Anion Exchange Membranes with Dynamic Redox-Responsive Properties.

Abstract

Redox-responsive anion exchange membranes were developed using photoinitiated free-radical polymerization and reversible oxidation and reduction of viologen. The membranes were formulated using poly(ethylene glycol diacrylate) and diurethane dimethacrylate oligomers, dipentaerythritol penta-/hexa-acrylate cross-linker, photoinitiators, and 4-vinylbenzyl chloride as precursors for functionalization. In the membrane, 4,4'-bipyridine reacted with the 4-vinylbenzyl chloride residues, and subsequently, unreacted amines were methylated with iodomethane to obtain viologen as both the ion carrier and redox-responsive group. Upon oxidation, viologen supports two cations, where the reduced form only contains one cation. Thus, the redox responsiveness changed the membrane ionicity by a factor of 2. The area-specific resistance of the membranes in the oxidized, +2, state was lower than in the reduced, +1, state. The resistance increased between 40.6 ± 0.1 and 111.6 ± 0.1%, depending on membrane thickness, with the most significant increment being a resistance change from 4.88 × 10-4 Ω m2 in the oxidized state to 1.03 × 10-3 Ω m2 in the reduced state. Membrane permselectivity in the reduced, +1, state was between 15.9 ± 0.1 and 26.5 ± 0.01% lower than in the oxidized, +2, state, with no change in water uptake, spanning an average of 0.87 ± 0.02 in the oxidized state to an average of 0.7 ± 0.01 in the reduced state. Upon reduction, membrane ion-exchange capacity decreases, increasing ionic resistance and decreasing membrane permselectivity due to a reduction in fixed charge concentration without a measurable change in water uptake. This trend is not generally observed for ion-exchange membranes and explains that the changes in transport properties result from changes in ionicity, not water uptake or domain size. The reversibility and stability of the stimuli responsiveness were confirmed by the absence of transport property changes after redox cycling.