High-Spatiotemporal-Resolution Electrochemical Measurements of Electrocatalytic Reactivity.

The real-time measurement of the individual or local electrocatalytic reactivity of catalyst particles instead of ensemble behavior is considerably challenging but very critical to uncover fundamental insights into catalytic mechanisms. Recent remarkable efforts have been made to the development of high-spatiotemporal-resolution electrochemical techniques, which allow the imaging of the topography and reactivity of fast electron-transfer processes at the nanoscale. This Perspective summarizes emerging powerful electrochemical measurement techniques for studying various electrocatalytic reactions on different types of catalysts. Principles of scanning electrochemical microscopy, scanning electrochemical cell microscopy, single-entity measurement, and molecular probing technique have been discussed for the purpose of measuring important parameters in electrocatalysis. We further demonstrate recent advances in these techniques that reveal quantitative information about the thermodynamic and kinetic properties of catalysts for various electrocatalytic reactions associated with our perspectives. Future research on the next-generation electrochemical techniques is anticipated to be focused on the development of instrumentation, correlative multimodal techniques, and new applications, thus enabling new opportunities for elucidating structure-reactivity relationships and dynamic information at the single active-site level.