Dynamic Electron Redistribution on Rooted-Type High-Entropy Perovskite-Supported Ir Catalysts for Durable Proton-Exchange-Membrane Water Electrolysis.

Addressing the inherent trade-off between low iridium loading and operational durability is of paramount importance for advancing proton-exchange-membrane water electrolysis (PEMWE) technology toward green hydrogen production, yet it remains a formidable challenge. Here, we develop a multilevel stabilization strategy to dynamically stabilize Ir under industrial current densities. This approach combines strong physical anchoring, achieved by constructing a rooted-type embedded architecture on a high-entropy perovskite support (Ir/HESIO), with dynamic electronic state regulation of the active supported layer via in situ electron redistribution. In situ spectroscopic characterization and theoretical simulations jointly verify that the synergy between structural confinement and in situ electronic regulation effectively suppresses the migration, overoxidation, and subsequent dissolution of Ir active species. Owing to these attributes, the developed Ir/HESIO exhibits a low cell voltage of 1.71 and 1.80 V to achieve industrial current densities of 2 and 3 A cm-2, meeting the DOE 2026 target (1.80 V @ 3A cm-2) and outperforming most reported catalysts. Moreover, it demonstrates outstanding operational stability, maintaining stable operation over 3800 h at 2 A cm-2 with just 2.2% potential decay and over 3200 h at 3 A cm-2 with just 4.7% potential decay. This work not only presents a highly promising electrocatalyst for water electrolysis but also establishes a dynamic electronic structure regulation strategy that is broadly applicable for stabilizing other heterogeneous catalysts.