Constructing Structurally Ordered High‐Entropy Alloy Nanoparticles on Nitrogen‐Rich Mesoporous Carbon Nanosheets for High‐Performance Oxygen Reduction

Abstract Recent efforts have observed nanoscaled chemical short‐range order in bulk high‐entropy alloys (HEAs). Simultaneously inspired with the nanostructuring technology, HEA nanoparticles (NPs) with complete chemical order may be achieved. Herein, structurally ordered HEA (OHEA) NPs are constructed on a novel 2D nitrogen‐rich mesoporous carbon sandwich framework (OHEA‐mNC) by combining a ligand‐assisted interfacial assembly with NH₃ annealing. Characterization results show that the resultant materials possess an ultrathin 2D nanosheet structure with large mesopores (≈10 nm), where structurally ordered HEA NPs with an L1₂ phase are homogeneously dispersed. The atom‐resolved chemical analyses explicitly determine the location of each atomic site. When being evaluated for the oxygen reduction reaction, the OHEA‐mNC NPs afford a greatly enhanced catalytic performance, including a large half‐wave potential (0.90 eV) and a high durability (0.01 V decay after 10 000 cycles) compared with the disordered HEA and commercial Pt/C catalysts. The excellent performance is attributed to the enhanced mass transfer rate, improved electron conductivity, and the presence of the stable chemically ordered HEA phase, as revealed by both the experimental results and theoretical calculation. This study suggests a highly feasible process to achieve structurally ordered HEA NPs with advanced mesoporous function in the electrochemical field.