∼512.6 m2/g from ∼138.20 m2/g. The resulting G-KOH was used firstly as an adsorbent for the removal of ciprofloxacin (CIP) in aqueous solutions. Experimental results indicated that G-KOH has excellent adsorption capacity (∼194.6 mg/g). The alkali-activation treatment introduced oxygen-containing functional groups on the surface of G-KOH, which would be beneficial to improving the adsorption affinity of G-KOH for the removal of CIP. Kinetic regression results showed that the adsorption kinetic was more accurately represented by a pseudo-second-order model. The overall adsorption process was jointly controlled by external mass transfer and intra-particle diffusion, and intra-particle diffusion played a dominant role. A Langmuir isotherm model showed a better fit with adsorption data than a Freundlich isotherm model for the adsorption of CIP on G-KOH. The remarkable adsorption capacity of CIP onto G-KOH can be attributed to the multiple adsorption interaction mechanisms (hydrogen bonding, π–π electron donor–acceptor interactions, and electrostatic interactions). Results of this work are of great significance for environmental applications of activated graphene with higher SSA as a promising adsorbent for organic pollutants from aqueous solutions.

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References

  • Al-Degs YS, El-Barghouthi MI, Issa AA, Khraisheh MA, Walker GM (2006) Sorption of Zn(II), Pb(II), and Co(II) using natural sorbents: equilibrium and kinetic studies. Water Res 40:2645–2658

    Article  CAS  Google Scholar 

  • Apul OG, Shao T, Zhang SJ, Karanfil T (2012) Impact of carbon nanotube morphology on phenanthrene adsorption. Environ Toxicol Chem 31:73–78

    Article  CAS  Google Scholar 

  • Behnajady MA, Modirshahla N, Fathi H (2006) Kinetics of decolorization of an azo dye in UV alone and UV/H2O2 processes. J Hazard Mater 136:816–821

    Article  CAS  Google Scholar 

  • Crini G (2006) Non-conventional low-cost adsorbents for dye removal: a review. Bioresour Technol 97:1061–1085

    Article  CAS  Google Scholar 

  • Dogan M, Abak H, Alkan M (2009) Adsorption of methylene blue onto hazelnut shell: kinetics, mechanism and activation parameters. J Hazard Mater 164:172–181

    Article  CAS  Google Scholar 

  • Freundlich HMF (1906) Over the adsorption in solution. J Phys Chem 57:385–471

    CAS  Google Scholar 

  • Ghaedi M, Hassanzadeh A, Kokhdan SN (2011) Multiwalled carbon nanotubes as adsorbents for the kinetic and equilibrium study of the removal of Alizarin Red S and Morin. J Chem Eng Data 56:2511–2520

    Article  CAS  Google Scholar 

  • Gupta VK, Ali I (2008) Removal of endosulfan and methoxychlor from water on carbon slurry. Environ Sci Technol 42:766–770

    Article  CAS  Google Scholar 

  • Gupta VK, Mittal A, Gajbe V, Mittal J (2008) Adsorption of basic fuchsin using waste materials-bottom ash and deoiled soya-as adsorbents. J Colloid Interface Sci 319:30–39

    Article  CAS  Google Scholar 

  • Gupta VK, Mittal A, Malviya A, Mittal J (2009) Adsorption of carmoisine A from wastewater using waste materials-Bottom ash and deoiled soya. J Colloid Interface Sci 335:24–33

    Article  CAS  Google Scholar 

  • Gupta VK, Gupta B, Rastogi A, Agarwal S, Nayak A (2011) A comparative investigation on adsorption performances of mesoporous activated carbon prepared from waste rubber tire and activated carbon for a hazardous azo dye-Acid Blue 113. J Hazard Mater 186:891–901

    Article  CAS  Google Scholar 

  • Hirata M, Gotou T, Horiuchi S, Fujiwara M, Ohba M (2004) Thin-film particles of graphite oxide 1: high-yield synthesis and flexibility of the particles. Carbon 42:2929–2937

    CAS  Google Scholar 

  • Huang LH, Wang M, Shi CX, Huang J, Zhang B (2014) Adsorption of tetracycline and ciprofloxacin on activated carbon prepared from lignin with H3PO4 activation. Desalin Water Treat 52:2678–2687

