Electrochemical sensor for sulfite determination based on a nanostructured copper-salen film modified electrode

• Published in: Electrochimica acta 2009-07, Vol.54 (19), p.4552-4558
• Main Authors: Dadamos, Tony R.L., Teixeira, Marcos F.S.
• Format: Article
• Language: English
• Subjects: Amperometric detection; Analytical chemistry; Anions; CHEMICAL ANALYSIS; Chemistry; Copper-salen complex; Electrochemical methods; Electrodes; Exact sciences and technology; Logarithms; MICA; MICROSTRUCTURES; Modified electrode; Nanostructure; Nanostructured polymer; Oxidation; Platinum; Sensors; Sulfite; Sulfites
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2009.03.045

The electrochemical preparation described herein involved the electrocatalytic oxidation of sulfite on a platinum electrode modified with nanostructured copper salen (salen = N, N′-ethylene bis(salicylideneiminato)) polymer films. The complex was prepared and electropolymerized at a platinum electrode in a 0.1 mol L −1 solution of tetrabutylammonium perchlorate in acetonitrile by cyclic voltammetry between 0 and 1.4 V vs. SCE. After cycling the modified electrode in a 0.50 mol L −1 KCl solution, the estimated surface concentration was found to be equal to 2.2 × 10 −9 mol cm −2. This is a typical behavior of an electrode surface immobilized with a redox couple that can usually be considered as a reversible single-electron reduction/oxidation of the copper(II)/copper(III) couple. The potential peaks of the modified electrode in the electrolyte solution (aqueous) containing the different anions increase with the decrease of the ionic radius, demonstrating that the counter-ions influence the voltammetric behavior of the sensor. The potential peak was found to be linearly dependent upon the ratio [ionic charge]/[ionic radius]. The oxidation of the sulfite anion was performed at the platinum electrode at +0.9 V vs. SCE. However, a significant decrease in the overpotential (+0.45 V) was obtained while using the sensor, which minimized the effect of oxidizable interferences. A plot of the anodic current vs. the sulfite concentration for chronoamperometry (potential fixed = +0.45 V) at the sensor was linear in the 4.0 × 10 −6 to 6.9 × 10 −5 mol L −1 concentration range and the concentration limit was 1.2 × 10 −6 mol L −1. The reaction order with respect to sulfite was determined by the slope of the logarithm of the current vs. the logarithm of the sulfite concentration.