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The key is to find an effective photocatalyst to do the trick. Defect engineering of semiconductors with oxygen vacancies (OVs) is an emerging strategy for catalyst fabrication. OVs can trap electrons to promote charge separation and serving as adsorption sites for O<jats:sub>2<\/jats:sub> activation. However, the randomly distribution of OVs on the semiconductor surface often results in mismatching the charge carrier dynamics under irradiation, thus failing to fulfill the unique advantages of OVs for photoredox functions. Herein, we demonstrate that abundant OVs can be facilely generated and precisely located adjacent to the reductive sites on reducible oxide semiconductors such as tungsten oxide (WO<jats:sub>3<\/jats:sub>) via a simple photochemistry strategy. Such photoinduced OVs are well suited for photocatalytic benzene oxidation with O<jats:sub>2<\/jats:sub> as they readily capture photogenerated electrons from the reductive sites of WO<jats:sub>3<\/jats:sub> to activate adsorbed O<jats:sub>2<\/jats:sub>. The oxygen\u2010isotope\u2010labeling experiments further confirm that the OVs also facilitate the integration of oxygen atoms from O<jats:sub>2<\/jats:sub> into phenol, revealing in detail the pathway for photocatalytic benzene hydroxylation. This study demonstrates that the photochemistry approach is an appealing strategy for the synthesis of high\u2010performance OVs\u2010rich photocatalysts for solar\u2010induced chemical conversion.<\/jats:p>","DOI":"10.1002\/anie.202417703","type":"journal-article","created":{"date-parts":[[2024,10,9]],"date-time":"2024-10-09T03:14:16Z","timestamp":1728443656000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":37,"title":["Visible\u2010Light\u2010Driven Oxidation of Benzene to Phenol with O<sub>2<\/sub> over Photoinduced Oxygen\u2010Vacancy\u2010Rich WO<sub>3<\/sub>"],"prefix":"10.1002","volume":"64","author":[{"given":"Wenhui","family":"Zhou","sequence":"first","affiliation":[{"name":"State Key Laboratory of Photocatalysis on Energy and Environment College of Chemistry Fuzhou University  Fuzhou 350108 P. R. China"},{"name":"School of Chemistry and Chemical Engineering Shanghai Jiao Tong University  Shanghai 200240 P. R. 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