Abstract
Studying nanoparticle (NP)-electrode interactions in single nanoparticle collision events is critical to understanding dynamic processes such as nanoparticle motion, adsorption, oxidation, and catalytic activity, which are abundant on electrode surfaces. Herein, NP-electrode electrostatic interactions are studied by tracking the oxidation of AgNPs at Au microelectrodes functionalized with charged self-assembled monolayers (SAMs). Tuning the charge of short alkanethiol-based monolayers and selecting AgNPs that can be partially or fully oxidized upon impact enabled probing the influence of attractive and repulsive NP-electrode electrostatic interactions on collision frequency, electron transfer, and nanoparticle sizing. We find that repulsive electrostatic interactions lead to a significant decrease in collision frequency and erroneous nanoparticle sizing. In stark difference, attractive electrostatic interactions dramatically increase the collision frequency and extend the sizing capability to larger nanoparticle sizes. Thus, these findings demonstrate how NP-monolayer interactions can be studied and manipulated by combining nanoimpact electrochemistry and functionalized SAMs.