超临界二氧化碳中亚胺类共价有机骨架材料COF-LZU1的合成与表征

doi:10.7503/cjcu20200185

高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (8): 1792.doi: 10.7503/cjcu20200185

超临界二氧化碳中亚胺类共价有机骨架材料COF-LZU1的合成与表征

王洋¹, 王思迪², 唐韶坤^1,2

1. 天津大学化工学院绿色合成与转化教育部重点实验室, 天津 300072;
2. 天津化学化工协同创新中心, 天津 300072

收稿日期:2020-04-07 出版日期:2020-08-10 发布日期:2020-07-31
通讯作者: 唐韶坤,女,博士,教授,主要从事绿色溶剂技术、功能材料与纳米技术等领域的研究.E-mail:shktang@tju.edu.cn E-mail:shktang@tju.edu.cn
基金资助:
Supported by the National Natural Science Foundation of China(No.51971001) and the Open Project Program of Key Laboratory of Metallurgical Emission Reduction & Resources Recycling(Anhui University of Technology), Ministry of Education, China(No.JKF20-6).

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

WANG Yang¹, WANG Sidi², TANG Shaokun^1,2

1. Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering&Technology, Tianjin University, Tianjin 300072, China;
2. Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Tianjin University, Tianjin 300072, China

Received:2020-04-07 Online:2020-08-10 Published:2020-07-31
Supported by:
Supported by the National Natural Science Foundation of China(No.51971001) and the Open Project Program of Key Laboratory of Metallurgical Emission Reduction & Resources Recycling(Anhui University of Technology), Ministry of Education, China(No.JKF20-6).

摘要/Abstract

摘要： 研究了超临界流体技术在共价有机骨架材料（COF）合成中的应用，以均苯三甲醛和对苯二胺为原料，N，N-二甲基甲酰胺为共溶剂，醋酸为催化剂，在超临界二氧化碳（scCO₂）中合成了亚胺类共价有机骨架材料COF-LZU1.考察了共溶剂、反应温度、反应压力、反应时间、醋酸含量和反应物摩尔比对COF-LZU1材料的晶体结构和微观形貌的影响.实验结果表明，反应温度的升高有利于提高scCO₂的传质速率及增加反应物在scCO₂中的溶解度，从而促进反应的进行；反应时间的延长有利于晶体的成熟和结晶度的提高；醋酸不仅是反应催化剂，还具有形貌导向剂的作用，通过改变醋酸用量分别获得了球状、块状和棒状形貌的COF-LZU1；反应物中对苯二胺含量过高会干扰反应过程中醛基与氨基的有序结合，导致结晶度的降低以及形貌规整程度的下降.在反应温度为60℃，反应压力为20 MPa，反应时间为6 h，均苯三甲醛与对苯二胺摩尔比为1：1.5，醋酸（3 mol/L）与N，N-二甲基甲酰胺体积比为1：1的条件下，制备的COF-LZU1呈现截面直径为80 nm的纳米棒形貌，具有良好的结晶度和优异的热稳定性，热分解温度高达550℃.本文首次在超临界环境中制备了COFs材料，为COFs的绿色合成提供了新途径.

关键词: 亚胺类共价有机骨架材料, 超临界流体, 反应结晶

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

中图分类号:

O621.3

TrendMD:

王洋, 王思迪, 唐韶坤. 超临界二氧化碳中亚胺类共价有机骨架材料COF-LZU1的合成与表征. 高等学校化学学报, 2020, 41(8): 1792.

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

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超临界二氧化碳中亚胺类共价有机骨架材料COF-LZU1的合成与表征

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

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