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Title: Tuning the Adsorption-Induced Phase Change in the Flexible Metal–Organic Framework Co(bdp)

Abstract

Metal–organic frameworks that flex to undergo structural phase changes upon gas adsorption are promising materials for gas storage and separations, and achieving synthetic control over the pressure at which these changes occur is crucial to the design of such materials for specific applications. To this end, a new family of materials based on the flexible metal–organic framework Co(bdp) (bdp2– = 1,4-benzenedipyrazolate) has been prepared via the introduction of fluorine, deuterium, and methyl functional groups on the bdp2– ligand, namely, Co(F-bdp), Co(p-F2-bdp), Co(o-F2-bdp), Co(D4-bdp), and Co(p-Me2-bdp). These frameworks are isoreticular to the parent framework and exhibit similar structural flexibility, transitioning from a low-porosity, collapsed phase to high-porosity, expanded phases with increasing gas pressure. Powder X-ray diffraction studies reveal that fluorination of the aryl ring disrupts edge-to-face π–π interactions, which work to stabilize the collapsed phase at low gas pressures, while deuteration preserves these interactions and methylation strengthens them. In agreement with these observations, high-pressure CH4 adsorption isotherms show that the pressure of the CH4-induced framework expansion can be systematically controlled by ligand functionalization, as materials without edge-to-face interactions in the collapsed phase expand at lower CH4 pressures, while frameworks with strengthened edge-to-face interactions expand at higher pressures. This work puts forthmore » a general design strategy relevant to many other families of flexible metal–organic frameworks, which will be a powerful tool in optimizing these phase-change materials for industrial applications.« less

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Univ. of California, Berkeley, CA (United States)
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1330728
Alternate Identifier(s):
OSTI ID: 1334156
Grant/Contract Number:  
AR0000251; AC02-05CH11231; SC0001015
Resource Type:
Journal Article: Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 138 Journal Issue: 45; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Taylor, Mercedes K., Runčevski, Tomče, Oktawiec, Julia, Gonzalez, Miguel I., Siegelman, Rebecca L., Mason, Jarad A., Ye, Jinxing, Brown, Craig M., and Long, Jeffrey R. Tuning the Adsorption-Induced Phase Change in the Flexible Metal–Organic Framework Co(bdp). United States: N. p., 2016. Web. doi:10.1021/jacs.6b09155.
Taylor, Mercedes K., Runčevski, Tomče, Oktawiec, Julia, Gonzalez, Miguel I., Siegelman, Rebecca L., Mason, Jarad A., Ye, Jinxing, Brown, Craig M., & Long, Jeffrey R. Tuning the Adsorption-Induced Phase Change in the Flexible Metal–Organic Framework Co(bdp). United States. https://doi.org/10.1021/jacs.6b09155
Taylor, Mercedes K., Runčevski, Tomče, Oktawiec, Julia, Gonzalez, Miguel I., Siegelman, Rebecca L., Mason, Jarad A., Ye, Jinxing, Brown, Craig M., and Long, Jeffrey R. 2016. "Tuning the Adsorption-Induced Phase Change in the Flexible Metal–Organic Framework Co(bdp)". United States. https://doi.org/10.1021/jacs.6b09155.
@article{osti_1330728,
title = {Tuning the Adsorption-Induced Phase Change in the Flexible Metal–Organic Framework Co(bdp)},
author = {Taylor, Mercedes K. and Runčevski, Tomče and Oktawiec, Julia and Gonzalez, Miguel I. and Siegelman, Rebecca L. and Mason, Jarad A. and Ye, Jinxing and Brown, Craig M. and Long, Jeffrey R.},
abstractNote = {Metal–organic frameworks that flex to undergo structural phase changes upon gas adsorption are promising materials for gas storage and separations, and achieving synthetic control over the pressure at which these changes occur is crucial to the design of such materials for specific applications. To this end, a new family of materials based on the flexible metal–organic framework Co(bdp) (bdp2– = 1,4-benzenedipyrazolate) has been prepared via the introduction of fluorine, deuterium, and methyl functional groups on the bdp2– ligand, namely, Co(F-bdp), Co(p-F2-bdp), Co(o-F2-bdp), Co(D4-bdp), and Co(p-Me2-bdp). These frameworks are isoreticular to the parent framework and exhibit similar structural flexibility, transitioning from a low-porosity, collapsed phase to high-porosity, expanded phases with increasing gas pressure. Powder X-ray diffraction studies reveal that fluorination of the aryl ring disrupts edge-to-face π–π interactions, which work to stabilize the collapsed phase at low gas pressures, while deuteration preserves these interactions and methylation strengthens them. In agreement with these observations, high-pressure CH4 adsorption isotherms show that the pressure of the CH4-induced framework expansion can be systematically controlled by ligand functionalization, as materials without edge-to-face interactions in the collapsed phase expand at lower CH4 pressures, while frameworks with strengthened edge-to-face interactions expand at higher pressures. This work puts forth a general design strategy relevant to many other families of flexible metal–organic frameworks, which will be a powerful tool in optimizing these phase-change materials for industrial applications.},
doi = {10.1021/jacs.6b09155},
url = {https://www.osti.gov/biblio/1330728}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 45,
volume = 138,
place = {United States},
year = {2016},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1021/jacs.6b09155

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Cited by: 8 works
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