Enhancing ion-selective polymeric membrane electrodes by instrumental control

• Interrogation by dynamic electrochemistry makes ion-selective membranes more useful.
• Applied current controls ion fluxes across the membrane to improve detection limits.
• Applied current can effect localized titration with non-redox active ionic species.
• Thin-layer coulometry at ion-selective membranes promises calibration-free sensors.
• Stripping ion transfer voltammetry on thin solid-state film lowers detection limits.

This review aims to highlight a recent important direction to place ion-selective electrodes based on polymeric sensing materials under dynamic electrochemistry control. This allows one to design sensors with a range of improved characteristics. This review also showcases developments to achieve calibration-free ion-sensing strategies by using thin layer coulometry at ion-selective membranes. Finally, strategies to fabricate electrochemically-addressable ion-selective thin membrane layers are discussed, especially in view of realizing stripping ion-transfer voltammetric sensors.