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Reversible solvent interactions with UiO-67 metal-organic frameworks.

Isabella Goodenough1, Mikaela C Boyanich1, Ryan P McDonnell1

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|January 31, 2024
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This study explores how simple molecules interact with UiO-67 Metal-Organic Frameworks (MOFs). We found that analytes like isopropanol, acetone, and n-heptane bind reversibly, interacting with internal MOF hydroxyl groups.

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Area of Science:

  • Materials Science
  • Chemical Physics
  • Nanotechnology

Background:

  • Understanding host-guest interactions in Metal-Organic Frameworks (MOFs) is crucial for their practical applications.
  • UiO-67 MOFs are a promising class of materials, but their specific interactions with various analytes need detailed investigation.

Purpose of the Study:

  • To investigate the intermolecular interactions between UiO-67 MOFs and simple polar (acetone, isopropanol) and non-polar (n-heptane) analytes.
  • To elucidate the binding mechanisms and strength influenced by MOF and analyte functionality.

Main Methods:

  • Utilized temperature programmed desorption mass spectrometry (TPD-MS) to study analyte desorption behavior.
  • Employed temperature programmed Fourier transform infrared spectroscopy (TP-FTIR) to probe in situ molecular interactions within the MOF pores.

Main Results:

  • Isopropanol, acetone, and n-heptane exhibit reversible and non-destructive binding to UiO-67 MOFs.
  • Binding strengths were found to be ordered as n-heptane ≈ isopropanol > acetone, influenced by molecular functionality.
  • Analytes diffuse into the MOF pores and interact with μ3-OH groups, evidenced by characteristic IR spectral changes (e.g., ν(μ3-OH), ν(CH), and ν(C=O) modes).

Conclusions:

  • The study provides in situ insights into the specific interactions between functional groups of analytes and UiO-67 MOFs.
  • This work establishes a foundational understanding for evaluating MOF interactions with more complex molecular systems.