High‐entropy alloys (HEAs), composed of multiple principal elements in near‐equiatomic ratios, offer vast compositional tunability and synergistic electronic interactions for heterogeneous catalysis. Here, we report a nitrogen‐doped carbon nanofiber (N–CNF) encapsulated HEA catalyst, Fe 26 Co 13 Ni 24 Cr 10 Cu 17 Pd 10 @N–CNFs, synthesized via electrospinning followed by controlled thermal treatment. The resulting ~16 nm HEA nanoparticles are uniformly embedded within a conductive N‐doped carbon matrix, forming a robust core–shell architecture. Despite the low Pd loading (10 at%), the catalyst achieves 99% nitrobenzene conversion with >99% aniline selectivity at 60°C—an 8.9‐fold activity enhancement over Pd@N–CNFs. Furthermore, it retains >95% conversion after five consecutive reaction cycles, underscoring its excellent structural and catalytic durability. The outstanding performance arises from Pd‐induced electronic modulation within the entropy‐stabilized multimetallic matrix and synergistic confinement by the N‐doped carbon framework. This work establishes a cost‐efficient and durable HEA‐based platform for selective hydrogenation, offering new insights into entropy‐driven electronic regulation in multimetallic catalysts.
Gao et al. (Sun,) studied this question.