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.