Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Ultrathin graphene-based membrane with precise molecular sieving and ultrafast solvent permeation

Nature Materials volume 16, pages 1198–1202 (2017)Cite this article

Subjects

Abstract

Graphene oxide (GO) membranes continue to attract intense interest due to their unique molecular sieving properties combined with fast permeation1,2,3,4,5,6,7,8,9. However, their use is limited to aqueous solutions because GO membranes appear impermeable to organic solvents1, a phenomenon not yet fully understood. Here, we report efficient and fast filtration of organic solutions through GO laminates containing smooth two-dimensional (2D) capillaries made from large (10–20 μm) flakes. Without modification of sieving characteristics, these membranes can be made exceptionally thin, down to ∼10 nm, which translates into fast water and organic solvent permeation. We attribute organic solvent permeation and sieving properties to randomly distributed pinholes interconnected by short graphene channels with a width of 1 nm. With increasing membrane thickness, organic solvent permeation rates decay exponentially but water continues to permeate quickly, in agreement with previous reports1,2,3,4. The potential of ultrathin GO laminates for organic solvent nanofiltration is demonstrated by showing >99.9% rejection of small molecular weight organic dyes dissolved in methanol. Our work significantly expands possibilities for the use of GO membranes in purification and filtration technologies.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Get just this article for as long as you need it

$39.95

Learn more

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Ultrathin HLGO membrane.
Figure 2: Molecular sieving and organic solvent nanofiltration through HLGO membranes.
Figure 3: Probing molecular permeation through HLGO membranes.

References

  1. Nair, R. R., Wu, H. A., Jayaram, P. N., Grigorieva, I. V. & Geim, A. K. Unimpeded permeation of water through helium-leak-tight graphene-based membranes. Science 335, 442–444 (2012).

    Article  CAS  Google Scholar 

  2. Sun, P., Wang, K. & Zhu, H. Recent developments in graphene-based membranes: structure, mass-transport mechanism and potential applications. Adv. Mater. 28, 2287–2310 (2016).

    Article  CAS  Google Scholar 

  3. Liu, G., Jin, W. & Xu, N. Graphene-based membranes. Chem. Soc. Rev. 44, 5016–5030 (2015).

    Article  CAS  Google Scholar 

  4. Fathizadeh, M., Xu, W. L., Zhou, F., Yoon, Y. & Yu, M. Graphene oxide: a novel 2-dimensional material in membrane separation for water purification. Adv. Mater. Interfaces 4, 1600918 (2017).

    Article  Google Scholar 

  5. Joshi, R. K. et al. Precise and ultrafast molecular sieving through graphene oxide membranes. Science 343, 752–754 (2014).

    Article  CAS  Google Scholar 

  6. Li, H. et al. Ultrathin, molecular-sieving graphene oxide membranes for selective hydrogen separation. Science 342, 95–98 (2013).

    Article  CAS  Google Scholar 

  7. Akbari, A. et al. Large-area graphene-based nanofiltration membranes by shear alignment of discotic nematic liquid crystals of graphene oxide. Nat. Commun. 7, 10891 (2016).

    Article  CAS  Google Scholar 

  8. Abraham, J. et al. Tuneable sieving of ions using graphene oxide membranes. Nat. Nanotech. 12, 546–550 (2017).

    Article  CAS  Google Scholar 

  9. Hong, S. et al. Scalable graphene-based membranes for ionic sieving with ultrahigh charge selectivity. Nano Lett. 17, 728–732 (2017).

    Article  CAS  Google Scholar 

  10. Mulder, J. Basic Principles of Membrane Technology (Springer Science & Business Media, 2012).

    Google Scholar 

  11. Koros, W. J. & Zhang, C. Materials for next-generation molecularly selective synthetic membranes. Nat. Mater. 16, 289–297 (2017).

    Article  CAS  Google Scholar 

  12. Wang, L. et al. Molecular valves for controlling gas phase transport made from discrete ångström-sized pores in graphene. Nat. Nanotech. 10, 785–790 (2015).

    Article  CAS  Google Scholar 

  13. Jain, T. et al. Heterogeneous sub-continuum ionic transport in statistically isolated graphene nanopores. Nat. Nanotech. 10, 1053–1057 (2015).

    Article  CAS  Google Scholar 

  14. Celebi, K. et al. Ultimate permeation across atomically thin porous graphene. Science 344, 289–292 (2014).

    Article  CAS  Google Scholar 

  15. Han, Y., Xu, Z. & Gao, C. Ultrathin graphene nanofiltration membrane for water purification. Adv. Funct. Mater. 23, 3693–3700 (2013).

    Article  CAS  Google Scholar 

  16. Marchetti, P., Jimenez Solomon, M. F., Szekely, G. & Livingston, A. G. Molecular separation with organic solvent nanofiltration: a critical review. Chem. Rev. 114, 10735–10806 (2014).

    Article  CAS  Google Scholar 

  17. Vandezande, P., Gevers, L. E. & Vankelecom, I. F. Solvent resistant nanofiltration: separating on a molecular level. Chem. Soc. Rev. 37, 365–405 (2008).

    Article  CAS  Google Scholar 

  18. Jimenez-Solomon, M. F., Song, Q., Jelfs, K. E., Munoz-Ibanez, M. & Livingston, A. G. Polymer nanofilms with enhanced microporosity by interfacial polymerization. Nat. Mater. 15, 760–767 (2016).

    Article  CAS  Google Scholar 

  19. Karan, S., Jiang, Z. & Livingston, A. G. Sub–10 nm polyamide nanofilms with ultrafast solvent transport for molecular separation. Science 348, 1347–1351 (2015).

