Solid-Contact Potentiometric Anion Sensing Based on Classic Silver/Silver Insoluble Salts Electrodes without Ion-Selective Membrane

Current solid potentiometric ion sensors mostly rely on polymeric-membrane-based, solid-contact, ion-selective electrodes (SC-ISEs). However, anion sensing has been a challenge with respect to cations due to the rareness of anion ionophores. Classic metal/metal insoluble salt electrodes (such as Ag/AgCl) without an ion-selective membrane (ISM) offer an alternative. In this work, we first compared the two types of SC-ISEs of Cl(−) with/without the ISM. It is found that the ISM-free Ag/AgCl electrode discloses a comparable selectivity regarding organic chloride ionophores. Additionally, the electrode exhibits better comprehensive performances (stability, reproducibility, and anti-interference ability) than the ISM-based SC-ISE. In addition to Cl(−), other Ag/AgX electrodes also work toward single and multi-valent anions sensing. Finally, a flexible Cl(−) sensor was fabricated for on-body monitoring the concentration of sweat Cl(−) to illustrate a proof-of-concept application in wearable anion sensors. This work re-emphasizes the ISM-free SC-ISEs for solid anion sensing.