Enhancing selectivity of ZIF-8 membranes by short-duration postsynthetic ligand-exchange modification

Lin Lang, Fateme Banihashemi, Joshua B. James, Jiansong Miao, Jerry Y.S. Lin

Research output: Contribution to journalArticlepeer-review

28 Scopus citations


Post-synthesis modification of zeolitic imidazolate framework (ZIF) membranes offers new opportunities to tailor ZIF structures and improve their separation performance. This work utilizes membrane surface ligand exchange (MSLE) to replace methylimidazole (MeIM) with 5,6-dimethylbenzimidazole (DBIM) and investigates its effect on the gas separation properties of ZIF-8 membranes containing varying amounts of intercrystalline defects (perfect and imperfect membranes). Upon short time (0.5 h) MSLE modification, the pristine ZIF-8 membrane shows a significant enhancement in H2/C2H6 selectivity (12–22) and C3H6/C3H8 selectivity (150–188) with small declines in gas permeance (29.5% for H2, 6.5% for C3H6). MSLE modification also improves the separation performance of imperfect ZIF-8 membranes, but to a lesser extent (C3H6/C3H8 selectivity increasing from 37.5 to 63.3). Some of the MeIM in the ZIF-8 membrane crystals are replaced by bulkier DBIM, facilitated by the presence of the intercrystalline pores resulting in more exchange on the imperfect membrane. The short-duration ligand exchange reduces intracrystalline pore diffusivity, to a greater extent for larger molecules as compared to smaller molecules, leading to a reduction in gas permeance and an increase in separation factor. However, long-duration (5 h) MSLE modification on a perfect ZIF-8 membrane lowers the C3H6/C3H8 selectivity due to an increase in the intercrystalline transport for bulkier C3H8 with an increase in C3H6 permeance due to enhanced solubility within the modified ZIF-8 structure.

Original languageEnglish (US)
Article number118743
JournalJournal of Membrane Science
StatePublished - Feb 1 2021


  • Membrane separation
  • Membrane surface ligand exchange
  • Selectivity
  • Surface defects
  • ZIF-8 membrane

ASJC Scopus subject areas

  • Biochemistry
  • General Materials Science
  • Physical and Theoretical Chemistry
  • Filtration and Separation


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