Lang Xianjun, Leow Wan Ru, Zhao Jincai, Chen Xiaodong
School of Materials Science and Engineering , Nanyang Technological University , 50 Nanyang Avenue , Singapore 639798 , Singapore . Email:
Key Laboratory of Photochemistry , Beijing National Laboratory for Molecular Sciences , Institute of Chemistry , Chinese Academy of Sciences , Beijing 100190 , China . Email:
Chem Sci. 2015 Feb 1;6(2):1075-1082. doi: 10.1039/c4sc02891k. Epub 2014 Oct 30.
Selective photocatalytic aerobic oxidation, which can be conducted under ambient conditions, is of great importance towards achieving sustainable chemistry. However, its practical applications are undermined by several challenges, such as low selectivity, sluggish reaction rates, and the requirement of UV light irradiation. Herein, we report a new concept of synergistic photocatalytic oxidation, for which two seemingly irrelevant reactions can be achieved in one photocatalytic system through the synergistic interplay of reactants and catalyst. As proof of concept, two challenging reactions, the aerobic oxidation of sulfide and the aerobic oxidative formylation of amine with methanol, were employed to demonstrate such synergistic photocatalytic aerobic oxidation under visible-light irradiation. This work could pave the way for highly selective photoredox catalysis rational design based on mechanistic insight.
可在环境条件下进行的选择性光催化需氧氧化对于实现可持续化学极为重要。然而，其实际应用受到诸多挑战的影响，如选择性低、反应速率缓慢以及需要紫外光照射等。在此，我们报道了一种协同光催化氧化的新概念，通过反应物与催化剂的协同相互作用，在一个光催化体系中可以实现两个看似不相关的反应。作为概念验证，采用了两个具有挑战性的反应——硫化物的需氧氧化和胺与甲醇的需氧氧化甲酰化反应，来证明在可见光照射下这种协同光催化需氧氧化。这项工作可为基于机理洞察的高选择性光氧化还原催化合理设计铺平道路。
