Simultaneous voltammetric determination of cadmium(II), lead(II), mercury(II), zinc(II), and copper(II) using a glassy carbon electrode modified with magnetite (Fe₃O₄) nanoparticles and fluorinated multiwalled carbon nanotubes

A method is described for the simultaneous voltammetric determination of the heavy metal ions cadmium(II), lead(II), mercury(II), zinc(II), and copper(II) using a glassy carbon electrode (GCE) modified with magnetite (Fe₃O₄) nanoparticles and fluorinated multiwalled carbon nanotubes (Fe₃O₄/F-MWCNTs). The Fe₃O₄/F-MWCNT composite was synthesized by a hydrothermal method and characterized by X-ray photoelectron spectroscopy, X-ray diffraction, transmission electron microscopy, scanning electron microscopy, elemental mapping, electrochemical impedance spectroscopy, and square wave stripping voltammetry. Under the optimum conditions, the electrode displays excellent response to the ions. Figures of merit for Cd(II), Pb(II), Hg(II), Zn(II), and Cu(II), respectively, include (a) high electrochemical sensitivity (29.88, 43.50, 120.86, 47.34 and 90.31 (μA μM^-1 cm^-2), (b) well separated peaks (at -0.70, -0.53, +0.37, -1.11 and + 0.01 V vs. Ag/AgCl); (c) low limits of detection (0.014, 0.0084, 0.0039, 0.012, and 0.0053 μM); and (d) wide linear ranges (0.048-30.0, 0.028-30.0, 0.013-32.5, 0.039-32.5, and 0.017-31.5 μM). The modified GCE displays satisfying selectivity in the presence of potentially interfering other metal ions, stability for 30 days, and reproducibility of electrodes (with a relative standard deviation between 1.2 and 4.8% for n = 6). The modified GCE was applied to the determination of several heavy metal ions in (spiked) water and rice samples, and the results agreed well with data obtained by atomic fluorescence spectrometry or inductively coupled plasma-mass spectrometry. The dramatic performance probably result from the semi-ionic C-F bond on F-MWCNTs surface with a strong negative charge, the good electrical conductivity of the F-MWCNTs and Fe₃O₄, the synergistic interaction between Fe₃O₄ and F-MWCNTs, and the nafion conductive membrane improving the stability of the modified layer and enhanced cation adsorption. Graphical abstract An environmentally-friendly, low-cost, high-throughput Fe₃O₄/fluorinated multi-walled carbon nanotube composite (Fe₃O₄/F-MWCNTs) modified glassy carbon electrode is described. It was applied to simultaneous electrochemical determination of Cd(II), Pb(II), Hg(II), Zn(II), and Cu(II) by square wave stripping voltammetry.