Hefei National Laboratory for Physical Science at the Microscale, CAS Center for Excellence in Nanoscience, iChEM , University of Science and Technology of China , Hefei 230026 , People's Republic of China.
College of Chemistry, Chemical Engineering and Materials Science , Shandong Normal University , Jinan 250014 , People's Republic of China.
J Am Chem Soc. 2019 Mar 6;141(9):3797-3801. doi: 10.1021/jacs.8b13051. Epub 2019 Feb 21.
Photocatalytic selective oxidation reactions hold great promise for the design of high-value-added organic intermediates, but many of these reactions suffer from low conversion efficiency and selectivity due to uncontrollable oxidation processes. In view of using photogenerated reactive oxygen species as the key oxidant in a selective oxidation reaction, we propose that a highly selective oxidation reaction can be achieved by modulating the corresponding photocatalytic molecular oxygen (O) activation processes. Using cubic indium sulfide (β-InS) nanosheets as a model system, we show that the charge carriers involved in O activation can be optimized with the introduction of surface S vacancies. Benefiting from the enhanced charge separation and transfer processes, the InS nanosheets with S vacancies could simultaneously activate O into superoxide radicals via electron transfer under visible-light irradiation to display outstanding activity for the selective oxidation of alcohols to aldehydes with high conversion and selectivity. This study offers a new strategy to optimize photocatalytic selective oxidation reactions.
光催化选择性氧化反应在设计高附加值有机中间体方面具有广阔的前景，但由于氧化过程不可控，许多此类反应的转化率和选择性较低。鉴于使用光生活性氧物种作为选择性氧化反应中的关键氧化剂，我们提出可以通过调节相应的光催化分子氧（O）激活过程来实现高选择性氧化反应。我们使用立方硫化铟（β-InS）纳米片作为模型体系，表明通过引入表面 S 空位可以优化涉及 O 激活的电荷载流子。受益于增强的电荷分离和转移过程，具有 S 空位的 InS 纳米片可以在可见光照射下通过电子转移将 O 同时激活为超氧自由基，从而在选择性氧化醇为醛的反应中表现出高转化率和高选择性的优异活性。本研究为优化光催化选择性氧化反应提供了一种新策略。
