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Visualizing dual-sites synergistic catalysis in non-iridium catalysts for acidic oxygen evolution reaction
Meihuan Liu1, Qianqian Xu1, Peiqiong Zhou1
1State Key Laboratory for Powder Metallurgy, Central South University, Changsha, Hunan, China.
None:
Understanding electron transfer at the solid/liquid electrochemical interface is critical for deciphering synergistic catalysis, yet elucidating how metal dopants mediate charge transfer between adjacent active centers remains challenging. Here, we incorporate a series of metal dopants (Cu, Mn, W) into RuO2 to investigate how dual-site (M-Ru) electron transfer affects catalytic activity and stability. Combining in situ characterization with theoretical simulations, we reveal that Mn doping intensifies Ru 4d-O 2p orbital coupling and establishes unidirectional electron transfer, which peroxidizes Ru under high voltage and accelerates performance degradation. In contrast, W doping modulates the Ru 4d- and O 2p-band centers to reduce orbital overlap, weakening Ru-O covalency and enabling bidirectional electron transfer. Functioning as a voltage-gated electron regulator, the W site dynamically switches roles: at low potentials it acts as an electron acceptor to activate Ru sites and promote water dissociation, while at high potentials it serves as an electron donor to suppress Ru peroxidation. This mechanism endows the catalyst with good stability, showing negligible activity decay during 300 hours of operation at 500 mA cm⁻².
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