Design of Hierarchical Porosity Via Manipulating Chemical and Microstructural Complexities in High‐Entropy Alloys for Efficient Water Electrolysis

Achieving a porous architecture with multiple‐length scales and utilizing the synergetic effects of multicomponent chemicals bring up new opportunities for further improving the electrocatalytic performance of nanocatalysts. Herein, the synthesis of a self‐supported hierarchical porous electrocatalyst based on a high‐entropy alloy (HEA) containing multiple transitional metals via physical metallurgy and dealloying strategies is reported. Microscale phase separation and nanoscale spinodal decomposition are modulated in a highly concentrated FeCoNiCu HEA, which makes it possible to obtain a porous structure with different length scales, i.e., relatively large porous channels formed by removing one separated phase and ultrafine mesopores obtained from leaching out one decomposition phase. The resultant hierarchical porous HEA exhibits superior water splitting performance, which takes full advantage of the enlarged surface area offered by the bi‐continuous mesoporous structure with the exceptional intrinsic reactivity originating from the synergetic electronic effects of the different components in alloying. Moreover, the microscale porous structure plays an important role in the significantly improved mass transportation, as well as the durability during electrocatalysis. This effective strategy that simultaneously utilizes the chemical and microstructural advantages of HEAs opens up a new avenue for developing HEA‐based, high‐performance porous electrocatalysts for various energy conversion/store applications. A self‐supported hierarchical porous high‐entropy alloy (HEA)‐based electrocatalyst is fabricated via physical metallurgy and dealloying strategies. Microscale phase separation and nanoscale spinodal decomposition are modulated in HEAs to obtain the porous structure with different length scales, which not only provides a large effective surface area but also accelerates charge and mass transport path for efficient water electrolysis.