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Title: Understanding and controlling water stability of MOF-74

Abstract

Metal organic framework (MOF) materials in general, and MOF-74 in particular, have promising properties for many technologically important processes. However, their instability under humid conditions severely restricts practical use. We show that this instability and the accompanying reduction of the CO2 uptake capacity of MOF-74 under humid conditions originate in the water dissociation reaction H2O → OH + H at the metal centers. After this dissociation, the OH groups coordinate to the metal centers, explaining the reduction in the MOF's CO2 uptake capacity. This reduction thus strongly depends on the catalytic activity of MOF-74 towards the water dissociation reaction. We further show that—while the water molecules themselves only have a negligible effect on the crystal structure of MOF-74—the OH and H products of the dissociation reaction significantly weaken the MOF framework and lead to the observed crystal structure breakdown. With this knowledge, we propose a way to suppress this particular reaction by modifying the MOF-74 structure to increase the water dissociation energy barrier and thus control the stability of the system under humid conditions.

Authors:
 [1];  [2];  [2];  [3];  [3];  [2];  [1]
  1. Department of Physics; Wake Forest University; Winston-Salem; USA
  2. Department of Materials Science and Engineering; University of Texas at Dallas; Richardson; USA
  3. Department of Chemistry and Chemical Biology; Rutgers University; Piscataway; USA
Publication Date:
Research Org.:
Oak Ridge National Laboratory, Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1565461
DOE Contract Number:  
AC05-00OR22725; FG02-08ER46491
Resource Type:
Journal Article
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 4; Journal Issue: 14; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Energy & Fuels; Materials Science

Citation Formats

Zuluaga, Sebastian, Fuentes-Fernandez, Erika M. A., Tan, Kui, Xu, Feng, Li, Jing, Chabal, Yves J., and Thonhauser, Timo. Understanding and controlling water stability of MOF-74. United States: N. p., 2016. Web. doi:10.1039/c5ta10416e.
Zuluaga, Sebastian, Fuentes-Fernandez, Erika M. A., Tan, Kui, Xu, Feng, Li, Jing, Chabal, Yves J., & Thonhauser, Timo. Understanding and controlling water stability of MOF-74. United States. doi:10.1039/c5ta10416e.
Zuluaga, Sebastian, Fuentes-Fernandez, Erika M. A., Tan, Kui, Xu, Feng, Li, Jing, Chabal, Yves J., and Thonhauser, Timo. Fri . "Understanding and controlling water stability of MOF-74". United States. doi:10.1039/c5ta10416e.
@article{osti_1565461,
title = {Understanding and controlling water stability of MOF-74},
author = {Zuluaga, Sebastian and Fuentes-Fernandez, Erika M. A. and Tan, Kui and Xu, Feng and Li, Jing and Chabal, Yves J. and Thonhauser, Timo},
abstractNote = {Metal organic framework (MOF) materials in general, and MOF-74 in particular, have promising properties for many technologically important processes. However, their instability under humid conditions severely restricts practical use. We show that this instability and the accompanying reduction of the CO2 uptake capacity of MOF-74 under humid conditions originate in the water dissociation reaction H2O → OH + H at the metal centers. After this dissociation, the OH groups coordinate to the metal centers, explaining the reduction in the MOF's CO2 uptake capacity. This reduction thus strongly depends on the catalytic activity of MOF-74 towards the water dissociation reaction. We further show that—while the water molecules themselves only have a negligible effect on the crystal structure of MOF-74—the OH and H products of the dissociation reaction significantly weaken the MOF framework and lead to the observed crystal structure breakdown. With this knowledge, we propose a way to suppress this particular reaction by modifying the MOF-74 structure to increase the water dissociation energy barrier and thus control the stability of the system under humid conditions.},
doi = {10.1039/c5ta10416e},
journal = {Journal of Materials Chemistry. A},
issn = {2050-7488},
number = 14,
volume = 4,
place = {United States},
year = {2016},
month = {1}
}

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