Electrospinning synthesis of N-doped graphene encapsulated FeCoNiCrCu high-entropy alloy nanoparticles for efficient nitrobenzene hydrogenation

Selective reduction of aromatic nitro compounds to functionalized anilines remains a formidable challenge due to the competitive reducible functional groups. High-entropy alloys (HEAs) with multiple elements in near-equiatomic proportions hold great promise given their exceptional physicochemical properties. Herein, we developed nitrogen-doped carbon nanofiber-encapsulated HEA nanoparticles (FeCoNiCrCu@N-CNFs) for efficient nitrobenzene hydrogenation to aniline. The FeCoNiCrCu@N-CNFs catalyst demonstrated exceptional activity with 99 % aniline yield at 60℃, outperforming the FeCoNi@N-CNFs counterpart by a factor of 6.6. The HEA-NC heterojunction was constructed on the surface of the catalyst given the intimate contact between the N-doped carbon layer and the alloy particles. Density functional theory (DFT) calculations revealed that the elevated d‐band center of the HEA, induced by carbon interaction, enhances the intermediates adsorption. This synergistic interplay between HEA and nitrogen-doped carbon provides a novel strategy for designing selective hydrogenation catalysts.