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Title: Cluster assisted water dissociation mechanism in MOF-74 and controlling it using helium

Abstract

We show that the water dissociation reaction H2O → OH + H in the confined environment of MOF-74 channels can be precisely controlled by the addition of noble gas He. Elucidating the entire reaction process using ab initio methods and infrared (IR) spectroscopy, we prove that the interaction between water molecules is critical to the formation of water clusters, which reduce the dissociation barrier by up to 37% and thus influence the reaction significantly. Our time-resolved IR measurements confirm that the formation of these clusters can be suppressed by introducing He gas, providing unprecedented control over water dissociation rates. Since the water dissociation reaction is the cause of the structural instability of MOF-74 in the presence of water, our finding of the reaction mechanism lays the groundwork for designing water stable versions of MOF-74 as well as understanding water related phenomena in MOFs in general.

Authors:
 [1];  [2];  [2];  [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:
1565462
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: 29; 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, Li, Jing, Chabal, Yves J., and Thonhauser, Timo. Cluster assisted water dissociation mechanism in MOF-74 and controlling it using helium. United States: N. p., 2016. Web. doi:10.1039/c6ta02501c.
Zuluaga, Sebastian, Fuentes-Fernandez, Erika M. A., Tan, Kui, Li, Jing, Chabal, Yves J., & Thonhauser, Timo. Cluster assisted water dissociation mechanism in MOF-74 and controlling it using helium. United States. doi:10.1039/c6ta02501c.
Zuluaga, Sebastian, Fuentes-Fernandez, Erika M. A., Tan, Kui, Li, Jing, Chabal, Yves J., and Thonhauser, Timo. Fri . "Cluster assisted water dissociation mechanism in MOF-74 and controlling it using helium". United States. doi:10.1039/c6ta02501c.
@article{osti_1565462,
title = {Cluster assisted water dissociation mechanism in MOF-74 and controlling it using helium},
author = {Zuluaga, Sebastian and Fuentes-Fernandez, Erika M. A. and Tan, Kui and Li, Jing and Chabal, Yves J. and Thonhauser, Timo},
abstractNote = {We show that the water dissociation reaction H2O → OH + H in the confined environment of MOF-74 channels can be precisely controlled by the addition of noble gas He. Elucidating the entire reaction process using ab initio methods and infrared (IR) spectroscopy, we prove that the interaction between water molecules is critical to the formation of water clusters, which reduce the dissociation barrier by up to 37% and thus influence the reaction significantly. Our time-resolved IR measurements confirm that the formation of these clusters can be suppressed by introducing He gas, providing unprecedented control over water dissociation rates. Since the water dissociation reaction is the cause of the structural instability of MOF-74 in the presence of water, our finding of the reaction mechanism lays the groundwork for designing water stable versions of MOF-74 as well as understanding water related phenomena in MOFs in general.},
doi = {10.1039/c6ta02501c},
journal = {Journal of Materials Chemistry. A},
issn = {2050-7488},
number = 29,
volume = 4,
place = {United States},
year = {2016},
month = {1}
}

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