All-Solid-State Polymeric Membrane Ion-Selective Electrodes Based on NiCo₂S₄ as a Solid Contact

The performance criteria for the design of all-solid-state ion-selective electrodes mainly include high electrode-to-electrode reproducibility and a low potential drift. Here, we introduce nickel cobalt sulfide (NiCo₂S₄) as a solid contact for ion-to-electron transduction based on multiple redox couples. NiCo₂S₄ materials with different morphologies can be prepared through a facile hydrothermal/solvothermal method. A NiCo₂S₄-based solid-contact Ca²⁺-ISE has been developed, which exhibits a Nernstian slope of 27.5 ± 0.2 mV/dec in the activity range from 1.0 × 10^-6 to 2.9 × 10^-2 M with a detection limit of 5.0 × 10^-7 M. A variation of the standard potential E° for eight individual solid-contact electrodes can be obtained as low as 0.35 mV. Due to the synergistic effect of cobalt and nickel ions in the ternary sulfide, an excellent redox capacitance (565 μF) of the buried solid contact coated with the ion-selective membrane can be achieved and is much larger than those obtained from other redox solid-contact materials reported so far, thus yielding a high potential stability of 2.2 ± 0.4 μV/h. In addition, the NiCo₂S₄-based solid-contact Ca²⁺-ISE shows a reduced water layer at the sensing membrane/NiCo₂S₄ interface and provides an excellent resistance to the interferences from light, O₂, and CO₂. The proposed strategy utilizing NiCo₂S₄ as a solid contact is a promising alternative for the fabrication of calibration-free ASS-ISEs.