Deciphering Complex Electrochemical Reaction Dynamics and Interactions of Single Nanoentities via Evanescent Scattering Microscopy

Abstract Electrochemical reactions at the nanoscale are governed by intricate surface interactions, yet existing imaging techniques often lack the surface sensitivity and throughput needed to resolve these dynamics clearly. Here, we introduce electrochemical evanescent scattering microscopy (EC‐ESM), a high‐throughput, surface‐sensitive imaging technique that enables real‐time tracking of single‐nanoentity electrochemistry with high resolution. Using EC‐ESM, we monitored the motion and dissolution dynamics of silver nanoparticles and identified a clear relationship between nanoparticle velocity and electron transfer rates. The high throughput of EC‐ESM not only ensures statistical reliability but also allows the detection of rare electron transfer events in molecularly modified AgNPs. Additionally, EC‐ESM's high resolution enabled direct imaging of both single and interacting silver nanowires, revealing diverse dissolution behaviors that provide insights into structural and surface properties. We envision EC‐ESM as a powerful platform for advancing nanoscale electrochemical research and interfacial charge transfer studies.