Nafion®/2,2′-bipyridyl-modified bismuth film electrode for anodic stripping voltammetry

This paper describes the fabrication, characterisation and the application of a Nafion/2,2'-bipyridyl/bismuth composite film-coated glassy carbon electrode (NC(Bpy)BiFE) for the anodic stripping voltammetric determination of trace metal ions (Zn2+, Cd2+ and Pb2+). The NC(Bpy)BiFE electrode is prepared by first applying a 2.5 mm(3) drop of a coating solution containing 0.5 wt% Nafion and 0.1% (w/v) 2,2'-bipyridil (Bpy) onto the surface of a glassy carbon electrode, while the Bi film was plated in situ simultaneously with the target metal ions at -1.4V. The main advantage of the polymer coated bismuth film electrode is that the sensitivity of the stripping responses is increased considerably due to the incorporation of the neutral chelating agent of 2,2'-bipyridyl (Bpy) in the Nafion film, while the Nafion coating improved the mechanical stability of the bismuth film and its resistance to the interference of surfactants. The key experimental parameters relevant to both the electrode fabrication and the voltammetric measurement were optimized on the basis of the stripping signals. With a 2 min deposition time in the presence of oxygen, linear calibration curves were obtained in a wide concentration range (about 2-0.001 mu M) with detection limits of 8.6 nM (0.56 mu g dm(-3)) for Zn2+, 1.1 nM (0.12 mu g dm(-3)) for Cd2+ and 0.37 nM (0.077 mu g dm(-3)) for Pb2+. For nine successive preconcentration/determination/electrode renewal experiments the standard deviations were between 3 and 5% at 1.2 mu M for zinc and 0.3-0.3 mu M concentration level for lead and cadmium, respectively, and the method exhibited excellent selectivity in the presence of the excess of several potential interfering metal ions. The analytical utility of the stripping voltammetric method elaborated was tested in the assay of heavy metals in some real samples and the method was validated by ICP-MS technique. (C) 2008 Elsevier B.V. All rights reserved.