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Anion Exchange Membranes with Dynamic Redox-Responsive Properties.

Clara Capparelli, Carlos R Fernandez Pulido, Raymond Lopez-Hallman

  • 1Department of Chemical Engineering , University of Virginia , Charlottesville , Virginia 22904 , United States.

ACS Applied Materials & Interfaces
|July 5, 2019
PubMed
Summary

New redox-responsive anion exchange membranes were created using viologen, altering ionicity by a factor of two. These membranes show tunable resistance and permselectivity, crucial for advanced separation technologies.

Keywords:
anion exchange membranesredox-responsive membranesstimuli-responsive membranestransport propertiesviologen

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Area of Science:

  • Materials Science
  • Polymer Chemistry
  • Electrochemistry

Background:

  • Development of stimuli-responsive materials is critical for advanced separation and energy applications.
  • Ion-exchange membranes (IEMs) are essential components in electrochemical devices, but their transport properties are often static.
  • Designing IEMs with tunable properties offers new possibilities for controlling ion transport.

Purpose of the Study:

  • To synthesize and characterize novel redox-responsive anion exchange membranes (IEMs).
  • To investigate the effect of viologen's redox state on membrane ionicity, resistance, and permselectivity.
  • To evaluate the reversibility and stability of the developed redox-responsive IEMs.

Main Methods:

  • Photoinitiated free-radical polymerization was employed to create the membrane matrix using poly(ethylene glycol diacrylate) and diurethane dimethacrylate.
  • Viologen moieties were incorporated into the membrane via functionalization with 4-vinylbenzyl chloride and subsequent reaction with 4,4'-bipyridine and methylation.
  • Membrane properties, including area-specific resistance, permselectivity, and water uptake, were measured in both oxidized (+2) and reduced (+1) viologen states.

Main Results:

  • The redox-responsive IEMs exhibited a tunable ionicity, changing by a factor of two between oxidized and reduced states.
  • Area-specific resistance increased significantly upon reduction (e.g., from 4.88 × 10-4 Ω m2 to 1.03 × 10-3 Ω m2).
  • Permselectivity decreased in the reduced state (15.9–26.5% lower) without significant changes in water uptake, indicating ionicity-driven transport changes.

Conclusions:

  • The developed viologen-based IEMs demonstrate effective redox-responsive control over ion transport properties.
  • Changes in ion-exchange capacity and fixed charge concentration, rather than water uptake or domain size, govern the observed transport variations.
  • The reversibility and stability of the redox-responsive behavior were confirmed, highlighting their potential for dynamic separation processes.