Aggregation-Dependent Oxidation of Metal Nanoparticles.

Here we describe the effect of aggregation on the oxidation of citrate-stabilized Au nanoparticles (NPs) attached electrostatically to amine-functionalized glass/ITO electrodes. When the Au NPs are attached to the electrode from a solution with pH greater than ∼3.0, they are well-separated on the electrode and oxidize in bromide-containing electrolyte at 0.698, 0.757, and 0.943 V (vs Ag/AgCl) for 4, 15, and 50 nm diameter Au NPs, respectively, in line with their size-dependent oxidation behavior. In solutions below pH 3.0, the Au NPs aggregate in solution and attach to the electrode in the aggregated form. The solution UV-vis spectra and scanning electron microscopy images of the electrodes show clear evidence of aggregation. The oxidation potential for aggregated 4 and 15 nm diameter Au NPs shifts positive by a maximum of 230 and 180 mV, respectively. The magnitude of the shift depends on the extent of aggregation, which was controlled by the solution pH and time. NP aggregation leads to a significant reduction in the surface area-to-volume ratio, which is likely responsible for the positive shift in the oxidation potential. The oxidation potential does not shift at all for aggregated 50 nm diameter Au NPs.