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Title: Interactions of SO2-Containing Acid Gases with ZIF-8: Structural Changes and Mechanistic Investigations

Abstract

Zeolitic imidazolate frameworks (ZIFs) are a set of nanoporous metal–organic frameworks (MOFs) with tunable porosity and functionality. Among MOFs, they also show relatively good stability with respect to temperature and humidity. These characteristics lead to their possible applications in separation processes. In many practical separation processes, adsorbents are exposed to a variety of molecular species including acid gases. However, there is little knowledge of the effects of such acid gas exposure on the adsorption and separation properties of ZIFs. Here, the stability of a model ZIF material (ZIF-8) under SO2 exposure in dry, humid, and aqueous environments has been investigated in detail. Combined characterization by several techniques (PXRD, N2 physisorption, EDX, XPS, and FTIR) allowed us to track the structural and compositional properties of ZIF-8 before and after SO2 exposure. We found ZIF-8 is stable after prolonged exposure in dry SO2 and in humid air without SO2. However, exposure to 10–20 ppm concentrations of SO2 in the presence of high relative humidity led to its irreversible structural degradation over time as evidenced by substantial losses in crystallinity and textural properties. Exposure to similar concentrations of aqueous SO2 did not lead to bulk degradation. Humid SO2 exposed ZIF-8 showed a significantmore » presence of sulfur (S) even after reactivation, with vibrational characteristics corresponding to (bi)sulfite and (bi)sulfate groups. A mechanism of ZIF-8 degradation combining the synergistic effects of SO2 and humidity is proposed. Attack by sulfuric and sulfurous acid species (generated in humid SO2) leads to protonation of nitrogen in the imidazole ring, resulting in cleavage of metal–linker (Zn–N) bonds. Our detailed experimental findings serve as a starting point for developing a generalized mechanism of acid gas interactions with ZIF materials.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1]
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  1. Georgia Inst. of Technology, Atlanta, GA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-Induced Evolution of Materials for Energy (UNCAGE-ME); Georgia Institute of Technology, Atlanta, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1388782
Grant/Contract Number:  
SC0012577
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 48; 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

Bhattacharyya, Souryadeep, Pang, Simon H., Dutzer, Michael R., Lively, Ryan P., Walton, Krista S., Sholl, David S., and Nair, Sankar. Interactions of SO2-Containing Acid Gases with ZIF-8: Structural Changes and Mechanistic Investigations. United States: N. p., 2016. Web. doi:10.1021/acs.jpcc.6b09197.
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Bhattacharyya, Souryadeep, Pang, Simon H., Dutzer, Michael R., Lively, Ryan P., Walton, Krista S., Sholl, David S., & Nair, Sankar. Interactions of SO2-Containing Acid Gases with ZIF-8: Structural Changes and Mechanistic Investigations. United States. https://doi.org/10.1021/acs.jpcc.6b09197
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Bhattacharyya, Souryadeep, Pang, Simon H., Dutzer, Michael R., Lively, Ryan P., Walton, Krista S., Sholl, David S., and Nair, Sankar. Wed . "Interactions of SO2-Containing Acid Gases with ZIF-8: Structural Changes and Mechanistic Investigations". United States. https://doi.org/10.1021/acs.jpcc.6b09197. https://www.osti.gov/servlets/purl/1388782.
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@article{osti_1388782,
title = {Interactions of SO2-Containing Acid Gases with ZIF-8: Structural Changes and Mechanistic Investigations},
author = {Bhattacharyya, Souryadeep and Pang, Simon H. and Dutzer, Michael R. and Lively, Ryan P. and Walton, Krista S. and Sholl, David S. and Nair, Sankar},
abstractNote = {Zeolitic imidazolate frameworks (ZIFs) are a set of nanoporous metal–organic frameworks (MOFs) with tunable porosity and functionality. Among MOFs, they also show relatively good stability with respect to temperature and humidity. These characteristics lead to their possible applications in separation processes. In many practical separation processes, adsorbents are exposed to a variety of molecular species including acid gases. However, there is little knowledge of the effects of such acid gas exposure on the adsorption and separation properties of ZIFs. Here, the stability of a model ZIF material (ZIF-8) under SO2 exposure in dry, humid, and aqueous environments has been investigated in detail. Combined characterization by several techniques (PXRD, N2 physisorption, EDX, XPS, and FTIR) allowed us to track the structural and compositional properties of ZIF-8 before and after SO2 exposure. We found ZIF-8 is stable after prolonged exposure in dry SO2 and in humid air without SO2. However, exposure to 10–20 ppm concentrations of SO2 in the presence of high relative humidity led to its irreversible structural degradation over time as evidenced by substantial losses in crystallinity and textural properties. Exposure to similar concentrations of aqueous SO2 did not lead to bulk degradation. Humid SO2 exposed ZIF-8 showed a significant presence of sulfur (S) even after reactivation, with vibrational characteristics corresponding to (bi)sulfite and (bi)sulfate groups. A mechanism of ZIF-8 degradation combining the synergistic effects of SO2 and humidity is proposed. Attack by sulfuric and sulfurous acid species (generated in humid SO2) leads to protonation of nitrogen in the imidazole ring, resulting in cleavage of metal–linker (Zn–N) bonds. Our detailed experimental findings serve as a starting point for developing a generalized mechanism of acid gas interactions with ZIF materials.},
doi = {10.1021/acs.jpcc.6b09197},
journal = {Journal of Physical Chemistry. C},
number = 48,
volume = 120,
place = {United States},
year = {Wed Nov 02 00:00:00 EDT 2016},
month = {Wed Nov 02 00:00:00 EDT 2016}
}
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https://doi.org/10.1021/acs.jpcc.6b09197
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Works referenced in this record:

