Photoexcited Hole‐Enabled Synthesis of Surface High‐Valent Cobalt‐Oxo Species with Water as the Oxygen Atom Source for Water Purification

作者：Ruidian Su, Zhen Liu, Jieshan Qiu, Nan Li, Xing Xu, Baoyu Gao, Qian Li · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202507085 · 被引用次数：24 · 研究领域：Advanced Photocatalysis Techniques、Catalytic Processes in Materials Science、Copper-based nanomaterials and applications

Abstract High‐valent cobalt‐oxo species (Co IV ═O) are key intermediates in catalytic chemistry but suffer a great challenge in their efficient and mild synthesis due to the strong electronic repulsion between the cobalt center and the oxygen ligand. Herein, we report a new approach to synthesizing surface Co IV ═O on the Co 3 O 4 /BiVO 4 (CoBi) catalyst via a photoexcited hole‐induced process using water as the oxygen atom source. The interfacial Co 2+ ─O─Bi 3+ bonds act as the atomic‐level channels to directionally transport photoexcited holes driven by the internal electric field effect. It has been found that H 2 O was photolyzed to cobalt‐coordinated hydroxyls that were turned to Co IV ═O via a photoexcited hole‐induced deprotonation. The isotopic labeling experiments confirmed that the oxygen atom source of Co IV ═O was derived from water rather than chlorite. A synergistic effect was formed between photocatalysis and transition metal‐catalyzed chlorite activation, which enhanced the degradation of sulfadiazine (SDZ) and elevated the conversion ratio of chlorite to chlorine dioxide (ClO 2 ) from 40% to 60%. The present work has elucidated the essential role of H 2 O and photoexcited holes in the formation of Co IV ═O and provides a viable strategy to synthesize surface high‐valent metal species utilizing ubiquitous water and sunlight for water purification.