    Article  CAS  Google Scholar 

  • Hummers WS Jr, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339

    Article  CAS  Google Scholar 

  • Iriarte-Velasco U, Chimeno-Alanis N, Gonzalez-Marcos MP, Alvarez-Uriarte JI (2011) Relationship between thermodynamic data and adsorption/desorption performance of acid and basic dyes onto activated carbons. J Chem Eng Data 56:2100–2109

    Article  CAS  Google Scholar 

  • Jovanovic BM, Vukasinovic-Pesic VL, Rajakovic LV (2011) Enhanced arsenic sorption by hydrated iron (III) oxide-coated materials-mechanism and performances. Water Environ Res 83:498–506

    Article  CAS  Google Scholar 

  • Kumar KV, Ramamurthi V, Sivanesan S (2005) Modeling the mechanism involved during the sorption of methylene blue onto fly ash. J Colloid Interface Sci 284:14–21

    Article  CAS  Google Scholar 

  • Kuppireddy SKR, Rashid K, Al Shoaibi A, Srinivasakannan C (2014) Production and characterization of porous carbon from date palm seeds by chemical activation with H3PO4: process optimization for maximizing adsorption of methylene blue. Chem Eng Commun 201:1021–1040

    Article  CAS  Google Scholar 

  • Langmuir I (1918) The adsorption of gases on plane surfaces of glass, mica and platinum. J Am Chem Soc 40:1361–1403

    Article  CAS  Google Scholar 

  • Li YM, van Zijll M, Chiang S, Pan N (2011) KOH modified graphene nanosheets for supercapacitor electrodes. J Power Sources 196:6003–6006

    Article  CAS  Google Scholar 

  • Li HB, Zhang D, Han XZ, Xing BS (2014) Adsorption of antibiotic ciprofloxacin on carbon nanotubes: pH dependence and thermodynamics. Chemosphere 95:150–155

    Article  CAS  Google Scholar 

  • Lillo-Rodenas MA, Cazorla-Amoros D, Linares-Solano A (2003) Understanding chemical reactions between carbons and NaOH and KOH - an insight into the chemical activation mechanism. Carbon 41:267–275

    Article  CAS  Google Scholar 

  • Lillo-Rodenas MA, Juan-Juan J, Cazorla-Amoros D, Linares-Solano A (2004) About reactions occurring during chemical activation with hydroxides. Carbon 42:1371–1375

    Article  CAS  Google Scholar 

  • Ma J, Wang JN (2008) Purification of single-walled carbon nanotubes by a highly efficient and nondestructive approach. Chem Mater 20:2895–2902

    Article  CAS  Google Scholar 

  • Ma J, Wang JN, Wang XX (2009) Large-diameter and water-dispersible single-walled carbon nanotubes: synthesis, characterization and applications. J Mater Chem 19:3033–3041

    Article  CAS  Google Scholar 

  • Ma J, Yu F, Zhou L, Jin L, Yang MX, Luan JS, Tang YH, Fan HB, Yuan ZW, Chen JH (2012) Enhanced adsorptive removal of methyl orange and methylene blue from aqueous solution by alkali-activated multiwalled carbon nanotubes. ACS Appl Mater Inter 4:5749–5760

    Article  CAS  Google Scholar 

  • Ma J, Zhou L, Li C, Yang JH, Meng T, Zhou HM, Yang MX, Yu F, Chen JH (2014) Surfactant-free synthesis of graphene-functionalized carbon nanotube film as a catalytic counter electrode in dye-sensitized solar cells. J Power Sources 247:999–1004

    Article  CAS  Google Scholar 

  • Onyango MS, Kojima Y, Aoyi O, Bernardo EC, Matsuda H (2004) Adsorption equilibrium modeling and solution chemistry dependence of fluoride removal from water by trivalent-cation-exchanged zeolite F-9. J Colloid Interface Sci 279:341–350

    Article  CAS  Google Scholar 

  • Rengaraj S, Kim Y, Joo CK, Yi J (2004) Removal of copper from aqueous solution by aminated and protonated mesoporous aluminas: kinetics and equilibrium. J Colloid Interface Sci 273:14–21

    Article  CAS  Google Scholar 

  • Saka C (2012) BET, TG-DTG, FT-IR, SEM, iodine number analysis and preparation of activated carbon from acorn shell by chemical activation with ZnCl2. J Anal Appl Pyrol 95:21–24

