Pt Nanoparticle Collisions Detected by Electrocatalytic Amplification and Atomic Force Microscopy Imaging: Nanoparticle Collision Frequency, Adsorption, and Random Distribution at an Ultramicroelectrode Surface.

We demonstrate good agreement between the theoretical and experimental collision frequency of individual Pt nanoparticles (NPs) undergoing collisions at a Au ultramicroelectrode (UME) (5 μm radius) using electrocatalytic amplification provided by 15 mM hydrazine in 5 mM phosphate buffer (PB; pH 7) over 100 to 300 s. Dynamic light scattering (DLS) measurements demonstrated that Pt NP aggregation in this solution had the least impact on NP diffusion coefficient and concentration values, which are directly proportional to collision frequency. We show that the smaller, uniform current steps are indicative of NPs of metallic radii in agreement with those determined by transmission electron microscopy (TEM), with corresponding larger NP diffusion coefficient and concentration, in agreement with DLS results. These contribute to the larger NP collision frequency observed experimentally. Using atomic force microscopy (AFM) imaging, we show good agreement between the number of NPs imaged on the UME surface and the number of NP collisions that led to their adsorption, a spherical NP shape with a metallic radius size distribution comparable to that determined by TEM, and a random NP distribution on the UME surface. Through the Pt NP electroactive surface area, we show that all NPs on the UME surface after collision are attached and electrochemically active. Collectively, these results demonstrate for the first time that, within experimental error, every NP collision is successful and occurs through a sticking mechanism. Thus, collision experiments can be used to prepare small NP ensembles on a UME (i.e., UME-NPEs). In electrocatalysis, such UME-NPEs bridge the gap between classical ensemble studies on large platforms and isolated single NP investigations.