Tailoring the Electronic Landscape and Metal–Support Interface of High-Entropy Alloys for Efficient Bifunctional Electrocatalysis

High-entropy alloy (HEA) electrocatalysts exhibit a rich diversity of synergistic active sites but still face persistent challenges, such as unstable metal–support interfaces and intricate electronic structure modulation. Here, inspired by cell membrane-embedded synthetase catalytic units in the photosystem, we report a MnFeCoNiCuRu x HEA electrocatalyst anchored on carbon nanofibers (CNFs) via the concurrent growth of HEA nanocrystals and CNF film support, which exhibits stable and strong metal–carbon interface coupling. In this architecture, trace Ru (∼4 wt %) acts as an electronic modulator, shifting the d-band center closer to the Fermi level and modulating the linear correlation between adsorption energies and the d-band center, thereby greatly enhancing intrinsic catalytic activity. Large-scale surface screening reveals the presence of catalytically active centers and delineates the associated reaction pathways. When integrated into zinc-air battery systems, the electrocatalyst demonstrates enhanced bifunctional activity for oxygen evolution and reduction reactions. This investigation offers valuable insights into HEA catalytic mechanisms through electronic structure tailoring and interface optimization, offering a feasible pathway for designing high-performance bifunctional electrocatalysts.