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Dynamic Reconstruction of Vanadium Oxide Species Modified Ruthenium-Cerium Catalysts: Electron Bridge and
Jiawei Li1, Ziyang Zhu1, Zirui Wang1
1College of Chemistry, Beijing University of Chemical Technology, Beijing, P. R. China.
Abstract:
Developing efficient electrocatalysts for the hydrogen evolution reaction (HER) in acidic media is critical for proton exchange membrane water electrolyzers (PEMWEs). Herein, we report a Ru-CeVOX catalyst with oxygen vacancies and surface vanadium oxide species. The optimized Ru-CeVOX exhibits excellent HER activity in 0.5 M H2SO4, achieving overpotentials of 35.9 mV at 10 mA cm-2 and 193.6 mV at 1000 mA cm-2, outperforming commercial Pt/C. In a PEMWE device, it delivers 1 A cm-2 at 1.80 V and maintains stability for over 400 h at 500 mA cm-2. Time-resolved ICP-OES reveals in situ reconstruction, during which Ru0 redeposits to form a dynamically stable, Ru-rich active surface. Vanadium plays a dual critical role. The vanadium oxide species anchor onto the CeO2 surface, constructing a Ru-O-Ce-O-V electron bridge that withdraws electrons from Ru, stabilizing Ru0 and optimizing its d-band center for near-ideal H* adsorption. vanadium oxide species actively disrupt the interfacial hydrogen-bonding network, reducing strongly bound water and increasing free water molecules. This disruption facilitates H* recombination on adjacent Ru sites, accelerating the Tafel step which is the rate-determining step of HER on Ru-CeVOX. Thus, vanadium-induced reconstruction, combining electron bridging and hydrogen-bond disruption, offers a powerful strategy for designing high-performance acidic HER catalysts.
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