Electrocatalytic Reduction of Benzyl Bromide during Single Ag Nanoparticle Collisions

Previous reports of the electrocatalytic activity of Ag nanoparticles (AgNPs) toward the reduction of organic halides have been limited to measurements of immobilized nanoparticle ensembles. Here, we have investigated the electrochemical reduction of benzyl bromide (PhCH₂Br) occurring at single AgNPs (4.2 to 37 nm radius) in methanol, where the effects of nanoparticle size on catalytic behavior can be more thoroughly examined and rigorously quantified. AgNP collisions at a 6.3 μm radius Au ultramicroelectrode (UME) result in measurable electrocatalytic amplification currents from the reduction of PhCH₂Br, where collision events are indicated by a sudden step increase in the reduction current recorded in the current-time trace. The dependence of the height of these steps on the applied potential allowed for an analysis of reaction kinetics based on the Butler-Volmer model, resulting in an estimation of the standard rate constant (k⁰) as a function of AgNP size. Measured values of k⁰ range from 4.0 × 10^-4 to 8.0 × 10^-4 cm/s on AgNPs with radii of 14, 29, and 37 nm, whereas k⁰ was found to be 6.2 × 10^-4 cm/s at a 12.3 μm radius Ag disk UME. The results indicate that the kinetics of PhCH₂Br reduction are independent of AgNP size and are similar to the reaction kinetics observed at a Ag UME. The frequency of observed particle collisions was found to be dependent on particle size, where 14 nm radius AgNPs resulted in the highest-frequency collisions. The potential- and size-dependent interactions of AgNPs with the Au UME are discussed in terms of the DLVO theory.