Beyond Doping: Rare‐Earth Mediated Strategies for Rational Design of Multifunctional Electrocatalysts

ABSTRACT With the rapid development of renewable energy, electrocatalysis has assumed a central role in the conversion and storage of sustainable energy. Rare‐earth (RE) elements, characterized by their unique 4f electronic configurations, reversible multivalent states, and highly tunable physicochemical properties, offer a fundamentally distinct pathway for achieving precise control over catalyst electronic structures, interfacial chemistry, and reaction pathways. This review presents a comprehensive and mechanistic perspective on the distinctive, multi‐faceted roles of RE elements in advanced electrocatalysis. By systematically analyzing their intrinsic properties, the review elucidates the quantum‐chemical origins of their advantages in electronic structure modulation, stabilization of high‐energy intermediates, and enhancement of interfacial charge transport. Building upon these foundations, some major catalyst design strategies, encompassing atomic doping, defect engineering, nanostructuring, and interface construction, are critically summarized. Then, recent progress of RE‐based catalysts in various electrocatalytic reactions, including oxygen and hydrogen evolution, and carbon dioxide and nitrogen reduction reactions, are thoroughly reviewed to establish structure‐activity correlations. Finally, the review outlines future prospects and emerging frontiers in RE‐mediated catalysis, such as multi‐electron reaction pathway regulation and the construction of adaptive interfaces. This work aims to provide a fundamental understanding and strategic guidance for the rational design of efficient electrocatalysts enabled by RE elements.