Article

Effective NaCl and dye rejection of hybrid graphene oxide/graphene layered membranes

  • Nature Nanotechnology 12, 10831088 (2017)
  • doi:10.1038/nnano.2017.160
  • Download Citation
Received:
Accepted:
Published online:

Abstract

Carbon nanomaterials are robust and possess fascinating properties useful for separation technology applications, but their scalability and high salt rejection when in a strong cross flow for long periods of time remain challenging. Here, we present a graphene-based membrane that is prepared using a simple and environmentally friendly method by spray coating an aqueous dispersion of graphene oxide/few-layered graphene/deoxycholate. The membranes were robust enough to withstand strong cross-flow shear for a prolonged period (120 h) while maintaining NaCl rejection near 85% and 96% for an anionic dye. Experimental results and molecular dynamic simulations revealed that the presence of deoxycholate enhances NaCl rejection in these graphene-based membranes. In addition, these novel hybrid-layered membranes exhibit better chlorine resistance than pure graphene oxide membranes. The desalination performance and aggressive shear and chlorine resistance of these scalable graphene-based membranes are promising for use in practical water separation applications.

  • Subscribe to Nature Nanotechnology for full access:

    $59

    Subscribe

Additional access options:

Already a subscriber?  Log in  now or  Register  for online access.

References

  1. 1.

    et al. Nanofiltration membranes review: recent advances and future prospects. Desalination 356, 226–254 (2015).

  2. 2.

    , , & Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321, 385–388 (2008).

  3. 3.

    & Mechanical strength of nanoporous graphene as a desalination membrane. Nano Lett. 14, 6171–6178 (2014).

  4. 4.

    & Water desalination across nanoporous graphene. Nano Lett. 12, 3602–3608 (2012).

  5. 5.

    et al. Water desalination using nanoporous single-layer graphene. Nat. Nanotech. 10, 459–464 (2015).

  6. 6.

    , & Scale-up and purification of graphite oxide as intermediate for functionalized graphene. Carbon 75, 432–442 (2014).

  7. 7.

    Selling graphene by the ton. Nat. Nanotech. 4, 612–614 (2009).

  8. 8.

    & Nanofluidic ion transport through reconstructed layered materials. J. Am. Chem. Soc. 134, 16528–16531 (2012).

  9. 9.

    , & Graphene oxide films, fibers, and membranes. Nanotechnol. Rev. 5, 377–391 (2016).

  10. 10.

    , & Ultrathin graphene nanofiltration membrane for water purification. Adv. Funct. Mater. 23, 3693–3700 (2013).

  11. 11.

    et al. All-carbon nanoarchitectures as high-performance separation membranes with superior stability. Adv. Funct. Mater. 25, 7348–7359 (2015).

  12. 12.

    et al. Ultrafast viscous water flow through nanostrand-channelled graphene oxide membranes. Nat. Commun. 4, 2979 (2013).

  13. 13.

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

  14. 14.

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

  15. 15.

    , , , & On the origin of the stability of graphene oxide membranes in water. Nat. Chem. 7, 166–170 (2015).

  16. 16.

    et al. Graphene oxide papers modified by divalent ions—enhancing mechanical properties via chemical cross-linking. ACS Nano 2, 572–578 (2008).

  17. 17.

    et al. Nanotechnology: ‘buckypaper’ from coaxial nanotubes. Nature 433, 476 (2005).

  18. 18.

    , & Polymeric modification of graphene through esterification of graphite oxide and poly(vinyl alcohol). Macromolecules 42, 6331–6334 (2009).

  19. 19.

    , & Tunable water desalination across graphene oxide framework membranes. Phys. Chem. Chem. Phys. 16, 8646–8654 (2014).

  20. 20.

    Membrane Technology and Applications (Wiley, 2012).

  21. 21.

    et al. Declining flux and narrowing nanochannels under wrinkles of compacted graphene oxide nanofiltration membranes. Carbon 108, 568–575 (2016).

  22. 22.

    & Enabling graphene oxide nanosheets as water separation membranes. Environ. Sci. Technol. 47, 3715–3723 (2013).

  23. 23.

    , & High-flux graphene oxide nanofiltration membrane intercalated by carbon nanotubes. ACS Appl. Mater. Interfaces 7, 8147–8155 (2015).

  24. 24.

    et al. Zwitterion functionalized carbon nanotube/polyamide nanocomposite. ACS Nano 7, 5308–5319 (2013).

  25. 25.

    et al. Ion-responsive channels of zwitterion-carbon nanotube membrane for rapid water permeation and ultrahigh. ACS Nano 9, 7488–7496 (2015).

  26. 26.

    et al. Graphene oxide for high-efficiency separation membranes: role of electrostatic interactions. Carbon 110, 56–61 (2016).

  27. 27.

