LAUSR

The lattice oxygen oxidation mechanism typically requires the removal of electrons from the metal-oxygen band, which may cause structural instability due to a decrease in the metal-oxygen bond order. To address this challenge, we introduce low-valence, non-catalytically active Na to construct oxygen non-bonding bands on high-entropy hydroxides, allowing electrons to be removed from the oxygen non-bonding band rather than the metal-oxygen bonds, thereby improving the stability of the catalyst. Na doped high-entropy layered double hydroxide (Na-HE LDH) with a low overpotential of 176 mV@10 mA cm⁻² under alkaline conditions. Furthermore, the Pt/C | |Na-HE LDH electrode pair operates continuously for 2000 h at ~500 mA cm⁻² in an anion-exchange membrane electrolyzer (30 wt% KOH, 60 °C). In-situ spectroscopic and density functional theory calculations identify that the introduction of Na facilitates the formation of oxygen non-bonding band thereby mitigating structural instability. This study offers a strategy for designing efficient and stable lattice oxygen catalysts and provides valuable insights for developing catalysts capable of withstanding the rigorous demands of industrial hydrogen production environments. Developing efficient and stable electrocatalysts is crucial for the oxygen evolution reaction. The authors introduce low-valence Na to construct oxygen non-bonding bands on high-entropy hydroxides, achieving 2000 hours of stability at 500 mA cm⁻² in an anion-exchange membrane electrolyzer.