Journal of Materials Science

, Volume 54, Issue 6, pp 4546–4558 | Cite as

Mechanochemical reaction using weak acid salts enables dispersion and exfoliation of nanomaterials in polar solvents

  • Yoshihiko AraoEmail author
  • Jonathon Tanks
  • Kojiro Aida
  • Masatoshi Kubouchi
Chemical routes to materials


Nanomaterials, such as carbon nanotubes, graphene, and various types of nanosheets, form aggregates in dry powder due to attractive van der Walls forces. To bring out their unique properties, dispersion of the nanomaterial in solid or liquid is essential. However, the dispersion media for these materials are limited; the surface tension of liquid should be as close as possible to that of the nanomaterial. This limitation restricts the effective usage of nanomaterials. Here, we find that nanomaterials are easily dispersed or exfoliated in water and low-boiling point solvents after simple pretreatment. Pulverization of nanomaterials induces many dangling bonds at the newly created edge, and these active species react with weak acid salts. In polar solvent, the bonded salts are dissociated and enhance the negative charging of nanomaterials. The enhanced electric charging prevents the aggregation or restacking of nanosheets even in typically incompatible solvent such as water and alcohol. The functionalized powder can be easily exfoliated, giving more than 20% yield of nanosheets after only 5 min of sonication.



This work was supported by JSPS KAKENHI Grant Number 15H05504 and the fujikura foundation. We acknowledge the Center for Advanced Materials Analysis in Tokyo Institute of Technology for XRD and Raman analysis.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10853_2018_3156_MOESM1_ESM.docx (6.2 mb)
Supplementary material 1 (DOCX 6373 kb)


