pH Sensing Properties of Co₃O₄-RuO₂-Based Electrodes and Their Application in Baltic Sea Water Quality Monitoring

Water is critical for the sustenance of life and pH is an important parameter in monitoring its quality. Solid-state pH sensors provide a worthy alternative to glass-based electrodes due to many advantages such as low cost, longer shelf life, simpler manufacturing, easier operation, miniaturization, and integration into electronic systems. Cobalt oxides are relatively cheaper and more abundantly available than ruthenium oxide. This work aims to reduce the environmental impact of screen-printed pH sensors by mixing Co₃O₄ and RuO₂ in five molar proportions (30%, 40%, 50%, 60%, and 70%) and investigating the influence of oxide proportions on the pH-sensing properties of the resulting composition using potentiometric characterization, scanning electron microscopy, X-ray diffraction, surface profilometry, and electron dispersive spectroscopy. Although all the developed compositions showed super- or near-Nernstian sensitivity with good linearity, the sensors based on 50 mol% Co₃O₄-50 mol% RuO₂ were the best due to superior sensitivity, selectivity, and stability. Fabricated sensors were applied in real-life environmental, municipal, and commercial water samples, including those from various depths in the Baltic Sea, and were found to be accurate in comparison to a glass electrode.