Durable acidic water oxidation ruthenium based electrocatalyst by fluorination induced symmetry breaking.

Jin, Mengyuan; Chen, Jiadong; Han, Xiang; Guo, Yaqing; Liu, Yiyan; Wang, Juan; Li, Jun; Yuan, Yifei et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

Ru-based materials exhibit high electrocatalytic activity for the acidic oxygen evolution reaction, but they are prone to transform into soluble RuO<sub>4</sub> species via traditional lattice oxygen mechanism at high oxidation potentials, resulting in rapid inactivation. Herein, density functional theory calculations predict that the F induced symmetry-breaking can alter the oxygen evolution reaction route of RuO<sub>2</sub> from the lattice oxygen mechanism route to the stable adsorption evolution mechanism pathway. Consequently, we fabricate an efficient F-RuO<sub>2</sub>/FC electrocatalyst by substituting a portion of O in RuO<sub>2</sub> with F. Specifically, it can operate continuously for over 1440 h (2 months) at 100, 500 and 1000 mA cm<sup>-2</sup> when using F-RuO<sub>2</sub>/FC as anode electrocatalyst in proton exchange membrane water electrolyzer. Detailed in situ experiments demonstrate that the adsorption of intermediates is impacted by the presence of F in RuO<sub>2</sub>, thus forcing the oxygen evolution reaction to proceed via the adsorption evolution mechanism. This study provides experimental and theoretical insights for customizing stable Ru-based electrocatalysts for water splitting and beyond.