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.

  • Letter
  • Published:

Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal–organic framework nanocrystals

Nature Materials volume 15, pages 845–849 (2016)Cite this article

Subjects

Abstract

The implementation of membrane-based separations in the petrochemical industry has the potential to reduce energy consumption significantly relative to conventional separation processes1. Achieving this goal, however, requires the development of new membrane materials with greater selectivity, permeability and stability than available at present. Here, we report composite materials consisting of nanocrystals of metal–organic frameworks dispersed within a high-performance polyimide, which can exhibit enhanced selectivity for ethylene over ethane, greater ethylene permeability and improved membrane stability. Our results suggest that framework–polymer interactions reduce chain mobility of the polymer while simultaneously boosting membrane separation performance. The increased stability, or plasticization resistance, is expected to improve membrane utility under real process conditions for petrochemical separations and natural gas purification. Furthermore, this approach can be broadly applied to numerous polymers that encounter aggressive environments, potentially making gas separations possible that were previously inaccessible to membranes.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Figure 1: Physical and adsorptive properties for M2(dobdc) nanocrystals.
Figure 2: Ethylene/ethane separation performance for M2(dobdc)/6FDA-DAM membranes.
Figure 3: Cross-sectional images of M2(dobdc)/6FDA-DAM membranes.
Figure 4: Enhanced membrane stability, reduction in plasticization and high mixed-gas selectivities.

Similar content being viewed by others

References

  1. Materials for Separation Technology: Energy and Emission Reduction Opportunities (US Department of Energy, 2005).

  2. Eldridge, R. B. Olefin/paraffin separation technology: a review. Ind. Eng. Chem. Res. 32, 2208–2212 (1993).

    Article  Google Scholar 

  3. Rungta, M., Zheng, C. & Koros, W. J. Membrane-based ethylene/ethane separation: the upper bound and beyond. AIChE J. 59, 3475–3489 (2013).

    Article  CAS  Google Scholar 

  4. Baker, R. W. & Low, B. T. Gas separation membrane materials: a perspective. Macromolecules 47, 6999–7013 (2014).

    Article  CAS  Google Scholar 

  5. Peng, Y. et al. Metal–organic framework nanosheets as building blocks for molecular sieving membranes. Science 346, 1356–1359 (2014).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  8. Brown, A. J. et al. Interfacial processing of metal–organic framework hollow fiber membranes. Science 345, 72–75 (2014).

    Article  CAS  Google Scholar 

  9. Park, H. B. et al. Polymers with cavities tuned for fast selective transport of small molecules and ions. Science 318, 254–258 (2007).

    Article  CAS  Google Scholar 

  10. Wind, J. D., Staudt-Bickel, C., Paul, D. R. & Koros, W. J. The effects of crosslinking chemistry on CO2 plasticization of polyimide gas sepation membranes. Ind. Eng. Chem. Res. 41, 6139–6148 (2002).

    Article  CAS  Google Scholar 

  11. Bloch, E. D. et al. Hydrocarbon separations in a metal–organic framework with open iron(II) coordination sites. Science 335, 1606–1610 (2012).

    Article  CAS  Google Scholar 

  12. Qiu, S., Xue, M. & Zhu, G. Metal–organic framework membranes: from synthesis to separation application. Chem. Soc. Rev. 43, 6116–6140 (2014).

    Article  CAS  Google Scholar 

  13. Zhang, C., Dai, Y., Johnson, J. R., Karvan, O. & Koros, W. J. High performance ZIF-8/6FDA-DAM mixed-matrix membranes for propylene/propane separations. J. Membr. Sci. 389, 34–42 (2012).

    Article  CAS  Google Scholar 

  14. Rodenas, T. et al. Metal–organic framework nanosheets in polymer composite materials for gas separation. Nature Mater. 14, 48–55 (2015).

    Article  CAS  Google Scholar 

  15. Bae, T.-H. & Long, J. R. CO2/N2 separations with mixed-matrix membranes containing Mg2(dobdc) nanocrystals. Energy Environ. Sci. 6, 3565–3569 (2013).

    Article  CAS  Google Scholar 

  16. Liu, C., McCulloch, B., Wilson, S. T., Benin, A. I. & Schott, M. E. Metal organic framework-polymer mixed matrix membranes. US patent 7,637,983 B1 (2009).

  17. Ranjan, R. & Tsapatsis, M. Microporous metal organic framework membrane on porous support using the seeded growth method. Chem. Mater. 21, 4920–4924 (2009).

    Article  CAS  Google Scholar 

  18. Seoane, B. et al. Metal–organic framework based mixed matrix membranes: a solution for highly efficient CO2 capture? Chem. Soc. Rev. 44, 2421–2454 (2015).

    Article  CAS  Google Scholar 

  19. Venna, S. R. et al. Fabrication of MMMs with improved gas separation properties using externally-functionalized MOF particles. J. Chem. Mater. A 3, 5014–5022 (2015).

    Article  CAS  Google Scholar 

  20. Ploegmakers, J., Japip, S. & Nijmeijer, K. Mixed matrix membranes containing MOFs for ethylene/ethane separation Part A: Membrane preparation and characterization. J. Membr. Sci. 428, 445–453 (2013).

    Article  CAS  Google Scholar 

  21. Bux, H., Chmelik, C., Krishna, R. & Caro, J. Ethylene/ethane separation by the MOF membrane ZIF-8: molecular correlation of permeation, adsorption, diffusion. J. Membr. Sci. 369, 284–289 (2011).

