An Oxidizable Anion‐Excluding Polymer‐Overlayer for Oxygen Electrodes

Here we describe an anion excluding ion‐permeable membrane, which we evaluate on an O₂‐electroreducing cathode poised at a strongly oxidizing potential, near the reversible potential of the O₂/H₂O half cell. The bioelectrocatalyst of the O₂ cathode consists of the cross‐linked electrostatic adduct of a polycationic redox hydrogel and bilirubin oxidase (BOD), a polyanion at neutral at pH 7.3. If an uncured Nafion dispersion is applied on this bioelectrocatalyst, the polyanionic Nafion displaces the BOD in the electrostatic adduct, de‐wiring the BOD. We show here that insertion of a polycationic poly(acrylamide‐co‐vinylimidazole) (PAA‐PVI) between the bioelectrocatalyst and the Nafion prevents the dewiring of BOD. The resulting bi‐layer membrane effectively excludes the urate, thiocyanate and NADH anions.