Modified carbon paste ion selective electrode for determining Cr(iii) ions in aqueous solutions and some real samples using tetragonal zirconia nanoparticles

Abstract

Tetragonal zirconia (t-ZrO₂) nanoparticles (ionophore) are used in newly designed and improved ion selective electrodes for chromium ion detection as an alternative, low-cost, high-precision, and selectivity method. Tetragonal zirconia nanoparticles were synthesized using a modified co-precipitation technique and calcined at 1000 °C for an hour. The phase composition, surface area, microstructure, pore size and particle size of synthesized t-ZrO₂ nanoparticles were examined using the X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), transmission electron microscope (TEM) and scanning electron microscopy (SEM) attached with an EDAX unit, respectively. Results from XRD showed that the t-zirconia was synthesized and have nanocrystallites size about 20.2 nm. The nano size of t-ZrO₂ was confirmed by the SEM and TEM (the particle size between 26.48 and 40.4 nm), the mesoporous character (average pore size about 4.868 nm) and large surface area (76.2802 m² g⁻¹) was confirmed by BET analysis. The paste composition with 67.3 : 30.5 : 2.7 (wt%) graphite, t-ZrO₂, and TCP, respectively, exhibited the best results. With a detection limit of 1.0 × 10⁻⁸ mol L⁻¹, the electrode displayed a good Nernstian slope of 19.50 ± 0.10 mV decade⁻¹ over the concentration range from 1.0 × 10⁻² to 1.0 × 10⁻⁸ mol L⁻¹ of Cr(III) ions. The built-in sensor displayed a quick response time (7 s), was highly thermally stable in the range of 10 to 60 °C without departing from Nernstian behaviour and could be used for about 60 days in the pH range of 2.0 to 6.0. The electrode demonstrated excellent selectivity for the Cr(III) ion towards a variety of metal ions. For chromium ion determination, numerous spiked real samples, including honey, water, tea, coffee, milk, cheese, and cosmetics, were used. Validation methods were used, and the results showed that there is no significant difference between the two methods (ICP and ISE) at a 95% confidence level. In several real water samples, the estimated limits of detection, limits of quantification, percent recovery, standard deviation, and relative standard deviation showed the effectiveness of the proposed electrode in the potentiometric detection of Cr(III) ions.