Skip to main content

Advertisement

SpringerLink
Log in

Direct exfoliation of graphite into graphene in aqueous solution using a novel surfactant obtained from used engine oil

  • Chemical routes to materials
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

Large-scale production of high-quality graphene is very critical for practical applications of graphene materials and devices. Exfoliation of graphite in an aqueous solution of surfactants is one of the most promising approaches to produce graphene. In this study, a novel anionic surfactant [sulfonated used engine oil (SUEO)], which was prepared from used engine oil, was employed to exfoliate the graphite nanoplatelets into graphene sheets in an aqueous solution under sonication to form a stable dispersion. The efficiency of SUEO for exfoliating and dispersing graphene was investigated and compared with that of traditional surfactants, such as sodium dodecyl sulfate, sodium dodecyl benzene sulfate, cetyl trimethyl ammonium bromide, and polyvinylpyrrolidone. Result showed that the graphene dispersion with excellent stability had a higher concentration (0.477 mg/mL) than others at 0.5 g/L optimal SUEO dosage in 4 h sonication time. The superior performance of SUEO can be attributed to its special molecular structures, whose hydrophobic moieties contain cycloalkanes/aromatics with different molecular weights and/or side chain –R with different lengths. Structural diversities are very helpful to the “jigsaw-puzzle” process on the graphene surface, where the total interfacial energy of the mixture system was minimized. Microscopic (SEM, TEM, and AFM) and spectroscopic (XRD, XPS, and Raman) measurements revealed that the dispersion consisted of few-layer graphene sheets with lower levels of defects or oxidation. This study presents a new class of dispersing agents for graphene that assists in the exfoliation process in water with high concentration and the stabilization of the graphene sheets against reaggregation.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10

Similar content being viewed by others

References

  1. Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, Grigorieva IV, Firsov AA (2004) Electric field effect in atomically thin carbon films. Science 306:666–669

    Article  Google Scholar 

  2. Geim AK, Novoselov KS (2007) The rise of grapheme. Nat Mater 6:183–191

    Article  Google Scholar 

  3. Guo CX, Yang HB, Sheng ZM, Lu ZS, Song QL, Li CM (2010) Layered graphene/quantum dots for photovoltaic devices. Angew Chem Int Ed 49:3014–3017

    Article  Google Scholar 

  4. Allen MJ, Tung VC, Kaner RB (2009) Honeycomb carbon: a review of grapheme. Chem Rev 110:132–145

    Article  Google Scholar 

  5. Dai L (2012) Functionalization of graphene for efficient energy conversion and storage. Acc Chem Res 46:31–42

    Article  Google Scholar 

  6. Fernández-Merino MJ, Paredes JI, Villar-Rodil S, Guardia L, Solís-Fernández P, Salinas-Torres D, Cazorla-Amorós D, Morallón E, Martínez-Alonso A, Tascón JMD (2012) Investigating the influence of surfactants on the stabilization of aqueous reduced graphene oxide dispersions and the characteristics of their composite films. Carbon 50:3184–3194

    Article  Google Scholar 

  7. Chae SJ, Güneş F, Kim KK, Kim ES, Han GH, Kim SM, Shin HJ, Yoon SM, Choi JY, Park MH, Yang CW, Pribat D, Lee YH (2009) Synthesis of large-area graphene layers on poly-nickel substrate by chemical vapor deposition: wrinkle formation. Adv Mater 21:2328–2333

    Article  Google Scholar 

  8. Emtsev KV, Bostwick A, Horn K, Jobst J, Kellogg GL, Ley L, McChesney JL, Ohta T, Reshanov SA, Röhrl J, Rotenbery E, Schmid AK, Waldmann D, Weber HB, Seyller T (2009) Towards wafer-size graphene layers by atmospheric pressure graphitization of silicon carbide. Nat Mater 8:203–207

    Article  Google Scholar 

  9. Lee JH, Shin DW, Makotchenko VG, Nazarov AS, Fedorov VE, Kim YH, Choi JY, Kim JM, Yoo JB (2009) One-step exfoliation synthesis of easily soluble graphite and transparent conducting graphene sheets. Adv Mater 21:4383–4387

    Article  Google Scholar 

  10. Park S, Ruoff RS (2009) Chemical methods for the production of graphemes. Nat Nanotechnol 4:217–224

    Article  Google Scholar 

  11. Khan U, O’Neill A, Lotya M, De S, Coleman JN (2010) High-concentration solvent exfoliation of grapheme. Small 6:864–871

    Article  Google Scholar 

  12. Lee JH, Shin DW, Makotchenko VG, Nazarov AS, Fedorov VE, Yoo JH, Yu SM, Choi JY, Kim JM, Yoo JB (2010) The superior dispersion of easily soluble graphite. Small 6:58–62

    Article  Google Scholar 

  13. Ramalingam P, Pusuluri ST, Periasamy S, Veerabahu R, Kulandaivel J (2013) Role of deoxy group on the high concentration of graphene in surfactant/water media. RSC Adv 3:2369–2378

