Computational Studies of CO 2 Sorption and Separation in an Ultramicroporous Metal–Organic Material

Handle URI:
http://hdl.handle.net/10754/597824
Title:
Computational Studies of CO 2 Sorption and Separation in an Ultramicroporous Metal–Organic Material
Authors:
Forrest, Katherine A.; Pham, Tony; Hogan, Adam; McLaughlin, Keith; Tudor, Brant; Nugent, Patrick; Burd, Stephen D.; Mullen, Ashley; Cioce, Christian R.; Wojtas, Lukasz; Zaworotko, Michael J.; Space, Brian
Abstract:
Grand canonical Monte Carlo (GCMC) simulations of CO2 sorption and separation were performed in [Zn(pyz)2SiF6], a metal-organic material (MOM) consisting of a square grid of Zn2+ ions coordinated to pyrazine (pyz) linkers and pillars of SiF6 2- ions. This MOM was recently shown to have an unprecedented selectivity for CO2 over N2, CH4, and H 2 under industrially relevant conditions. The simulated CO 2 sorption isotherms and calculated isosteric heat of adsorption, Qst, values were in excellent agreement with the experimental data for all the state points considered. CO2 saturation in [Zn(pyz) 2SiF6] was achieved at near-ambient temperatures and pressures lower than 1.0 atm. Moreover, the sorbed CO2 molecules were representative of a liquid/fluid under such conditions as confirmed through calculating the isothermal compressibility, βT, values. The simulated CO2 uptakes within CO2/N2 (10:90), CO2/CH4 (50:50), and CO2/H2 (30:70) mixture compositions, characteristic of flue gas, biogas, and syngas, respectively, were comparable to those that were produced in the single-component CO2 sorption simulations. The modeled structure at saturation revealed a loading of 1 CO2 molecule per unit cell. The favored CO2 sorption site was identified as the attraction of the carbon atoms of CO2 molecules to four equatorial fluorine atoms of SiF6 2- anions simultaneously, resulting in CO2 molecules localized at the center of the channel. Furthermore, experimental studies have shown that [Zn(pyz)2SiF6] sorbed minimal amounts of CO2 and N2 at their respective liquid temperatures. Analysis of the crystal structure at 100 K revealed that the unit cell undergoes a slight contraction in all dimensions and contains pyrazine rings that are mildly slanted with an angle of 13.9. Additionally, molecular dynamics (MD) simulations revealed that the sorbate molecules are anchored to the framework at low temperatures, which inhibits diffusion. Thus, it is hypothesized that the sorbed molecules become trapped in the pores and block other sorbate molecules from entering the MOM at low temperatures. © 2013 American Chemical Society.
Citation:
Forrest KA, Pham T, Hogan A, McLaughlin K, Tudor B, et al. (2013) Computational Studies of CO 2 Sorption and Separation in an Ultramicroporous Metal–Organic Material . The Journal of Physical Chemistry C 117: 17687–17698. Available: http://dx.doi.org/10.1021/jp405781c.
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry C
KAUST Grant Number:
FIC/2010/06
Issue Date:
29-Aug-2013
DOI:
10.1021/jp405781c
Type:
Article
ISSN:
1932-7447; 1932-7455
Sponsors:
This work was supported by the National Science Foundation (Award No. CHE-1152362). Computations were performed under a XSEDE Grant (No. TG-DMR090028) to B.S. This publication is also based on work supported by Award No. FIC/2010/06, made by King Abdullah University of Science and Technology (KAUST). The authors also thank the Space Foundation (Basic and Applied Research) for partial support. The authors would like to acknowledge the use of the services provided by Research Computing at the University of South Florida. Lastly, the authors would like to thank Professor Mohamed Eddaoudi and his co-workers for supplying us with the raw data for experimental isosteric heats of adsorption and the CO<INF>2</INF> sorption isotherms at high temperatures.
