Rhodium-Based Electrocatalysts for Ethanol Oxidation Reaction: Mechanistic Insights, Structural Engineering, and Performance Optimization

Direct ethanol fuel cells (DEFCs) have gained considerable attention as promising power sources for sustainable energy conversion due to their high energy density, low toxicity, and renewable ethanol feedstock. However, the sluggish ethanol oxidation reaction (EOR) kinetics and the formation of strongly adsorbed intermediates (e.g., CO*, CHx*) severely hinder catalytic efficiency and durability. Rhodium (Rh)-based catalysts stand out for their balanced intermediate adsorption, efficient C–C bond cleavage, and superior CO tolerance arising from their unique electronic structure. This review summarizes recent advances in Rh-based EOR catalysts, including monometallic Rh nanostructures, Rh-based alloys, and Rh–support composites. The effects of morphology, alloying, and metal–support interactions on activity, selectivity, and stability are discussed in detail. Strategies for structural and electronic regulation—such as nanoscale design, alloying modulation and interfacial engineering—are highlighted to enhance catalytic performance. Finally, current challenges and future directions are outlined, emphasizing the need for Rh-based catalysts with high activity, selectivity and stability, integrating in situ characterization with theoretical modeling. This work provides insights into the structure–activity relationships of Rh-based catalysts and guidance for designing efficient and durable anode catalysts for practical DEFC applications.