Entropy‐Mediated Gradient Oxygenophilic Architecture on High‐Entropy Alloy for Dynamic Spillover and Bifunctional Hydrogen Electrocatalysis

ABSTRACT Breaking scaling relations and overcoming kinetic limitations in multistep hydrogen electrocatalysis remains a fundamental challenge. In this work, we designed and synthesized a high‐entropy alloy catalyst comprising Ir, Ru, Mo, W, and Cu supported on nitrogen‐doped carbon spheres. This unique structure creates active sites with a quasi‐continuous distribution of binding energies for H* and OH* intermediates. Density functional theory (DFT) calculations confirm that the random spatial arrangement of sites enables low‐energy‐barrier spillover pathways for H* and OH* (χ H* max = 0.27 eV; χ OH* max = 0.61 eV), while continuous d‐orbital coupling facilitates efficient electron transfer. This design enables each elementary step of hydrogen oxidation and evolution reactions (HOR/HER) to be directed to a site with favorable energetics. As a result, it exhibits exceptional bifunctional performance with a HOR mass activity of 8.83 A mg −1 and an HER overpotential of only 11 mV at 10 mA cm −2 , significantly outperforming commercial Pt/C com and previously reported catalysts. Operando spectroscopy and DFT analyses reveal that the gradient energy landscape promotes dynamic intermediate spillover, preventing site blocking and enhancing reaction kinetics. This work establishes a universal design strategy develop high‐performance electrocatalysts that transcend conventional Sabatier principle limitations.