DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Stability of Zeolitic Imidazolate Frameworks in NO2

Abstract

The use of nanoporous zeolitic imidazolate frameworks (ZIFs) in separation processes is promising, but the presence of acid gases such as SOx or NOx in process streams can have detrimental results. Although we have recently developed a mechanistic picture of SOx–ZIF interactions, here we describe the remarkably different effects of NO2 on ZIFs. ZIFs with a representative range of SOx stabilities are all unstable—as defined by loss of crystallinity and porosity—in dry and humid NO2, whereas most ZIFs are stable in dry SOx and some even in humid SOx. A detailed mechanism is developed based on Fourier transform infrared spectroscopy and density functional theory calculations. H-abstraction by free radical NO2 and subsequent acidic species formation are the major degradation pathways, while adsorbed HNO3 formation in humid conditions is an additional pathway in hydrophilic ZIFs. These findings strongly suggest that new strategies to stabilize ZIFs/metal–organic frameworks toward NO2 attack are required.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Georgia Inst. of Technology, Atlanta, GA (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:
1566526
Grant/Contract Number:  
SC0012577
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 4; 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

Bhattacharyya, Souryadeep, Han, Rebecca, Joshi, Jayraj N., Zhu, Guanghui, Lively, Ryan P., Walton, Krista S., Sholl, David S., and Nair, Sankar. Stability of Zeolitic Imidazolate Frameworks in NO2. United States: N. p., 2019. Web. doi:10.1021/acs.jpcc.8b11377.
Bhattacharyya, Souryadeep, Han, Rebecca, Joshi, Jayraj N., Zhu, Guanghui, Lively, Ryan P., Walton, Krista S., Sholl, David S., & Nair, Sankar. Stability of Zeolitic Imidazolate Frameworks in NO2. United States. https://doi.org/10.1021/acs.jpcc.8b11377
Bhattacharyya, Souryadeep, Han, Rebecca, Joshi, Jayraj N., Zhu, Guanghui, Lively, Ryan P., Walton, Krista S., Sholl, David S., and Nair, Sankar. Fri . "Stability of Zeolitic Imidazolate Frameworks in NO2". United States. https://doi.org/10.1021/acs.jpcc.8b11377. https://www.osti.gov/servlets/purl/1566526.
@article{osti_1566526,
title = {Stability of Zeolitic Imidazolate Frameworks in NO2},
author = {Bhattacharyya, Souryadeep and Han, Rebecca and Joshi, Jayraj N. and Zhu, Guanghui and Lively, Ryan P. and Walton, Krista S. and Sholl, David S. and Nair, Sankar},
abstractNote = {The use of nanoporous zeolitic imidazolate frameworks (ZIFs) in separation processes is promising, but the presence of acid gases such as SOx or NOx in process streams can have detrimental results. Although we have recently developed a mechanistic picture of SOx–ZIF interactions, here we describe the remarkably different effects of NO2 on ZIFs. ZIFs with a representative range of SOx stabilities are all unstable—as defined by loss of crystallinity and porosity—in dry and humid NO2, whereas most ZIFs are stable in dry SOx and some even in humid SOx. A detailed mechanism is developed based on Fourier transform infrared spectroscopy and density functional theory calculations. H-abstraction by free radical NO2 and subsequent acidic species formation are the major degradation pathways, while adsorbed HNO3 formation in humid conditions is an additional pathway in hydrophilic ZIFs. These findings strongly suggest that new strategies to stabilize ZIFs/metal–organic frameworks toward NO2 attack are required.},
doi = {10.1021/acs.jpcc.8b11377},
journal = {Journal of Physical Chemistry. C},
number = 4,
volume = 123,
place = {United States},
year = {2019},
month = {1}
}

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

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Reactive Adsorption of NO 2 on Copper-Based Metal−Organic Framework and Graphite Oxide/Metal−Organic Framework Composites
journal, November 2010

  • Levasseur, Benoit; Petit, Camille; Bandosz, Teresa J.
  • ACS Applied Materials & Interfaces, Vol. 2, Issue 12
  • DOI: 10.1021/am100790v

SO x /NO x Removal from Flue Gas Streams by Solid Adsorbents: A Review of Current Challenges and Future Directions
journal, August 2015


Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011

  • Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
  • Chemical Reviews, Vol. 112, Issue 2, p. 724-781
  • DOI: 10.1021/cr2003272

