An Asymmetric Electrochemical System with Complementary Tunability in Hydrophobicity for Selective Separations of Organics

[Image: see text] Conducting polymers modified with redox-active moieties or amphiphilic surfactants are promising adsorbent materials for the separation of neutral organic species from water. We develop an asymmetric system combining a polyvinylferrocene–polypyrrole hybrid (PVF–PPy) and an amphiphilic surfactant dioctyl sulfosuccinate (AOT)-doped polypyrrole (PPy(AOT)) that have complementary hydrophobicity tunability in response to electrochemical modulations. Both materials are hydrophobic in their respective neutral states, exhibiting high affinities toward organics. Upon application of a mild potential to oxidize PVF–PPy and reduce PPy(AOT), these polymers can be simultaneously rendered hydrophilic, thereby driving desorption of organics and regeneration of the materials. The asymmetric system can be used in a cyclic fashion, through repeated electrical shorting of the two electrodes to program the capture of organics from a large volume of feed solution, and application of a potential (above 0.9 V) to stimulate the release of the adsorbed organics into a small volume of desorption solution. The asymmetric configuration has multiple benefits, including suppression of water parasitic reactions, high energetic efficiency, and selectivity for target organic species. Therefore, the electrode system has the potential to reduce the energy consumption in the mitigation of organic contaminants over conventional methods, with the additional ability to recover valuable organic products, opening up new possibilities for addressing the water–energy nexus.