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Updated: Jun 29, 2025

Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance
Published on: September 5, 2018
Tailoring β-ketoenamine covalent organic framework with azo for blue light-driven selective oxidation of amines with
Kanghui Xiong1, Yuexin Wang1, Fengwei Huang1
1Hubei Key Lab on Organic and Polymeric Optoelectronic Materials, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
Abstract:
Covalent organic frameworks (COFs) present bright prospects in visible light photocatalysis with abundant active sites and exceptional stability. Tailoring an established COF with photoactive group is a prudent strategy to extend visible light absorption toward broad photocatalysis. Here, a β-ketoenamine COF, TpBD-COF, constructed with 1,3,5-triformylphloroglucinol (Tp) and 4,4'-biphenyldiamine (BD), is tailored with azo to validate this strategy. The insertion of azo into BD affords 4,4'-azodianiline (Azo); TpAzo-COF is successfully constructed with Tp and Azo. Intriguingly, the insertion of azo enhances π-conjugation, thereby facilitating visible light absorption and intramolecular electron transfer. Moreover, TpAzo-COF, with an appropriate electronic structure and impressive specific surface area of 1855 m2 g-1, offers substantial active sites conducive to the reduction of oxygen (O2) to superoxide. Compared with TpBD-COF, TpAzo-COF exhibits superior performance for blue light-driven oxidation of amines with O2. Superoxide controls the selective formation of product imines. This work foreshadows the remarkable capacity of tailoring COFs with photoactive group toward broad visible light photocatalysis.
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