Sai-Nan Guo, Si-Wen Zhang, Meng Qiao, Jie-Xin Wang
The shift to sustainable energy requires efficient hydrogen production through water electrolysis. However, alkaline hydrogen evolution reaction (alkaline HER) technologies suffer from slow kinetics, high overpotential (>200 mV), and dependence on expensive Pt/Ru catalysts. High-entropy alloys (HEAs) offer promising tunability but suffer from oxidative deactivation, disordered active sites, and limited surface area. Herein, we first synthesize PtRuCoNiCu HEA nanodendrites (HEA-NDs) via a one-pot hydrothermal method, featuring a defect-rich 3D branching structure. The shortened Pt–Pt bond (2.61 Å) induces tensile strain, optimizing the hydrogen adsorption energy (Δ G * H = – 0.06 eV). The HEA-NDs achieve an ultralow overpotential of 10 mV at 10 mA cm –2 (82% lower than Pt/C), a Tafel slope of 23.4 mV dec –1, and greater than 95% stability over 100 h. Notably, they also exhibit exceptional mass activity in the methanol oxidation reaction (MOR) (4830 mA mg –1 ) and CO antipoisoning capability, demonstrating multifunctional catalytic superiority. The excellent catalytic performance of HEA-NDs is further elucidated by density functional theory-based mechanistic studies of HER and MOR pathways. The synergy between lattice strain and high-entropy effects in these dendritic nanostructures establishes a new paradigm for designing next-generation electrocatalysts for water electrolysis.