Thermo-Electro-Responsive Redox-Copolymers for Amplified Solvation, Morphological Control, and Tunable Ion Interactions

Chen, Raylin; Wang, Hanyu; Doucet, Mathieu; Browning, James F.; Su, Xiao

doi:10.1021/jacsau.3c00486

Title: Thermo-Electro-Responsive Redox-Copolymers for Amplified Solvation, Morphological Control, and Tunable Ion Interactions

Journal Article · 21 November 2023 · JACS Au

DOI: https://doi.org/10.1021/jacsau.3c00486 · OSTI ID:2217399

Chen, Raylin ^[1]; Wang, Hanyu ^[2];

^[3]; Browning, James F. ^[3];

^[1]

Univ. of Illinois at Urbana-Champaign, IL (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Electro-responsive metallopolymers can possess highly specific and tunable ion interactions, and have been explored extensively as electrode materials for ion-selective separations. However, there remains a limited understanding of the role of solvation and polymer–solvent interactions in ion binding and selectivity. The elucidation of ion–solvent–polymer interactions, in combination with the rational design of tailored copolymers, can lead to new pathways for modulating ion selectivity and morphology. Here, we present thermo-electrochemical-responsive copolymer electrodes of N-isopropylacrylamide (NIPAM) and ferrocenylpropyl methacrylamide (FPMAm) with tunable polymer–solvent interactions through copolymer ratio, temperature, and electrochemical potential. As compared to the homopolymer PFPMAm, the P(NIPAM_0.9-co-FPMAm_0.1) copolymer ingressed 2 orders of magnitude more water molecules per doping ion when electrochemically oxidized, as measured by electrochemical quartz crystal microbalance. P(NIPAM_0.9-co-FPMAm_0.1) exhibited a unique thermo-electrochemically reversible response and swelled up to 83% after electrochemical oxidation, then deswelled below its original size upon raising the temperature from 20 to 40 °C, as measured through spectroscopic ellipsometry. Reduced P(NIPAM_0.9-co-FPMAm_0.1) had an inhomogeneous depth profile, with layers of low solvation. In contrast, oxidized P(NIPAM_0.9-co-FPMAm_0.1) displayed a more uniform and highly solvated depth profile, as measured through neutron reflectometry. P(NIPAM_0.9-co-FPMAm_0.1) and PFPMAm showed almost a fivefold difference in selectivity for target ions, evidence that polymer hydrophilicity plays a key role in determining ion partitioning between solvent and the polymer interface. Our work points to new macromolecular engineering strategies for tuning ion selectivity in stimuli-responsive materials.

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Research Organization:: Univ. of Illinois at Urbana-Champaign, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE

Grant/Contract Number:: SC0021409; AC05-00OR22725

OSTI ID:: 2217399

Alternate ID(s):: OSTI ID: 2263298; OSTI ID: 2281112

Journal Information:: JACS Au, Vol. 3, Issue 12; ISSN 2691-3704

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
stimuli-responsive polymers
redox-electrochemistry
solvation
electrochemical separations

Title: Thermo-Electro-Responsive Redox-Copolymers for Amplified Solvation, Morphological Control, and Tunable Ion Interactions

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