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Title: Influence of Hydrogen Sulfide Exposure on the Transport and Structural Properties of the Metal–Organic Framework ZIF-8

Abstract

In this paper, the interaction between hydrogen sulfide and ZIF-8 was studied via structural characterizations and guest molecule diffusion measurements. It was found that hydrogen sulfide reacts with the ZIF-8 external particle surface to form a surface barrier that excludes the uptake of larger molecules (ethanol) and slows down the uptake of smaller molecules (carbon dioxide). Nonetheless, bulk transport properties were unaltered, as supported by pulsed field gradient nuclear magnetic resonance studies. Dispersion-corrected density functional theory calculations revealed that H2S is consumed by reactions occurring at the ZIF external surface. These reactions result in water and defect formation, both of which were found to be exothermic and independent of both crystallographic facets ({001} and {110}) and surface termination. Finally, we concluded that these surface reactions lead to structural and chemical changes to the ZIF-8 external surface that generate surface barriers to molecular transport.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3];  [4]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Florida, Gainesville, FL (United States). Dept. of Chemical Engineering
  2. Univ. of Wisconsin, Madison, WI (United States). Theoretical Chemistry Inst. Dept. of Chemistry
  3. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical and Biomolecular Engineering
  4. Univ. of Florida, Gainesville, FL (United States). National High Magnetic Field Lab.
Publication Date:
Research Org.:
Georgia Institute of Technology, Atlanta, GA (United States); Univ. of Florida, Gainesville, FL (United States); Energy Frontier Research Centers (EFRC) (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); National Science Foundation (NSF)
OSTI Identifier:
1428044
Grant/Contract Number:  
SC0012577; ECCS-1542174; DMR-1157490
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 13; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Dutta, Akshita, Tymi?ska, Nina, Zhu, Guanghui, Collins, James, Lively, Ryan P., Schmidt, J. R., and Vasenkov, Sergey. Influence of Hydrogen Sulfide Exposure on the Transport and Structural Properties of the Metal–Organic Framework ZIF-8. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b00798.
Dutta, Akshita, Tymi?ska, Nina, Zhu, Guanghui, Collins, James, Lively, Ryan P., Schmidt, J. R., & Vasenkov, Sergey. Influence of Hydrogen Sulfide Exposure on the Transport and Structural Properties of the Metal–Organic Framework ZIF-8. United States. https://doi.org/10.1021/acs.jpcc.8b00798
Dutta, Akshita, Tymi?ska, Nina, Zhu, Guanghui, Collins, James, Lively, Ryan P., Schmidt, J. R., and Vasenkov, Sergey. Fri . "Influence of Hydrogen Sulfide Exposure on the Transport and Structural Properties of the Metal–Organic Framework ZIF-8". United States. https://doi.org/10.1021/acs.jpcc.8b00798. https://www.osti.gov/servlets/purl/1428044.
@article{osti_1428044,
title = {Influence of Hydrogen Sulfide Exposure on the Transport and Structural Properties of the Metal–Organic Framework ZIF-8},
author = {Dutta, Akshita and Tymi?ska, Nina and Zhu, Guanghui and Collins, James and Lively, Ryan P. and Schmidt, J. R. and Vasenkov, Sergey},
abstractNote = {In this paper, the interaction between hydrogen sulfide and ZIF-8 was studied via structural characterizations and guest molecule diffusion measurements. It was found that hydrogen sulfide reacts with the ZIF-8 external particle surface to form a surface barrier that excludes the uptake of larger molecules (ethanol) and slows down the uptake of smaller molecules (carbon dioxide). Nonetheless, bulk transport properties were unaltered, as supported by pulsed field gradient nuclear magnetic resonance studies. Dispersion-corrected density functional theory calculations revealed that H2S is consumed by reactions occurring at the ZIF external surface. These reactions result in water and defect formation, both of which were found to be exothermic and independent of both crystallographic facets ({001} and {110}) and surface termination. Finally, we concluded that these surface reactions lead to structural and chemical changes to the ZIF-8 external surface that generate surface barriers to molecular transport.},
doi = {10.1021/acs.jpcc.8b00798},
journal = {Journal of Physical Chemistry. C},
number = 13,
volume = 122,
place = {United States},
year = {2018},
month = {3}
}

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Figures / Tables:

Table 1 Table 1: Concentrations of Probe Molecules (Ethylene and Carbon Dioxide) in the As-Prepared and H2S-Exposed ZIF-8 Samples at 298 K as Determined Using 13C NMR Signal Analysis

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Works referenced in this record:

Chemical and biological technologies for hydrogen sulfide emission control in sewer systems: A review
journal, January 2008


Review on the Use of Ionic Liquids (ILs) as Alternative Fluids for CO 2 Capture and Natural Gas Sweetening
journal, November 2010

  • Karadas, Ferdi; Atilhan, Mert; Aparicio, Santiago
  • Energy & Fuels, Vol. 24, Issue 11
  • DOI: 10.1021/ef1011337

Recent advances in the science and technology of ultra low sulfur diesel (ULSD) production
journal, July 2010


Hazards in the work environment--hydrogen sulfide. Spectrophotometric determination of hydrogen sulfide.
journal, March 1979