A Combined Experimental-Computational Study on the Effect of Topology on Carbon Dioxide Adsorption in Zeolitic Imidazolate Frameworks
journal, November 2012

  • Morris, William; He, Ning; Ray, Keith G.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 45
  • DOI: 10.1021/jp307170a

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

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

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

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

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

Thermal swing adsorption process for removing trace impurities from a multi-component gas mixture: (Landfill gas)
journal, March 1991

Trace Flue Gas Contaminants Poison Coordinatively Unsaturated Metal–Organic Frameworks: Implications for CO 2 Adsorption and Separation
journal, September 2012

  • Yu, Kuang; Kiesling, Kalin; Schmidt, J. R.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 38
  • DOI: 10.1021/jp307894e

Ionic liquid-amine blends and CO2BOLs: Prospective solvents for natural gas sweetening and CO2 capture technology—A review
journal, January 2014

Unexpected Molecular Sieving Properties of Zeolitic Imidazolate Framework-8
journal, July 2012

  • Zhang, Chen; Lively, Ryan P.; Zhang, Ke
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 16
  • DOI: 10.1021/jz300855a

Exploring the Framework Hydrophobicity and Flexibility of ZIF-8: From Biofuel Recovery to Hydrocarbon Separations
journal, October 2013

  • Zhang, Ke; Lively, Ryan P.; Zhang, Chen
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 21
  • DOI: 10.1021/jz402019d

Investigating the Intrinsic Ethanol/Water Separation Capability of ZIF-8: An Adsorption and Diffusion Study
journal, March 2013

  • Zhang, Ke; Lively, Ryan P.; Zhang, Chen
  • The Journal of Physical Chemistry C, Vol. 117, Issue 14
  • DOI: 10.1021/jp401548b

Adsorptive separations for the recovery and purification of biobutanol
journal, September 2012

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

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

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

Virtual High Throughput Screening Confirmed Experimentally: Porous Coordination Polymer Hydration
journal, November 2009

  • Low, John J.; Benin, Annabelle I.; Jakubczak, Paulina
  • Journal of the American Chemical Society, Vol. 131, Issue 43
  • DOI: 10.1021/ja9061344

Thermal stability of ZIF-8 under oxidative and inert environments: A practical perspective on using ZIF-8 as a catalyst support
journal, October 2015

Carbon Dioxide Sensitivity of Zeolitic Imidazolate Frameworks
journal, May 2014

  • Mottillo, Cristina; Friščić, Tomislav
  • Angewandte Chemie International Edition, Vol. 53, Issue 29
  • DOI: 10.1002/anie.201402082

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

Kinetics of ZIF-8 Thermal Decomposition in Inert, Oxidizing, and Reducing Environments
journal, June 2016

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

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

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

Water-based synthesis of zeolitic imidazolate framework-8 with high morphology level at room temperature
journal, January 2015

  • Jian, Meipeng; Liu, Bao; Liu, Ruiping
  • RSC Advances, Vol. 5, Issue 60
  • DOI: 10.1039/C5RA04033G

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

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

Crystal and Molecular Structure Analysis of 2-Methylimidazole
journal, September 2009

  • Hachuła, Barbara; Nowak, Maria; Kusz, Joachim
  • Journal of Chemical Crystallography, Vol. 40, Issue 3
  • DOI: 10.1007/s10870-009-9634-9

Red-, Blue-, or No-Shift in Hydrogen Bonds:  A Unified Explanation
journal, April 2007

  • Joseph, Jorly; Jemmis, Eluvathingal D.
  • Journal of the American Chemical Society, Vol. 129, Issue 15
  • DOI: 10.1021/ja067545z

Infrared Spectra and Characteristic Frequencies of Inorganic Ions
journal, August 1952

  • Miller, F. A.; Wilkins, C. H.
  • Analytical Chemistry, Vol. 24, Issue 8
  • DOI: 10.1021/ac60068a007

FTIR Characterization of the Interaction of Oxygen with Zinc Sulfide
journal, February 1995

  • Siriwardane, Ranjani V.; Woodruff, Steven
  • Industrial & Engineering Chemistry Research, Vol. 34, Issue 2
  • DOI: 10.1021/ie00041a032

In Situ Fourier Transform Infrared Characterization of Sulfur Species Resulting from the Reaction of Water Vapor and Oxygen with Zinc Sulfide
journal, December 1997

