Rhombohedral Pd–Sb Nanoplates with Pd‐Terminated Surface: An Efficient Bifunctional Fuel‐Cell Catalyst

Abstract Developing high‐performance electrocatalysts for the ethanol oxidation reaction (EOR) and the oxygen reduction reaction (ORR) is essential for the commercialization of direct ethanol fuel cells, but it is still formidably challenging. In this work, a novel Pd–Sb hexagonal nanoplate for boosting both cathodic and anodic fuel cell reactions is prepared. Detailed characterizations reveal that the nanoplates have ordered rhombohedral phase of Pd₈Sb₃ (denoted as Pd₈Sb₃ HPs). The Pd₈Sb₃ HPs exhibit much enhanced activity toward the oxidation of various alcohols. Particularly, Pd₈Sb₃ HPs/C displays superior specific and mass activities of 29.3 mA cm⁻² and 4.5 A mg_Pd⁻¹ toward the EOR, which are 7.0 and 11.3 times higher than those of commercial Pd/C, and 9.8 and 3.8 times higher than those of commercial Pt/C, respectively, representing one of the best EOR catalysts reported to date. In situ electrochemical attenuated total reflectance surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) measurements reveal that Pd₈Sb₃ HPs/C can effectively promote the C₂ pathway of the EOR. As revealed by density functional theory calculations, the high EOR activity of the Pd₈Sb₃ HPs can be ascribed to the reduced energy barrier of ethanol dehydrogenation. Additionally, Pd₈Sb₃ HPs/C also shows superior performance in the ORR. This work advances the controllable synthesis of the Pd–Sb nanostructure, giving huge impetus for the design of high‐efficiency electrocatalysts for energy conversion and beyond.