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Full metadata record

DC FieldValue Language
dc.contributor.authorForrest, Katherine A.en
dc.contributor.authorPham, Tonyen
dc.contributor.authorHogan, Adamen
dc.contributor.authorMcLaughlin, Keithen
dc.contributor.authorTudor, Branten
dc.contributor.authorNugent, Patricken
dc.contributor.authorBurd, Stephen D.en
dc.contributor.authorMullen, Ashleyen
dc.contributor.authorCioce, Christian R.en
dc.contributor.authorWojtas, Lukaszen
dc.contributor.authorZaworotko, Michael J.en
dc.contributor.authorSpace, Brianen
dc.date.accessioned2016-02-25T12:57:21Zen
dc.date.available2016-02-25T12:57:21Zen
dc.date.issued2013-08-29en
dc.identifier.citationForrest KA, Pham T, Hogan A, McLaughlin K, Tudor B, et al. (2013) Computational Studies of CO 2 Sorption and Separation in an Ultramicroporous Metal–Organic Material . The Journal of Physical Chemistry C 117: 17687–17698. Available: http://dx.doi.org/10.1021/jp405781c.en
dc.identifier.issn1932-7447en
dc.identifier.issn1932-7455en
dc.identifier.doi10.1021/jp405781cen
dc.identifier.urihttp://hdl.handle.net/10754/597824en
dc.description.abstractGrand canonical Monte Carlo (GCMC) simulations of CO2 sorption and separation were performed in [Zn(pyz)2SiF6], a metal-organic material (MOM) consisting of a square grid of Zn2+ ions coordinated to pyrazine (pyz) linkers and pillars of SiF6 2- ions. This MOM was recently shown to have an unprecedented selectivity for CO2 over N2, CH4, and H 2 under industrially relevant conditions. The simulated CO 2 sorption isotherms and calculated isosteric heat of adsorption, Qst, values were in excellent agreement with the experimental data for all the state points considered. CO2 saturation in [Zn(pyz) 2SiF6] was achieved at near-ambient temperatures and pressures lower than 1.0 atm. Moreover, the sorbed CO2 molecules were representative of a liquid/fluid under such conditions as confirmed through calculating the isothermal compressibility, βT, values. The simulated CO2 uptakes within CO2/N2 (10:90), CO2/CH4 (50:50), and CO2/H2 (30:70) mixture compositions, characteristic of flue gas, biogas, and syngas, respectively, were comparable to those that were produced in the single-component CO2 sorption simulations. The modeled structure at saturation revealed a loading of 1 CO2 molecule per unit cell. The favored CO2 sorption site was identified as the attraction of the carbon atoms of CO2 molecules to four equatorial fluorine atoms of SiF6 2- anions simultaneously, resulting in CO2 molecules localized at the center of the channel. Furthermore, experimental studies have shown that [Zn(pyz)2SiF6] sorbed minimal amounts of CO2 and N2 at their respective liquid temperatures. Analysis of the crystal structure at 100 K revealed that the unit cell undergoes a slight contraction in all dimensions and contains pyrazine rings that are mildly slanted with an angle of 13.9. Additionally, molecular dynamics (MD) simulations revealed that the sorbate molecules are anchored to the framework at low temperatures, which inhibits diffusion. Thus, it is hypothesized that the sorbed molecules become trapped in the pores and block other sorbate molecules from entering the MOM at low temperatures. © 2013 American Chemical Society.en
dc.description.sponsorshipThis work was supported by the National Science Foundation (Award No. CHE-1152362). Computations were performed under a XSEDE Grant (No. TG-DMR090028) to B.S. This publication is also based on work supported by Award No. FIC/2010/06, made by King Abdullah University of Science and Technology (KAUST). The authors also thank the Space Foundation (Basic and Applied Research) for partial support. The authors would like to acknowledge the use of the services provided by Research Computing at the University of South Florida. Lastly, the authors would like to thank Professor Mohamed Eddaoudi and his co-workers for supplying us with the raw data for experimental isosteric heats of adsorption and the CO<INF>2</INF> sorption isotherms at high temperatures.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleComputational Studies of CO 2 Sorption and Separation in an Ultramicroporous Metal–Organic Materialen
dc.typeArticleen
dc.identifier.journalThe Journal of Physical Chemistry Cen
dc.contributor.institutionUniversity of South Florida Tampa, Tampa, United Statesen
kaust.grant.numberFIC/2010/06en
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