摘要

Classical electrochemical characterization tools cannot avoid averaging between the active reaction sites and their support, thus obscuring their intrinsic roles. Single‐molecule electrochemical techniques are thus in high demand. Here, we demonstrate super‐resolution imaging of Ru(bpy)32+ based reactions on Au plates using single‐molecule electrochemiluminescence microscopy. By converting electrochemical signals into optical signals, we manage to achieve the ultimate sensitivity of single‐entity chemistry, that is directly resolving the single photons from individual electrochemical reactions. High spatial resolution, up to 37?nm, further enables mapping Au chemical activity and the reaction kinetics. The spatiotemporally resolved dynamic structure–activity relationship on Au plates shows that the restructuring of catalysts plays an important role in determining the reactivity. Our approach may lead to gaining new insights towards evaluating and designing electrocatalytic systems.(#br)Understanding the structure–activity relationship is of crucial importance to the evaluation and the rational design of novel catalysts. Herein, single‐molecule electrochemiluminescence microscopy is employed for super‐resolution mapping of the chemical activity and kinetic analysis of Ru(bpy)32+‐based reactions on single gold plates, which enables spatiotemporal characterizations down to the single‐reaction level.