ABSTRACT Electrocatalysis powered by renewable electricity is a promising strategy for clean energy transformation and achieving carbon neutrality goals. In resource molecules conversion (e.g., CO 2 and NO 3 − ), electrolytes serve multiple roles as reaction media, proton donors, and mass‐transport carriers, with their composition and physicochemical properties exerting a significant influence on reaction pathways, intermediate stability, and product selectivity. Most research endeavors have predominantly concentrated on catalyst design, often oversimplifying electrolytes as inert backgrounds. This minireview proposes a classification framework for electrolyte effects into short‐, medium‐, and long‐range interactions, highlighting their active regulatory roles at electrified interfaces. A comprehensive overview is provided of recent advancements in methodologies for investigating solvent effects, accompanied by an in‐depth analysis of representative electrocatalytic systems. This analysis elucidates how the composition of electrolytes influences molecular‐level elementary reaction steps, the dynamic reorganization and equilibrium of the interfacial microenvironment, as well as macroscopic catalytic performance, through a variety of distinct mechanisms. Finally, the key challenges and opportunities are also discussed, emphasizing electrolyte engineering as a strategic tool to reshape reaction environments and accelerate the practical deployment of electrocatalytic technologies.
Wu et al. (Fri,) studied this question.