  • Waernbaum, Gösta; Wallin, Inga
  • Scandinavian Journal of Work, Environment & Health, Vol. 5, Issue 1
  • DOI: 10.5271/sjweh.2668

Hydrogen Sulphide
journal, October 1996


Susceptibility of FeS 2 hydrogen evolution performance to sulfide poisoning
journal, September 2015


Comparative Theoretical Study of the Chemistry of Hydrogen Sulfide on Cu(100) and Au(100): Implications for Sulfur Tolerance of Water Gas Shift Nanocatalysts
journal, October 2016

  • Tang, Qian-Lin; Duan, Xiao-Xuan; Zhang, Tian-Tian
  • The Journal of Physical Chemistry C, Vol. 120, Issue 44
  • DOI: 10.1021/acs.jpcc.6b07050

Comparative Study of Hydrogen Sulfide Adsorption in the MIL-53(Al, Cr, Fe), MIL-47(V), MIL-100(Cr), and MIL-101(Cr) Metal−Organic Frameworks at Room Temperature
journal, July 2009

  • Hamon, Lomig; Serre, Christian; Devic, Thomas
  • Journal of the American Chemical Society, Vol. 131, Issue 25
  • DOI: 10.1021/ja901587t

H2S interaction with HKUST-1 and ZIF-8 MOFs: A multitechnique study
journal, May 2015


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

Adsorptive removal of carbon dioxide using polyethyleneimine-loaded mesoporous silica materials
journal, August 2008


Relationship between mixed and pure gas self-diffusion for ethane and ethene in ZIF-8/6FDA-DAM mixed-matrix membrane by pulsed field gradient NMR
journal, February 2016


Pulsed field gradient stimulated echo methods for improved NMR diffusion measurements in heterogeneous systems
journal, June 1989


Diffusion in Nanoporous Materials
book, April 2012


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

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

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


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

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

Catalysis of Transesterification by a Nonfunctionalized Metal−Organic Framework: Acido-Basicity at the External Surface of ZIF-8 Probed by FTIR and ab Initio Calculations
journal, September 2010

  • Chizallet, Céline; Lazare, Sandrine; Bazer-Bachi, Delphine
  • Journal of the American Chemical Society, Vol. 132, Issue 35
  • DOI: 10.1021/ja103365s

External Surface of Zeolite Imidazolate Frameworks Viewed Ab Initio: Multifunctionality at the Organic−Inorganic Interface
journal, November 2009

  • Chizallet, Céline; Bats, Nicolas
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 1
  • DOI: 10.1021/jz900192x

Surface and Stability Characterization of a Nanoporous ZIF-8 Thin Film
journal, June 2014

  • Tian, Fangyuan; Cerro, Andrew M.; Mosier, Amber M.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 26
  • DOI: 10.1021/jp5041053

Revelation of the Molecular Assembly of the Nanoporous Metal Organic Framework ZIF-8
journal, August 2011

  • Moh, Pak Y.; Cubillas, Pablo; Anderson, Michael W.
  • Journal of the American Chemical Society, Vol. 133, Issue 34
  • DOI: 10.1021/ja205900f

Unravelling surface and interfacial structures of a metal–organic framework by transmission electron microscopy
journal, February 2017

  • Zhu, Yihan; Ciston, Jim; Zheng, Bin
  • Nature Materials, Vol. 16, Issue 5
  • DOI: 10.1038/nmat4852

Ethanol and water adsorption in methanol-derived ZIF-71
journal, January 2011

  • Lively, Ryan P.; Dose, Michelle E.; Thompson, Joshua A.
  • Chemical Communications, Vol. 47, Issue 30
  • DOI: 10.1039/c1cc12728d

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


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

Microscopic Model of the Metal–Organic Framework/Polymer Interface: A First Step toward Understanding the Compatibility in Mixed Matrix Membranes
journal, December 2015

  • Semino, Rocio; Ramsahye, Naseem A.; Ghoufi, Aziz
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 1
  • DOI: 10.1021/acsami.5b10150

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points
journal, December 2000

  • Henkelman, Graeme; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22
  • DOI: 10.1063/1.1323224

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

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

NMR studies of carbon dioxide and methane self-diffusion in ZIF-8 at elevated gas pressures
journal, September 2012


Ethene/ethane mixture diffusion in the MOF sieve ZIF-8 studied by MAS PFG NMR diffusometry
journal, January 2012


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

New options for measuring molecular diffusion in zeolites by MAS PFG NMR
journal, May 2005


Revealing complex formation in acetone–n-alkane mixtures by MAS PFG NMR diffusion measurement in nanoporous hosts
journal, January 2008

  • Fernandez, Moises; Pampel, André; Takahashi, Ryoji
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 28
  • DOI: 10.1039/b802929f

Works referencing / citing this record:

Ethane diffusion in mixed linker zeolitic imidazolate framework-7-8 by pulsed field gradient NMR in combination with single crystal IR microscopy
journal, January 2018

  • Berens, Samuel; Chmelik, Christian; Hillman, Febrian
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 37
  • DOI: 10.1039/c8cp04889d