Manipulation of Electron Spins with Oxygen Vacancy on Amorphous/Crystalline Composite-Type Catalyst

By substituting the oxygen evolution reaction (OER) with the anodic urea oxidation reaction (UOR), it not only reduces energy consumption for green hydrogen generation but also allows purification of urea-rich wastewater. Spin engineering of the d orbital and oxygen-containing adsorbates has been recognized as an effective pathway for enhancing the performance of electrocatalysts. In this work, we report the fabrication of a bifunctional electrocatalyst composed of amorphous RuO₂-coated NiO ultrathin nanosheets (a-RuO₂/NiO) with abundant amorphous/crystalline interfaces for hydrogen evolution reaction (HER) and UOR. Impressively, only 1.372 V of voltage is required to attain a current density of 10 mA cm^-2 over a urea electrolyzer. The increased oxygen vacancies in a-RuO₂/NiO by incorporation of amorphous RuO₂ enhance the total magnetization and entail numerous spin-polarized electrons during the reaction, which speeds up the UOR reaction kinetics. The density functional theory study reveals that the amorphous/crystalline interfaces promote charge-carrier transfer, and the tailored d-band center endows the optimized adsorption of oxygen-generated intermediates. This kind of oxygen vacancy induced spin-polarized electrons toward boosting HER and UOR kinetics and provides a reliable reference for exploration of advanced electrocatalysts.