Scanning Electrochemical Microscopy of Single Spherical Nanoparticles: Theory and Particle Size Evaluation.

Experiments at individual metal nanoparticles (NPs) can provide important information about their electrochemical and catalytic properties. The scanning electrochemical microscope (SECM) equipped with a nanometer-sized tip was recently used to image single 10 or 20 nm gold particles and quantitatively investigate electrochemical reactions occurring at their surfaces. In this Article, the theory is developed for SECM current vs distance curves obtained with a disk-shaped tip approaching a comparably sized, surface-bound conductive or insulating spherical NP. The possibility of evaluating the size of a surface-bound particle by fitting the experimental current-distance curve to the theory is shown for NPs and tips of different radii. The effects of the NP being partially buried into an insulating layer and the imperfect positioning of the tip with respect to the NP center are considered. The collection efficiency is calculated for redox species generated at the nanoparticle surface and collected at the tip.