Oxygen‐Vacancy‐Engineered Ru–V Dual Sites in InVO ₄ for Synergistic Photocatalytic N ₂ Activation and Reactive Hydrogen Supply

ABSTRACT

Photocatalytic reduction of nitrogen to produce ammonia exhibits promise, and has increasingly attracted attention. However, this process is still limited by hindrances such as low water molecule dissociation efficiency and sluggish nitrogen hydrogenation kinetics. This study developed a catalyst composed of Ru nanoparticles directionally anchored at oxygen vacancies of indium vanadate (Ru/InVO ₄ ‐Vo), achieving an ammonia production rate of 87.86 μmol g ⁻¹  h ⁻¹ . It was found that oxygen vacancy not only forms unsaturated V sites but also serves as an anchoring site for Ru nanoparticles, establishing a stable Ru–V coordination structure through electronic metal–support interactions. These sites enhance the adsorption and activation of N ₂ through interfacial electron redistribution. Mechanistic studies reveal that Ru site promotes the adsorption of H ₂ O and accelerates H–OH bond cleavage, thereby providing a continuous supply of active hydrogen species (*H). Furthermore, Ru–V bimetallic interface induces electron redistribution, accelerating both N ₂ adsorption and hydrogenation steps in NRR. This unique two‐site cooperative mechanism enables the directed transfer of *H to a key intermediate (*NNH → *NNH ₂ ), thereby significantly accelerating the stepwise hydrogenation of nitrogen. This work not only revealed the key mechanism of dynamic *H supply in photocatalytic nitrogen fixation but also provided an innovative strategy for designing high‐performance NRR catalysts through defect‐mediated dual active site engineering.