Imaging Dynamic Collision and Oxidation of Single Silver Nanoparticles at the Electrode/Solution Interface.

The electrochemical interface is an ultrathin interfacial region between the electrode surface and the electrolyte solution and is often characterized by numerous dynamic processes, such as solvation and desolvation, heterogeneous electron transfer, molecular adsorption and desorption, diffusion, and surface rearrangement. Many of these processes are driven and modulated by the presence of a large interfacial potential gradient. The study and better understanding of the electrochemical interface is important for designing better electrochemical systems where their applications may include batteries, fuel cells, electrocatalytic water splitting, corrosion protection, and electroplating. This, however, has proved to be a challenging analytical task due to the ultracompact and dynamic evolving nature of the electrochemical interface. Here, we describe the use of an electrochemical nanocell to image the dynamic collision and oxidation process of single silver nanoparticles at the surface of a platinum nanoelectrode. A nanocell is prepared by depositing a platinum nanoparticle at the tip of a quartz nanopipette forming a bipolar nanoelectrode. The compact size of the nanocell confines the motion of the silver nanoparticle in a 1-D space. The highly dynamic process of nanoparticle collision and oxidation is imaged by single-particle fluorescence microscopy. Our results demonstrate that silver nanoparticle collision and oxidation is highly dynamic and likely controlled by a strong electrostatic effect at the electrode/solution interface. We believe that the use of a platinum nanocell and single molecule/nanoparticle fluorescence microscopy can be extended to other systems to yield highly dynamic information about the electrochemical interface.