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

• DOI: 10.1021/jacs.0c11266
• Publication Date: 2021-01-15T02:12:19Z
• Authors: Lee Robison; Xinyi Gong; Austin M. Evans; Florencia A. Son; Xingjie Wang; Louis R. Redfern; Megan C. Wasson; Zoha H. Syed; Zhijie Chen; Karam B. Idrees; Timur Islamoglu; Massimiliano Delf...; William R. Dichtel; François-Xavier C...; Nathan C. Gianneschi; Omar K. Farha
• Keywords: transmission electron microscopy; [CHIM.MATE]Chemical Sciences/Material chemistry; 02 engineering and technology; mechanical properties; 0210 nano-technology; metal-organic frameworks; 7. Clean energy; catenation

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.