Understanding structure-reactivity relationships at electrochemical interfaces is central to unraveling key electrochemical processes, including electrocatalysis and battery operation. However, these interfaces often exhibit structural heterogeneity, comprising distinct facets, grain boundaries, and localized variations that obscure the conventional electrochemical methods due to ensemble averaging. In this presentation, I will highlight our recent advancements in developing and applying electroanalytical techniques—particularly scanning electrochemical probe microscopy (SEPM) and correlative microscopy—to uncover critical insights into electrochemical interfacial heterogeneity.
First, I will describe our efforts in simultaneously probing local electrocatalytic activity and product selectivity using a hybrid SEPM technique, analogous to a miniature rotating ring-disk electrode. Integrated with correlative electron microscopy, this approach enables direct mapping of facet-dependent activity and selectivity during the oxygen reduction reaction (ORR) on polycrystalline Au and Pt surfaces. Next, I will discuss our approach to quantifying site-specific nucleation kinetics and energetics in electrodeposition, a crucial aspect influencing metal anode stability and battery cyclability. Finally, I will explore how controlled electrodeposition can accelerate materials discovery, paving the way for efficient identification and optimization of functional materials for electrochemical applications