skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Propagation of Degradation-Induced Defects in Zeolitic Imidazolate Frameworks

Abstract

Isolated defects induced by water and acid gases have been extensively characterized in ZIF-8, a prototypical metal–organic framework material, yet there is little understanding regarding how these single bond-breaking events lead to the structural amorphization observed after prolonged experimental exposure in acidic environments. We use density functional theory calculations to provide the first analysis of defect propagation in a zeolitic imidazolate framework (ZIF) material. Given a single bond-breaking event (the first step in the formation of any defect state), we exhaustively explore the energetics of subsequent defect states and find strong preference for additional bond-breaking located adjacent to the previous defect in both two-defect and three-defect systems. This series of favorable reaction energies is more exothermic when we replace water with sulfuric acid as a protonating agent, in agreement with experimental observations that ZIF-8 degradation is accelerated in humid acid gas environments. To offer initial insights into experimental signatures of defect propagation, we compare the simulated powder pattern in structures at varying levels of defect concentrations.

Authors:
 [1];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States)
  2. Univ. of Wisconsin, Madison, WI (United States)
Publication Date:
Research Org.:
Univ. of Texas, Austin, TX (United States). Energy Frontier Research Center (EFRC); Georgia Institute of Technology, Atlanta, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1566530
Grant/Contract Number:  
SC0012577
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 11; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); defects; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

Han, Rebecca, Tymińska, Nina, Schmidt, J. R., and Sholl, David S. Propagation of Degradation-Induced Defects in Zeolitic Imidazolate Frameworks. United States: N. p., 2019. Web. doi:10.1021/acs.jpcc.9b00304.
Han, Rebecca, Tymińska, Nina, Schmidt, J. R., & Sholl, David S. Propagation of Degradation-Induced Defects in Zeolitic Imidazolate Frameworks. United States. doi:10.1021/acs.jpcc.9b00304.
Han, Rebecca, Tymińska, Nina, Schmidt, J. R., and Sholl, David S. Tue . "Propagation of Degradation-Induced Defects in Zeolitic Imidazolate Frameworks". United States. doi:10.1021/acs.jpcc.9b00304. https://www.osti.gov/servlets/purl/1566530.
@article{osti_1566530,
title = {Propagation of Degradation-Induced Defects in Zeolitic Imidazolate Frameworks},
author = {Han, Rebecca and Tymińska, Nina and Schmidt, J. R. and Sholl, David S.},
abstractNote = {Isolated defects induced by water and acid gases have been extensively characterized in ZIF-8, a prototypical metal–organic framework material, yet there is little understanding regarding how these single bond-breaking events lead to the structural amorphization observed after prolonged experimental exposure in acidic environments. We use density functional theory calculations to provide the first analysis of defect propagation in a zeolitic imidazolate framework (ZIF) material. Given a single bond-breaking event (the first step in the formation of any defect state), we exhaustively explore the energetics of subsequent defect states and find strong preference for additional bond-breaking located adjacent to the previous defect in both two-defect and three-defect systems. This series of favorable reaction energies is more exothermic when we replace water with sulfuric acid as a protonating agent, in agreement with experimental observations that ZIF-8 degradation is accelerated in humid acid gas environments. To offer initial insights into experimental signatures of defect propagation, we compare the simulated powder pattern in structures at varying levels of defect concentrations.},
doi = {10.1021/acs.jpcc.9b00304},
journal = {Journal of Physical Chemistry. C},
number = 11,
volume = 123,
place = {United States},
year = {2019},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Vapor‐Phase Linker Exchange of the Metal–Organic Framework ZIF‐8: A Solvent‐Free Approach to Post‐synthetic Modification
journal, November 2019

  • Marreiros, João; Van Dommelen, Lenz; Fleury, Guillaume
  • Angewandte Chemie, Vol. 131, Issue 51
  • DOI: 10.1002/ange.201912088

Vapor‐Phase Linker Exchange of the Metal–Organic Framework ZIF‐8: A Solvent‐Free Approach to Post‐synthetic Modification
journal, November 2019

  • Marreiros, João; Van Dommelen, Lenz; Fleury, Guillaume
  • Angewandte Chemie International Edition, Vol. 58, Issue 51
  • DOI: 10.1002/anie.201912088