TY - JOUR
T1 - Thermo-Electro-Responsive Redox-Copolymers for Amplified Solvation, Morphological Control, and Tunable Ion Interactions
AU - Chen, Raylin
AU - Wang, Hanyu
AU - Doucet, Mathieu
AU - Browning, James F.
AU - Su, Xiao
N1 - Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.
PY - 2023/12/25
Y1 - 2023/12/25
N2 - 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(NIPAM0.9-co-FPMAm0.1) copolymer ingressed 2 orders of magnitude more water molecules per doping ion when electrochemically oxidized, as measured by electrochemical quartz crystal microbalance. P(NIPAM0.9-co-FPMAm0.1) 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(NIPAM0.9-co-FPMAm0.1) had an inhomogeneous depth profile, with layers of low solvation. In contrast, oxidized P(NIPAM0.9-co-FPMAm0.1) displayed a more uniform and highly solvated depth profile, as measured through neutron reflectometry. P(NIPAM0.9-co-FPMAm0.1) 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.
AB - 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(NIPAM0.9-co-FPMAm0.1) copolymer ingressed 2 orders of magnitude more water molecules per doping ion when electrochemically oxidized, as measured by electrochemical quartz crystal microbalance. P(NIPAM0.9-co-FPMAm0.1) 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(NIPAM0.9-co-FPMAm0.1) had an inhomogeneous depth profile, with layers of low solvation. In contrast, oxidized P(NIPAM0.9-co-FPMAm0.1) displayed a more uniform and highly solvated depth profile, as measured through neutron reflectometry. P(NIPAM0.9-co-FPMAm0.1) 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.
KW - electrochemical separations
KW - redox-electrochemistry
KW - solvation
KW - stimuli-responsive polymers
UR - http://www.scopus.com/inward/record.url?scp=85179153483&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85179153483&partnerID=8YFLogxK
U2 - 10.1021/jacsau.3c00486
DO - 10.1021/jacsau.3c00486
M3 - Article
C2 - 38155652
AN - SCOPUS:85179153483
SN - 2691-3704
VL - 3
SP - 3333
EP - 3344
JO - JACS Au
JF - JACS Au
IS - 12
ER -