Carbon-Based Transducers for Solid-Contact Calcium Ion-Selective Electrodes: Mesopore and Nitrogen-Doping Effects

Solid-contact ion-selective electrodes (SC-ISEs) exhibit great potential in the detection of routine and portable ions which rely on solid-contact (SC) materials for the transduction of ions to electron signals. Carbon-based materials are state-of-the-art SC transducers due to their high electrical double-layer (EDL) capacitance and hydrophobicity. However, researchers have long searched for ways to enhance the interfacial capacitance in order to improve the potential stability. Herein, three representative carbon-based SC materials including nitrogen-doped mesoporous carbon (NMC), reduced graphene oxide (RGO), and carbon nanotubes (CNT) were compared. The results disclose that the NMC has the highest EDL capacitance owing to its mesopore structure and N-doping while maintaining high hydrophobicity so that no obvious water-layer effect was observed. The Ca²⁺-SC-ISEs based on the SC of NMC exhibited high potential stability compared with RGO and CNT. This work offers a guideline for the development of carbon-material-based SC-ISEs through mesoporous and N-doping engineering to improve the interfacial capacitance. The developed NMC-based solid-contact Ca²⁺-SC-ISE exhibited a Nernstian slope of 26.3 ± 3.1 mV dec^-1 ranging from 10 μM to 0.1 M with a detection limit of 3.2 μM. Finally, a practical application using NMC-based SC-ISEs was demonstrated through Ca²⁺ ion analysis in mineral water and soil leaching solutions.