Influence of Pore Size on Carbon Dioxide Diffusion in Two Isoreticular Metal–Organic Frameworks

Forse, Alexander C.; Colwell, Kristen A.; Gonzalez, Miguel I.; Benders, Stefan; Torres-Gavosto, Rodolfo M.; Blümich, Bernhard; Reimer, Jeffrey A.; Long, Jeffrey R.

doi:10.1021/acs.chemmater.0c00745

Title: Influence of Pore Size on Carbon Dioxide Diffusion in Two Isoreticular Metal–Organic Frameworks

Journal Article · Mon Apr 06 00:00:00 EDT 2020 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.0c00745· OSTI ID:1637550

^[1]; Colwell, Kristen A.; Gonzalez, Miguel I.; Benders, Stefan ^[2]; Torres-Gavosto, Rodolfo M.; Blümich, Bernhard ^[2];

^[3];

^[3]

Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, U.K.
Institut für Technische und Makromolekulare Chemie (ITMC), RWTH Aachen University, Worringerweg 2, D-52074 Aachen, Germany
Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States

The rapid diffusion of molecules in porous materials is critical for numerous applications including separations, energy storage, sensing, and catalysis. A common strategy for tuning guest diffusion rates is to vary the material pore size, although detailed studies that isolate the effect of changing this particular variable are lacking. Here in this paper, we begin to address this challenge by measuring the diffusion of carbon dioxide in two isoreticular metal–organic frameworks featuring channels with different diameters, Zn$$_2$$(dobdc) (dobdc$$^{4-}$$ = 2,5-dioxidobenzene-1,4-dicarboxylate) and Zn$$_2$$(dobpdc) (dobpdc$$^{4-}$$ = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate), using pulsed field gradient NMR spectroscopy. An increase in the pore diameter from 15 Å in Zn$$_2$$(dobdc) to 22 Å in Zn$$_2$$(dobpdc) is accompanied by an increase in the self-diffusion of CO$$_2$$ by a factor of 4 to 6, depending on the gas pressure. Analysis of the diffusion anisotropy in Zn$$_2$$(dobdc) reveals that the self-diffusion coefficient for motion of CO$$_2$$ along the framework channels is at least 10000 times greater than for motion between the framework channels. Our findings should aid the design of improved porous materials for a range of applications where diffusion plays a critical role in determining performance.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Philomathia Foundation; Berkeley Energy and Climate Institute

Grant/Contract Number:: SC0019992; AC02-05CH11231; AC02-06CH11357

OSTI ID:: 1637550

Alternate ID(s):: OSTI ID: 1633280

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Vol. 32 Journal Issue: 8; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 26 works

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Title: Influence of Pore Size on Carbon Dioxide Diffusion in Two Isoreticular Metal–Organic Frameworks

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