    Article  Google Scholar 

  14. McAllister MJ, Li JL, Adamson DH, Schniepp H, Abdala AA, Liu J, Herrera-Alonso M, Milius DL, Car R, Prud’homme RK (2007) Single sheet functionalized graphene by oxidation and thermal expansion of graphite. Chem Mater 19:4396–4404

    Article  Google Scholar 

  15. Stankovich S, Piner RD, Nguyen SBT, Ruoff RS (2006) Synthesis and exfoliation of isocyanate-treated graphene oxide nanoplatelets. Carbon 44:3342–3347

    Article  Google Scholar 

  16. Stankovich S, Piner RD, Chen XQ, Wu NQ, Nguyen S, Ruoff R (2006) Stable aqueous dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite oxide in the presence of poly (sodium 4-styrenesulfonate). J Mater Chem 16:155–158

    Article  Google Scholar 

  17. Lotya M, Hernandez Y, King PJ, Smith RJ, Nicolosi V, Karlsson LS, Blighe FM, De S, Wang Z, McGovern IT, Duesberg GS, Coleman JN (2009) Liquid phase production of graphene by exfoliation of graphite in surfactant/water solutions. J Am Chem Soc 131:3611–3620

    Article  Google Scholar 

  18. Kang MS, Kim KT, Lee JU, Jo WH (2013) Direct exfoliation of graphite using a non-ionic polymer surfactant for fabrication of transparent and conductive graphene films. J Mater Chem C 1:1870–1875

    Article  Google Scholar 

  19. Hernandez Y, Nicolosi V, Lotya M, Blighe FM, Sun ZY, De S, McGovern IT, Holland B, Byrne M, Gun’ko YK, Boland JJ, Niraj P, Duesberg G, Krishnamurthy S, Goodhue R, Hutchison J, Scardaci V, Ferrari AC, Coleman JN (2008) High-yield production of graphene by liquid-phase exfoliation of graphite. Nat Nanotechnol 3:563–568

    Article  Google Scholar 

  20. Korkut S, Roy-Mayhew JD, Dabbs DM, Milius DL, Aksay IA (2011) High surface area tapes produced with functionalized grapheme. ACS Nano 5:5214–5222

    Article  Google Scholar 

  21. Liu Z, Robinson JT, Sun X, Dai H (2008) PEGylated nanographene oxide for delivery of water-insoluble cancer drugs. J Am Chem Soc 130:10876–10877

    Article  Google Scholar 

  22. Pu NW, Wang CA, Liu YM, Sung Y, Wang DS, Ger MD (2012) Dispersion of graphene in aqueous solutions with different types of surfactants and the production of graphene films by spray or drop coating. J Taiwan Inst Chem E 43:140–146

    Article  Google Scholar 

  23. He P, Sun J, Tian SY, Yang SW, Ding SJ, Ding GQ, Xie XM, Jiang MH (2014) Processable aqueous dispersions of graphene stabilized by graphene quantum dots. Chem Mater 27:218–226

    Article  Google Scholar 

  24. Ciesielski A, Samorì P (2014) Graphene via sonication assisted liquid-phase exfoliation. Chem Soc Rev 43:381–398

    Article  Google Scholar 

  25. Zhang L, Zhang Z, He C, Dai L, Liu J, Wang L (2014) Rationally designed surfactants for few-layered graphene exfoliation: ionic groups attached to electron-deficient π-conjugated unit through alkyl spacers. ACS Nano 8:6663–6670

    Article  Google Scholar 

  26. Ehli C, Rahman GMA, Jux N, Balbinot D, Guldi DM, Paolucci F, Marcaccio M, Paolucci D, Melle-Franco M, Zerbetto F, Campidelli S, Prato M (2006) Interactions in single wall carbon nanotubes/pyrene/porphyrin nanohybrids. J Am Chem Soc 128:11222–11231

    Article  Google Scholar 

  27. Lu J, Yang J, Wan J, Lim A, Wang S, Loh KP (2009) One-pot synthesis of fluorescent carbon nanoribbons, nanoparticles, and graphene by the exfoliation of graphite in ionic liquids. ACS Nano 3:2367–2375

    Article  Google Scholar 

  28. Zhang K, Jin LE, Cao Q (2016) Evaluation of modified used engine oil acting as a dispersant for concentrated coal–water slurry. Fuel 175:202–209

    Article  Google Scholar 

  29. Wei Y, Sun Z (2015) Liquid-phase exfoliation of graphite for mass production of pristine few-layer grapheme. Curr Opin Colloid Int 20:311–321

    Article  Google Scholar 

  30. Zhan X, Facchetti A, Barlow S, Marks TJ, Ratner MA, Wasielewski MR, Marder SR (2011) Rylene and related diimides for organic electronics. Adv Mater 23:268–284

    Article  Google Scholar 

  31. Guardia L, Fernández-Merino MJ, Paredes JI, Solís-Fernández P, Villar-Rodil S, Martínez-Alonso A, Tascón JMD (2011) High-throughput production of pristine graphene in an aqueous dispersion assisted by non-ionic surfactants. Carbon 49:1653–1662

