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

Bhattacharyya, Souryadeep; Pang, Simon H.; Dutzer, Michael R.; Lively, Ryan P.; Walton, Krista S.; Sholl, David S.; Nair, Sankar

doi:10.1021/acs.jpcc.6b09197

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

Journal Article · Wed Nov 02 00:00:00 EDT 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b09197· OSTI ID:1388782

Bhattacharyya, Souryadeep ^[1]; Pang, Simon H. ^[1]; Dutzer, Michael R. ^[1]; Lively, Ryan P. ^[1]; Walton, Krista S. ^[1]; Sholl, David S. ^[1]; Nair, Sankar ^[1]

Georgia Inst. of Technology, Atlanta, GA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-Induced Evolution of Materials for Energy (UNCAGE-ME); Georgia Inst. of Technology, Atlanta, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012577

OSTI ID:: 1388782

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 48 Vol. 120; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

Carbon Dioxide Sensitivity of Zeolitic Imidazolate Frameworks Mottillo, Cristina; Friščić, Tomislav Angewandte Chemie International Edition, Vol. 53, Issue 29 https://doi.org/10.1002/anie.201402082	journal	May 2014
Can Metal-Organic Framework Materials Play a Useful Role in Large-Scale Carbon Dioxide Separations? Keskin, Seda; van Heest, Timothy M.; Sholl, David S. ChemSusChem, Vol. 3, Issue 8 https://doi.org/10.1002/cssc.201000114	journal	August 2010
Zeolitic Imidazolate Frameworks: Next-Generation Materials for Energy-Efficient Gas Separations Pimentel, Brian R.; Parulkar, Aamena; Zhou, Er-kang ChemSusChem, Vol. 7, Issue 12 https://doi.org/10.1002/cssc.201402647	journal	October 2014
The Conversion of SO ₂ to Sulfate in the Atmosphere Eatough, D. J.; Caka, F. M.; Farber, R. J. Israel Journal of Chemistry, Vol. 34, Issue 3-4 https://doi.org/10.1002/ijch.199400034	journal	January 1994
Adsorptive separations for the recovery and purification of biobutanol Cousin Saint Remi, J.; Baron, G.; Denayer, J. Adsorption, Vol. 18, Issue 5-6 https://doi.org/10.1007/s10450-012-9415-1	journal	September 2012
Crystal and Molecular Structure Analysis of 2-Methylimidazole Hachuła, Barbara; Nowak, Maria; Kusz, Joachim Journal of Chemical Crystallography, Vol. 40, Issue 3 https://doi.org/10.1007/s10870-009-9634-9	journal	September 2009
On the uncatalyzed oxidation of atmospheric SO2 by oxygen in aqueous systems Beilke, S.; Lamb, D.; Müller, J. Atmospheric Environment (1967), Vol. 9, Issue 12 https://doi.org/10.1016/0004-6981(75)90183-3	journal	January 1975
The contribution of in-cloud oxidation of SO2 to wet scavenging of sulfur in convective clouds Scire, Joseph S.; Venkatram, A. Atmospheric Environment (1967), Vol. 19, Issue 4 https://doi.org/10.1016/0004-6981(85)90043-5	journal	January 1985
Radiation treatment of exhaust gases—II. Oxidation of sulfur dioxide in the moist mixture of oxygen and nitrogen Tokunaga, Okihiro; Nishimura, Koichi; Washino, Masamitsu The International Journal of Applied Radiation and Isotopes, Vol. 29, Issue 2 https://doi.org/10.1016/0020-708X(78)90028-5	journal	February 1978
Laser Raman and FT-IR studies of pure and Zn-doped TGS Sivanesan, G.; Kolandaivel, P.; Pandian, S. Selvasekara Materials Chemistry and Physics, Vol. 34, Issue 1 https://doi.org/10.1016/0254-0584(93)90123-4	journal	April 1993
Thermal swing adsorption process for removing trace impurities from a multi-component gas mixture: (Landfill gas) Kumar, R.; Golden, T. C. Gas Separation & Purification, Vol. 5, Issue 1 https://doi.org/10.1016/0950-4214(91)80044-6	journal	March 1991
