Abstract
Abstract Electrochemical CO 2 conversion (ECC) has emerged as a promising strategy to address global carbon emissions while producing valuable fuels and chemicals. This mini review examines the fundamental mechanisms of CO 2 reduction on catalytic surfaces, where the interplay between adsorption energies, intermediate stabilization, and charge transfer governs reaction pathways and selectivity. We systematically analyze the key factors determining catalyst performance, including surface electronic structure, active site coordination, and local microenvironment effects. The discussion highlights innovative strategies for enhancing ECC efficiency: (1) precise control of top coating on catalysts to optimize active sites and local reaction environment, and (2) rational engineering of reaction environments through electrolyte modulation and pH management. A dedicated focus is placed on surface coating techniques as a transformative approach—protective layers can simultaneously stabilize catalysts against reconstruction, tailor interfacial charge transfer, and mitigate competing reactions. By correlating recent advances in material design with mechanistic insights, this mini review provides a framework for developing next‐generation ECC systems, bridging fundamental surface science with practical catalytic engineering.