    Article  Google Scholar 

  32. Li D, Müller MB, Gilje S, Kaner RB, Wallace GG (2008) Processable aqueous dispersions of graphene nanosheets. Nat Nanotechnol 3:101–105

    Article  Google Scholar 

  33. Halim U, Zheng CR, Yu C, Lin ZY, Jiang S, Cheng R, Huang Y, Duan XF (2013) A rational design of cosolvent exfoliation of layered materials by directly probing liquid–solid interaction. Nat Commun 4:2213

    Article  Google Scholar 

  34. Liu WS, Zhou R, Zhou D, Ding GQ, Soah JM, Yue CY, Lu XH (2015) Lignin-assisted direct exfoliation of graphite to graphene in aqueous media and its application in polymer composites. Carbon 83:188–197

    Article  Google Scholar 

  35. Xu MH, Zhang W, Yu F, Ma YJ, Hu NT, Su YJ, He DN, Liang Q, Yang Z, Zhang YF (2015) One-pot liquid-phase exfoliation from graphite to graphene with carbon quantum dots. Nanoscale 7:10527–10534

    Article  Google Scholar 

  36. Lotya M, King PJ, Khan U, De S, Coleman JN (2010) High-concentration, surfactant-stabilized graphene dispersions. ACS Nano 4:3155–3162

    Article  Google Scholar 

  37. Sun ZY, Nicolosi V, Rickard D, Bergin SD, Aherne D, Coleman JN (2008) Quantitative evaluation of surfactant-stabilized single-walled carbon nanotubes: dispersion quality and its correlation with zeta potential. J Phys Chem C 112:10692–10699

    Article  Google Scholar 

  38. Chen W, Yan L (2011) In situ self-assembly of mild chemical reduction graphene for three-dimensional architectures. Nanoscale 3:3132–3137

    Article  Google Scholar 

  39. Cao MW, Wang NN, Wang L, Zhang Y, Chen YC, Xie ZL, Li ZY, Pambou E, Li RH, Chen CX, Pan F, Xu H, Penny J, Webster JRP, Lu JR (2016) Direct exfoliation of graphite into graphene in aqueous solutions of amphiphilic peptides. J Mater Chem B 4:152–161

    Article  Google Scholar 

  40. Yang H, Hernandez Y, Schlierf A, Felten A, Eckmann A, Johal S, Louette P, Pireaux JJ, Feng X, Mullen K, Palermo V, Casiraghi C (2013) A simple method for graphene production based on exfoliation of graphite in water using 1-pyrenesulfonic acid sodium salt. Carbon 53:357–365

    Article  Google Scholar 

  41. Ferrari AC (2007) Raman spectroscopy of graphene and graphite: disorder, electron–phonon coupling, doping and nonadiabatic effects. Solid State Commun 143:47–57

    Article  Google Scholar 

  42. Skaltsas T, Ke X, Bittencourt C, Tagmatarchis N (2013) Ultrasonication induces oxygenated species and defects onto exfoliated grapheme. J Phys Chem C 117:23272–23278

    Article  Google Scholar 

  43. Chen IWP, Chen YS, Kao NJ, Wu CW, Zhang YW, Li HT (2015) Scalable and high-yield production of exfoliated graphene sheets in water and its application to an all-solid-state supercapacitor. Carbon 90:16–24

    Article  Google Scholar 

  44. Shih CJ, Vijayaraghavan A, Krishnan R, Sharma R, Han JH, Ham MH, Jin Z, Lin S, Paulus GL, Reuel NF, Wang QH, Blankschtein D, Strano MS (2011) Bi-and trilayer graphene solutions. Nat Nanotechnol 6:439–445

    Article  Google Scholar 

  45. Shih CJ, Paulus GL, Wang QH, Jin Z, Blankschtein D, Strano MS (2012) Understanding surfactant/graphene interactions using a graphene field effect transistor: relating molecular structure to hysteresis and carrier mobility. Langmuir 28:8579–8586

    Article  Google Scholar 

Download references

Acknowledgements

The authors are very grateful for the financial support of the National Natural Science Foundation of China NSFC (Grant No. 51174144).

Author information

Authors and Affiliations

  1. Institute of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan, 030024, People’s Republic of China

    Kang Zhang, Xiaohua Zhang, Hengxiang Li, Xiaohan Xing, Li’e Jin, Qing Cao & Ping Li

Authors
  1. Kang Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiaohua Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hengxiang Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xiaohan Xing
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Li’e Jin
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Qing Cao
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Ping Li
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Qing Cao.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, K., Zhang, X., Li, H. et al. Direct exfoliation of graphite into graphene in aqueous solution using a novel surfactant obtained from used engine oil. J Mater Sci 53, 2484–2496 (2018). https://doi.org/10.1007/s10853-017-1729-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-017-1729-7

Keywords

Search

Navigation