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Title: Insights into the Stability of Zeolitic Imidazolate Frameworks in Humid Acidic Environments from First-Principles Calculations

Abstract

Understanding the degradation mechanisms of zeolitic imidazolate frameworks (ZIFs) is crucial to improve their chemical stability and realize their potential industrial applications. In this work, we conduct a comprehensive study utilizing dispersion-corrected density functional theory calculations to investigate the chemical stability of bulk ZIFs and their external surfaces under conditions of acid-gas exposure. We examine the influence of steric factors such as topology and ligand functionalization on the relative chemical stability of prototypical ZIFs (ZIF-2 and ZIF-8), including their hypothetical polymorphs. We find that defect formation is more thermodynamically and kinetically favorable at ZIF external surfaces versus the bulk, and that both topology and ligand functionalization impact defect formation. In addition, we provide a detailed mechanism for the reaction of ZIFs with sulfurous and sulfuric acids, of which the latter serves as a catalyst in potential degradation reactions of ZIFs. We also provide information about the adsorption strength of a range of acid gases to defective ZIF structures, which can inform potential strategies to regenerate ZIFs and/or achieve defect engineering in these materials.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]
  1. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical & Biomolecular Engineering; Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemistry & Biochemistry
  2. Univ. of Wisconsin, Madison, WI (United States). Theoretical Chemistry Inst., and Dept. of Chemistry; Central South Univ., Changsha, Hunan (China). School of Minerals Processing and Bioengineering
  3. Univ. of Wisconsin, Madison, WI (United States). Theoretical Chemistry Inst., and Dept. of Chemistry
  4. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical & Biomolecular Engineering
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470287
Grant/Contract Number:  
SC0012577
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 8; Related Information: UNCAGE-ME partners with Georgia Institute of Technology (lead); Lehigh University; Oak Ridge National Laboratory; University of Alabama; University of Florida; University of Wisconsin; Washington University in St. Louis; 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, Chu, Zhang, Chenyang, Tymińska, Nina, Schmidt, J. R., and Sholl, David S. Insights into the Stability of Zeolitic Imidazolate Frameworks in Humid Acidic Environments from First-Principles Calculations. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.7b12058.
Han, Chu, Zhang, Chenyang, Tymińska, Nina, Schmidt, J. R., & Sholl, David S. Insights into the Stability of Zeolitic Imidazolate Frameworks in Humid Acidic Environments from First-Principles Calculations. United States. doi:10.1021/acs.jpcc.7b12058.
Han, Chu, Zhang, Chenyang, Tymińska, Nina, Schmidt, J. R., and Sholl, David S. Mon . "Insights into the Stability of Zeolitic Imidazolate Frameworks in Humid Acidic Environments from First-Principles Calculations". United States. doi:10.1021/acs.jpcc.7b12058. https://www.osti.gov/servlets/purl/1470287.
@article{osti_1470287,
title = {Insights into the Stability of Zeolitic Imidazolate Frameworks in Humid Acidic Environments from First-Principles Calculations},
author = {Han, Chu and Zhang, Chenyang and Tymińska, Nina and Schmidt, J. R. and Sholl, David S.},
abstractNote = {Understanding the degradation mechanisms of zeolitic imidazolate frameworks (ZIFs) is crucial to improve their chemical stability and realize their potential industrial applications. In this work, we conduct a comprehensive study utilizing dispersion-corrected density functional theory calculations to investigate the chemical stability of bulk ZIFs and their external surfaces under conditions of acid-gas exposure. We examine the influence of steric factors such as topology and ligand functionalization on the relative chemical stability of prototypical ZIFs (ZIF-2 and ZIF-8), including their hypothetical polymorphs. We find that defect formation is more thermodynamically and kinetically favorable at ZIF external surfaces versus the bulk, and that both topology and ligand functionalization impact defect formation. In addition, we provide a detailed mechanism for the reaction of ZIFs with sulfurous and sulfuric acids, of which the latter serves as a catalyst in potential degradation reactions of ZIFs. We also provide information about the adsorption strength of a range of acid gases to defective ZIF structures, which can inform potential strategies to regenerate ZIFs and/or achieve defect engineering in these materials.},
doi = {10.1021/acs.jpcc.7b12058},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 8,
volume = 122,
place = {United States},
year = {2018},
month = {2}
}

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Cited by: 18 works
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