Polymer-Coordinated Heterogeneous Zeolitic Imidazolate Framework-8 with Exceptional Propylene/Propane Molecular Sieving Effect

Sunghwan Park; Ho Jin Jung; Se Hun Kim; Hoang Vu Ly; Seung Soo Kim; Dong A. Kang; Young Je Kwon; Seunghyeon Joo; Kie Yong Cho; Hae Kwon Jeong

doi:10.1002/smll.202505746

Polymer-Coordinated Heterogeneous Zeolitic Imidazolate Framework-8 with Exceptional Propylene/Propane Molecular Sieving Effect

Sunghwan Park, Ho Jin Jung, Se Hun Kim, Hoang Vu Ly, Seung Soo Kim, Dong A. Kang, Young Je Kwon, Seunghyeon Joo, Kie Yong Cho, Hae Kwon Jeong

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

Zeolitic imidazolate framework-8 (ZIF-8) is a promising material for C₃H₆/C₃H₈ separation; however, its inherent linker flexibility compromises molecular sieving effect. To address this limitation, a novel ZIF-8, namely heterogeneous ZIF-8 (hZIF-8), is developed, consisting of nanocrystalline ZIF-8 phases with a minor amorphous polymer component introduced via in situ coordination. hZIF-8 is synthesized through a Lewis-acid-catalyzed cationic ring-opening polymerization of tetrahydrofuran (THF), generating polytetramethylene ether glycol (PTMEG) chains that competitively coordinate with zinc ions during ZIF-8 crystallization. This coordination-mediated heterogeneous structure exhibits unique characteristics distinct from conventional ZIF-8 and other polymer hybrid MOFs such as PolyMOFs. The polymer phase effectively restricts the linker flexibility of the nanocrystalline phase at the molecular level, leading to significantly enhanced molecular sieving properties. As a result, hZIF-8-containing mixed-matrix membranes (MMMs) exhibit a significant enhancement in C₃H₆/C₃H₈ separation performance, with the separation factor increasing from 13.3 to 75.5 (by 468%) and the C₃H₆ permeability from 7.4 to 17.4 Barrer (by 135%) at 30 wt.% loading. Furthermore, the intrinsic selectivity of hZIF-8 is predicted to reach ≈3700, representing an order-of-magnitude improvement over that of pristine ZIF-8 (≈180).

Original language	English
Article number	e05746
Journal	Small
Volume	21
Issue number	37
DOIs	https://doi.org/10.1002/smll.202505746
State	Published - Sep 18 2025
Externally published	Yes

Funding

S.P. and H.J.J. contributed equally to this work. Dr. H. K. J. gratefully acknowledges the financial support from the National Science Foundation (CBET-1929596). This publication was made possible in part by NPRP grant # 12S-0209-190064 from the Qatar National Research Fund (a member of the Qatar Foundation). The findings achieved herein are solely the responsibility of the authors. The National Science Foundation supported the FE-SEM acquisition under Grant DBI-0116835, the VP for Research Office, and the Texas A&M Engineering Experimental Station. Dr. K. Y. C. acknowledges financial support through the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (No. NRF-2022R1C1C1003313). Dr. S.P. acknowledges partial financial support from the Ministry of Trade, Industry and Energy (MOTIE) (No. RS-2023-00266205). S.P. and H.J.J. contributed equally to this work. Dr. H. K. J. gratefully acknowledges the financial support from the National Science Foundation (CBET‐1929596). This publication was made possible in part by NPRP grant # 12S‐0209‐190064 from the Qatar National Research Fund (a member of the Qatar Foundation). The findings achieved herein are solely the responsibility of the authors. The National Science Foundation supported the FE‐SEM acquisition under Grant DBI‐0116835, the VP for Research Office, and the Texas A&M Engineering Experimental Station. Dr. K. Y. C. acknowledges financial support through the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (No. NRF‐2022R1C1C1003313). Dr. S.P. acknowledges partial financial support from the Ministry of Trade, Industry and Energy (MOTIE) (No. RS‐2023‐00266205).

Keywords

CH/CH separation
coordination polymers
metal-organic frameworks
mixed-matrix membranes
zeolitic imidazolate frameworks

Access to Document

10.1002/smll.202505746

Cite this

@article{6b81eabbc4cb4bdba7805f9df0fa7a26,

title = "Polymer-Coordinated Heterogeneous Zeolitic Imidazolate Framework-8 with Exceptional Propylene/Propane Molecular Sieving Effect",

abstract = "Zeolitic imidazolate framework-8 (ZIF-8) is a promising material for C3H6/C3H8 separation; however, its inherent linker flexibility compromises molecular sieving effect. To address this limitation, a novel ZIF-8, namely heterogeneous ZIF-8 (hZIF-8), is developed, consisting of nanocrystalline ZIF-8 phases with a minor amorphous polymer component introduced via in situ coordination. hZIF-8 is synthesized through a Lewis-acid-catalyzed cationic ring-opening polymerization of tetrahydrofuran (THF), generating polytetramethylene ether glycol (PTMEG) chains that competitively coordinate with zinc ions during ZIF-8 crystallization. This coordination-mediated heterogeneous structure exhibits unique characteristics distinct from conventional ZIF-8 and other polymer hybrid MOFs such as PolyMOFs. The polymer phase effectively restricts the linker flexibility of the nanocrystalline phase at the molecular level, leading to significantly enhanced molecular sieving properties. As a result, hZIF-8-containing mixed-matrix membranes (MMMs) exhibit a significant enhancement in C3H6/C3H8 separation performance, with the separation factor increasing from 13.3 to 75.5 (by 468\%) and the C3H6 permeability from 7.4 to 17.4 Barrer (by 135\%) at 30 wt.\% loading. Furthermore, the intrinsic selectivity of hZIF-8 is predicted to reach ≈3700, representing an order-of-magnitude improvement over that of pristine ZIF-8 (≈180).",

