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Reversibly Phase-Transformative Zeolitic Imidazolate Framework-108 and the Membrane Separation Utility.

Yingwu Zhou1,2, Yujie Ban1,2, Weishen Yang1,2

  • 1State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian116023, China.

Inorganic Chemistry
|October 21, 2022
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Summary

Zeolitic imidazolate framework (ZIF)-108 exhibits reversible phase transformations between sodalite, diamondoid, and large pore-sodalite structures triggered by water, DMF, and heat. These transformations enhance mixed matrix membrane performance for gas separation.

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Area of Science:

  • Materials Science
  • Crystallography
  • Chemical Engineering

Background:

  • Reversible phase transformations (RPTs) in metal-organic frameworks (MOFs) offer tunable material properties and self-healing capabilities.
  • Achieving spatiotemporal control over bond cleavage and reconstruction in MOF RPTs remains a significant challenge.
  • Zeolitic imidazolate framework (ZIF)-108, with its moderate Zn-N coordination bonds, presents a promising platform for studying RPTs.

Purpose of the Study:

  • To investigate and report the reversible phase transformations of zeolitic imidazolate framework (ZIF)-108.
  • To identify the different crystal phases and the triggers for their interconversion.
  • To evaluate the impact of these phase transformations on the performance of mixed matrix membranes for gas separation.

Main Methods:

  • Synthesis and characterization of ZIF-108 crystal phases.
  • Induction of RPTs using water, water vapor, dimethylformamide (DMF), DMF vapor, and high-temperature treatments.
  • Analysis of phase transformations between sodalite (SOD), diamondoid (DIA), and large pore-sodalite (lp_SOD) topologies.
  • Fabrication and evaluation of mixed matrix membranes incorporating different ZIF-108 phases.

Main Results:

  • Three distinct phases of ZIF-108 were identified: sodalite (SOD), diamondoid (DIA), and large pore-sodalite (lp_SOD).
  • Specific RPT pathways were established: SOD ↔ DIA (water/DMF), SOD ↔ lp_SOD (heat/DMF), and lp_SOD ↔ DIA (water).
  • The lp_SOD phase, when incorporated into mixed matrix membranes, demonstrated improved interfacial adhesion with polymer chains and enhanced molecular sieving for CO2 and CH4.

Conclusions:

  • ZIF-108 is a versatile MOF capable of undergoing controlled, multi-stage reversible phase transformations.
  • The observed RPTs are driven by specific environmental stimuli (water, DMF, heat) and structural reorganization.
  • The lp_SOD phase of ZIF-108 significantly enhances mixed matrix membrane performance for gas separation applications due to improved filler-polymer interaction and pore structure.