Control of Pore Size and Functionality in Isoreticular Zeolitic Imidazolate Frameworks and their Carbon Dioxide Selective Capture Properties
journal, March 2009

  • Banerjee, Rahul; Furukawa, Hiroyasu; Britt, David
  • Journal of the American Chemical Society, Vol. 131, Issue 11, p. 3875-3877
  • DOI: 10.1021/ja809459e

Synthesis, Structure, and Carbon Dioxide Capture Properties of Zeolitic Imidazolate Frameworks
journal, January 2010

  • Phan, Anh; Doonan, Christian J.; Uribe-Romo, Fernando J.
  • Accounts of Chemical Research, Vol. 43, Issue 1, p. 58-67
  • DOI: 10.1021/ar900116g

Zeolitic Imidazolate Frameworks: Next-Generation Materials for Energy-Efficient Gas Separations
journal, October 2014

  • Pimentel, Brian R.; Parulkar, Aamena; Zhou, Er-kang
  • ChemSusChem, Vol. 7, Issue 12
  • DOI: 10.1002/cssc.201402647

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


Heat-Treatment of Defective UiO-66 from Modulated Synthesis: Adsorption and Stability Studies
journal, October 2017

  • Jiao, Yang; Liu, Yang; Zhu, Guanghui
  • The Journal of Physical Chemistry C, Vol. 121, Issue 42
  • DOI: 10.1021/acs.jpcc.7b07772

Synergistic Effects of Water and SO 2 on Degradation of MIL-125 in the Presence of Acid Gases
journal, November 2016

  • Mounfield, William P.; Han, Chu; Pang, Simon H.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 48
  • DOI: 10.1021/acs.jpcc.6b09264

Metal–organic frameworks for the removal of toxic industrial chemicals and chemical warfare agents
journal, January 2017

  • Bobbitt, N. Scott; Mendonca, Matthew L.; Howarth, Ashlee J.
  • Chemical Society Reviews, Vol. 46, Issue 11
  • DOI: 10.1039/c7cs00108h

Metal–Organic Frameworks for Air Purification of Toxic Chemicals
journal, April 2014

  • DeCoste, Jared B.; Peterson, Gregory W.
  • Chemical Reviews, Vol. 114, Issue 11
  • DOI: 10.1021/cr4006473

Reactive adsorption of acidic gases on MOF/graphite oxide composites
journal, May 2012


A UiO-66 analogue with uncoordinated carboxylic acids for the broad-spectrum removal of toxic chemicals
journal, January 2015

  • DeCoste, Jared B.; Demasky, Tyler J.; Katz, Michael J.
  • New Journal of Chemistry, Vol. 39, Issue 4
  • DOI: 10.1039/c4nj02093f

Interactions of NO 2 with Zr-Based MOF: Effects of the Size of Organic Linkers on NO 2 Adsorption at Ambient Conditions
journal, December 2012

  • Ebrahim, Amani M.; Levasseur, Benoit; Bandosz, Teresa J.
  • Langmuir, Vol. 29, Issue 1
  • DOI: 10.1021/la302869m

Extraordinary NO 2 Removal by the Metal-Organic Framework UiO-66-NH 2
journal, April 2016

  • Peterson, Gregory W.; Mahle, John J.; DeCoste, Jared B.
  • Angewandte Chemie International Edition, Vol. 55, Issue 21
  • DOI: 10.1002/anie.201601782

High-Throughput Screening of Metal–Organic Frameworks for CO 2 Separation
journal, March 2012

  • Han, Sangil; Huang, Yougui; Watanabe, Taku
  • ACS Combinatorial Science, Vol. 14, Issue 4
  • DOI: 10.1021/co3000192

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

Ten new predicted covalent organic frameworks with strong optical response in the visible and near infrared
journal, June 2015

  • Yang, Li-Ming; Dornfeld, Matthew; Hui, Pik-Mai
  • The Journal of Chemical Physics, Vol. 142, Issue 24
  • DOI: 10.1063/1.4923081

Computation-Ready, Experimental Metal–Organic Frameworks: A Tool To Enable High-Throughput Screening of Nanoporous Crystals
journal, October 2014

  • Chung, Yongchul G.; Camp, Jeffrey; Haranczyk, Maciej
  • Chemistry of Materials, Vol. 26, Issue 21
  • DOI: 10.1021/cm502594j

