DOI: 10.1021/acsnano.6c00524 ISSN: 1936-0851

Dynamic Dissolution-Replenishment Equilibrium Enables Efficient and Durable Oxygen Evolution on Self-Reconstructing High-Entropy Alloys

Yi He, Rui Li, Yanan Zhang, Zhibin Li, Weihong Liu, Xiongjun Liu, Zhaoping Lu

Abstract

Achieving an efficient and stable oxygen evolution reaction (OER) at industrial current densities remains challenging for non-noble electrocatalysts due to irreversible surface degradation under harsh oxidative conditions. Here, we report a FeCoNiCrW0.6 dual-phase high-entropy alloy electrocatalyst that undergoes controllable in situ surface reconstruction during high-current-density OER, enabling simultaneous high activity and exceptional durability. The reconstruction generates a honeycombed porous architecture covered by a multicomponent amorphous oxide layer, which promotes a transition from the adsorbate evolution mechanism to the lattice oxygen mechanism, thereby enhancing the intrinsic activity. More importantly, the catalyst maintains long-term stability through a dynamic dissolution-replenishment equilibrium, in which selective leaching of W and Cr from the underlying FCC matrix continuously regenerates the surface-active layer, while the high-entropy effect suppresses excessive degradation. As a result, the reconstructed catalyst delivers a low overpotential of 223 mV at 10 mA cm–2 and stable operation for over 700 h at ampere-level current densities. When implemented into an anion-exchange membrane electrolyzer, it enables efficient alkaline and seawater electrolysis at 1 A cm–2 with a low cell voltage of 1.79 V and excellent durability. This work establishes a dynamic self-reconstruction paradigm for designing stable, high-performance electrocatalysts for industrial water electrolysis.

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