Thermal stability of ZIF-8 under oxidative and inert environments: A practical perspective on using ZIF-8 as a catalyst support Yin, Hang; Kim, Hyungmin; Choi, Jungkyu Chemical Engineering Journal, Vol. 278 https://doi.org/10.1016/j.cej.2014.08.075	journal	October 2015
Protonic Conductivity of Nanocrystalline Zeolitic Imidazolate Framework 8 Barbosa, Paula; Rosero-Navarro, Nataly C.; Shi, Fa-Nian Electrochimica Acta, Vol. 153 https://doi.org/10.1016/j.electacta.2014.11.093	journal	January 2015
Comparison of energy efficiency and economics of process designs for biobutanol production from sugarcane molasses van der Merwe, A. B.; Cheng, H.; Görgens, J. F. Fuel, Vol. 105 https://doi.org/10.1016/j.fuel.2012.06.058	journal	March 2013
Ionic liquid-amine blends and CO2BOLs: Prospective solvents for natural gas sweetening and CO2 capture technology—A review Kumar, Satish; Cho, Jae Hyun; Moon, Il International Journal of Greenhouse Gas Control, Vol. 20 https://doi.org/10.1016/j.ijggc.2013.10.019	journal	January 2014
On the structural and optical properties of nano-ZnO and its morphologies Rajamanickam, N.; Rajashabala, S.; Ramachandran, K. Journal of Luminescence, Vol. 146 https://doi.org/10.1016/j.jlumin.2013.09.074	journal	February 2014
Characterization of metal-organic frameworks by water adsorption Küsgens, Pia; Rose, Marcus; Senkovska, Irena Microporous and Mesoporous Materials, Vol. 120, Issue 3, p. 325-330 https://doi.org/10.1016/j.micromeso.2008.11.020	journal	April 2009
Systematic study of the chemical and hydrothermal stability of selected “stable” Metal Organic Frameworks Leus, Karen; Bogaerts, Thomas; De Decker, Jeroen Microporous and Mesoporous Materials, Vol. 226 https://doi.org/10.1016/j.micromeso.2015.11.055	journal	May 2016
Microstructure, optical and FTIR studies of Ni, Cu co-doped ZnO nanoparticles by co-precipitation method Ashokkumar, M.; Muthukumaran, S. Optical Materials, Vol. 37 https://doi.org/10.1016/j.optmat.2014.08.012	journal	November 2014
Synthesis, structural and optical properties of ZnO and Ni-doped ZnO hexagonal nanorods by Co-precipitation method Raja, K.; Ramesh, P. S.; Geetha, D. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 120 https://doi.org/10.1016/j.saa.2013.09.103	journal	February 2014
Infrared Spectra and Characteristic Frequencies of Inorganic Ions Miller, F. A.; Wilkins, C. H. Analytical Chemistry, Vol. 24, Issue 8 https://doi.org/10.1021/ac60068a007	journal	August 1952
Facet-Specific Stability of ZIF-8 in the Presence of Acid Gases Dissolved in Aqueous Solutions Pang, Simon H.; Han, Chu; Sholl, David S. Chemistry of Materials, Vol. 28, Issue 19 https://doi.org/10.1021/acs.chemmater.6b02643	journal	September 2016
Hydrolysis of Sulfur Dioxide in Small Clusters of Sulfuric Acid: Mechanistic and Kinetic Study Liu, Jingjing; Fang, Sheng; Wang, Zhixiu Environmental Science & Technology, Vol. 49, Issue 22 https://doi.org/10.1021/acs.est.5b02977	journal	October 2015
Kinetics of ZIF-8 Thermal Decomposition in Inert, Oxidizing, and Reducing Environments James, Joshua B.; Lin, Y. S. The Journal of Physical Chemistry C, Vol. 120, Issue 26 https://doi.org/10.1021/acs.jpcc.6b01208	journal	June 2016
Synergistic Effects of Water and SO ₂ on Degradation of MIL-125 in the Presence of Acid Gases Mounfield, William P.; Han, Chu; Pang, Simon H. The Journal of Physical Chemistry C, Vol. 120, Issue 48 https://doi.org/10.1021/acs.jpcc.6b09264	journal	November 2016
Elusive Sulfurous Acid: Gas-Phase Basicity and IR Signature of the Protonated Species Sinha, Rajeev K.; Scuderi, Debora; Maitre, Philippe The Journal of Physical Chemistry Letters, Vol. 6, Issue 9 https://doi.org/10.1021/acs.jpclett.5b00450	journal	April 2015
