Surface coverage and reconstruction analyses bridge the correlation between structure and activity for electrocatalysis.

Electrocatalysis is key to realizing a sustainable future for our society. However, the complex interface between electrocatalysts and electrolytes presents an ongoing challenge in electrocatalysis, hindering the accurate identification of effective/authentic structure-activity relationships and determination of favourable reaction mechanisms. Surface coverage and reconstruction analyses of electrocatalysts are important to address each conjecture and/or conflicting viewpoint on surface-active phases and their corresponding electrocatalytic origin, , so-called structure-activity relationships. In this review, we emphasize the importance of surface states in electrocatalysis experimentally and theoretically, providing guidelines for research practices in discovering promising electrocatalysts. Then, we summarize some recent progress of how surface states determine the adsorption strengths and reaction mechanisms of occurring electrocatalytic reactions, exemplified in the electrochemical oxygen evolution reaction, oxygen reduction reaction, nitrogen reduction reaction, CO reduction reaction, CO and N co-reductions, and hydrogen evolution reaction. Finally, the review proposes deep insights into the study of surface states, their efficient building and the application of surface Pourbaix diagrams. This review will accelerate the development of electrocatalysts and electrocatalysis theory by arousing broad consensus on the significance of surface states.