Effective charge and energy transfers within a metal-organic framework for efficient photocatalytic oxidation of amines and sulfides

作者：Wang, Shao-Dan; Lai, Chun-Lin; Zhang, Yi-Xuan; Bao, Shu-Tong; Lv, Kang-Le; Wen, Li-Li^*

来源：Journal of Materials Chemistry A, 2022, 10(39): 20975-20983.

DOI：10.1039/d2ta05218k

• SELECTIVE AEROBIC OXIDATION
• PORPHYRIN FRAMEWORK
• LIGHT
• MOFS
• AGGREGATION
• REDUCTION
• POLYMERS
• IMINES
• GOLD

The photocatalytic reaction is regarded as an efficient and sustainable strategy to convert solar energy into chemical energy. In the work, a novel metal-organic framework Zn-5(TPyP)(BCTC)(2)(H2O)(3) (denoted as CCNU-16, H2TPyP = 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine, H4BCTC = [9,9 '-bicarbazole]-3,3 ',6,6 '-tetracarboxylic acid) was successfully synthesized from porphyrin- and carbazole-based organic linkers, which exhibits excellent visible-light-responsive characteristic. CCNU-16 was further applied toward photo-induced aerobic oxidation of amines and sulfides in air under visible light illumination and ambient conditions. Outstandingly, the turnover frequency (TOF) of the photocatalytic oxidative coupling of benzylamine over CCNU-16 is at the high end among MOF-based photocatalysts, so far, even under green and mild conditions. The excellent photocatalytic activity is attributed to superoxide radical anion (O-2(.-)) and singlet oxygen (O-1(2)) generated by the synergistic charge transfer (CT) and energy transfer (ET) processes, which provide a reasonable and efficient method for the photocatalytic oxidation of organic transformations.

• 单位
  中国科学院福建物质结构研究所