    , & Streaming potential measurements to assess the variation of nanofiltration membranes surface charge with the concentration of salt solutions. Sep. Purif. Technol. 22–23, 52–541 (2001).

  28. 28.

    , , & The effect of feed ionic strength on salt passage through reverse osmosis membranes. Desalination 184, 185–195 (2005).

  29. 29.

    et al. High-performance multi-functional reverse osmosis membranes obtained by carbon nanotube·polyamide nanocomposite. Sci. Rep. 5, 13562 (2015).

  30. 30.

    , & Understanding water permeation in graphene oxide membranes. Appl. Mater. Interfaces 6, 5877–5883 (2014).

  31. 31.

    , & Origin of anomalous water permeation through graphene oxide membrane. Nano Lett. 13, 3930–3935 (2013).

  32. 32.

    & Dissolution mechanism of semicrystalline poly(vinyl alcohol) in water. J. Polym. Sci. 34, 1339–1346 (1996).

  33. 33.

    et al. Improved synthesis of graphene oxide. ACS Nano 4, 4806–4814 (2010).

  34. 34.

    et al. Synthesis and solid-state NMR structural characterization of 13C-labeled graphite oxide. Science 321, 1815–1817 (2008).

  35. 35.

    & A short description of DL_POLY. Mol. Simul. 32, 935–943 (2006).

  36. 36.

    , & DREIDING: a generic force field for molecular simulations. J. Phys. Chem. 101, 8897–8909 (1990).

  37. 37.

    et al. NWChem: a comprehensive and scalable open-source solution for large scale molecular simulations. Comput. Phys. Commun. 181, 1477–1489 (2010).

  38. 38.

    , & VMD—Visual Molecular Dynamics. J. Mol. Graph. 14, 33–38 (1996).

  39. 39.

    & The spatial structure in liquid water. Science 265, 1219–1221 (1994).

Download references

Acknowledgements

This work was supported by the Center of Innovation Program, Global Aqua Innovation Center for Improving Living Standards and Water Sustainability, from the Japan Science and Technology Agency (JST).

Author information

Affiliations

  1. Global Aqua Innovation Center, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553, Japan

    • Aaron Morelos-Gomez
    • , Rodolfo Cruz-Silva
    • , Josue Ortiz-Medina
    • , Takumi Araki
    • , Syogo Tejima
    • , Kenji Takeuchi
    •  & Morinobu Endo
  2. Institute of Carbon Science and Technology, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553, Japan

    • Hiroyuki Muramatsu
    • , Takuya Hayashi
    • , Mauricio Terrones
    •  & Morinobu Endo
  3. Research Organization for Information Science & Technology, 2-32-3, Kitashinagawa, Shinagawa-ku, Tokyo, 140-0001, Japan

    • Takumi Araki
    •  & Syogo Tejima
  4. Showa Denko K.K., Institute for Advanced and Core Technology, 1-1-1, Ohnodai, Midori-ku, Chiba-shi, Chiba, 267-0056, Japan

    • Tomoyuki Fukuyo
  5. Department of Physics, Department of Chemistry, Department of Materials Science and Engineering, Center for 2-Dimensional and Layered Materials and Center for Atomically Thin Multifunctional Coatings (ATOMIC), The Pennsylvania State University, University Park, Pennsylvania 16802, USA

    • Mauricio Terrones

Authors

  1. Search for Aaron Morelos-Gomez in:

  2. Search for Rodolfo Cruz-Silva in:

  3. Search for Hiroyuki Muramatsu in:

  4. Search for Josue Ortiz-Medina in:

  5. Search for Takumi Araki in:

  6. Search for Tomoyuki Fukuyo in:

  7. Search for Syogo Tejima in:

  8. Search for Kenji Takeuchi in:

  9. Search for Takuya Hayashi in:

  10. Search for Mauricio Terrones in:

  11. Search for Morinobu Endo in:

Contributions

A.M.-G. designed the experiments, performed FTIR, SEM, Raman spectroscopy and desalination, and wrote the manuscript. R.C.-S. carried out GO synthesis and XPS, and wrote the manuscript. H.M. performed discussion and preliminary DWCNT samples. J.O.-M. performed XRD and wrote the manuscript. T.A. and S.T. performed molecular dynamic simulations. T.F. provided valuable technical assistance. T.H. performed TEM observations. K.T., M.T. and M.E. participated in discussions and wrote the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Aaron Morelos-Gomez or Morinobu Endo.

Supplementary information

PDF files

  1. 1.

    Supplementary information

    Supplementary Information

Videos

  1. 1.

    Supplementary Movie 1

    Supplementary Movie 1

  2. 2.

    Supplementary Movie 2

    Supplementary Movie 2

  3. 3.

    Supplementary Movie 3

    Supplementary Movie 3

  4. 4.

    Supplementary Movie 4

    Supplementary Movie 4