Tunable CO 2 Adsorbents by Mixed-Linker Synthesis and Postsynthetic Modification of Zeolitic Imidazolate Frameworks

Handle URI:
http://hdl.handle.net/10754/600089
Title:
Tunable CO 2 Adsorbents by Mixed-Linker Synthesis and Postsynthetic Modification of Zeolitic Imidazolate Frameworks
Authors:
Thompson, Joshua A.; Brunelli, Nicholas A.; Lively, Ryan P.; Johnson, J. R.; Jones, Christopher W.; Nair, Sankar
Abstract:
The incorporation of accessible amine functionality in zeolitic imidazolate frameworks (ZIFs) is used to improve the adsorption selectivity for CO 2/CH4 gas separation applications. Two synthetic approaches are described in this work to introduce functionality into the ZIF: (i) mixed-linker ZIF synthesis with 2-aminobenzimidazole as a substitution linker and (ii) postsynthetic modification of a mixed-linker ZIF with ethylenediamine. Using 2-aminobenzimidazole, a linker with a primary amine functional group, substitution of the ZIF-8 linker during synthesis allows for control over the adsorption properties while maintaining the ZIF-8 structure with up to nearly 50% substitution in the mixed-linker ZIF framework, producing a material with tunable pore size and amine functionality. Alternatively, postsynthetic modification of a mixed-linker ZIF containing an aldehyde functional group produces a ZIF material with a primary amine without detrimental loss of micropore volume by controlling the amount of functional group sites for modification. Both approaches using mixed-linker ZIFs yield new materials that show improvement in adsorption selectivity for the CO 2/CH4 gas pair over ZIF-8 and commercially available adsorbents as well as an increase in the heat of adsorption for CO2 without significant changes to the crystal structure. These results indicate that tuning the surface properties of ZIFs by either mixed-linker synthesis and/or postsynthetic modification may generate new materials with improved gas separation properties, thereby providing a new method for tailoring metal-organic frameworks. © 2013 American Chemical Society.
Citation:
Thompson JA, Brunelli NA, Lively RP, Johnson JR, Jones CW, et al. (2013) Tunable CO 2 Adsorbents by Mixed-Linker Synthesis and Postsynthetic Modification of Zeolitic Imidazolate Frameworks . The Journal of Physical Chemistry C 117: 8198–8207. Available: http://dx.doi.org/10.1021/jp312590r.
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry C
KAUST Grant Number:
KUS-Il-011-21
Issue Date:
25-Apr-2013
DOI:
10.1021/jp312590r
Type:
Article
ISSN:
1932-7447; 1932-7455
Sponsors:
This work was supported by King Abdullah University of Science and Technology under Award KUS-Il-011-21.
Appears in Collections:
Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorThompson, Joshua A.en
dc.contributor.authorBrunelli, Nicholas A.en
dc.contributor.authorLively, Ryan P.en
dc.contributor.authorJohnson, J. R.en
dc.contributor.authorJones, Christopher W.en
dc.contributor.authorNair, Sankaren
dc.date.accessioned2016-02-28T06:35:49Zen
dc.date.available2016-02-28T06:35:49Zen
dc.date.issued2013-04-25en
dc.identifier.citationThompson JA, Brunelli NA, Lively RP, Johnson JR, Jones CW, et al. (2013) Tunable CO 2 Adsorbents by Mixed-Linker Synthesis and Postsynthetic Modification of Zeolitic Imidazolate Frameworks . The Journal of Physical Chemistry C 117: 8198–8207. Available: http://dx.doi.org/10.1021/jp312590r.en
dc.identifier.issn1932-7447en
dc.identifier.issn1932-7455en
dc.identifier.doi10.1021/jp312590ren
dc.identifier.urihttp://hdl.handle.net/10754/600089en
dc.description.abstractThe incorporation of accessible amine functionality in zeolitic imidazolate frameworks (ZIFs) is used to improve the adsorption selectivity for CO 2/CH4 gas separation applications. Two synthetic approaches are described in this work to introduce functionality into the ZIF: (i) mixed-linker ZIF synthesis with 2-aminobenzimidazole as a substitution linker and (ii) postsynthetic modification of a mixed-linker ZIF with ethylenediamine. Using 2-aminobenzimidazole, a linker with a primary amine functional group, substitution of the ZIF-8 linker during synthesis allows for control over the adsorption properties while maintaining the ZIF-8 structure with up to nearly 50% substitution in the mixed-linker ZIF framework, producing a material with tunable pore size and amine functionality. Alternatively, postsynthetic modification of a mixed-linker ZIF containing an aldehyde functional group produces a ZIF material with a primary amine without detrimental loss of micropore volume by controlling the amount of functional group sites for modification. Both approaches using mixed-linker ZIFs yield new materials that show improvement in adsorption selectivity for the CO 2/CH4 gas pair over ZIF-8 and commercially available adsorbents as well as an increase in the heat of adsorption for CO2 without significant changes to the crystal structure. These results indicate that tuning the surface properties of ZIFs by either mixed-linker synthesis and/or postsynthetic modification may generate new materials with improved gas separation properties, thereby providing a new method for tailoring metal-organic frameworks. © 2013 American Chemical Society.en
dc.description.sponsorshipThis work was supported by King Abdullah University of Science and Technology under Award KUS-Il-011-21.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleTunable CO 2 Adsorbents by Mixed-Linker Synthesis and Postsynthetic Modification of Zeolitic Imidazolate Frameworksen
dc.typeArticleen
dc.identifier.journalThe Journal of Physical Chemistry Cen
dc.contributor.institutionGeorgia Institute of Technology, Atlanta, United Statesen
dc.contributor.institutionAlgenol Biofuels, , United Statesen
kaust.grant.numberKUS-Il-011-21en
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