Abstract

<h2>Summary</h2> The development of high-efficiency energy storage and conversion devices requires a deeper understanding of the structure-activity relationship of electrocatalysts, material transformations during electrocatalysis processes, and complex electrochemical processes at electrode-electrolyte interfaces. Scanning probe microscopy (SPM) is a powerful tool for visualizing the surface properties and localized electrochemical activity down to the atomic scale <i>in situ</i> and even operando, thus plays an essential role in studying heterogeneous electrocatalysis mechanisms. We summarize recent advancements in SPM for investigating energy-related electrocatalysis based on three unique characteristics of SPM—surface property imaging, <i>in situ</i>/operando monitoring, and nanoscale electrochemical mapping,outline the application of SPM in investigating the structure-activity relationship, material transformations, and electrochemical processes. The specific SPM techniques discussed here include scanning tunneling microscopy, atomic force microscopy, scanning electrochemical microscopy, scanning ion conductance microscopy, and scanning electrochemical cell microscopy. Finally, the opportunities and challenges of SPM in electrocatalysis are discussed.

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