Effect of Cation and Anion Vacancies in Ruthenium Oxide on the Activity and Stability of Acidic Oxygen Evolution

Electrocatalysts capable of working efficiently in acidic media for the oxygen evolution reaction (OER) are highly demanded for the large-scale utilization of proton exchange membrane (PEM) water electrolysis. This study focuses on the design and fabrication of cation/oxygen vacancy-enriched RuO2 catalysts to investigate the impact of defect types on the OER activity and stability of RuO2. The comprehensive blend of experimental and theoretical approaches elucidates that the presence of Ru vacancies in Ru1–xO2 modulates the d-band center and optimizes the adsorption energy of the OER intermediates, thereby augmenting the intrinsic OER activity. Conversely, the presence of oxygen vacancies in RuO2-x diminishes the strength of Ru–O bonds, suppressing the involvement of the lattice oxygen oxidation mechanism (LOM) and Ru dissolution, consequently enhancing long-term stability. Notably, Ru1–xO2 exhibits the lowest overpotential of 212 mV at 10 mA cmgeo–2, while RuO2–x demonstrates superior stability, enduring 400 h under 10 mA cmgeo–2, surpassing many catalysts for acidic OER in the literature. Our findings demonstrate that defect engineering is a promising strategy to achieve electrocatalysts with super catalytic performance in acid media for water electrolysis.