Addressing the surface coverage of Au nano-agglomerates and the electrochemical properties of modified carbon paste electrodes: Experimental and theoretical studies on ascorbic acid oxidation

Abstract

This article shows the formation of Au nano-agglomerates when increasing amounts of gold nanoparticles (AuNP) are incorporated into carbon paste electrodes. The surface coverage by this agglomerates is related to the electro-oxidation of a widely studied redox compound, ascorbic acid (AA); by analyzing the effect on the oxidation peak potential (Ep,a) and oxidation peak current (ip,a). The effects of pH and scan rate on the Ep,a and ip,a were investigated by cyclic voltammetry, and enabled to estimate the transfer coefficient and the number of electrons involved in the rate determining step (αnα), the standard heterogeneous rate constant (ks), and the diffusion coefficient of the redox compound, being 0.52 and 3.5 × 10−3 cm s−1 and 6.3 × 10−6 cm2 s−1, respectively. On the other hand, the sensing ability of the modified electrode was evaluated, obtaining a sensitivity of (63.2 ± 2.5) μA mM−1, a detection limit of 2.7 μM and a quantification limit of 8.9 μM.Additionally, a computational model based on lattice-gas model and Monte Carlo simulations in the Grand Canonical Ensemble was proposed in order to reproduce the behavior of the system, in terms of ip,a and Ep,a shift with increasing surface coverage by Au nano-agglomerates.