Poly(3,−polyethylene glycol (PEDOT:PEG) is a conductive material adopted in bioelectronics due to its biocompatibility and stability. While PEDOT has established its utility in cationic solid-contact ion-selective electrodes (sc-ISEs), its anionic counterpart remains less explored. Herein, we report the first example of PEDOT:PEG as a solution-printable solid-contact for all-solid-state nitrate-selective electrodes and a simple ion exchange treatment which can significantly enhance nitrate selectivity. Electrochemical impedance spectroscopy revealed that the sc-ISEs with perchlorate (ClO 4 − )-doped PEDOT:PEG suffered a large overall resistance. Removal of the ClO 4 − dopant via ion exchange reduced the resistance, resulting in significant improvement in sc-ISE performance. The optimal sc-ISE exhibited near-Nernstian response (−55.8 mV/ decade) across a wide dynamic range (0.1 M to 1.12 μM) and excellent Hofmeister selectivity, which was maintained after prolonged continuous usage. This simple drop-cast and ion-exchange protocol is amenable to the scalable preparation of flexible anion sc-ISEs.
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