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

作者：Yanfu Tong, Xuejin Li, Xiaoning Wang, Lianming Zhao, Weiyue Luo, Zhenyu Huang, Pengyun Liu, Zifeng Yan, Yuan Pan, Wei Xing · 发表于：Advanced Materials · 年份：2025 · DOI：10.1002/adma.202517450 · 被引用次数：9 · 研究领域：Electrocatalysts for Energy Conversion、Ammonia Synthesis and Nitrogen Reduction、High Entropy Alloys Studies

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.