Mixed-matrix membranes containing nanocage-like hollow ZIF-8 polyhedral nanocrystals in graft copolymers for carbon dioxide/methane separation

Jae Hun Lee, Hyuk Taek Kwon, Sunyoung Bae, Jinsoo Kim, Jong Hak Kim

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20 Citations (Scopus)


Nanocage-like, hollow ZIF-8 (H-ZIF) polyhedral nanocrystals were synthesized via the use of seed crystals, epitaxial ZIF-8 growth, and excavation of ZIF-67 sacrificial templates. The highly porous and hollow structure of the H-ZIF polyhedral nanocrystals was confirmed by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction (XRD), and Brunauer-Emmett-Teller analysis. The H-ZIF nanocrystals were distributed in an amphiphilic poly(vinyl chloride)-g-poly(oxyethylene methacrylate) (PVC-g-POEM) graft copolymer matrix to form mixed-matrix membranes (MMMs) for CO2/CH4 separation. The microphase-separated nature of the structure of the PVC-g-POEM was induced by the solubility difference between the hydrophobic PVC backbone and the hydrophilic POEM side chains. Specific interactions between the micro-structured PVC-g-POEM polymer matrix and the imidazole moiety of the H-ZIF enhanced the interfacial contact and improved the dispersion of the H-ZIF within the MMM; this was confirmed by XRD, FE-SEM, and differential scanning calorimetry. The hollow structure of the H-ZIF reduced the gas diffusion resistance of the MMM, resulting in increased gas permeability. Moreover, the molecular sieving properties and CO2-philic amine groups in the imidazole linkers of the H-ZIF led to high CO2 separation performance. The PVC-g-POEM/H-ZIF MMM exhibited an approximately fivefold increase in CO2 permeability, with a value of 210.6 barrer, compared to 43.5 barrer for a pristine PVC-g-POEM membrane with a CO2/CH4 selectivity of 14.3, which is close to upper bound reported by Robeson in 2008.

Original languageEnglish
Pages (from-to)427-434
Number of pages8
JournalSeparation and Purification Technology
Publication statusPublished - 2018 Dec 22

Bibliographical note

Funding Information:
This work was supported by the National Research Foundation (NRF) of South Korea grant funded by the Ministry of Science, ICT and Future Planning ( NRF-2016R1A2B4014805 and NRF-2017M1A2A2043448 ). JH Lee acknowledges the Students' Association of the Graduate School of Yonsei University, funded by the Graduate School of Yonsei University.

Publisher Copyright:
© 2018 Elsevier B.V.

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry
  • Filtration and Separation


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