Abstract
Carbon molecular sieve (CMS) membranes with precise molecular discrimination ability and facile scalability are attractive next-generation membranes for large-scale, energy-efficient gas separations. Here, structurally engineered CMS membranes derived from a tailor-made cross-linkable copolyimide with kinked structure are reported. We demonstrate that combining two features, kinked backbones and cross-linkable backbones, to engineer polyimide precursors while controlling pyrolysis conditions allows the creation of CMS membranes with improved gas separation performance. Our results indicate that the CMS membranes provide a versatile platform for a broad spectrum of challenging gas separations. The gas transport properties of the resulting CMS membranes are interpreted in terms of a model reflecting both molecular sieving Langmuir domains and a disordered continuous phase, thereby providing insight into structure evolution from the cross-linkable polyimide precursor to a final CMS membrane. With this understanding of CMS membrane structure and separation performance, these systems are promising for environmentally friendly gas separations.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
The data that support the findings in this study are available within the paper and Supplementary Information. Source data are provided with this paper.
References
Sholl, D. S. & Lively, R. P. Seven chemical separations to change the world. Nature 532, 435–437 (2016).
Koros, W. J. & Lively, R. P. Water and beyond: expanding the spectrum of large‐scale energy efficient separation processes. AIChE J. 58, 2624–2633 (2012).
Lively, R. P. & Sholl, D. S. From water to organics in membrane separations. Nat. Mater. 16, 276–279 (2017).
Park, H. B., Kamcev, J., Robeson, L. M., Elimelech, M. & Freeman, B. D. Maximizing the right stuff: the trade-off between membrane permeability and selectivity. Science 356, eaab0530 (2017).
Koros, W. J. & Zhang, C. Materials for next-generation molecularly selective synthetic membranes. Nat. Mater. 16, 289–297 (2017).
Lei, L. et al. Carbon hollow fiber membranes for a molecular sieve with precise-cutoff ultramicropores for superior hydrogen separation. Nat. Commun. 12, 268 (2021).
Omidvar, M. et al. Unexpectedly strong size-sieving ability in carbonized polybenzimidazole for membrane H2/CO2 separation. ACS Appl. Mater. Interfaces 11, 47365–47372 (2019).
Ngamou, P. T., Ivanova, M., Guillon, O. & Meulenberg, W. A. High-performance carbon molecular sieve membranes for hydrogen purification and pervaporation dehydration of organic solvents. J. Mater. Chem. A. 7, 7082–7091 (2019).
Ismail, A. F. & David, L. A review on the latest development of carbon membranes for gas separation. J. Membr. Sci. J. Membr. Sci. 193, 1–18 (2001).
Vu, D. Q., Koros, W. J. & Miller, S. J. High pressure CO2/CH4 separation using carbon molecular sieve hollow fiber membranes. Ind. Eng. Chem. Res. 41, 367–380 (2002).
Ma, X., Lin, Y., Wei, X. & Kniep, J. Ultrathin carbon molecular sieve membrane for propylene/propane separation. AIChE J. 62, 491–499 (2016).
Rungta, M., Xu, L. & Koros, W. J. Carbon molecular sieve dense film membranes derived from Matrimid® for ethylene/ethane separation. Carbon 50, 1488–1502 (2012).
Koh, D.-Y., McCool, B. A., Deckman, H. W. & Lively, R. P. Reverse osmosis molecular differentiation of organic liquids using carbon molecular sieve membranes. Science 353, 804–807 (2016).
Yang, Z. et al. Surpassing Robeson upper limit for CO2/N2 separation with fluorinated carbon molecular sieve membranes. Chem 6, 631–645 (2020).
Ning, X. & Koros, W. J. Carbon molecular sieve membranes derived from Matrimid® polyimide for nitrogen/methane separation. Carbon 66, 511–522 (2014).
Zhang, C. & Koros, W. J. Ultraselective carbon molecular sieve membranes with tailored synergistic sorption selective properties. Adv. Mater. 29, 1701631 (2017).
Fu, S., Sanders, E. S., Kulkarni, S. S. & Koros, W. J. Carbon molecular sieve membrane structure–property relationships for four novel 6FDA based polyimide precursors. J. Membr. Sci. 487, 60–73 (2015).