A Comprehensive Set of High-Quality Point Charges for Simulations of Metal–Organic Frameworks
journal, January 2016


Adsorption and Diffusion of Small Alcohols in Zeolitic Imidazolate Frameworks ZIF-8 and ZIF-90
journal, February 2013

  • Gee, Jason A.; Chung, Jaeyub; Nair, Sankar
  • The Journal of Physical Chemistry C, Vol. 117, Issue 6
  • DOI: 10.1021/jp312489w

Alcohol and water adsorption in zeolitic imidazolate frameworks
journal, January 2013

  • Zhang, Ke; Lively, Ryan P.; Dose, Michelle E.
  • Chemical Communications, Vol. 49, Issue 31
  • DOI: 10.1039/c3cc39116g

Applicability of the BET Method for Determining Surface Areas of Microporous Metal−Organic Frameworks
journal, July 2007

  • Walton, Krista S.; Snurr, Randall Q.
  • Journal of the American Chemical Society, Vol. 129, Issue 27
  • DOI: 10.1021/ja071174k

A new method of generation of gases at parts per million levels for preparation of standard gases
journal, April 1980

  • Hashimoto, Yoshikazu.; Tanaka, Shigeru.
  • Environmental Science & Technology, Vol. 14, Issue 4
  • DOI: 10.1021/es60164a006

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

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


Crystals as Molecules Postsynthesis Covalent Functionalization of Zeolitic Imidazolate Frameworks
journal, September 2008

  • Morris, William; Doonan, Christian J.; Furukawa, Hiroyasu
  • Journal of the American Chemical Society, Vol. 130, Issue 38, p. 12626-12627
  • DOI: 10.1021/ja805222x

MOFomics: Computational pore characterization of metal–organic frameworks
journal, January 2013


Projector augmented-wave method
journal, December 1994


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

Interactions of SO 2 -Containing Acid Gases with ZIF-8: Structural Changes and Mechanistic Investigations
journal, November 2016

  • Bhattacharyya, Souryadeep; Pang, Simon H.; Dutzer, Michael R.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 48
  • DOI: 10.1021/acs.jpcc.6b09197

H 2 O-Functionalized Zeolitic Zn(2-methylimidazole) 2 Framework (ZIF-8) for H 2 Storage
journal, September 2014

  • Cheng, Peifu; Hu, Yun Hang
  • The Journal of Physical Chemistry C, Vol. 118, Issue 38
  • DOI: 10.1021/jp507030g

In situ high pressure study of ZIF-8 by FTIR spectroscopy
journal, January 2011

  • Hu, Yue; Kazemian, Hossein; Rohani, Sohrab
  • Chemical Communications, Vol. 47, Issue 47
  • DOI: 10.1039/c1cc15525c

Reaction of hexane soot with nitrogen dioxide/nitrogen oxide (N2O4)
journal, October 1984

  • Akhter, M. S.; Chughtai, A. R.; Smith, D. M.
  • The Journal of Physical Chemistry, Vol. 88, Issue 22
  • DOI: 10.1021/j150666a046

Heterogeneous Reaction of NO 2 on Hexane Soot:  A Knudsen Cell and FT-IR Study
journal, December 2000

  • Al-Abadleh, Hind A.; Grassian, V. H.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 51
  • DOI: 10.1021/jp002918i

Nature and thermal stability of adsorbed intermediates formed during the reaction of diesel soot with nitrogen dioxide
journal, December 2006


Spectroscopic Characterization of Biofield Treated Metronidazole and Tinidazole
journal, January 2015


Raman and i.r. spectra of zinc, cadmium and calcium nitrate: A study of the low temperature phase transitions in calcium nitrate
journal, January 1976


Control Preparation of Zinc Hydroxide Nitrate Nanocrystals and Examination of the Chemical and Structural Stability
journal, April 2012

  • Li, Peng; Xu, Zhi Ping; Hampton, Marc A.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 18
  • DOI: 10.1021/jp300045u

Low temperature synthesis and characterization of rosette-like nanostructures of ZnO using solution process
journal, February 2009


Synthesis, Characterization and Effect of pH Variation on Zinc Oxide Nanostructures
journal, January 2009


