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Title: Water Adsorption and Insertion in MOF-5

Abstract

The high surface areas and tunable properties of metal–organic frameworks (MOFs) make them attractive materials for applications in catalysis and the capture, storage, and separation of gases. Nevertheless, the limited stability of some MOFs under humid conditions remains a point of concern. Understanding the atomic-scale mechanisms associated with MOF hydrolysis will aid in the design of new compounds that are stable against water and other reactive species. Toward revealing these mechanisms, the present study employs van der Waals-augmented density functional theory, transition-state finding techniques, and thermodynamic integration to predict the thermodynamics and kinetics of water adsorption/insertion into the prototype compound, MOF-5. Adsorption and insertion energetics were evaluated as a function of water coverage, while accounting for the full periodicity of the MOF-5 crystal structure, that is, without resorting to cluster approximations or structural simplifications. The calculations suggest that the thermodynamics of MOF hydrolysis are coverage-dependent: water insertion into the framework becomes exothermic only after a sufficient number of H 2O molecules are coadsorbed in close proximity on a Zn–O cluster. Above this coverage threshold, the adsorbed water clusters facilitate facile water insertion via breaking of Zn–O bonds: the calculated free-energy barrier for insertion is very low, 0.17 eV at 0more » K and 0.04 eV at 300 K. Our calculations provide a highly realistic description of the mechanisms underlying the hydrolysis of MOFs under humid working conditions.« less

Authors:
 [1]; ; ORCiD logo
  1. Department of Physics, University of Michigan, 1440 Randall Laboratory, 450 Church Street, Ann Arbor, Michigan 48109-1040, United States
Publication Date:
Research Org.:
Ford Motor Company, Detroit, MI (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1376733
Alternate Identifier(s):
OSTI ID: 1532905
Grant/Contract Number:  
FC36-GO19002; FC36-09GO19002
Resource Type:
Published Article
Journal Name:
ACS Omega
Additional Journal Information:
Journal Name: ACS Omega Journal Volume: 2 Journal Issue: 8; Journal ID: ISSN 2470-1343
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry

Citation Formats

Ming, Yang, Kumar, Nitin, and Siegel, Donald J. Water Adsorption and Insertion in MOF-5. United States: N. p., 2017. Web. doi:10.1021/acsomega.7b01129.
Ming, Yang, Kumar, Nitin, & Siegel, Donald J. Water Adsorption and Insertion in MOF-5. United States. doi:10.1021/acsomega.7b01129.
Ming, Yang, Kumar, Nitin, and Siegel, Donald J. Thu . "Water Adsorption and Insertion in MOF-5". United States. doi:10.1021/acsomega.7b01129.
@article{osti_1376733,
title = {Water Adsorption and Insertion in MOF-5},
author = {Ming, Yang and Kumar, Nitin and Siegel, Donald J.},
abstractNote = {The high surface areas and tunable properties of metal–organic frameworks (MOFs) make them attractive materials for applications in catalysis and the capture, storage, and separation of gases. Nevertheless, the limited stability of some MOFs under humid conditions remains a point of concern. Understanding the atomic-scale mechanisms associated with MOF hydrolysis will aid in the design of new compounds that are stable against water and other reactive species. Toward revealing these mechanisms, the present study employs van der Waals-augmented density functional theory, transition-state finding techniques, and thermodynamic integration to predict the thermodynamics and kinetics of water adsorption/insertion into the prototype compound, MOF-5. Adsorption and insertion energetics were evaluated as a function of water coverage, while accounting for the full periodicity of the MOF-5 crystal structure, that is, without resorting to cluster approximations or structural simplifications. The calculations suggest that the thermodynamics of MOF hydrolysis are coverage-dependent: water insertion into the framework becomes exothermic only after a sufficient number of H2O molecules are coadsorbed in close proximity on a Zn–O cluster. Above this coverage threshold, the adsorbed water clusters facilitate facile water insertion via breaking of Zn–O bonds: the calculated free-energy barrier for insertion is very low, 0.17 eV at 0 K and 0.04 eV at 300 K. Our calculations provide a highly realistic description of the mechanisms underlying the hydrolysis of MOFs under humid working conditions.},
doi = {10.1021/acsomega.7b01129},
journal = {ACS Omega},
number = 8,
volume = 2,
place = {United States},
year = {2017},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acsomega.7b01129

Citation Metrics:
Cited by: 10 works
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Works referencing / citing this record:

Function-regeneration of non-porous hydrolyzed-MOF-derived materials
journal, July 2019


URJC‐1‐MOF as New Heterogeneous Recyclable Catalyst for C‐Heteroatom Coupling Reactions
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Zinc-based metal–organic frameworks as nontoxic and biodegradable platforms for biomedical applications: review study
journal, July 2019


URJC‐1‐MOF as New Heterogeneous Recyclable Catalyst for C‐Heteroatom Coupling Reactions
journal, June 2019


Function-regeneration of non-porous hydrolyzed-MOF-derived materials
journal, July 2019


Zinc-based metal–organic frameworks as nontoxic and biodegradable platforms for biomedical applications: review study
journal, July 2019