Bifunctional Zirconium Phosphate with Greigite for Electrochemical Detection and Simultaneous Removal of Heavy Metal...

Electrochemical sensing is emerging as a method of choice for the sensing and monitoring of contaminants in water. Various sensing platforms have been designed for sensing heavy metal ions and organic pollutants in water bodies. Herein, we report a new electrochemical platform that can be used for the detection of both heavy metal ions and nitro-based organic contaminants in water bodies. The electrochemical sensor uses a modified electrode based on Fe₃S₄-impregnated zirconium phosphate (ZrP) nanoparticles synthesized by a simple ultrasonication method. The ZrP@Fe₃S₄ nanoparticles were thoroughly characterized by power X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX), and ζ-potential studies. The material exhibits an excellent electrochemical performance for the detection of Pb²⁺, Hg²⁺, nitrophenol, nitroaniline, and picric acid with low limits of detection of ca. 0.93, 0.70, 0.98, 1.10, and 1.53 ppm, respectively. Since ZrP@Fe₃S₄ nanoparticles are magnetically recyclable, their adsorption capacity and recyclability have been thoroughly investigated for the uptake of Pb²⁺ and Hg²⁺ ions from contaminated water. We observed that the adsorption of Pb²⁺ and Hg²⁺ ions on ZrP@Fe₃S₄ is best described by the Langmuir isotherm and pseudo-second-order kinetic models, with adsorption capacities of 219.44 and 118.4 mg/g, respectively. Similarly, the removal efficiency of ZrP@Fe₃S₄ was found to be 91, 57.6, and 31.3% for nitrophenol, nitroaniline, and picric acid, respectively. Furthermore, the theoretical calculations using density functional theory (DFT) were carried out to find the adsorption energy, affinity, and point of adsorption, which are in line with the experimental results. DFT calculations further suggest that the incorporation of Fe₃S₄ on ZrP improves the surface charge density and promotes efficient electron transfer between the electrode and the analyte. We have shown the real-time analysis of Dal lake water as a proof of concept, and the synthesized composite exhibits good recovery and promising results for metal ion sensing. ZrP@Fe₃S₄ demonstrated an excellent cycling stability and long-term stability without noticeable degradation for 1 week.