  • Siriwardane, Ranjani V.; Woodruff, Steven
  • Industrial & Engineering Chemistry Research, Vol. 36, Issue 12
  • DOI: 10.1021/ie970343e

Crystallization Of Zinc Sulphate Single Crystals And Its Structural, Thermal And Optical Characterization
journal, January 1970

Laser Raman and FT-IR studies of pure and Zn-doped TGS
journal, April 1993

  • Sivanesan, G.; Kolandaivel, P.; Pandian, S. Selvasekara
  • Materials Chemistry and Physics, Vol. 34, Issue 1
  • DOI: 10.1016/0254-0584(93)90123-4

On the structural and optical properties of nano-ZnO and its morphologies
journal, February 2014

Microstructure, optical and FTIR studies of Ni, Cu co-doped ZnO nanoparticles by co-precipitation method
journal, November 2014

Synthesis, structural and optical properties of ZnO and Ni-doped ZnO hexagonal nanorods by Co-precipitation method
journal, February 2014

  • Raja, K.; Ramesh, P. S.; Geetha, D.
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 120
  • DOI: 10.1016/j.saa.2013.09.103

In situ synthesis of permselective zeolitic imidazolate framework-8/graphene oxide composites: rotating disk electrode and Langmuir adsorption isotherm
journal, January 2015

  • Luanwuthi, Santamon; Krittayavathananon, Atiweena; Srimuk, Pattarachai
  • RSC Advances, Vol. 5, Issue 58
  • DOI: 10.1039/C5RA05950J

NiO-PTA supported on ZIF-8 as a highly effective catalyst for hydrocracking of Jatropha oil
journal, March 2016

  • Liu, Jing; He, Jing; Wang, Luying
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep23667

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

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

The Conversion of SO 2 to Sulfate in the Atmosphere
journal, January 1994

  • Eatough, D. J.; Caka, F. M.; Farber, R. J.
  • Israel Journal of Chemistry, Vol. 34, Issue 3-4
  • DOI: 10.1002/ijch.199400034

The contribution of in-cloud oxidation of SO2 to wet scavenging of sulfur in convective clouds
journal, January 1985

On the competing hydrations of sulfur dioxide and sulfur trioxide in our atmosphere
journal, January 2000

  • Loerting, Thomas; Liedl, Klaus R.; Kroemer, Romano T.
  • Chemical Communications, Issue 12
  • DOI: 10.1039/b002602f

Radiation treatment of exhaust gases—II. Oxidation of sulfur dioxide in the moist mixture of oxygen and nitrogen
journal, February 1978

  • Tokunaga, Okihiro; Nishimura, Koichi; Washino, Masamitsu
  • The International Journal of Applied Radiation and Isotopes, Vol. 29, Issue 2
  • DOI: 10.1016/0020-708X(78)90028-5

Chemical Reaction of Sulfur Dioxide at High Humidity and Temperature: Implications for Accelerated Testing
journal, March 1981

  • Flamm, Daniel L.; Bacon, D. D.; Kinsbron, E.
  • Journal of The Electrochemical Society, Vol. 128, Issue 3
  • DOI: 10.1149/1.2127480

Elusive Sulfurous Acid: Gas-Phase Basicity and IR Signature of the Protonated Species
journal, April 2015

  • Sinha, Rajeev K.; Scuderi, Debora; Maitre, Philippe
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 9
  • DOI: 10.1021/acs.jpclett.5b00450

Hydrolysis of Sulfur Dioxide in Small Clusters of Sulfuric Acid: Mechanistic and Kinetic Study
journal, October 2015

  • Liu, Jingjing; Fang, Sheng; Wang, Zhixiu
  • Environmental Science & Technology, Vol. 49, Issue 22
  • DOI: 10.1021/acs.est.5b02977

Mechanism of the Gaseous Hydrolysis Reaction of SO 2 : Effects of NH 3 versus H 2 O
journal, December 2014

  • Liu, Jingjing; Fang, Sheng; Liu, Wei
  • The Journal of Physical Chemistry A, Vol. 119, Issue 1
  • DOI: 10.1021/jp5086075

On the uncatalyzed oxidation of atmospheric SO2 by oxygen in aqueous systems
journal, January 1975

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    Efficient removal of formaldehyde with ZIF-8 growth on TiO2-coated activated carbon fiber felts prepared via atomic layer deposition
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    A zeolitic imidazolate framework-8-based indocyanine green theranostic agent for infrared fluorescence imaging and photothermal therapy
    journal, January 2018

    • Wang, Tianzheng; Li, Siqi; Zou, Zhen
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    • Rieth, Adam J.; Wright, Ashley M.; Dincă, Mircea
    • Nature Reviews Materials, Vol. 4, Issue 11
    • DOI: 10.1038/s41578-019-0140-1

    Preparation of ZIF‐8/natural Plant Fiber Composites via Biomimetic Mineralization for Highly Efficient Removal of Formaldehyde
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    journal, January 2017

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