Heterogeneous reactions of NO2 and NO–O2 on the surface of carbons
journal, February 2003


Vibrational spectrum, torsional potential, and bonding of gaseous N 2 O 4
journal, August 1974

  • Bibart, Charles H.; Ewing, George E.
  • The Journal of Chemical Physics, Vol. 61, Issue 4
  • DOI: 10.1063/1.1682051

Infrared absorption intensities of nitrous acid (HONO) fundamental bands
journal, July 1983

  • Kagann, Robert H.; Maki, Arthur G.
  • Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 30, Issue 1
  • DOI: 10.1016/0022-4073(83)90071-7

Protonic Conductivity of Nanocrystalline Zeolitic Imidazolate Framework 8
journal, January 2015


Hydrophobic-ZIF-71 filled PEBA mixed matrix membranes for recovery of biobutanol via pervaporation
journal, November 2013


Nanocrystals and nanomaterials of isoreticular zeolitic imidazolate frameworks
journal, November 2015


Highly permeable zeolitic imidazolate framework (ZIF)-71 nano-particles enhanced polyimide membranes for gas separation
journal, October 2014


A superhydrophobic zeolitic imidazolate framework (ZIF-90) with high steam stability for efficient recovery of bioalcohols
journal, January 2016

  • Liu, Chuanyao; Liu, Qian; Huang, Aisheng
  • Chemical Communications, Vol. 52, Issue 16
  • DOI: 10.1039/c5cc10171a

Room-temperature synthesis of ZIF-90 nanocrystals and the derived nano-composite membranes for hydrogen separation
journal, January 2013

  • Yang, Tingxu; Chung, Tai-Shung
  • Journal of Materials Chemistry A, Vol. 1, Issue 19
  • DOI: 10.1039/c3ta10928c

The Reactivity And Structure Of Nitrogen Dioxide
journal, December 1955


Reaction of NO 2 with Selected Conjugated Alkenes
journal, December 2013

  • Bernard, François; Cazaunau, Mathieu; Mu, Yujing
  • The Journal of Physical Chemistry A, Vol. 117, Issue 51
  • DOI: 10.1021/jp408771r

Gas/Solid Reactions with Nitrogen Dioxide
journal, September 1995

  • Kaupp, Gerd; Schmeyers, Jens
  • The Journal of Organic Chemistry, Vol. 60, Issue 17
  • DOI: 10.1021/jo00122a031

Reaction of nitrogen dioxide with alkenes and polyunsaturated fatty acids: addition and hydrogen-abstraction mechanisms
journal, December 1982

  • Pryor, William A.; Lightsey, John W.; Church, Daniel F.
  • Journal of the American Chemical Society, Vol. 104, Issue 24
  • DOI: 10.1021/ja00388a035

Rates and mechanisms of reactions of nitrogen dioxide with alkenes in solution
journal, November 1987

  • Giamalva, David H.; Kenion, Grant B.; Church, Daniel F.
  • Journal of the American Chemical Society, Vol. 109, Issue 23
  • DOI: 10.1021/ja00257a025

Interaction of NO 2 with Hydrocarbon Soot:  Focus on HONO Yield, Surface Modification, and Mechanism
journal, July 2007

  • Aubin, Daniel G.; Abbatt, Jonathan P. D.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 28
  • DOI: 10.1021/jp068884h

Features of mechanism of free radical initiation in polymers under exposure to nitrogen oxides
journal, January 2008

  • Davydov, E. Y.; Gaponova, I. S.; Pokholok, T. V.
  • Polymers for Advanced Technologies, Vol. 19, Issue 6
  • DOI: 10.1002/pat.1094

Adsorption and reduction of NO2 over activated carbon at low temperature
journal, January 2011


Interaction mechanism of NO2 with carbon black: effect of surface oxygen complexes
journal, August 2004

  • Jeguirim, M.; Tschamber, V.; Brilhac, J. F.
  • Journal of Analytical and Applied Pyrolysis, Vol. 72, Issue 1
  • DOI: 10.1016/j.jaap.2004.03.008

Reaction of NO 2 with Activated Carbon at Ambient Temperature
journal, June 2008

  • Zhang, Wei-Jun; Bagreev, Andrey; Rasouli, Firooz
  • Industrial & Engineering Chemistry Research, Vol. 47, Issue 13
  • DOI: 10.1021/ie800249s

