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

doi:10.1021/acs.jpcc.8b00798

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:

Dutta, Akshita ^[1];

^[2];

^[3]; Collins, James ^[4];

^[3];

^[2];

^[1]

Univ. of Florida, Gainesville, FL (United States). Dept. of Chemical Engineering
Univ. of Wisconsin, Madison, WI (United States). Theoretical Chemistry Inst. Dept. of Chemistry
Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical and Biomolecular Engineering
Univ. of Florida, Gainesville, FL (United States). National High Magnetic Field Lab.

Publication Date:: 2018-03-09

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.

Copy to clipboard


                    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.  doi:10.1021/acs.jpcc.8b00798.

Copy to clipboard


                    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.  doi:10.1021/acs.jpcc.8b00798.  https://www.osti.gov/servlets/purl/1428044.

Copy to clipboard


                    
@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}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: 10.1021/acs.jpcc.8b00798

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 2 works

Citation information provided by
Web of Science

Figures / Tables:

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

All figures and tables (13 total)

Save / Share:

Export Metadata

Save to My Library

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

Figures / Tables found in this record:

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

Similar Records in DOE PAGES and OSTI.GOV collections:

Facet-Specific Stability of ZIF-8 in the Presence of Acid Gases Dissolved in Aqueous Solutions

Journal Article Pang, Simon H. ; Han, Chu ; Sholl, David S. ; ... - Chemistry of Materials

ZIF-8 is a crystalline microporous material that has been widely studied because of its thermal and chemical stability relative to other metal–organic frameworks (MOFs) and its potential for use in a number of gas adsorption, separation, and catalysis applications. However, most studies focus on characterization of the bulk structure of ZIF-8, ignoring the potential effect of the particle shape and the external surface on these applications. This report describes studies that examined the stability of the {110} and {100} crystallographic facets of ZIF-8 under mildly acidic conditions. Though the {110} facet is more thermodynamically stable than the {100} facet, itmore »« less
Cited by 49
DOI: 10.1021/acs.chemmater.6b02643

Full Text Available
Anomaly in the Chain Length Dependence of n-Alkane Diffusion in ZIF-4 Metal-Organic Frameworks

Journal Article Hwang, Seungtaik ; Gopalan, Arun ; Hovestadt, Maximilian ; ... - Molecules

Molecular diffusion is commonly found to slow down with increasing molecular size. Deviations from this pattern occur in some host materials with pore sizes approaching the diameters of the guest molecules. A variety of theoretical models have been suggested to explain deviations from this pattern, but robust experimental data are scarcely available. Here in this paper, we present such data, obtained by monitoring the chain length dependence of the uptake of n-alkanes in the zeolitic imidazolate framework ZIF-4. A monotonic decrease in diffusivity from ethane to n-butane was observed, followed by an increase for n-pentane, and another decrease for n-hexane.more »« less
Cited by 3
DOI: 10.3390/molecules23030668

Full Text Available
Metal-organic and zeolite imidazolate frameworks (MOFs and ZIFs) for highly selective separations

Technical Report Yaghi, Omar M

Metal-organic and zeolite imidazolate frameworks (MOFs and ZIFs) have been investigated for the realization as separation media with high selectivity. These structures are held together with strong bonds, making them architecturally, chemically, and thermally stable. Therefore, employing well designed building units, it is possible to discover promising materials for gas and vapor separation. This grant was focused on the study of MOFs and ZIFs with these specific objectives: (i) to develop a strategy for producing MOFs and ZIFs that combine high surface areas with active sites for their use in gas adsorption and separation of small organic compounds, (ii) tomore »« less
DOI: 10.2172/1050881

Full Text Available
Computational Characterization of Defects in Metal–Organic Frameworks: Spontaneous and Water-Induced Point Defects in ZIF-8

Journal Article Zhang, Chenyang ; Han, Chu ; Sholl, David S. ; ... - Journal of Physical Chemistry Letters

Zeolitic imidazolate frameworks (ZIFs) are an important class of porous crystalline metal–organic framework (MOF) materials that have attracted widespread attention for applications ranging from gas adsorption and separation to catalysis. Although the bulk crystal structures of MOFs are typically well-characterized, comparatively little is known regarding MOF defect structures. Drawing on analogies with conventional silicon-based zeolites, we utilize computational methods to examine the structure and stability of putative point-defect structures (including vacancies, substitutions, and “dangling” linkers) within the prototypical ZIF-8 structure. Considering both postsynthetic (gas-phase) and synthetic (solution-phase) conditions, we find that several of the defect structures lie low in energymore »« less
Cited by 51
DOI: 10.1021/acs.jpclett.5b02683

Full Text Available
Molecular dynamics simulation of framework flexibility effects on noble gas diffusion in HKUST-1 and ZIF-8

Journal Article Parkes, Marie V. ; Demir, Hakan ; Teich-McGoldrick, Stephanie L. ; ... - Microporous and Mesoporous Materials

Molecular dynamics simulations were used to investigate trends in noble gas (Ar, Kr, Xe) diffusion in the metal-organic frameworks HKUST-1 and ZIF-8. Diffusion occurs primarily through inter-cage jump events, with much greater diffusion of guest atoms in HKUST-1 compared to ZIF-8 due to the larger cage and window sizes in the former. We compare diffusion coefficients calculated for both rigid and flexible frameworks. For rigid framework simulations, in which the framework atoms were held at their crystallographic or geometry optimized coordinates, sometimes dramatic differences in guest diffusion were seen depending on the initial framework structure or the choice of frameworkmore »« less
Cited by 24
DOI: 10.1016/j.micromeso.2014.03.027

Full Text Available

Similar Records

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

Abstract

Citation Formats

Figures / Tables:

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

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