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[Por-sp²c-COF] 2D sp2 Carbon-Conjugated Porphyrin COFs for Cooperative Photocatalysis with TEMPO
Summary:
The authors from Wuhan University developed a 2D sp² carbon-conjugated porphyrin covalent organic framework (Por-sp²c-COF) with excellent stability and red-light absorption, achieving highly selective oxidation of amines into imines under red LED illumination in the field of photocatalysis.
Background:
1. To address the problem of limited visible light absorption and poor stability of traditional COFs, previous researchers conducted work, achieving success in synthesizing COFs with p-electron delocalization, yet there are problems with synthesis difficulty and limited absorption in the visible region.
2. The authors in this work proposed an innovative method of combining Por-sp²c-COF photocatalysis with TEMPO catalysis, obtaining unprecedented reaction efficiency and high selectivity under red light illumination.
Research Content:
1. Synthesis:
The authors synthesized the Por-sp²c-COF using the Knoevenagel condensation reaction of 5,10,15,20-tetrakis(4-benzaldehyde)porphyrin (p-Por-CHO) with 1,4-phenylenediacetonitrile (PDAN) in optimized ratio.
2. Characterizations:
1) Results of BET show a high specific surface area of 714 m²g⁻¹, and pore size distribution reveals a pore size of 1.91 nm.
2) SEM/TEM tests show the particle size of the material with a honeycomb-like internal structure.
3) Other electrochemical or optical tests reveal a broad absorption band in the visible light region and improved oxidation peak current with the addition of TEMPO.
3. Application:
The material was tested in the photocatalytic oxidation of various amines, achieving high conversions (up to 97%) and selectivities (up to 99%) within 30 min under red LED illumination.
4. Mechanism:
The analysis of the experiment results indicates that the linker-to-linkage charge transfer process in Por-sp²c-COF under red light illumination leads to effective e⁻-h⁺ separation, and the presence of TEMPO enhances the oxidation ability and promotes the selective oxidation of amines to imines.
Outlook:
This research provides a novel strategy for optimizing charge separation and transfer of COFs photocatalysis in cooperation with TEMPO catalysis, pushing forward visible-light-induced selective oxidation of amines and stimulating further discoveries on selective chemical transformations by cooperative photocatalysis.
2D sp² Carbon-Conjugated Porphyrin Covalent Organic Framework for Cooperative Photocatalysis with TEMPO
Authors: Ji-Long Shi, Rufan Chen, Huimin Hao, Cheng Wang, and Xianjun Lang
DOI：10.1002/anie.202000723
Link：https://onlinelibrary.wiley.com/doi/10.1002/anie.202000723
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