A Solid-Contact Reference Electrode Based on Silver/Silver Organic Insoluble Salt for Potentiometric Ion Sensing

[Image: see text] Solid-contact ion-selective electrodes are a type of ion measurement devices that have been focused in wearable biotechnology based on the features of miniaturization and integration. However, the solid-contact reference electrodes (SC-REs) remain relatively less focused compared with numerous working (or indicator) electrodes. Most SC-REs in wearable sensors rely on Ag/AgCl reference electrodes with solid electrolytes, for example, the hydrophilic electrolyte salts in polymer matrix, but face the risk of electrolyte leakage. Herein, we report a type of SC-REs based on the silver/silver tetraphenylborate (Ag/AgTPB) organic insoluble electrode. The SC-RE consists of a Ag substrate, a solid contact (AgTPB), and a plasticized poly(vinyl chloride) (PVC) membrane containing the hydrophobic organic salt of tetrabutylammonium tetraphenylborate (TBATPB). The potentiometric measurements demonstrated that the SC-RE of Ag/AgTPB/PVC-TBATPB showed a reproducible standard potential in various electrolytes and disclosed high long-term stability. This SC-RE was further fabricated on a flexible substrate and integrated into all-solid-state wearable potentiometric ion sensor for sweat Cl(–) monitoring.