Synthesis and Characterization of Imine-based Covalent Organic Framework(COF-LZU1) in Supercritical Carbon Dioxide

doi:10.7503/cjcu20200185

Abstract

Abstract: This study concerned the utilization of supercritical CO₂(scCO₂) for the synthesis of covalent organic framework(COF). One kind of imine-based covalent organic framework, COF-LZU1, was prepared via the condensation of 1,3,5-triformylbenzene and p-phenylenediamine with acetic acid as catalyst and N,N-dimethylformamide(DMF) as co-solvent in scCO₂. The effects of co-solvent type, temperature, pressure, time, acid volume and molar ratio of reactants on the crystal structure and microstructure of COF-LZU1 were investigated. Increasing the reaction temperature could increase the solubility of the reactants in scCO₂ and promote the reaction. The extension of the reaction time was conducive to the maturity of crystals and the improvement of crystallinity. Acetic acid not only catalyzed the reaction, but also acted as a morphology guide agent, different morphologies of COF-LZU1(spheres, blocks and nanorods) could be obtained by changing volume of acetic acid. When the content of p-phenylenediamine in the reaction was too high, it would interfered with the orderly combination of aldehyde groups and amino groups in the reaction process, resulting in a reduction in crystallinity and the declining degree of appearance. The particles synthesized with the molar ratio of 1,3,5-triformylbenzene to p-phenylenediamine as 1:1.5 and the volume ratio of HAc to DMF as 1:1 at 60℃, 20 MPa only within 6 h have the advantages of good crystallinity, nanoscale size, and excellent thermal stability up to 550℃. It is the first time that COF materials was successfully synthesized in scCO₂. This method offers new route for facile and green synthesis of COFs.

Key words: Imine-based covalent organic framework(COF-LZU1), Supercritical fluid, Reaction crystallization

CLC Number:

O621.3

TrendMD:

WANG Yang, WANG Sidi, TANG Shaokun. Synthesis and Characterization of Imine-based Covalent Organic Framework(COF-LZU1) in Supercritical Carbon Dioxide[J]. Chem. J. Chinese Universities, 2020, 41(8): 1792.

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