Mathematical Analysis of Cyclic and Sampled Current Voltammetries for the Description of Nucleation and Growth Processes of Metallic Nanoparticles

The electrodeposition of metallic nanoparticles was studied using numerical methods under progressive and instantaneous nucleation regimes to calculate cyclic and sampled current voltammetries. The cyclic voltammograms (CV) for both types of nucleation were calculated using diffusion and kinetics limited growth conditions. The sampled current voltammograms (SCV) were built from numerically generated chronoamperometric curves. Comparison of the SCV and CV curves shows that the current response corresponding to the progressive nucleation was similar under both growth regimes, although the nuclei density was considerably different. Under instantaneous nucleation, the CV and SCV showed similar current responses only under kinetic control due to similar cluster growth, and the diffusion-controlled growth showed a similar cluster growth, but a different current response. The comparison made in this work provides a guideline to understand experimental electrodeposition results and makes a good argument for using SCV to complement the CV curves.