    Article  CAS  Google Scholar 

  • Sankar M, Sekaran G, Sadulla S, Ramasami T (1999) Removal of diazo and triphenylmethane dyes from aqueous solutions through an adsorption process. J Chem Technol Biotechnol 74:337–344

    Article  CAS  Google Scholar 

  • Souza Filho A, Jorio A, Samsonidze GG, Dresselhaus G, Pimenta M, Dresselhaus M, Swan AK, Ünlü M, Goldberg B, Saito R (2003) Competing spring constant versus double resonance effects on the properties of dispersive modes in isolated single-wall carbon nanotubes. Phys Rev B 67:035427

    Article  Google Scholar 

  • Tahir SS, Rauf N (2006) Removal of a cationic dye from aqueous solutions by adsorption onto bentonite clay. Chemosphere 63:1842–1848

    Article  CAS  Google Scholar 

  • Wang ZY, Yu XD, Pan B, Xing BS (2010) Norfloxacin sorption and its thermodynamics on surface-modified carbon nanotubes. Environ Sci Technol 44:978–984

    Article  CAS  Google Scholar 

  • Wu QF, Li ZH, Hong HL, Yin K, Tie LY (2010) Adsorption and intercalation of ciprofloxacin on montmorillonite. Appl Clay Sci 50:204–211

    Article  CAS  Google Scholar 

  • Wu SL, Zhao XD, Li YH, Zhao CT, Du QJ, Sun JK, Wang YH, Peng XJ, Xia YZ, Wang ZH, Xia LH (2013) Adsorption of ciprofloxacin onto biocomposite fibers of graphene oxide/calcium alginate. Chem Eng J 230:389–395

    Article  CAS  Google Scholar 

  • Xia BY, Yan Y, Wang X, Lou XW (2014) Recent progress on graphene-based hybrid electrocatalysts. Mater Horiz 1:379–399

    Article  CAS  Google Scholar 

  • Yang K, Wu WH, Jing QF, Zhu LZ (2008) Aqueous adsorption of aniline, phenol, and their substitutes by multi-walled carbon manotubes. Environ Sci Technol 42:7931–7936

    Article  CAS  Google Scholar 

  • Yu F, Ma J, Wu YQ (2011) Adsorption of toluene, ethylbenzene and m-xylene on multi-walled carbon nanotubes with different oxygen contents from aqueous solutions. J Hazard Mater 192:1370–1379

    Article  CAS  Google Scholar 

  • Yu F, Wu YQ, Ma J (2012) Influence of the pore structure and surface chemistry on adsorption of ethylbenzene and xylene isomers by KOH-activated multi-walled carbon nanotubes. J Hazard Mater 237:102–109

    Article  Google Scholar 

  • Zhu YW, Murali S, Stoller MD, Ganesh KJ, Cai WW, Ferreira PJ, Pirkle A, Wallace RM, Cychosz KA, Thommes M, Su D, Stach EA, Ruoff RS (2011) Carbon-based supercapacitors produced by activation of graphene. Science 332:1537–1541

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This research was supported by the National Natural Science Foundation of China (No. 21207100 and No. 51408362), Specialized Research Fund for the Doctoral Program of Higher Education (20120072120058), the Shanghai Institute of Technology Scientific Research Foundation for Introduced Talent, China (No. YJ2014-30), the Key Research Projects of the Science and Technology Commission of Shanghai Municipality (12231201702), and the Central Finance Special Fund to Support the Development of Local Colleges and Universities (City Safety Engineering). We are also thankful to anonymous reviewers for their valuable comments to improve this manuscript.

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Authors and Affiliations

  1. School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Hai Quan Road, Shanghai, 201418, China

    Fei Yu & Dongsu Bi

  2. State Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai, 200092, China

    Fei Yu & Jie Ma

Authors
  1. Fei Yu
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  2. Jie Ma
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Correspondence to Jie Ma or Dongsu Bi.

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Responsible editor: Philippe Garrigues

Fei Yu and Jie Ma contributed equally to this work.

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Yu, F., Ma, J. & Bi, D. Enhanced adsorptive removal of selected pharmaceutical antibiotics from aqueous solution by activated graphene. Environ Sci Pollut Res 22, 4715–4724 (2015). https://doi.org/10.1007/s11356-014-3723-9

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Keywords

  • Activated graphene
  • Adsorption
  • Ciprofloxacin