Spatially Resolving and Regulating Heterogeneity of Electronic Coupling at the Single Silver Nanoentity Level.

Interfacial electron transfer governs electrochemical heterogeneity at the single-entity level. Herein, we investigated the electronic coupling event during electrodissolution processes of single silver nanoentities on a Au electrode through a synchronized electrochemical-optical tracking platform. By implementing strategic control of interfacial gap distances and electrolyte composition, a marked differentiation of single-particle reaction dynamics can be achieved. The integration of superlocalization methodology reveals position-correlated optical centroid shifts during electrodissolution processes, demonstrating heterogeneous oxidation dynamics arising from spatially nonuniform surface oxide formation. Crucially, SAM-mediated gap regulation enables the precise regulation of interfacial electric field enhancement. Our methodology resolves electronic coupling heterogeneity at subnanowire scale while proving molecular interlayer-dependent modulation of coupling lifetimes. This electrochemical-optical imaging strategy establishes nanoscale spatial mapping of electrochemical dynamics, quantitative correlation between interfacial structure and coupling efficiency, and real-time tracking of transient electronic states. These findings demonstrate the capability of advanced optical imaging methodologies in elucidating structure-activity relationships at nanoscale interfaces, providing mechanistic insights for single-entity electrochemistry and nanoscale energy conversion systems.