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Transient Catenation in a Zirconium-Based Metal-Organic Framework and Its Effect on Mechanical Stability and Sorption Properties.

Lee RobisonXinyi GongAustin M EvansFlorencia A SonXingjie WangLouis R RedfernMegan C WassonZoha H SyedZhijie ChenKaram B IdreesTimur IslamogluMassimiliano DelferroWilliam R DichtelFrançois-Xavier CoudertNathan C GianneschiOmar K Farha
Published in: Journal of the American Chemical Society (2021)
Interpenetration of two or more sublattices is common among many metal-organic frameworks (MOFs). Herein, we study the evolution of one zirconium cluster-based, 3,8-connected MOF from its non-interpenetrated (NU-1200) to interpenetrated (STA-26) isomer. We observe this transient catenation process indirectly using ensemble methods, such as nitrogen porosimetry and X-ray diffraction, and directly, using high-resolution transmission electron microscopy. The approach detailed here will serve as a template for other researchers to monitor the interpenetration of their MOF samples at the bulk and single-particle limits. We investigate the mechanical stability of both lattices experimentally by pressurized in situ X-ray diffraction and nanoindentation as well as computationally with density functional theory calculations. Both lines of study reveal that STA-26 is considerably more mechanically stable than NU-1200. We conclude this study by demonstrating the potential of these MOFs and their mixed phases for the capture of gaseous n-hexane, used as a structural mimic for the chemical warfare agent sulfur mustard gas.
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