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Visible‐Light‐Driven Oxidation of Benzene to Phenol with O<sub>2</sub> over Photoinduced Oxygen‐Vacancy‐Rich WO<sub>3</sub>

Wenhui Zhou, Xiaoyi Wang, Xiaoyi Wang, Feng Lin, Sikang Xue, Wei Lin, Yidong Hou, Zhiyang Yu, Masakazu Anpo, Jimmy C. Yu, Jinshui Zhang, Xinchen Wang, Xinchen Wang

2024Angewandte Chemie15 citationsDOI

Abstract

Abstract Direct photocatalytic conversion of benzene to phenol with molecular oxygen (O 2 ) is a green alternative to the traditional synthesis. 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 2 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 3 ) via a simple photochemistry strategy. Such photoinduced OVs are well suited for photocatalytic benzene oxidation with O 2 as they readily capture photogenerated electrons from the reductive sites of WO 3 to activate adsorbed O 2 . The oxygen‐isotope‐labeling experiments further confirm that the OVs also facilitate the integration of oxygen atoms from O 2 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‐performance OVs‐rich photocatalysts for solar‐induced chemical conversion.

Topics & Concepts

PhenolPhotochemistryBenzeneOxygenVisible spectrumChemistryVacancy defectMaterials scienceOrganic chemistryCrystallographyOptoelectronicsCatalysis and Oxidation ReactionsCatalytic Processes in Materials SciencePorphyrin and Phthalocyanine Chemistry
Visible‐Light‐Driven Oxidation of Benzene to Phenol with O<sub>2</sub> over Photoinduced Oxygen‐Vacancy‐Rich WO<sub>3</sub> | Litcius