The Structure of Hexane Soot II: Extraction Studies
journal, January 1985


Production of molecular iodine from the heterogeneous reaction of nitrogen dioxide with solid potassium iodide
journal, January 2011

  • O'Neill, Erinn; Hinrichs, Ryan Z.
  • Journal of Geophysical Research, Vol. 116, Issue D1
  • DOI: 10.1029/2010jd014880

The chemistry of nitroso-compounds. Part 11. Nitrosation of amines by the two-phase interaction of amines in solution with gaseous oxides of nitrogen
journal, January 1979

  • Challis, Brian C.; Kyrtopoulos, Soterios A.
  • Journal of the Chemical Society, Perkin Transactions 1
  • DOI: 10.1039/p19790000299

Nitrous Acid And Nitrosation
journal, June 1959


N -Nitrosation of Amines by NO 2 and NO:  A Theoretical Study
journal, March 2007

  • Zhao, Yi-Lei; Garrison, Stephen L.; Gonzalez, Carlos
  • The Journal of Physical Chemistry A, Vol. 111, Issue 11
  • DOI: 10.1021/jp0677703

Atmospheric Chemistry of Toxic Contaminants. 6. Nitrosamines: Dialkyl Nitrosamines and Nitrosomorpholine
journal, March 1991


Heterogeneous reaction of NO2 on the surface of NaCl particles
journal, August 2006


A Diffuse Reflectance Infrared Fourier Transform Spectroscopic Study of the Surface Reaction of NaCl with Gaseous NO2 and HNO3
journal, April 1994

  • Vogt, Rainer; Finlayson-Pitts, Barbara J.
  • The Journal of Physical Chemistry, Vol. 98, Issue 14
  • DOI: 10.1021/j100065a033

Role of Nitrate Species in the “NO2-SCR” Mechanism over a Commercial Fe-zeolite Catalyst for SCR Mobile Applications
journal, March 2009


Reaction of NO 2 with Zn and ZnO:  Photoemission, XANES, and Density Functional Studies on the Formation of NO 3
journal, January 2000

  • Rodriguez, José A.; Jirsak, Tomas; Dvorak, Joseph
  • The Journal of Physical Chemistry B, Vol. 104, Issue 2
  • DOI: 10.1021/jp993224g

Surface reactions of NO2 with machined Zn, Cd, Cu and Ag surfaces studied by He I/II photoelectron spectroscopy
journal, December 1993


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

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

Prediction and experimental evidence for high air concentration of nitrous acid in indoor environments
journal, January 1991


Formation of nitrous acid and nitric oxide in the heterogeneous dark reaction of nitrogen dioxide and water vapor in a smog chamber
journal, October 1983

  • Sakamaki, Fumio; Hatakeyama, Shiro; Akimoto, Hajime
  • International Journal of Chemical Kinetics, Vol. 15, Issue 10
  • DOI: 10.1002/kin.550151006

Kinetics of the reaction between nitrogen dioxide and water vapour
journal, January 1987


The heterogeneous hydrolysis of NO2 in laboratory systems and in outdoor and indoor atmospheres: An integrated mechanism
journal, December 2002

  • Finlayson-Pitts, B. J.; Wingen, L. M.; Sumner, A. L.
  • Physical Chemistry Chemical Physics, Vol. 5, Issue 2
  • DOI: 10.1039/b208564j

The photochemical production of HONO during the heterogeneous hydrolysis of NO2
journal, January 2004

  • Ramazan, Kevin A.; Syomin, Dennis; Finlayson-Pitts, Barbara J.
  • Physical Chemistry Chemical Physics, Vol. 6, Issue 14
  • DOI: 10.1039/b402195a

Works referencing / citing this record:

Transistor‐Based Work‐Function Measurement of Metal–Organic Frameworks for Ultra‐Low‐Power, Rationally Designed Chemical Sensors
journal, September 2019

  • Gardner, David W.; Gao, Xiang; Fahad, Hossain M.
  • Chemistry – A European Journal, Vol. 25, Issue 57
  • DOI: 10.1002/chem.201902483

Structure and electronic properties of rare earth DOBDC metal–organic-frameworks
journal, January 2019

  • Vogel, Dayton J.; Sava Gallis, Dorina F.; Nenoff, Tina M.
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 41
  • DOI: 10.1039/c9cp04038b