Engineering Li/Na selectivity in 12-Crown-4–functionalized polymer membranes

Warnock, Samuel J.; Sujanani, Rahul; Zofchak, Everett S.; Zhao, Shou; Dilenschneider, Theodore J.; Hanson, Kalin G.; Mukherjee, Sanjoy; Ganesan, Venkat; Freeman, Benny D.; Abu-Omar, Mahdi M.; Bates, Christopher M.

doi:10.1073/pnas.2022197118

Title: Engineering Li/Na selectivity in 12-Crown-4–functionalized polymer membranes

Journal Article · 07 September 2021 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.2022197118 · OSTI ID:1819229

Warnock, Samuel J. ^[1];

^[2]; Zofchak, Everett S. ^[3];

^[1]; Dilenschneider, Theodore J. ^[3]; Hanson, Kalin G. ^[1];

^[1]; Ganesan, Venkat ^[3]; Freeman, Benny D. ^[3];

^[1];

^[1]

Univ. of California, Santa Barbara, CA (United States)
Univ. of Texas at Austin, TX (United States)
Univ. of Texas at Austin, TX (United States)

Lithium is widely used in contemporary energy applications, but its isolation from natural reserves is plagued by time-consuming and costly processes. While polymer membranes could, in principle, circumvent these challenges by efficiently extracting lithium from aqueous solutions, they usually exhibit poor ion-specific selectivity. Toward this end, we have incorporated host–guest interactions into a tunable polynorbornene network by copolymerizing 1) 12-crown-4 ligands to impart ion selectivity, 2) poly(ethylene oxide) side chains to control water content, and 3) a crosslinker to form robust solids at room temperature. Single salt transport measurements indicate these materials exhibit unprecedented reverse permeability selectivity (~2.3) for LiCl over NaCl—the highest documented to date for a dense, water-swollen polymer. As demonstrated by molecular dynamics simulations, this behavior originates from the ability of 12-crown-4 to bind Na⁺ ions more strongly than Li⁺ in an aqueous environment, which reduces Na⁺ mobility (relative to Li⁺) and offsets the increase in Na⁺ solubility due to binding with crown ethers. Under mixed salt conditions, 12-crown-4 functionalized membranes showed identical solubility selectivity relative to single salt conditions; however, the permeability and diffusivity selectivity of LiCl over NaCl decreased, presumably due to flux coupling. These results reveal insights for designing advanced membranes with solute-specific selectivity by utilizing host–guest interactions.

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Research Organization:: The University of Texas at Austin, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE

Grant/Contract Number:: SC0019272

OSTI ID:: 1819229

Alternate ID(s):: OSTI ID: 1878224

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 118, Issue 37; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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