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Title: Role of Structural Defects in the Water Adsorption Properties of MOF-801

Abstract

The nanoporous and tunable nature of metal–organic frameworks (MOFs) has made them promising adsorbents for water adsorption applications such as water harvesting and adsorptive heat pumps. In these applications, water adsorption properties in MOFs play a crucial role. However, understanding their structural defects and how defects influence adsorption thermodynamics remains limited to date. In this work, by employing Monte Carlo techniques and first-principle density functional theory calculations, we investigate the effect of defects on the water adsorption properties in MOF-801 structures at an atomic level. Our calculations show that the adsorption isotherm in perfect MOF-801 (without defects) greatly deviates from that measured experimentally. With the introduction of defects with a high density, a reasonably good agreement can be achieved, suggesting that a high defect density in MOF-801 may be responsible for its hydrophilic adsorptive behaviors. Further, water adsorption properties in MOF-801 structures are found to depend on the spatial configuration of defects, and water condensation in nanoporous MOF-801 is identified to occur preferentially along the $$\langle$$110$$\rangle$$ direction. Detailed structural characteristics (accessible volume, etc.) of MOF-801 structures and the adsorption energetics of water in the frameworks are also studied and correlated with the computed adsorption isotherms. Our findings reveal important insights into the role of defects, offering a microscopic picture to help facilitate the rational design of better MOFs for water adsorption applications.

Authors:
 [1]; ORCiD logo [2];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
  2. The Ohio State Univ., Columbus, OH (United States). William G. Lowrie Dept. of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1483797
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 10; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

Citation Formats

Choi, Jongwon, Lin, Li-Chiang, and Grossman, Jeffrey C. Role of Structural Defects in the Water Adsorption Properties of MOF-801. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b00014.
Choi, Jongwon, Lin, Li-Chiang, & Grossman, Jeffrey C. Role of Structural Defects in the Water Adsorption Properties of MOF-801. United States. doi:10.1021/acs.jpcc.8b00014.
Choi, Jongwon, Lin, Li-Chiang, and Grossman, Jeffrey C. Wed . "Role of Structural Defects in the Water Adsorption Properties of MOF-801". United States. doi:10.1021/acs.jpcc.8b00014. https://www.osti.gov/servlets/purl/1483797.
@article{osti_1483797,
title = {Role of Structural Defects in the Water Adsorption Properties of MOF-801},
author = {Choi, Jongwon and Lin, Li-Chiang and Grossman, Jeffrey C.},
abstractNote = {The nanoporous and tunable nature of metal–organic frameworks (MOFs) has made them promising adsorbents for water adsorption applications such as water harvesting and adsorptive heat pumps. In these applications, water adsorption properties in MOFs play a crucial role. However, understanding their structural defects and how defects influence adsorption thermodynamics remains limited to date. In this work, by employing Monte Carlo techniques and first-principle density functional theory calculations, we investigate the effect of defects on the water adsorption properties in MOF-801 structures at an atomic level. Our calculations show that the adsorption isotherm in perfect MOF-801 (without defects) greatly deviates from that measured experimentally. With the introduction of defects with a high density, a reasonably good agreement can be achieved, suggesting that a high defect density in MOF-801 may be responsible for its hydrophilic adsorptive behaviors. Further, water adsorption properties in MOF-801 structures are found to depend on the spatial configuration of defects, and water condensation in nanoporous MOF-801 is identified to occur preferentially along the $\langle$110$\rangle$ direction. Detailed structural characteristics (accessible volume, etc.) of MOF-801 structures and the adsorption energetics of water in the frameworks are also studied and correlated with the computed adsorption isotherms. Our findings reveal important insights into the role of defects, offering a microscopic picture to help facilitate the rational design of better MOFs for water adsorption applications.},
doi = {10.1021/acs.jpcc.8b00014},
journal = {Journal of Physical Chemistry. C},
number = 10,
volume = 122,
place = {United States},
year = {2018},
month = {2}
}

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