Voltammetric sensor for nitrite determination based on its electrocatalytic reduction at the surface of p-duroquinone modified carbon paste electrode

Abstract

A p-duroquinone (tetramethyl-p-benzoquinone) modified carbon paste electrode (DMCPE) was employed to study the electrocatalytic reduction of nitrite in aqueous solutions using cyclic voltammetry (CV), double potential-step chronoamperometry, and differential pulse voltammetry (DPV). It has found that under an optimum condition (pH 1.00), the reduction of nitrite at the surface of DMCPE occurs at a potential of about 660 mV less negative than that of an unmodified carbon paste electrode (CPE). The catalytic rate constant, k′h, based on Andrieux and Saveant theoretical model was calculated as \(k'_h = 4.56 \times 10^{ - 5} \,cm\,s^{ - 1} \) for scan rate 10 mV s-1. Also, the apparent diffusion coefficient, Dapp, was found as 2.5 × 10–10 and 3.61 × 10–5 cm2 s-1for p-duroquinone in carbon paste matrix and nitrite in aqueous buffered solution, respectively. The values for αnα were estimated to be −0.65 and −0.19 for the reduction of nitrite at the surface of DMCPE and CPE, respectively. The electrocatalytic reduction peak currents showed a linear dependence on the nitrite concentration, and a linear analytical curve was obtained in the ranges of 5.0 × 10–5 M to 8.0 × 10–3 M and 6.0 × 10–6 M to 8.0 × 10–4 M of nitrite concentration with CV and DPV methods, respectively. The detection limits (2σ) were determined as 2.5 × 10–5 M and 4.3 × 10–6 M by CV and DPV methods. This method was also applied as a simple, selective and precise method for determination of nitrite in real samples (the weak liquor from the wood and paper factory of Mazandaran province in Iran) by using a standard addition method.