Electrocatalytic reactions underpin critical technologies for energy conversion, environmental remediation, and chemical synthesis, yet their efficient regulation requires a precise understanding of underlying kinetic mechanisms. Conventional thermal catalysis, governed by equilibrium thermodynamics, offers limited insights into the dynamic and multistep nature of electrochemical processes. By integrating electrochemical principles with kinetic frameworks, electrochemical kinetics provides a powerful method to probe interfacial phenomena, including electron transfer, dynamic adsorption, and surface reconstruction at electrode–electrolyte interfaces. However, traditional methodologies often struggle to resolve molecular‐level temporal dynamics or to disentangle overlapping contributions from consecutive reaction steps, thereby constraining mechanistic interpretation. Recent advances in both experimental techniques (such as time‐resolved spectroscopy, in situ microscopy, and operando electrochemical probes) and theoretical approaches including multiscale simulations and machine learning models, are overcoming these challenges and enabling unprecedented resolution of interfacial dynamics. This review highlights these emerging methodologies, emphasizing their potential to capture transient phenomena, decouple complex pathways, and establish quantitative descriptors of catalytic activity. By systematically evaluating state‐of‐the‐art strategies, we aim to provide a comprehensive framework for advancing electrochemical kinetic studies and to inspire the development of next‐generation tools for rational catalyst design. Ultimately, refining electrochemical kinetic methodologies is essential for bridging atomic‐scale understanding with macroscopic catalytic performance, accelerating progress toward efficient, sustainable, and scalable electrochemical technologies.
Wu et al. (Wed,) studied this question.