From Electronic Structure to Catalytic Function: Rare Earth–Driven Strategies for CO 2 Electroreduction

ABSTRACT Electrochemical carbon dioxide reduction reaction (CO 2 RR) is a promising approach to mitigate carbon emissions while producing value‐added fuels and chemicals. However, conventional transition‐metal catalysts suffer from limited selectivity, high overpotentials, and poor durability. Rare‐earth elements, with their unique 4f orbital configurations, variable oxidation states, and strong oxophilicity, offer distinct opportunities to overcome these limitations. This review systematically summarizes recent advances in rare‐earth‐based electrocatalysts, including single‐atom catalysts (SACs), alloys, and oxides, highlighting their ability to tailor local coordination environments, stabilize oxygenated intermediates, and facilitate multi‐electron transfer pathways. Rare‐earth‐based SACs leverage atomic dispersion to modulate electronic structures and suppress competing hydrogen evolution, while rare‐earth‐containing alloys introduce synergistic effects that disrupt conventional scaling relationships, enhancing selectivity toward desired products. Furthermore, rare‐earth oxides and mixed phases offer active oxygen vacancies and redox flexibility, thereby promoting CO 2 activation and enhancing catalyst stability. Collectively, these strategies significantly improve activity, selectivity, and durability in CO 2 RR. Despite these advances, challenges remain regarding atomic dispersion stability, conductivity, and product selectivity toward multi‐carbon species. Future research should focus on rational design guided by operando characterization, defect engineering, and machine‐learning‐assisted discovery to realize rare‐earth‐based electrocatalysts for industrially relevant, carbon‐neutral CO 2 conversion.