    Article  CAS  Google Scholar 

  22. Herm, Z. R., Bloch, E. D. & Long, J. R. Hydrocarbon separations in metal–organic frameworks. Chem. Mater. 26, 323–338 (2014).

    Article  CAS  Google Scholar 

  23. Bae, Y.-S. et al. High propene/propane selectivity in isostructural metal–organic frameworks with high densities of open metal sites. Angew. Chem. Int. Ed. 51, 1857–1860 (2012).

    Article  CAS  Google Scholar 

  24. Bloch, E. D. et al. Selective binding of O2 over N2 in a redox-active metal-organic framework with open iron(II) coordination sites. J. Am. Chem. Soc. 133, 14814–14822 (2011).

    Article  CAS  Google Scholar 

  25. Rosi, N. L. Rod packings and metal–organic frameworks constructed from rod-shaped secondary building units. J. Am. Chem. Soc. 127, 1504–1518 (2005).

    Article  CAS  Google Scholar 

  26. Geier, S. J. et al. Selective adsorption of ethylene over ethane and propylene over propane in the metal-organic frameworks M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn). Chem. Sci. 4, 2054–2061 (2013).

    Article  CAS  Google Scholar 

  27. Caskey, S. R., Wong-Foy, A. G. & Matzger, A. J. Dramatic tunic of carbon dioxide uptake via metal substitution in a coordination polymer with cylindrical pores. J. Am. Chem. Soc. 130, 10870–10871 (2008).

    Article  CAS  Google Scholar 

  28. Tanaka, K., Taguchi, A., Hao, J., Kita, H. & Okamoto, K. Permeation and separation properties of polyimide membranes to olefins and paraffins. J. Membr. Sci. 121, 187–207 (1996).

    Article  Google Scholar 

  29. Bos, A., Punt, I. G. M., Wessling, M. & Strathmann, H. CO2-induced plasticization in glassy polymers. J. Membr. Sci. 31, 67–78 (1999).

    Article  Google Scholar 

  30. Frisch, H. L. The time lag in diffusion. J. Phys. Chem. 61, 93–95 (1957).

    Article  CAS  Google Scholar 

  31. Dymond, J. H., Marsh, K. N., Wilhoit, R. C. & Wong, K. C. (eds) The Virial Coefficients of Pure Gases and Mixtures Vol. IV (Oxford Univ. Press, 2001).

  32. Lemmon, E. W., Huber, M. L. & McLinden, M. O. NIST Standard Reference Database 23: NIST Reference Fluid Thermodynamic and Transport Properties (REFPROP) Version 8.0 (NIST, 2007).

  33. Queen, W. L. et al. Comprehensive study of carbon dioxide adsorption in metal-organic frameworks M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn). Chem. Sci. 5, 4569–4581 (2015).

    Article  Google Scholar 

  34. Paul, D. R. & Koros, W. J. Effect of partially immobilizing sorption on permeability and the diffusion time lag. J. Polym. Sci. 14, 675–685 (1976).

    CAS  Google Scholar 

  35. Ohya, H., Kudryavtsev, V. V. & Semenova, S. I. Polyimide Membranes: Applications, Fabrications, and Properties (Gordon and Breach, 1996).

    Google Scholar 

  36. Ghosh, M. K. & Mital, K. L. Polyimides: Fundamentals and Applications (Marcel, 1996).

    Google Scholar 

  37. Grubb, T. L. et al. Highly soluble polyimides from sterically hindered diamines. Polymer 40, 4279–4288 (1999).

    Article  CAS  Google Scholar 

  38. Matsuura, T., Hasuda, Y., Nishi, S. & Yamada, N. Polyimide derived from 2,2′-bis (triflouromethyl)-4,4′-diaminobiphenyl. S. synthesis and characterization of polyimides prepared with 2,2′-bis (3,4-dicarboxyphenyl)hexafluoropropane dianhydride or pyromellitic dianhydride. Macromolecules 24, 5001–5005 (1991).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This research was supported through the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0001015. We thank J. Mason for helpful discussions. We also thank the NSF for providing graduate fellowship support for J.E.B.

Author information

Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, USA

    Jonathan E. Bachman & Jeffrey R. Long

  2. Department of Chemistry, University of California, Berkeley, California 94720, USA

    Zachary P. Smith, Ting Xu & Jeffrey R. Long

  3. Department of Materials Science, University of California, Berkeley, California 94720, USA

    Tao Li & Ting Xu

  4. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    Ting Xu & Jeffrey R. Long

Authors
  1. Jonathan E. Bachman
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zachary P. Smith
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Tao Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ting Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jeffrey R. Long
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

J.E.B. and J.R.L. formulated the project. J.E.B. synthesized nanocrystals and fabricated membranes. Z.P.S. contributed valuable theoretical insights, synthesized 6FDA-DAM, and assisted in construction of permeation equipment. J.E.B. collected all powder diffraction, dynamic light scattering, scanning electron microscopy, Soxhlet extractions, gas adsorption, and gas permeation data. T.L. performed transmission electron microscopy imaging. J.E.B. and J.R.L. wrote the paper, and all authors contributed to revising the paper.

Corresponding author

Correspondence to Jeffrey R. Long.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 24310 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Bachman, J., Smith, Z., Li, T. et al. Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal–organic framework nanocrystals. Nature Mater 15, 845–849 (2016). https://doi.org/10.1038/nmat4621

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat4621

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