Tailoring Interfacial Water Via High-Entropy Orbital Reconstruction for Durable Alkaline Water Electrolysis

The hydrogen evolution reaction (HER) is central to clean hydrogen production, yet its application in alkaline water electrolysis is severely limited by intrinsically sluggish kinetics and the poor long-term stability of Pt-based catalysts, particularly at industrially relevant current densities. Here, we propose a high-entropy alloying strategy that enables synergistic tuning of the electronic structure and interfacial interactions. This strategy induces reconstruction of the Pt 5d orbitals, optimizing interfacial water dissociation kinetics and reshaping the interfacial water distribution. At the same time, it promotes a more delocalized electronic structure and stronger bonding through pronounced d-p, d-d, and sp orbital hybridization, as well as vibrational coupling driven by local atomic displacements. The downshifted Pt 5d band center weakens *H adsorption, thereby facilitating hydrogen desorption while effectively suppressing surface oxidation and particle agglomeration. As a result, the FeCoNiPtIn/MWCNT catalyst delivers an ultralow overpotential of 8 mV at 10 mA cm-2 and operates stably for over 5000 h at 250 mA cm-2, far outperforming commercial Pt/C. This work integrates orbital engineering with interfacial water regulation, establishing a compelling design paradigm for durable HER electrocatalysts for large-scale renewable energy conversion.