Interfacial Ru–O–W Orbital Coupling Enables Lattice Oxygen Stabilization for Enhanced Acidic OER

Abstract

Ruthenium dioxide (RuO₂) is highly active for acidic oxygen evolution reaction (OER) but suffers from instability due to lattice oxygen oxidation. Herein, we construct a RuO₂/WO₃ heterostructure that leverages strong Ru–O–W interfacial bridge bonding to fundamentally modulate electronic structure and reaction pathways. Density functional theory calculations reveal pronounced orbital hybridization at the interface, resulting in a simultaneous downshift of the Ru d-band and O p-band centers. This modulation weakens the Ru–O* interaction while strengthening the Ru–O bonds, effectively suppressing the lattice oxygen mechanism. Benefiting from this electronic structure regulation strategy, the RuO₂/WO₃ electrode delivers a substantially low overpotential of 203 mV at 10 mA cm⁻² and maintains exceptional structural and electrochemical integrity over 200 h of continuous acidic OER operation. This work unveils a new paradigm of orbital-level interface engineering for stabilizing noble-metal catalysts under harsh acidic conditions.

Keywords

acidic oxygen evolution reaction / orbital hybridization / robust Ru–O–W bond / supported catalyst

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