Selective separation of monovalent anions by PPy/pTS membrane electrodes in redox transistor electrodialysis

Selective separation of nitrate over chloride is crucial for eutrophication mitigation and nitrogen resource recovery but remains a challenge due to their similar ionic radius and the same valence. Herein, a polypyrrole membrane electrode (PME) was fabricated by polymerization of pyrrole (Py) and p-toluenesulfonate (pTS), which was used as a working electrode in redox transistor electrodialysis. The anions in the source solution were first incorporated into the PME at reduction potentials and then released to receiving solution at oxidation potentials. Pulse widths and potentials were optimized to maximize the ion separation performance of PME, resulting in the improvement of NO₃^-/Cl^- separation factor up to 6.93. The ion distributions in various depths of PME indicated that both NO₃^- and Cl^- were incorporated into PME at negative potentials. Then, NO₃^- was preferentially released from PME at positive potentials, but most Cl^- was retained. This was ascribed to the high binding energy between Cl^- and PPy/pTS structure, which was 51.4% higher than that between NO₃^- and PPy/pTS structure. Therefore, the higher transport rate of NO₃^- in comparison with Cl^- was achieved, leading to a high NO₃^- selectivity over Cl^-. This work provides a promising avenue for the selective separation of nitrate over chloride, which may contribute to nitrogen resource recycling and reuse.