Metal-Organic Frameworks (MOF) are robust hybrid materials with highly tunable geometries, allowing for direct control over chemical and physical properties making them suitable for a variety of filtration, catalytic and detection applications. While the ability to readily tune complex chemical and physical functionality is highly desirable for targeted applications, the thermal stability and impact on applications must also be considered. In this work, we provide a detailed characterization of the intrinsic thermal behavior of the UiO-67 series MOF and functional analogs using temperature-programmed FTIR and mass spectrometric techniques under ultra-high vacuum (UHV). The UiO-67 MOFs show reversible (&lt; 473 K) and irreversible (up to 1273 K) thermal behavior, revealed in the IR spectra. When coupled with mass spectrometry, we have identified the evolution of key structural transformations during the degradation process, including: node dehydration and total node-linker separation. Additionally, we have demonstrated that functionalization of the organic linker reduces thermal stability in the order: UiO-67 &gt; UiO-67-CH<sub>3</sub> &gt; UiO-67-NH<sub>2</sub>. Moreover, thermal treatment impacts the uptake of selected probe analytes as defects develop and heal, and as the pore structure of the MOF transforms. These results provide a fundamental understanding of how the properties of these UiO-67 MOFs govern their thermal stability which is critical for the future development of ultra-stable MOFs and for the interpretation of binding interactions with guest-molecules.

Intrinsic thermal framework stability of UiO-67 metal-organic frameworks

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.