Synergistic hybridization between third-period and fifth-period transition metal orbitals in entropy-stabilized...

The development of high-entropy electrocatalysts with optimized activity-stability balance represents a critical advancement in overcoming the efficiency limitations of oxygen evolution reaction (OER) for sustainable hydrogen production. Herein, a rational design of quinary high-entropy layered double hydroxide microspheres comprising synergistic 3d transition metals (Ni, Fe, Co, Mn) and high-valent 5d tungsten (W) is demonstrated through a facile hydrothermal strategy. The optimized NiFeCoMnW exhibits exceptional OER performance in alkaline media, achieving a remarkably low overpotential of 204 mV at 10 mA cm^-2. Particularly, the high entropy-induced structural stability results in unprecedented durability, with a current density decay of less than 6 % after 300 h of operation at 250 mA cm^-2. Systematic experiments and density functional theory calculations reveal that unique 3d-5d orbital hybridization precisely modulates the d-p band center, optimizing oxygen intermediate adsorption through multi-metal synergy. Simultaneously, the entropy-stabilized disordered structure with crystalline-amorphous coupling enables efficient electron transport and active site exposure, while W incorporation strengthens M-O bonding, ensuring structural durability. Overall, this work establishes a paradigm for engineering high-performance OER catalysts through entropy-mediated electronic and structural regulation, demonstrating significant potential for industrial water electrolysis applications.