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Flexible ZIFs: probing guest-induced flexibility with CO2, N2 and Ar adsorption

Flexible ZIFs: probing guest-induced flexibility with CO2, N2 and Ar adsorption
Flexible ZIFs: probing guest-induced flexibility with CO2, N2 and Ar adsorption

BACKGROUND: The effect of framework topology on the guest-induced flexibility of several crystalline zeolitic imidazolate frameworks (ZIF-7, ZIF-9, ZIF-11 and ZIF-12) was investigated via analysis of experimental nitrogen (N2), carbon dioxide (CO2) and argon (Ar) isotherms at 77 K (N2 and Ar) and 273 K (CO2) for gas pressures up to 0.13 MPa. RESULTS: The experimental isotherms of these frameworks were analysed in order to investigate their structural flexibility using gases with kinetic diameters equal to or larger than the diameters of their static pore apertures. The results of gas sorption measurements indicate guest-induced phase changes for ZIF-7 and ZIF-9 (SOD topologies). ZIF-12 (RHO topology) also shows uptake for gases, despite its pore-limiting diameter being smaller than the kinetic diameters of the adsorbed molecules.

CONCLUSIONS: This work highlights the ability of ZIFs with different framework topologies to change their structure and increase their pore aperture upon interaction with certain gases. These findings are key in the development of more selective ZIF-based materials for important industrial applications including low-energy gas separations, catalytic nanoreactors and sensor technology.

breathing structure, flexibility, gas adsorption, MOF, nanomaterials, ZIF
0268-2575
1-6
Noguera-Díaz, Antonio
bea37c4d-bae4-4946-98b4-9a3c367d94e4
Villarroel-Rocha, Jhonny
bae190ab-ab76-4720-a3d1-8eedf242ee41
Ting, Valeska P.
d4381878-2aad-4a3f-a7cc-021a7f7075eb
Bimbo, Nuno
53d9fc24-e2c1-4e2d-8d75-8dc640d8adda
Sapag, Karim
64660493-bf67-4a1f-9b05-ee18b2d27999
Mays, Timothy J.
d02351c7-1d8f-4a9e-8d16-675c1f7b3635
Noguera-Díaz, Antonio
bea37c4d-bae4-4946-98b4-9a3c367d94e4
Villarroel-Rocha, Jhonny
bae190ab-ab76-4720-a3d1-8eedf242ee41
Ting, Valeska P.
d4381878-2aad-4a3f-a7cc-021a7f7075eb
Bimbo, Nuno
53d9fc24-e2c1-4e2d-8d75-8dc640d8adda
Sapag, Karim
64660493-bf67-4a1f-9b05-ee18b2d27999
Mays, Timothy J.
d02351c7-1d8f-4a9e-8d16-675c1f7b3635

Noguera-Díaz, Antonio, Villarroel-Rocha, Jhonny, Ting, Valeska P., Bimbo, Nuno, Sapag, Karim and Mays, Timothy J. (2019) Flexible ZIFs: probing guest-induced flexibility with CO2, N2 and Ar adsorption. Journal of Chemical Technology and Biotechnology, 1-6. (doi:10.1002/jctb.5947).

Record type: Article

Abstract

BACKGROUND: The effect of framework topology on the guest-induced flexibility of several crystalline zeolitic imidazolate frameworks (ZIF-7, ZIF-9, ZIF-11 and ZIF-12) was investigated via analysis of experimental nitrogen (N2), carbon dioxide (CO2) and argon (Ar) isotherms at 77 K (N2 and Ar) and 273 K (CO2) for gas pressures up to 0.13 MPa. RESULTS: The experimental isotherms of these frameworks were analysed in order to investigate their structural flexibility using gases with kinetic diameters equal to or larger than the diameters of their static pore apertures. The results of gas sorption measurements indicate guest-induced phase changes for ZIF-7 and ZIF-9 (SOD topologies). ZIF-12 (RHO topology) also shows uptake for gases, despite its pore-limiting diameter being smaller than the kinetic diameters of the adsorbed molecules.

CONCLUSIONS: This work highlights the ability of ZIFs with different framework topologies to change their structure and increase their pore aperture upon interaction with certain gases. These findings are key in the development of more selective ZIF-based materials for important industrial applications including low-energy gas separations, catalytic nanoreactors and sensor technology.

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Noguera Diaz et al 2019 Journal of Chemical Technology & Biotechnology - Version of Record
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Accepted/In Press date: 22 January 2019
e-pub ahead of print date: 28 January 2019
Keywords: breathing structure, flexibility, gas adsorption, MOF, nanomaterials, ZIF

Identifiers

Local EPrints ID: 435211
URI: http://eprints.soton.ac.uk/id/eprint/435211
ISSN: 0268-2575
PURE UUID: 419cd4aa-42fb-4206-9226-8ef2d6a0dc88
ORCID for Nuno Bimbo: ORCID iD orcid.org/0000-0001-8740-8284

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Date deposited: 25 Oct 2019 16:30
Last modified: 07 Oct 2020 02:26

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Contributors

Author: Antonio Noguera-Díaz
Author: Jhonny Villarroel-Rocha
Author: Valeska P. Ting
Author: Nuno Bimbo ORCID iD
Author: Karim Sapag
Author: Timothy J. Mays

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