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Crystallizing atomic xenon in a flexible MOF to probe and understand its temperature-dependent breathing behavior and unusual gas adsorption phenomenon

DOI: 10.1021/jacs.0c09475 DOI Help

Authors: Hao Wang (Shenzhen Polytechnic; Rutgers University) , Mark Warren (Diamond Light Source) , Jacek Jagiello (Micromeritics Instrument Corporation) , Stephanie Jensen (Wake Forest University) , Sanjit K. Ghose (Brookhaven National Laboratory) , Kui Tan (University of Texas at Dallas) , Liang Yu (Shenzhen Polytechnic) , Thomas J. Emge (Rutgers University) , Timo Thonhauser (Wake Forest University) , Jing Li (Rutgers University; Shenzhen Polytechnic)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: November 2020
Diamond Proposal Number(s): 19670

Abstract: Flexible metal–organic frameworks (MOFs) hold great promise as smart materials for specific applications such as gas separation. These materials undergo interesting structural changes in response to guest molecules, which is often associated with unique adsorption behavior not possible for rigid MOFs. Understanding the dynamic behavior of flexible MOFs is crucial yet challenging as it involves weak host–guest interactions and subtle structural transformation not only at the atomic/molecular level but also in a nonsteady state. We report here an in-depth study on the adsorbate- and temperature-dependent adsorption in a flexible MOF by crystallizing atomic gases into its pores. Mn(ina)2 shows an interesting temperature-dependent response toward noble gases. Its nonmonotonic, temperature-dependent adsorption profile results in an uptake maximum at a temperature threshold, a phenomenon that is unusual. Full characterization of Xe-loaded MOF structures is performed by in situ single-crystal and synchrotron X-ray diffraction, IR spectroscopy, and molecular modeling. The X-ray diffraction analysis offers a detailed explanation into the dynamic structural transformation and provides a convincing rationalization of the unique adsorption behavior at the molecular scale. The guest and temperature dependence of the structural breathing gives rise to an intriguing reverse of Xe/Kr adsorption selectivity as a function of temperature. The presented work may provide further understanding of the adsorption behavior of noble gases in flexible MOF structures.

Journal Keywords: Structural dynamics; Adsorption; Crystal structure; Metal organic frameworks; Physical and chemical processes

Diamond Keywords: Gas Separation

Subject Areas: Materials, Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 16/11/2020 09:09

Discipline Tags:

Materials Science Metallurgy Metal-Organic Frameworks Chemistry Organometallic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)