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

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

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
Volume207
DOIs
Publication statusPublished - 2018 Dec 22

Fingerprint

Graft copolymers
Methane
Carbon Dioxide
Nanocrystals
Carbon dioxide
Membranes
Field emission
X ray diffraction
Scanning electron microscopy
Gas permeability
Diffusion in gases
Polymer matrix
Polyvinyl Chloride
Excavation
Polyvinyl chlorides
Amines
Differential scanning calorimetry
Solubility
poly(vinyl chloride)-g-poly(oxyethylene methacrylate)
Transmission electron microscopy

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry
  • Filtration and Separation

Cite this

@article{a4fbc0422bff4a208cfe42c59ae14042,
title = "Mixed-matrix membranes containing nanocage-like hollow ZIF-8 polyhedral nanocrystals in graft copolymers for carbon dioxide/methane separation",
abstract = "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.",
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Mixed-matrix membranes containing nanocage-like hollow ZIF-8 polyhedral nanocrystals in graft copolymers for carbon dioxide/methane separation. / Lee, Jae Hun; Kwon, Hyuk Taek; Bae, Sunyoung; Kim, Jinsoo; Kim, Jong Hak.

In: Separation and Purification Technology, Vol. 207, 22.12.2018, p. 427-434.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Mixed-matrix membranes containing nanocage-like hollow ZIF-8 polyhedral nanocrystals in graft copolymers for carbon dioxide/methane separation

AU - Lee, Jae Hun

AU - Kwon, Hyuk Taek

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AU - Kim, Jinsoo

AU - Kim, Jong Hak

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AB - 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.

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