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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. https://doi.org/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. https://doi.org/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}
}

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Works referenced in this record:

High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture
journal, February 2008


Seven chemical separations to change the world
journal, April 2016

  • Sholl, David S.; Lively, Ryan P.
  • Nature, Vol. 532, Issue 7600
  • DOI: 10.1038/532435a

Can Metal-Organic Framework Materials Play a Useful Role in Large-Scale Carbon Dioxide Separations?
journal, August 2010

  • Keskin, Seda; van Heest, Timothy M.; Sholl, David S.
  • ChemSusChem, Vol. 3, Issue 8
  • DOI: 10.1002/cssc.201000114

Chemical, thermal and mechanical stabilities of metal–organic frameworks
journal, February 2016


Characterization and properties of Zn/Co zeolitic imidazolate frameworks vs. ZIF-8 and ZIF-67
journal, January 2017

  • Zhou, Kui; Mousavi, Bibimaryam; Luo, Zhixiong
  • Journal of Materials Chemistry A, Vol. 5, Issue 3
  • DOI: 10.1039/c6ta07860e

Exceptional chemical and thermal stability of zeolitic imidazolate frameworks
journal, June 2006

  • Park, K. S.; Ni, Z.; Cote, A. P.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 27, p. 10186-10191
  • DOI: 10.1073/pnas.0602439103

Characterization of metal-organic frameworks by water adsorption
journal, April 2009


Water Stability and Adsorption in Metal–Organic Frameworks
journal, September 2014

  • Burtch, Nicholas C.; Jasuja, Himanshu; Walton, Krista S.
  • Chemical Reviews, Vol. 114, Issue 20, p. 10575-10612
  • DOI: 10.1021/cr5002589

Gas transport properties and propylene/propane separation characteristics of ZIF-8 membranes
journal, February 2014


Improvement of hydrothermal stability of zeolitic imidazolate frameworks
journal, January 2013

  • Liu, Xinlei; Li, Yanshuo; Ban, Yujie
  • Chemical Communications, Vol. 49, Issue 80
  • DOI: 10.1039/c3cc45308a

Stability of ZIF-8 membranes and crystalline powders in water at room temperature
journal, July 2015


Defects in Metal–Organic Frameworks: Challenge or Opportunity?
journal, August 2015


Computational Characterization of Defects in Metal–Organic Frameworks: Spontaneous and Water-Induced Point Defects in ZIF-8
journal, January 2016

  • Zhang, Chenyang; Han, Chu; Sholl, David S.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 3
  • DOI: 10.1021/acs.jpclett.5b02683

Insights into the Stability of Zeolitic Imidazolate Frameworks in Humid Acidic Environments from First-Principles Calculations
journal, February 2018

  • Han, Chu; Zhang, Chenyang; Tymińska, Nina
  • The Journal of Physical Chemistry C, Vol. 122, Issue 8
  • DOI: 10.1021/acs.jpcc.7b12058

Assessing the Impact of Point Defects on Molecular Diffusion in ZIF-8 Using Molecular Simulations
journal, June 2018

  • Han, Chu; Verploegh, Ross J.; Sholl, David S.
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 14
  • DOI: 10.1021/acs.jpclett.8b01749

Acid Gas Stability of Zeolitic Imidazolate Frameworks: Generalized Kinetic and Thermodynamic Characteristics
journal, May 2018


Defect-induced ripening of zeolitic-imidazolate framework ZIF-8 and its implication to vapor-phase membrane synthesis
journal, January 2016

  • Kwon, Hyuk Taek; Jeong, Hae-Kwon; Lee, Albert S.
  • Chemical Communications, Vol. 52, Issue 78
  • DOI: 10.1039/c6cc05433a

Defect-dependent stability of highly propylene-selective zeolitic-imidazolate framework ZIF-8 membranes
journal, May 2017


Stability of Zeolitic Imidazolate Frameworks in NO 2
journal, January 2019

  • Bhattacharyya, Souryadeep; Han, Rebecca; Joshi, Jayraj N.
  • The Journal of Physical Chemistry C, Vol. 123, Issue 4
  • DOI: 10.1021/acs.jpcc.8b11377

Recovery of Acid-Gas-Degraded Zeolitic Imidazolate Frameworks by Solvent-Assisted Crystal Redemption (SACRed)
journal, September 2017

  • Jayachandrababu, Krishna C.; Bhattacharyya, Souryadeep; Chiang, Yadong
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 40
  • DOI: 10.1021/acsami.7b11686

Systematic study of the chemical and hydrothermal stability of selected “stable” Metal Organic Frameworks
journal, May 2016


Facet-Specific Stability of ZIF-8 in the Presence of Acid Gases Dissolved in Aqueous Solutions
journal, September 2016


Dynamic acidity in defective UiO-66
journal, January 2016


Unusual and Highly Tunable Missing-Linker Defects in Zirconium Metal–Organic Framework UiO-66 and Their Important Effects on Gas Adsorption
journal, May 2013

  • Wu, Hui; Chua, Yong Shen; Krungleviciute, Vaiva
  • Journal of the American Chemical Society, Vol. 135, Issue 28
  • DOI: 10.1021/ja404514r

Correlated defect nanoregions in a metal–organic framework
journal, June 2014

  • Cliffe, Matthew J.; Wan, Wei; Zou, Xiaodong
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5176

Influence of Atomic Vacancies on the Properties of Transition-Metal Oxides. I. Ti O x and V O x
journal, April 1972


Nonstoichiometry in early transition metal compounds with the rocksalt structure
journal, January 1995


Correlation effects and energetics of point defects in uranium dioxide: a first principle investigation
journal, June 2007


Schottky defect formation energy in MgO calculated by diffusion Monte Carlo
journal, June 2005


Free Energy of Ligand Removal in the Metal–Organic Framework UiO-66
journal, April 2016

  • Bristow, Jessica K.; Svane, Katrine L.; Tiana, Davide
  • The Journal of Physical Chemistry C, Vol. 120, Issue 17
  • DOI: 10.1021/acs.jpcc.6b01659

Ab initio based rate theory model of radiation induced amorphization in β-SiC
journal, July 2011


Size distribution of black spot defects and their contribution to swelling in irradiated SiC
journal, August 2016


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/physrevlett.77.3865

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Defect energetics in MgO treated by first-principles methods
journal, November 1992


Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
journal, April 2005

  • VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi
  • Computer Physics Communications, Vol. 167, Issue 2
  • DOI: 10.1016/j.cpc.2004.12.014

Separable dual-space Gaussian pseudopotentials
journal, July 1996


Relativistic separable dual-space Gaussian pseudopotentials from H to Rn
journal, August 1998


Pseudopotentials for H to Kr optimized for gradient-corrected exchange-correlation functionals
journal, May 2005


Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases
journal, September 2007

  • VandeVondele, Joost; Hutter, Jürg
  • The Journal of Chemical Physics, Vol. 127, Issue 11
  • DOI: 10.1063/1.2770708

A hybrid Gaussian and plane wave density functional scheme
journal, October 1997

  • Lippert, By GERALD; Parrinello, JURG HUTTER and MICHELE
  • Molecular Physics, Vol. 92, Issue 3
  • DOI: 10.1080/002689797170220

Mercury CSD 2.0 – new features for the visualization and investigation of crystal structures
journal, March 2008

  • Macrae, Clare F.; Bruno, Ian J.; Chisholm, James A.
  • Journal of Applied Crystallography, Vol. 41, Issue 2
  • DOI: 10.1107/s0021889807067908

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011


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