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Title: Crystallizing Atomic Xenon in a Flexible MOF to Probe and Understand Its Temperature-Dependent Breathing Behavior and Unusual Gas Adsorption Phenomenon

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 workmore » may provide further understanding of the adsorption behavior of noble gases in flexible MOF structures.« less

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [5]; ORCiD logo [6];  [7];  [8]; ORCiD logo [4]; ORCiD logo [9]
+ Show Author Affiliations
  1. Shenzhen Polytechnic (China); Rutgers Univ., Piscataway, NJ (United States)
  2. Diamond Light Source Ltd., Didcot (United Kingdom)
  3. Micromeritics Instrument Corporation, Norcross, GA (United States)
  4. Wake Forest Univ., Winston-Salem, NC (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  6. Univ. of Texas at Dallas, Richardson, TX (United States)
  7. Shenzhen Polytechnic (China)
  8. Rutgers Univ., Piscataway, NJ (United States)
  9. Rutgers Univ., Piscataway, NJ (United States); Shenzhen Polytechnic (China)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Rutgers Univ., Piscataway, NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); Guangdong Natural Science Foundation; Scientific and Technical Innovation Council of Shenzhen; USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1749889
Alternate Identifier(s):
OSTI ID: 1787516
Report Number(s):
BNL-220745-2020-JAAM
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
SC0012704; FG02- 08ER46491; SC0019902; 21901166; 2019A1515010692; JCYJ20190809145615620
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 142; Journal Issue: 47; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; structural dynamics; adsorption; crystal structure; metal organic frameworks; physical and chemical processes

Citation Formats

Wang, Hao, Warren, Mark, Jagiello, Jacek, Jensen, Stephanie, Ghose, Sanjit K., Tan, Kui, Yu, Liang, Emge, Thomas J., Thonhauser, Timo, and Li, Jing. Crystallizing Atomic Xenon in a Flexible MOF to Probe and Understand Its Temperature-Dependent Breathing Behavior and Unusual Gas Adsorption Phenomenon. United States: N. p., 2020. Web. doi:10.1021/jacs.0c09475.
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Wang, Hao, Warren, Mark, Jagiello, Jacek, Jensen, Stephanie, Ghose, Sanjit K., Tan, Kui, Yu, Liang, Emge, Thomas J., Thonhauser, Timo, & Li, Jing. Crystallizing Atomic Xenon in a Flexible MOF to Probe and Understand Its Temperature-Dependent Breathing Behavior and Unusual Gas Adsorption Phenomenon. United States. https://doi.org/10.1021/jacs.0c09475
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Wang, Hao, Warren, Mark, Jagiello, Jacek, Jensen, Stephanie, Ghose, Sanjit K., Tan, Kui, Yu, Liang, Emge, Thomas J., Thonhauser, Timo, and Li, Jing. Tue . "Crystallizing Atomic Xenon in a Flexible MOF to Probe and Understand Its Temperature-Dependent Breathing Behavior and Unusual Gas Adsorption Phenomenon". United States. https://doi.org/10.1021/jacs.0c09475. https://www.osti.gov/servlets/purl/1749889.
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@article{osti_1749889,
title = {Crystallizing Atomic Xenon in a Flexible MOF to Probe and Understand Its Temperature-Dependent Breathing Behavior and Unusual Gas Adsorption Phenomenon},
author = {Wang, Hao and Warren, Mark and Jagiello, Jacek and Jensen, Stephanie and Ghose, Sanjit K. and Tan, Kui and Yu, Liang and Emge, Thomas J. and Thonhauser, Timo and Li, Jing},
abstractNote = {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.},
doi = {10.1021/jacs.0c09475},
journal = {Journal of the American Chemical Society},
number = 47,
volume = 142,
place = {United States},
year = {Tue Nov 10 00:00:00 EST 2020},
month = {Tue Nov 10 00:00:00 EST 2020}
}
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