Robust Potentiometric Microelectrodes for In Situ Sensing of Ion Fluxes with High Sensitivity

Simple, reproducible, and reliable preparation of robust potentiometric microelectrodes is both challenging and of great importance for noninvasive real-time ion sensing. Herein, we report a simple strategy for the large-scale synthesis of nickel cobalt sulfide (NiCo₂S₄) nanowire arrays grown on carbon fibers for potentiometric microelectrodes. The highly uniform NiCo₂S₄ nanowire array serving as a transduction layer can provide a high capillary pressure and viscous resistance for loading the ion sensing membrane and exhibit a large redox capacitance for improving the stability. An all-solid-state lead-selective microelectrode, which presents a detection limit of 2.5 × 10^-8 M in the simulated soil solution, was designed as a model for noninvasive, in situ, and real-time detection of ion fluxes near the rice root surface. Importantly, the microsensor enables sensitive detection of trace-level ion-fluxes. This work provides a simple yet general strategy for designing potentiometric microelectrodes.