In this work, different electrodes were employed for the determination of Cr(VI) by the cathodic square‑wave voltammetry (SWV) technique and the square-wave adsorptive stripping voltammetry (SWAdSV) technique in combination with diethylenetriaminepentaacetic acid. Using SWV, a comparison of the analytical performance of the bare glassy carbon electrode (GCE), ex situ electrodes (antimony-film—SbFE, copper-film—CuFE, and bismuth-film—BiFE), and the GCE modified with a new magnetic nanocomposite (MNC) material was performed. First, the MNC material was synthesized, i.e., MNPs@SiO2@Lys, where MNPs stands for magnetic maghemite nanoparticles, coated with a thin amorphous silica (SiO2) layer, which was additionally functionalized with derived lysine (Lys). The crystal structure of the prepared MNCs was confirmed by X-ray powder diffraction (XRD), while the morphology and nano-size of the MNCs were investigated by field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM), where TEM was additionally used to observe the MNP core and silica layer thickness. The presence of functional groups of the MNCs was investigated by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and surface analysis was performed by X-ray photoelectron spectroscopy (XPS). The hydrophilicity of the modified electrodes was also tested by static contact angle measurements. Then, MNPs@SiO2@Lys was applied onto the electrodes and used with the SWV and SWAdSV techniques. All electrodes tested with the SWV technique were effective for Cr(VI) trace determination. On the other hand, the SWAdSV technique was required for ultra-trace determination of Cr(VI). Using the SWAdSV technique, it was shown that a combination of ex situ BiFE with the deposited MNPs@SiO2@Lys resulted in excellent analytical performance (LOQ = 0.1 µg/L, a linear concentration range of 0.2–2.0 µg/L, significantly higher sensitivity compared to the SWV technique, an RSD representing reproducibility of 9.0%, and an average recovery of 98.5%). The applicability of the latter system was also demonstrated for the analysis of a real sample.
A Magnetic Nanocomposite Modifier for Improved Ultrasensitive Detection of Hexavalent Chromium in Water Samples