Wang Jie, Liang Jiahao, Hou Hao, Liu Wei, Wu Hongru, Sun Hongli, Ou Wei, Su Chenliang, Liu Bin
International Collaborative Laboratory of 2D Materials for Optoelectronic Science & Technology, Engineering Technology Research Center for 2D Materials Information Functional Devices and Systems of Guangdong Province, Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen, 518060, China.
State Key Laboratory of Radio Frequency Heterogeneous Integration, Shenzhen University, Shenzhen, 518060, China.
Nat Commun. 2024 Jun 4;15(1):4744. doi: 10.1038/s41467-024-48349-3.
Developing mild photocatalytic bromination strategies using sustainable bromo source has been attracting intense interests, but there is still much room for improvement. Full utilization of redox centers of photocatalysts for efficient generation of Br species is the key. Herein we report heterogenous organophotocatalytic HBr oxidation coupled with oxygen reduction to furnish Br and HO for effective bromination of arenes over AlO supported perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). Mechanism studies suggest that O-vacancy in AlO can provide Lewis-acid-type anchoring sites for O, enabling unexpected dual-electron transfer from anchored photoexcited PTCDA to chemically bound O to produce HO. The in-situ generated HO and Br over redox centers work together to generate HBrO for bromination of arenes. This work provides new insights that heterogenization of organophotocatalysts can not only help to improve their stability and recyclability, but also endow them with the ability to trigger unusual reaction mode via cooperative catalysis with supports.
开发使用可持续溴源的温和光催化溴化策略一直备受关注，但仍有很大的改进空间。充分利用光催化剂的氧化还原中心以高效生成溴物种是关键。在此，我们报道了非均相有机光催化HBr氧化与氧还原相结合，以提供Br和HO，用于在AlO负载的苝-3,4,9,10-四羧酸二酐（PTCDA）上对芳烃进行有效的溴化反应。机理研究表明，AlO中的氧空位可以为O提供路易斯酸型锚定位点，使锚定的光激发PTCDA向化学结合的O发生意外的双电子转移以产生HO。在氧化还原中心原位生成的HO和Br共同作用生成HBrO用于芳烃的溴化反应。这项工作提供了新的见解，即有机光催化剂的非均相化不仅有助于提高其稳定性和可回收性，还赋予它们通过与载体协同催化引发异常反应模式的能力。
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