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Accelerated Deprotonation Triggered by Fluorinated RuO <sub>2</sub> Enables Efficient and Stable Acidic Water Electrolysis

Jian Zheng, Zheng-Jie Chen, Wei Lü, Jiajing Wu, Tao Shi, Lili Zhang, Shida Bao, Siyi Ming, Baihua Feng, Fei Meng, Huanyu Jin, Yuanmiao Sun, Jing Peng, Changzheng Wu

2025Journal of the American Chemical Society16 citationsDOI

Abstract

Ru-based catalysts are considered highly promising candidates for enabling cost-effective proton exchange membrane water electrolyzers (PEMWEs). However, under the harsh conditions of acidic oxygen evolution reaction (OER), Ru sites are prone to undesired overoxidation, leading to substantial deterioration in catalytic activity. Herein, we demonstrate a hydrogen-bond-mediated mechanism triggered by fluoride ion (F – ) in RuO 2 (RuO 1.86 F 0.14 ) to achieve both high activity and stability. The spontaneous transfer of protons to bridging oxygen through hydrogen bonds accelerates the deprotonation of an oxo-intermediate, which improves the kinetics of the OER in acidic conditions. Moreover, the highly electronegative F – diminishes the covalency of Ru–O bonds and thus boosts the stability of RuO 2 . The optimized RuO 1.86 F 0.14 catalyst presents an ultralow overpotential of 153 mV at 10 mA cm –2 and can sustain for more than 980 h with a low degradation rate of 27 μV h –1 . Notably, the RuO 1.86 F 0.14 applied in PEMWEs requires only 1.63 V and maintains stable operation for over 100 h at 1 A cm –2 . This work demonstrates a promising anion-modulated approach to the design of high-performance acidic OER catalysts.

Topics & Concepts

ChemistryDeprotonationOverpotentialCatalysisOxygen evolutionElectrolysis of waterInorganic chemistryElectrolysisOxygenWater splittingPhotochemistryIonDegradation (telecommunications)KineticsHydrogen bondMembraneSynergistic catalysisProton transportProtonFluorideReaction mechanismChemical engineeringIon exchangeReaction intermediateElectrolytePolyoxometalateHybrid Renewable Energy SystemsElectrocatalysts for Energy ConversionIntegrated Energy Systems Optimization
Accelerated Deprotonation Triggered by Fluorinated RuO <sub>2</sub> Enables Efficient and Stable Acidic Water Electrolysis | Litcius