Kiyono, M., Williams, P. J. & Koros, W. J. Effect of polymer precursors on carbon molecular sieve structure and separation performance properties. Carbon 48, 4432–4441 (2010).
Kiyono, M., Williams, P. J. & Koros, W. J. Effect of pyrolysis atmosphere on separation performance of carbon molecular sieve membranes. J. Membr. Sci. 359, 2–10 (2010).
Suda, H. & Haraya, K. Gas permeation through micropores of carbon molecular sieve membranes derived from Kapton polyimide. J. Phys. Chem. B 101, 3988–3994 (1997).
Ma, Y. et al. Creation of well‐defined ‘mid‐sized’ micropores in carbon molecular sieve membranes. Angew. Chem. 131, 13393–13399 (2019).
Qiu, W. et al. Hyperaging tuning of a carbon molecular‐sieve hollow fiber membrane with extraordinary gas‐separation performance and stability. Angew. Chem. Int. Ed. 58, 11700–11703 (2019).
Adams, J. S. et al. New insights into structural evolution in carbon molecular sieve membranes during pyrolysis. Carbon 141, 238–246 (2019).
Sanyal, O. et al. A self‐consistent model for sorption and transport in polyimide‐derived carbon molecular sieve gas separation. Membr. Angew. Chem. Int. Ed. 59, 20343–20347 (2020).
Qiu, W., Li, F. S., Fu, S. & Koros, W. J. Isomer‐tailored carbon molecular sieve membranes with high gas separation performance. Chem. Sus. Chem. 13, 5318–5328 (2020).
Liang, J. et al. Effects on carbon molecular sieve membrane properties for a precursor polyimide with simultaneous flatness and contortion in the repeat unit. Chem. Sus. Chem. 13, 5531–5538 (2020).
Hu, C.-P. et al. The gas separation performance adjustment of carbon molecular sieve membrane depending on the chain rigidity and free volume characteristic of the polymeric precursor. Carbon 143, 343–351 (2019).
Qiu, W., Zhang, K., Li, F. S., Zhang, K. & Koros, W. J. Gas separation performance of carbon molecular sieve membranes based on 6FDA‐mPDA/DABA (3:2) polyimide. Chem. Sus. Chem. 7, 1186–1194 (2014).
Wang, Q., Huang, F., Cornelius, C. J. & Fan, Y. Carbon molecular sieve membranes derived from crosslinkable polyimides for CO2/CH4 and C2H4/C2H6 separations. J. Membr. Sci. 621, 118785 (2021).
Karunaweera, C., Musselman, I. H., Balkus, K. J. Jr & Ferraris, J. P. Fabrication and characterization of aging resistant carbon molecular sieve membranes for C3 separation using high molecular weight crosslinkable polyimide, 6FDA-DABA. J. Membr. Sci. 581, 430–438 (2019).
Liu, Z., Liu, Y., Qiu, W. & Koros, W. J. Molecularly engineered 6FDA‐based polyimide membranes for sour natural gas separation. Angew. Chem. Int. Ed. 59, 14877–14883 (2020).
Xu, L. et al. Olefins-selective asymmetric carbon molecular sieve hollow fiber membranes for hybrid membrane-distillation processes for olefin/paraffin separations. J. Membr. Sci. 423, 314–323 (2012).
Liu, Z., Qiu, W., Quan, W., Liu, Y. & Koros, W. J. Fine-tuned thermally cross-linkable 6FDA-based polyimide membranes for aggressive natural gas separation. J. Membr. Sci. https://doi.org/10.1016/j.memsci.2021.119474 (2021).
Jenkins, G. M., Jenkins, A. & Kawamura, K. Polymeric Carbons: Carbon Fibre, Glass and Char (Cambridge Univ. Press, 1976).
Swaidan, R., Ghanem, B. & Pinnau, I. Fine-tuned intrinsically ultramicroporous polymers redefine the permeability/selectivity upper bounds of membrane-based air and hydrogen separations. ACS Macro Lett. 4, 947–951 (2015).
Comesaña-Gándara, B. et al. Redefining the Robeson upper bounds for CO2/CH4 and CO2/N2 separations using a series of ultrapermeable benzotriptycene-based polymers of intrinsic microporosity. Energy Environ. Sci. 12, 2733–2740 (2019).
