Ordering‐Dependent Hydrogen Evolution and Oxygen Reduction Electrocatalysis of High‐Entropy Intermetallic Pt4FeCoCuNi

Disordered solid-solution high-entropy alloys have attracted wide research attention as robust electrocatalysts. In comparison, ordered high-entropy intermetallics have been hardly explored and the effects of the degree of chemical ordering on catalytic activity remain unknown. In this study, a series of multicomponent intermetallic Pt₄ FeCoCuNi nanoparticles with tunable ordering degrees is fabricated. The transformation mechanism of the multicomponent nanoparticles from disordered structure into ordered structure is revealed at the single-particle level, and it agrees with macroscopic analysis by selected-area electron diffraction and X-ray diffraction. The electrocatalytic performance of Pt₄ FeCoCuNi nanoparticles correlates well with their crystal structure and electronic structure. It is found that increasing the degree of ordering promotes electrocatalytic performance. The highly ordered Pt₄ FeCoCuNi achieves the highest mass activities toward both acidic oxygen reduction reaction (ORR) and alkaline hydrogen evolution reaction (HER) which are 18.9-fold and 5.6-fold higher than those of commercial Pt/C, respectively. The experiment also shows that this catalyst demonstrates better long-term stability than both partially ordered and disordered Pt₄ FeCoCuNi as well as Pt/C when subject to both HER and ORR. This ordering-dependent structure-property relationship provides insight into the rational design of catalysts and stimulates the exploration of many other multicomponent intermetallic alloys.