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Related Experiment Video

Updated: May 27, 2025

Synthesis and Characterization of Functionalized Metal-organic Frameworks
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Synthesis and Characterization of Functionalized Metal-organic Frameworks

Published on: September 5, 2014

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Phase Transformations in MOFs Induced by Adsorbate Exchange.

Alexander V Neimark1, Nicholas J Corrente1, François-Xavier Coudert2

  • 1Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, New Jersey 08854, United States.

Langmuir : the ACS Journal of Surfaces and Colloids
|February 17, 2025
PubMed
Summary
This summary is machine-generated.

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Ion exchange chromatography separates charged molecules from a solution by reversibly exchanging them with mobile, or 'active', ions associated with the oppositely charged stationary phase. This method can be used to separate ions, soften and deionize water, and purify solutions. The polymers comprising the ion-exchange column are high-molecular-weight and chemically stable polymers, crosslinked to be porous and essentially insoluble. They are also functionalized with either acidic or...
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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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Flexible metal-organic frameworks (MOFs) exhibit breathing phase transitions upon gas adsorption. A new theoretical framework explains how carbon dioxide displaces methane in MIL-53 MOF, triggering these transformations.

Area of Science:

  • Materials Science
  • Chemical Engineering
  • Nanotechnology

Background:

  • Gas adsorption induces deformation in nanoporous materials, crucial for applications like gas storage and separations.
  • Metal-organic frameworks (MOFs) exhibit 'breathing' phase transformations, involving significant volume changes with guest molecule adsorption/desorption.

Purpose of the Study:

  • To develop a theoretical framework for quantitatively describing breathing transitions in MOFs during binary gas mixture adsorption.
  • To elucidate the mechanisms of framework deformation and phase transformation (large pore to narrow pore) in MIL-53 MOF.

Main Methods:

  • Developed a theoretical framework based on the concept of adsorption stress.
  • Applied the framework to model the displacement of methane (CH4) by carbon dioxide (CO2) in MIL-53 MOF.

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  • Compared theoretical predictions with experimental data for adsorption and strain isotherms.

    • Main Results:

    • A small addition of CO2 destabilizes the large pore (LP) phase of MIL-53 MOF during methane adsorption, triggering a transition to the narrow pore (NP) phase.
    • The reverse narrow pore to large pore (NP-LP) transformation occurs as methane is further displaced by carbon dioxide.
    • Theoretical predictions of adsorption and strain isotherms show excellent agreement with experimental studies on MIL-53(Al).

    Conclusions:

    • The proposed theoretical approach accurately describes the breathing phase transitions in MOFs induced by binary gas mixtures.
    • The study reveals the underlying mechanisms of framework deformation driven by selective gas adsorption.
    • The general framework is applicable to other flexible nanoporous materials and gas mixtures.