Influence of hydrazine-induced aggregation on the electrochemical detection of platinum nanoparticles.

To study the catalytic activity of single nanoparticles (NPs) electrochemically, we investigated the applicability of a novel method for nanoparticle detection as a means to immobilize individual NPs. This method consists of analyzing the current steps that can be measured at an ultramicroelectrode (UME) when a colloid of NPs is injected into an electrolyte containing an electroactive species, that is turned over at the NP but not the UME surface. We have measured these current steps for the hydrazine oxidation at Pt NPs landing on a lithographically fabricated Au UME, showing a mean step size comparable to theory and prior measurements. We found a reduced landing frequency with respect to values reported in the literature and those predicted from theory, while the current step distribution showed a long tail of large current steps. This could be explained by the particle aggregation, which would lower the effective NP concentration and therefore lower the landing frequency and would result in higher current steps when aggregates reach the electrode. Cyclic voltammetry (CV) measurements of the Pt-modified Au UME showed a signal characteristic of the presence of Pt, while electron microscopy revealed aggregated NPs, after landings were performed in the presence of hydrazine or hydrogen gas. Conversely, no aggregates were found after particles were injected in absence of such reducing agents, while CV still suggested the presence of Pt, indicating individual particles. The finding, that landing nanoparticles in the presence of hydrazine yields NP aggregates on the surface, means that this particular method is currently not suited for the preparation of individually immobilized particles to facilitate catalysis studies at individual nanoparticles.