AbstractOxygen vacancy (Ov) sites play a critical role in the activation and deep oxidation of nitric oxide (NO). However, controlling the concentration and type of Ov remains a significant challenge. In this study, Bi2W(Mo)O6‐x is investigated as a model system and demonstrates that increasing the concentration of Ov substantially enhances the efficiency of air NO removal. Increasing the Ov concentrations in Bi2WO6‐x and Bi2MoO6‐x improves NO removal efficiency ≈12‐ and 11‐fold, respectively, compared to their low‐Ov counterparts. This enhancement is attributed to improved adsorption and activation of NO/O2 molecules, better separation and transfer of photogenerated carriers, and increased visible light absorption. Notably, Bi2WO6‐x remains highly stable over ten recycling tests for continuous air NO deep photooxidation, while Bi2MoO6‐x shows a 43.5% decrease in efficiency after ten runs. This sustained performance is attributed to stable Ovs without changes in metal ion valence, unlike Bi2MoO6‐x, where instability arises from the reduction of Mo6+ to Mo4+. In situ DRIFTS reveals possible pathways for the deep photooxidation of NO to nitrate (NO3−). This study provides valuable insights into designing high‐performance, durable catalysts by effectively controlling Ov concentration and type, paving the way for efficient photocatalytic air purification technologies.
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