Defects in Metal–Organic Frameworks: Challenge or Opportunity? Sholl, David S.; Lively, Ryan P. The Journal of Physical Chemistry Letters, Vol. 6, Issue 17 https://doi.org/10.1021/acs.jpclett.5b01135	journal	August 2015
Computational Characterization of Defects in Metal–Organic Frameworks: Spontaneous and Water-Induced Point Defects in ZIF-8 Zhang, Chenyang; Han, Chu; Sholl, David S. The Journal of Physical Chemistry Letters, Vol. 7, Issue 3 https://doi.org/10.1021/acs.jpclett.5b02683	journal	January 2016
Synthesis, Structure, and Carbon Dioxide Capture Properties of Zeolitic Imidazolate Frameworks Phan, Anh; Doonan, Christian J.; Uribe-Romo, Fernando J. Accounts of Chemical Research, Vol. 43, Issue 1, p. 58-67 https://doi.org/10.1021/ar900116g	journal	January 2010
High-Throughput Screening of Metal–Organic Frameworks for CO ₂ Separation Han, Sangil; Huang, Yougui; Watanabe, Taku ACS Combinatorial Science, Vol. 14, Issue 4 https://doi.org/10.1021/co3000192	journal	March 2012
Water Stability and Adsorption in Metal–Organic Frameworks Burtch, Nicholas C.; Jasuja, Himanshu; Walton, Krista S. Chemical Reviews, Vol. 114, Issue 20, p. 10575-10612 https://doi.org/10.1021/cr5002589	journal	September 2014
A new method of generation of gases at parts per million levels for preparation of standard gases Hashimoto, Yoshikazu.; Tanaka, Shigeru. Environmental Science & Technology, Vol. 14, Issue 4 https://doi.org/10.1021/es60164a006	journal	April 1980
FTIR Characterization of the Interaction of Oxygen with Zinc Sulfide Siriwardane, Ranjani V.; Woodruff, Steven Industrial & Engineering Chemistry Research, Vol. 34, Issue 2 https://doi.org/10.1021/ie00041a032	journal	February 1995
In Situ Fourier Transform Infrared Characterization of Sulfur Species Resulting from the Reaction of Water Vapor and Oxygen with Zinc Sulfide Siriwardane, Ranjani V.; Woodruff, Steven Industrial & Engineering Chemistry Research, Vol. 36, Issue 12 https://doi.org/10.1021/ie970343e	journal	December 1997
Red-, Blue-, or No-Shift in Hydrogen Bonds: A Unified Explanation Joseph, Jorly; Jemmis, Eluvathingal D. Journal of the American Chemical Society, Vol. 129, Issue 15 https://doi.org/10.1021/ja067545z	journal	April 2007
Control of Pore Size and Functionality in Isoreticular Zeolitic Imidazolate Frameworks and their Carbon Dioxide Selective Capture Properties Banerjee, Rahul; Furukawa, Hiroyasu; Britt, David Journal of the American Chemical Society, Vol. 131, Issue 11, p. 3875-3877 https://doi.org/10.1021/ja809459e	journal	March 2009
Virtual High Throughput Screening Confirmed Experimentally: Porous Coordination Polymer Hydration Low, John J.; Benin, Annabelle I.; Jakubczak, Paulina Journal of the American Chemical Society, Vol. 131, Issue 43 https://doi.org/10.1021/ja9061344	journal	November 2009
A Combined Experimental-Computational Study on the Effect of Topology on Carbon Dioxide Adsorption in Zeolitic Imidazolate Frameworks Morris, William; He, Ning; Ray, Keith G. The Journal of Physical Chemistry C, Vol. 116, Issue 45 https://doi.org/10.1021/jp307170a	journal	November 2012
Trace Flue Gas Contaminants Poison Coordinatively Unsaturated Metal–Organic Frameworks: Implications for CO ₂ Adsorption and Separation Yu, Kuang; Kiesling, Kalin; Schmidt, J. R. The Journal of Physical Chemistry C, Vol. 116, Issue 38 https://doi.org/10.1021/jp307894e	journal	September 2012
Adsorption and Diffusion of Small Alcohols in Zeolitic Imidazolate Frameworks ZIF-8 and ZIF-90 Gee, Jason A.; Chung, Jaeyub; Nair, Sankar The Journal of Physical Chemistry C, Vol. 117, Issue 6 https://doi.org/10.1021/jp312489w	journal	February 2013