Robeson, L. M. The upper bound revisited. J. Membr. Sci. 320, 390–400 (2008).
Burns, R. L. & Koros, W. J. Defining the challenges for C3H6/C3H8 separation using polymeric membranes. J. Membr. Sci. 211, 299–309 (2003).
Wijmans, J. G. & Baker, R. W. The solution-diffusion model: a review. J. Membr. Sci. 107, 1–21 (1995).
Swaidan, R., Ma, X., Litwiller, E. & Pinnau, I. High pressure pure-and mixed-gas separation of CO2/CH4 by thermally-rearranged and carbon molecular sieve membranes derived from a polyimide of intrinsic microporosity. J. Membr. Sci. 447, 387–394 (2013).
Kim, S.-J., Lee, P. S., Chang, J.-S., Nam, S.-E. & Park, Y.-I. Preparation of carbon molecular sieve membranes on low-cost alumina hollow fibers for use in C3H6/C3H8 separation. Sep. Purif. Technol. 194, 443–450 (2018).
Kamaruddin, H. D. & Koros, W. J. Some observations about the application of Fick’s first law for membrane separation of multicomponent mixtures. J. Membr. Sci. 135, 147–159 (1997).
Xu, L. et al. Physical aging in carbon molecular sieve membranes. Carbon 80, 155–166 (2014).
Wang, Y. et al. Polymers of intrinsic microporosity for energy-intensive membrane-based gas separations. Mater. Today Nano 3, 69–95 (2018).
Zhang, C., Dai, Y., Johnson, J. R., Karvan, O. & Koros, W. J. High performance ZIF-8/6FDA-DAM mixed matrix membrane for propylene/propane separations. J. Membr. Sci. 389, 34–42 (2012).
Liu, G. et al. Mixed matrix formulations with MOF molecular sieving for key energy-intensive separations. Nat. Mater. 17, 283–289 (2018).
Acknowledgements
W.J.K. acknowledges the support by the Roberto C. Goizueta Chair fund and the US Department of Energy grant (no. DE‐FG02‐04ER15510), and we acknowledge the Specialty Separations Center at Georgia Institute of Technology for assistance in equipment resource funds.
Author information
Authors and Affiliations
Contributions
Z.L., W. Qiu and W.J.K. conceived and designed the project. Z.L. prepared the CMS membranes and performed the membrane permeation and sorption tests. Z.L. and W. Qiu synthesized the copolyimide precursors. W. Quan carried out the X-ray diffraction measurement and pore size distribution test by CO2 physisorption. Z.L. conducted the gas diffusion analysis using the dual sorption and transport models. Z.L. W. Qiu and W.J.K. discussed the findings in this paper. Z.L. and W.J.K. drafted the paper, and all authors contributed to revising the paper.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Materials thanks the anonymous reviewers for their contribution to the peer review of this work.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Supplementary Information
Supplementary Notes 1–8, Figs. 1–23, Tables 1–24 and References 1–95.
Source data
Source Data Fig. 1
Source Data for NMR data plotted in Fig. 1b, TGA data plotted in Fig. 1c and ATR–FTIR data plotted in Fig. 1d.
Source Data Fig. 2
Source Data for Raman spectra data plotted in Fig. 2d, WAXRD data plotted in Fig. 2e and pore sizes plotted in Fig. 2f.
Source Data Fig. 3
Source Data for pure gas selectivity data plotted in Fig. 3a–c, and solubility/diffusivity data plotted in Fig. 3d–f.
Source Data Fig. 4
Source data for mixed-gas selectivity data plotted in Fig. 4a–d.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Liu, Z., Qiu, W., Quan, W. et al. Advanced carbon molecular sieve membranes derived from molecularly engineered cross-linkable copolyimide for gas separations. Nat. Mater. 22, 109–116 (2023). https://doi.org/10.1038/s41563-022-01426-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41563-022-01426-8
This article is cited by
-
Bimodal free volumes uplift gas separation
Nature Materials (2023)
-
Precise molecular sieving of ethylene from ethane using triptycene-derived submicroporous carbon membranes
Nature Materials (2023)