  1. 1.
    Hernandez Y, Nicolosi V, Lotya M, Blighe FM, Sun Z, De S et al (2008) High-yield production of graphene by liquid-phase exfoliation of graphite. Nat Nanotechnol 3:563–568CrossRefGoogle Scholar
  2. 2.
    Paton KR, Varrla E, Backes C, Smith RJ, Khan U, O’Neill A et al (2014) Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquid. Nat Mater 13:624–630CrossRefGoogle Scholar
  3. 3.
    Zhang Q, Huang JQ, Qian WZ, Zhang YY, Wei F (2013) The road for nanomaterials industry: a review of carbon nanotube production, post-treatment, and bulk applications for composites and energy storage. Small 9:1237–1265CrossRefGoogle Scholar
  4. 4.
    Nicolosi V, Chhowalla M, Kanatzidis MG, Strano MS, Coleman JN (2013) Liquid exfoliation of layered materials. Science 340:1226419CrossRefGoogle Scholar
  5. 5.
    Rao CNR, Gopalakrishnan K, Maitra U (2015) Comparative study of potential applications of graphene, MoS2, and other two-dimensional materials in energy devices, sensors, and related areas. ACS Appl Mater Interfaces 7:7809–7832CrossRefGoogle Scholar
  6. 6.
    Ferrari AC, Bonaccorso F, Fal’ko V, Novoselov KS, Roche S, Bøggild P et al (2015) Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems. Nanoscale 7:4598–4810CrossRefGoogle Scholar
  7. 7.
    Lee C, Wei XD, Kysar JW, Hone J (2008) Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321:385–388CrossRefGoogle Scholar
  8. 8.
    Balandin AA (2011) Thermal properties of graphene and nanostructured carbon materials. Nat Mater 10:569–581CrossRefGoogle Scholar
  9. 9.
    Huang YY, Terentjev EM (2012) Dispersion of carbon nanotubes: mixing, sonication, stabilization, and composite properties. Polymers 4:275–295CrossRefGoogle Scholar
  10. 10.
    Wang T, Quinn MDJ, Notley SM (2018) Enhanced electrical, mechanical and thermal properties by exfoliating graphene platelets of larger lateral dimensions. Carbon 129:191–198CrossRefGoogle Scholar
  11. 11.
    Grayfer ED, Kozlova MN, Fedorov VE (2017) Colloidal 2D nanosheets of MoS2 and other transition metal dichalcogenides through liquid-phase exfoliation. Adv Colloid Interface Sci 245:40–61CrossRefGoogle Scholar
  12. 12.
    Tao H, Zhang Y, Gao Y, Sun Z, Yan C, Texter J (2017) Scalable exfoliation and dispersion of two-dimensional materials—an update. Phys Chem Chem Phys 19:921–960CrossRefGoogle Scholar
  13. 13.
    Jawaid A, Nepal D, Park K, Jesperson M, Qualley A, Mirau P et al (2016) Mechanism for liquid phase exfoliation of MoS2. Chem Mater 28:337–348CrossRefGoogle Scholar
  14. 14.
    Coleman JN (2013) Liquid exfoliation of defect-free graphene. Acc Chem Res 46:14–22CrossRefGoogle Scholar
  15. 15.
    Boland CS, Khan U, Ryan G, Barwich S, Charifou R, Harvey A et al (2016) Sensitive electromechanical sensors using viscoelastic graphene–polymer nanocomposites. Science 354:1257–1260CrossRefGoogle Scholar
  16. 16.
    Kelly AG, Hallam T, Backes C, Harvey A, Esmaeily SS, Godwin I et al (2017) All-printed thin-film transistors from networks of liquid-exfoliated nanosheets. Science 356:69–73CrossRefGoogle Scholar
  17. 17.
    Stankovich S, Dikin DA, Piner RD, Kohlhaas KA, Kleinhammes A, Jia Y et al (2007) Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon 45:1558–1565CrossRefGoogle Scholar
  18. 18.
    Li D, Müller MB, Gilje S, Kaner RB, Wallace GG (2008) Processable aqueous dispersions of graphene nanosheets. Nat Nanotechnol 3:101–105CrossRefGoogle Scholar
  19. 19.
    Posudievsky OY, Khazieieva OA, Cherepanov VV, Dovbeshko GI, Koshechko VG, Pokhodenko VD (2016) Efficient dispersant-free liquid exfoliation down to the graphene-like state of solvent-free mechanochemically delaminated bulk hexagonal boron nitride. RSC Adv 6:47112–47119CrossRefGoogle Scholar
  20. 20.
    Posudievsky OY, Khazieieva OA, Cherepanov VV, Koshechko VG, Pokhodenko VD (2013) High yield of graphene by dispersant-free liquid exfoliation of mechanochemically delaminated graphite. J Nanopart Res 15:2046CrossRefGoogle Scholar
  21. 21.
    Pentecost A, Four S, Mochalin V, Knoke I, Gogotsi Y (2010) Deaggregation of nanodiamond powders using salt- and sugar-assisted milling. ACS Appl Mater Interfaces 2:3289–3294CrossRefGoogle Scholar
  22. 22.
    Iwashita N, Park CR, Fujimoto H, Shiraishi M, Inagaki M (2004) Specification for a standard procedure of X-ray diffraction measurements on carbon materials. Carbon 42:701–714CrossRefGoogle Scholar
  23. 23.
    Parvez K, Wu ZS, Li R, Liu X, Graf R, Feng X et al (2014) Exfoliation of graphite into graphene in aqueous solutions of inorganic salts. J Am Chem Soc 136:6083–6091CrossRefGoogle Scholar
  24. 24.
    Feng H, Cheng R, Zhao X, Duan X, Li J (2013) A low-temperature method to produce highly reduced graphene oxide. Nat Commun 4:1539CrossRefGoogle Scholar
  25. 25.
    Jeon IY, Bae SY, Seo JM, Baek JM (2015) Scalable production of edge-functionalized graphene nanoplatelets via mechanochemical ball-milling. Adv Funct Mater 25:6961–6975CrossRefGoogle Scholar
  26. 26.
    Liu WW, Wang JN, Wang XX (2012) Charging of unfunctionalized graphene in organic solvents. Nanoscale 4:425–428CrossRefGoogle Scholar
  27. 27.
    Halim U, Zheng CR, Chen Y, Lin Z, Jiang S, Cheng R et al (2013) A rational design of cosolvent exfoliation of layered materials by directly probing liquid-solid interaction. Nat Commun 13:3213Google Scholar
  28. 28.
    Shen J, He Y, Wu J, Gao C, Keyshar K, Zhang X et al (2015) Liquid phase exfoliation of two-dimensional materials by directly probing and matching surface tension components. Nano Lett 15:5449–5454CrossRefGoogle Scholar
  29. 29.
    AraoY Mori F, Kubouchi M (2017) Efficient solvent systems for improving production of few-layer graphene in liquid phase exfoliation. Carbon 118:18–24CrossRefGoogle Scholar
  30. 30.
    Khan U, Porwal H, O’Neill A, Nawaz K, May P, Coleman JN (2011) Solvent-exfoliated graphene at extremely high concentration. Langmuir 27:9077–9082CrossRefGoogle Scholar
  31. 31.
    Arao Y, Kubouchi M (2015) High-rate production of few-layer graphene by high-power probe sonication. Carbon 95:802–808CrossRefGoogle Scholar
  32. 32.
    Varrla E, Backes C, Paton KR, Harvey A, Gholamvand Z, McCauley J et al (2015) Large-scale production of size-controlled MoS2 nanosheets by shear exfoliation. Chem Mater 27:1129–1139CrossRefGoogle Scholar
  33. 33.
    Fan X, Xu P, Li YC, Zhou D, Sun Y, Nguyen MAT et al (2016) Controlled exfoliation of MoS2 crystals into trilayer nanosheets. J Am Chem Soc 138:5143–5149CrossRefGoogle Scholar
  34. 34.
    Bonaccorso F, Bartolotta A, Coleman JN, Backes C (2016) 2D-crystal based functional inks. Adv Mater 28:6136–6166CrossRefGoogle Scholar
  35. 35.
    Van Der Hoeven PhC, Lyklema J (1992) Electrostatic stabilization in non-aqueous media. Adv Colloid Interface Sci 42:205–277CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Chemical Science and EngineeringTokyo Institute of TechnologyMeguroJapan

Personalised recommendations