keywords = "CH/CH separation, coordination polymers, metal-organic frameworks, mixed-matrix membranes, zeolitic imidazolate frameworks",

author = "Sunghwan Park and Jung, \{Ho Jin\} and Kim, \{Se Hun\} and Ly, \{Hoang Vu\} and Kim, \{Seung Soo\} and Kang, \{Dong A.\} and Kwon, \{Young Je\} and Seunghyeon Joo and Cho, \{Kie Yong\} and Jeong, \{Hae Kwon\}",

note = "Publisher Copyright: {\textcopyright} 2025 The Author(s). Small published by Wiley-VCH GmbH.",

year = "2025",

month = sep,

day = "18",

doi = "10.1002/smll.202505746",

language = "English",

volume = "21",

journal = "Small",

issn = "1613-6810",

publisher = "wiley",

number = "37",

}

TY - JOUR

T1 - Polymer-Coordinated Heterogeneous Zeolitic Imidazolate Framework-8 with Exceptional Propylene/Propane Molecular Sieving Effect

AU - Park, Sunghwan

AU - Jung, Ho Jin

AU - Kim, Se Hun

AU - Ly, Hoang Vu

AU - Kim, Seung Soo

AU - Kang, Dong A.

AU - Kwon, Young Je

AU - Joo, Seunghyeon

AU - Cho, Kie Yong

AU - Jeong, Hae Kwon

PY - 2025/9/18

Y1 - 2025/9/18

N2 - Zeolitic imidazolate framework-8 (ZIF-8) is a promising material for C3H6/C3H8 separation; however, its inherent linker flexibility compromises molecular sieving effect. To address this limitation, a novel ZIF-8, namely heterogeneous ZIF-8 (hZIF-8), is developed, consisting of nanocrystalline ZIF-8 phases with a minor amorphous polymer component introduced via in situ coordination. hZIF-8 is synthesized through a Lewis-acid-catalyzed cationic ring-opening polymerization of tetrahydrofuran (THF), generating polytetramethylene ether glycol (PTMEG) chains that competitively coordinate with zinc ions during ZIF-8 crystallization. This coordination-mediated heterogeneous structure exhibits unique characteristics distinct from conventional ZIF-8 and other polymer hybrid MOFs such as PolyMOFs. The polymer phase effectively restricts the linker flexibility of the nanocrystalline phase at the molecular level, leading to significantly enhanced molecular sieving properties. As a result, hZIF-8-containing mixed-matrix membranes (MMMs) exhibit a significant enhancement in C3H6/C3H8 separation performance, with the separation factor increasing from 13.3 to 75.5 (by 468%) and the C3H6 permeability from 7.4 to 17.4 Barrer (by 135%) at 30 wt.% loading. Furthermore, the intrinsic selectivity of hZIF-8 is predicted to reach ≈3700, representing an order-of-magnitude improvement over that of pristine ZIF-8 (≈180).

AB - Zeolitic imidazolate framework-8 (ZIF-8) is a promising material for C3H6/C3H8 separation; however, its inherent linker flexibility compromises molecular sieving effect. To address this limitation, a novel ZIF-8, namely heterogeneous ZIF-8 (hZIF-8), is developed, consisting of nanocrystalline ZIF-8 phases with a minor amorphous polymer component introduced via in situ coordination. hZIF-8 is synthesized through a Lewis-acid-catalyzed cationic ring-opening polymerization of tetrahydrofuran (THF), generating polytetramethylene ether glycol (PTMEG) chains that competitively coordinate with zinc ions during ZIF-8 crystallization. This coordination-mediated heterogeneous structure exhibits unique characteristics distinct from conventional ZIF-8 and other polymer hybrid MOFs such as PolyMOFs. The polymer phase effectively restricts the linker flexibility of the nanocrystalline phase at the molecular level, leading to significantly enhanced molecular sieving properties. As a result, hZIF-8-containing mixed-matrix membranes (MMMs) exhibit a significant enhancement in C3H6/C3H8 separation performance, with the separation factor increasing from 13.3 to 75.5 (by 468%) and the C3H6 permeability from 7.4 to 17.4 Barrer (by 135%) at 30 wt.% loading. Furthermore, the intrinsic selectivity of hZIF-8 is predicted to reach ≈3700, representing an order-of-magnitude improvement over that of pristine ZIF-8 (≈180).

KW - CH/CH separation

KW - coordination polymers

KW - metal-organic frameworks

KW - mixed-matrix membranes

KW - zeolitic imidazolate frameworks

UR - https://www.scopus.com/pages/publications/105011963798

U2 - 10.1002/smll.202505746

DO - 10.1002/smll.202505746

M3 - Article

C2 - 40714739

AN - SCOPUS:105011963798

SN - 1613-6810

VL - 21

JO - Small

JF - Small

IS - 37

M1 - e05746

ER -

Polymer-Coordinated Heterogeneous Zeolitic Imidazolate Framework-8 with Exceptional Propylene/Propane Molecular Sieving Effect

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this