Investigating the Intrinsic Ethanol/Water Separation Capability of ZIF-8: An Adsorption and Diffusion Study Zhang, Ke; Lively, Ryan P.; Zhang, Chen The Journal of Physical Chemistry C, Vol. 117, Issue 14 https://doi.org/10.1021/jp401548b	journal	March 2013
H ₂ O-Functionalized Zeolitic Zn(2-methylimidazole) ₂ Framework (ZIF-8) for H ₂ Storage Cheng, Peifu; Hu, Yun Hang The Journal of Physical Chemistry C, Vol. 118, Issue 38 https://doi.org/10.1021/jp507030g	journal	September 2014
Mechanism of the Gaseous Hydrolysis Reaction of SO ₂ : Effects of NH ₃ versus H ₂ O Liu, Jingjing; Fang, Sheng; Liu, Wei The Journal of Physical Chemistry A, Vol. 119, Issue 1 https://doi.org/10.1021/jp5086075	journal	December 2014
Unexpected Molecular Sieving Properties of Zeolitic Imidazolate Framework-8 Zhang, Chen; Lively, Ryan P.; Zhang, Ke The Journal of Physical Chemistry Letters, Vol. 3, Issue 16 https://doi.org/10.1021/jz300855a	journal	July 2012
Exploring the Framework Hydrophobicity and Flexibility of ZIF-8: From Biofuel Recovery to Hydrocarbon Separations Zhang, Ke; Lively, Ryan P.; Zhang, Chen The Journal of Physical Chemistry Letters, Vol. 4, Issue 21 https://doi.org/10.1021/jz402019d	journal	October 2013
Seven chemical separations to change the world Sholl, David S.; Lively, Ryan P. Nature, Vol. 532, Issue 7600 https://doi.org/10.1038/532435a	journal	April 2016
NiO-PTA supported on ZIF-8 as a highly effective catalyst for hydrocracking of Jatropha oil Liu, Jing; He, Jing; Wang, Luying Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep23667	journal	March 2016
Water-based synthesis of zeolitic imidazolate framework-8 with high morphology level at room temperature Jian, Meipeng; Liu, Bao; Liu, Ruiping RSC Advances, Vol. 5, Issue 60 https://doi.org/10.1039/C5RA04033G	journal	January 2015
In situ synthesis of permselective zeolitic imidazolate framework-8/graphene oxide composites: rotating disk electrode and Langmuir adsorption isotherm Luanwuthi, Santamon; Krittayavathananon, Atiweena; Srimuk, Pattarachai RSC Advances, Vol. 5, Issue 58 https://doi.org/10.1039/C5RA05950J	journal	January 2015
On the competing hydrations of sulfur dioxide and sulfur trioxide in our atmosphere Loerting, Thomas; Liedl, Klaus R.; Kroemer, Romano T. Chemical Communications, Issue 12 https://doi.org/10.1039/b002602f	journal	January 2000
In situ high pressure study of ZIF-8 by FTIR spectroscopy Hu, Yue; Kazemian, Hossein; Rohani, Sohrab Chemical Communications, Vol. 47, Issue 47 https://doi.org/10.1039/c1cc15525c	journal	January 2011
Alcohol and water adsorption in zeolitic imidazolate frameworks Zhang, Ke; Lively, Ryan P.; Dose, Michelle E. Chemical Communications, Vol. 49, Issue 31 https://doi.org/10.1039/c3cc39116g	journal	January 2013
Exceptional chemical and thermal stability of zeolitic imidazolate frameworks Park, K. S.; Ni, Z.; Cote, A. P. Proceedings of the National Academy of Sciences, Vol. 103, Issue 27, p. 10186-10191 https://doi.org/10.1073/pnas.0602439103	journal	June 2006
Chemical Reaction of Sulfur Dioxide at High Humidity and Temperature: Implications for Accelerated Testing Flamm, Daniel L.; Bacon, D. D.; Kinsbron, E. Journal of The Electrochemical Society, Vol. 128, Issue 3 https://doi.org/10.1149/1.2127480	journal	March 1981
Crystallization Of Zinc Sulphate Single Crystals And Its Structural, Thermal And Optical Characterization Saha, Jk; Podder, J. Journal of Bangladesh Academy of Sciences, Vol. 35, Issue 2 https://doi.org/10.3329/jbas.v35i2.9426	journal	January 1970

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
carbon capture
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defects
materials and chemistry by design
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synthesis (scalable processing)
synthesis (self-assembly)