    Article  CAS  Google Scholar 

  20. Huang, K. et al. A graphene oxide membrane with highly selective molecular separation of aqueous organic solution. Angew. Chem. Int. Ed. 53, 6929–6932 (2014).

    Article  CAS  Google Scholar 

  21. Huang, L., Li, Y., Zhou, Q., Yuan, W. & Shi, G. Graphene oxide membranes with tunable semipermeability in organic solvents. Adv. Mater. 27, 3797–3802 (2015).

    Article  CAS  Google Scholar 

  22. Aba, N. F. D., Chong, J. Y., Wang, B., Mattevi, C. & Li, K. Graphene oxide membranes on ceramic hollow fibers—microstructural stability and nanofiltration performance. J. Membr. Sci. 484, 87–94 (2015).

    Article  CAS  Google Scholar 

  23. Huang, L. et al. Reduced graphene oxide membranes for ultrafast organic solvent nanofiltration. Adv. Mater. 28, 8669–8674 (2016).

    Article  CAS  Google Scholar 

  24. Lin, X. et al. Fabrication of highly-aligned, conductive, and strong graphene papers using ultralarge graphene oxide sheets. ACS Nano 6, 10708–10719 (2012).

    Article  CAS  Google Scholar 

  25. Wu, H., Gong, Q., Olson, D. H. & Li, J. Commensurate adsorption of hydrocarbons and alcohols in microporous metal organic frameworks. Chem. Rev. 112, 836–868 (2012).

    Article  CAS  Google Scholar 

  26. Secchi, E. et al. Massive radius-dependent flow slippage in carbon nanotubes. Nature 537, 210–213 (2016).

    Article  CAS  Google Scholar 

  27. Radha, B. et al. Molecular transport through capillaries made with atomic-scale precision. Nature 538, 222–225 (2016).

    Article  CAS  Google Scholar 

  28. Wilson, N. R. et al. Graphene oxide: structural analysis and application as a highly transparent support for electron microscopy. ACS Nano 3, 2547–2556 (2009).

    Article  CAS  Google Scholar 

  29. Loh, K. P., Bao, Q., Eda, G. & Chhowalla, M. Graphene oxide as a chemically tunable platform for optical applications. Nat. Chem. 2, 1015–1024 (2010).

    Article  CAS  Google Scholar 

  30. Dai, H., Liu, S., Zhao, M., Xu, Z. & Yang, X. Interfacial friction of ethanol–water mixtures in graphene pores. Microfluid. Nanofluid. 20, 141 (2016).

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the Royal Society, Engineering and Physical Sciences Research Council, UK (EP/K016946/1), Lloyd’s Register Foundation, and European Research Council (contract 679689). Q.Y. acknowledges support from the China Scholarship Council. We thank P. Bentley for assisting with XPS measurements, J. Waters for X-ray measurements, and K. Huang for assisting in setting up the cold trap for filtration experiments.

Author information

Author notes

  1. Q. Yang, Y. Su and C. Chi: These authors contributed equally to this work.

Authors and Affiliations

  1. National Graphene Institute, University of Manchester, Manchester M13 9PL, UK

    Q. Yang, Y. Su, C. Chi, C. T. Cherian, K. Huang & R. R. Nair

  2. School of Chemical Engineering and Analytical Science, University of Manchester, Manchester M13 9PL, UK

    Q. Yang, Y. Su, C. Chi, C. T. Cherian, K. Huang & R. R. Nair

  3. School of Physics and Astronomy, University of Manchester, Manchester M13 9PL, UK

    Q. Yang, V. G. Kravets, A. N. Grigorenko, F. Guinea & A. K. Geim

  4. Key Laboratory of Advanced Technologies of Materials (Ministry of Education), School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu, Sichuan 610031, China

    Q. Yang

  5. Department of Modern Mechanics, Chinese Academy of Sciences Key Laboratory of Mechanical Behavior and Design of Materials, University of Science and Technology of China, Hefei, Anhui 230027, China

    F. C. Wang

  6. Department of Physics, University of York, York YO10 5DD, UK

    J. C. Zhang & A. Pratt

  7. Imdea Nanociencia, Faraday 9, 28015 Madrid, Spain

    F. Guinea

Authors
  1. Q. Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Y. Su
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. C. Chi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. C. T. Cherian
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. K. Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. V. G. Kravets
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. F. C. Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. J. C. Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. A. Pratt
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. A. N. Grigorenko
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. F. Guinea
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. A. K. Geim
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. R. R. Nair
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

R.R.N. and Y.S. designed and supervised the project. Q.Y., Y.S. and C.C prepared the samples, performed the measurements and carried out the analysis with help from R.R.N. C.T.C. and K.H. helped in sample preparation, characterization and data analysis. J.C.Z. and A.P. contributed to XPS characterization. V.G.K. and A.N.G. contributed to optical measurements. F.G., F.C.W. and A.K.G. contributed to theoretical modelling. Y.S., A.N.G., A.K.G. and R.R.N. wrote the manuscript. All authors contributed to discussions.

Corresponding authors

Correspondence to Y. Su or R. R. Nair.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 1012 kb)

Supplementary Information

Supplementary movie 1 (MP4 19635 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Yang, Q., Su, Y., Chi, C. et al. Ultrathin graphene-based membrane with precise molecular sieving and ultrafast solvent permeation. Nature Mater 16, 1198–1202 (2017). https://doi.org/10.1038/nmat5025

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat5025

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing