In Situ Detection of Particle Aggregation on Electrode Surfaces

Partially blocked electrodes (PBEs) are important; many applications use non‐conductive nanoparticles (NPs) to introduce new electrode functionalities. As aggregation is a problem in NP immobilization, developing an in situ method to detect aggregation is vital to characterise such modified electrodes. We present chronoamperometry as a method for detection of NP surface aggregation and semi‐quantitative sizing of the formed aggregates, based on the diffusion limited current measured at PBEs as compared with the values calculated numerically for different blocking feature sizes. In contrast to voltammetry, no approximations on electrode kinetics are needed, making chronoamperometry a more general and reliable method. Sizing is shown for two modification methods. Upon drop casting, significant aggregation is observed, while it is minimized in electrophoretic NP deposition. The aggregate sizes determined are in semi‐quantitative agreement with ex situ microscopic analysis of the PBEs. A new in situ method to semi‐quantitatively size aggregates of non‐conductive particles on electrode surfaces by using chronoamperometry is developed. Importantly, the sensitivity of the electrochemical response of nanoparticle‐modified electrodes on the modification/immobilization technique used is highlighted.