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Title: Hydrolytic stability in hemilabile metal–organic frameworks

Abstract

Highly porous metal–organic frameworks (MOFs), which have undergone exciting developments over the past few decades, show promise for a wide range of applications. However, many studies indicate that they suffer from significant stability issues, especially with respect to their interactions with water, which severely limits their practical potential. Here we demonstrate how the presence of ‘sacrificial’ bonds in the coordination environment of its metal centres (referred to as hemilability) endows a dehydrated copper-based MOF with good hydrolytic stability. On exposure to water, in contrast to the indiscriminate breaking of coordination bonds that typically results in structure degradation, it is non-structural weak interactions between the MOF’s copper paddlewheel clusters that are broken and the framework recovers its as-synthesized, hydrated structure. This MOF retained its structural integrity even after contact with water for one year, whereas HKUST-1, a compositionally similar material that lacks these sacrificial bonds, loses its crystallinity in less than a day under the same conditions.

Authors:
ORCiD logo; ORCiD logo; ORCiD logo; ; ORCiD logo; ORCiD logo; ORCiD logo; ; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1566614
DOE Contract Number:  
AC02-05CH11231; SC0001015
Resource Type:
Journal Article
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 10; Journal Issue: 11; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
membrane, carbon capture, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

McHugh, Lauren N., McPherson, Matthew J., McCormick, Laura J., Morris, Samuel A., Wheatley, Paul S., Teat, Simon J., McKay, David, Dawson, Daniel M., Sansome, Charlotte E. F., Ashbrook, Sharon E., Stone, Corinne A., Smith, Martin W., and Morris, Russell E. Hydrolytic stability in hemilabile metal–organic frameworks. United States: N. p., 2018. Web. doi:10.1038/s41557-018-0104-x.
McHugh, Lauren N., McPherson, Matthew J., McCormick, Laura J., Morris, Samuel A., Wheatley, Paul S., Teat, Simon J., McKay, David, Dawson, Daniel M., Sansome, Charlotte E. F., Ashbrook, Sharon E., Stone, Corinne A., Smith, Martin W., & Morris, Russell E. Hydrolytic stability in hemilabile metal–organic frameworks. United States. doi:10.1038/s41557-018-0104-x.
McHugh, Lauren N., McPherson, Matthew J., McCormick, Laura J., Morris, Samuel A., Wheatley, Paul S., Teat, Simon J., McKay, David, Dawson, Daniel M., Sansome, Charlotte E. F., Ashbrook, Sharon E., Stone, Corinne A., Smith, Martin W., and Morris, Russell E. Mon . "Hydrolytic stability in hemilabile metal–organic frameworks". United States. doi:10.1038/s41557-018-0104-x.
@article{osti_1566614,
title = {Hydrolytic stability in hemilabile metal–organic frameworks},
author = {McHugh, Lauren N. and McPherson, Matthew J. and McCormick, Laura J. and Morris, Samuel A. and Wheatley, Paul S. and Teat, Simon J. and McKay, David and Dawson, Daniel M. and Sansome, Charlotte E. F. and Ashbrook, Sharon E. and Stone, Corinne A. and Smith, Martin W. and Morris, Russell E.},
abstractNote = {Highly porous metal–organic frameworks (MOFs), which have undergone exciting developments over the past few decades, show promise for a wide range of applications. However, many studies indicate that they suffer from significant stability issues, especially with respect to their interactions with water, which severely limits their practical potential. Here we demonstrate how the presence of ‘sacrificial’ bonds in the coordination environment of its metal centres (referred to as hemilability) endows a dehydrated copper-based MOF with good hydrolytic stability. On exposure to water, in contrast to the indiscriminate breaking of coordination bonds that typically results in structure degradation, it is non-structural weak interactions between the MOF’s copper paddlewheel clusters that are broken and the framework recovers its as-synthesized, hydrated structure. This MOF retained its structural integrity even after contact with water for one year, whereas HKUST-1, a compositionally similar material that lacks these sacrificial bonds, loses its crystallinity in less than a day under the same conditions.},
doi = {10.1038/s41557-018-0104-x},
journal = {Nature Chemistry},
issn = {1755-4330},
number = 11,
volume = 10,
place = {United States},
year = {2018},
month = {8}
}

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