富氮类共价有机骨架材料COF-MC催化Knoevenagel缩合反应的应用

doi:10.16085/j.issn.1000-6613.2021-1467

摘要/Abstract

摘要：

以三聚氰胺和三聚氯氰为前体，采用溶剂热法制备富氮类共价有机骨架材料 COF-MC[含氮量为55%（质量分数）]。利用傅里叶变换红外光谱（FTIR）、X射线衍射（XRD）、N₂吸附-脱附、扫描电子显微镜（SEM）、热重（TGA）和X射线光电子能谱（XPS）测试手段对COF-MC进行表征。通过对COF-MC在苯甲醛和丙二腈Knoevenagel缩合反应中催化性能的评价，考察反应条件与催化性能的关系，并对 Knoevenagel缩合反应的碱性催化机理进行了初步的探讨。实验结果表明，COF-MC作为催化剂在氮气环境中，无需借助其他溶剂，80℃回流搅拌2h后，苯甲醛转化率为98%，苄烯丙二腈选择性在99.9%以上。反应后的催化剂可以通过简单的热过滤分离，重复使用4次后苯甲醛转化率仍可达89%，且催化剂中无金属离子的参与，避免了金属对环境的污染。

关键词: 共价有机骨架材料, 催化剂, 制备, Knoevenagel 缩合反应, 催化作用

Abstract:

Nitrogen-rich covalent organic framework material COF-MC (mass fraction of nitrogen was 55%) was synthesized using melamine and cyanuric chloride as precursors by solvothermal method. COF-MC was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), N₂ adsorption-desorption, scanning electron microscopy (SEM), thermogravimetry (TGA) and X-ray photoelectron spectroscopy (XPS). Through the evaluation of the catalytic performance of COF-MC in the Knoevenagel condensation reaction of benzaldehyde and malononitrile, the relationship between reaction conditions and catalytic performance was investigated, and the basic catalytic mechanism of Knoevenagel condensation reaction was preliminarily discussed. The experimental results showed that: with COF-MC as the catalyst in the nitrogen environment without the help of other solvents, the conversion of benzaldehyde was 98% and the selectivity of benzalmalononitrile was over 99.9% after stirring at 80℃ for 2h. The reacted catalyst could be separated by simple thermal filtration, and the conversion of benzaldehyde could still reach 89% even after being utilized repeatedly four times. In addition, due to no metal ion in the catalyst, metal pollution to the environment was avoided.

Key words: covalent organic framework, catalyst, preparation, Knoevenagel condensation reaction, catalysis

中图分类号:

O643.32

吕杰琼, 谢晖, 高永平, 连丽丽, 王希越, 张浩, 高文秀, 娄大伟. 富氮类共价有机骨架材料COF-MC催化Knoevenagel缩合反应的应用[J]. 化工进展, 2022, 41(6): 2993-3001.

LYU Jieqiong, XIE Hui, GAO Yongping, LIAN Lili, WANG Xiyue, ZHANG Hao, GAO Wenxiu, LOU Dawei. Application of nitrogen-rich covalent organic framework material COF-MC catalyzing Knoevenagel condensation reaction[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 2993-3001.

图/表 13

图1 原料及COF-MC的红外谱图

图2 COF-MC的XRD谱图

图3 COF-MC的SEM图以及粒径分布直方图

图4 COF-MC氮气吸附-脱附等温线及NLDFT法测定的孔径分布曲线图

图5 COF-MC的热重谱图

图6 COF-MC的XPS谱图

表1 COF-MC中元素及不同种类氮质量分数

元素质量分数/%					不同种类氮质量分数/%
C	O	S	N		—N $? ????$	—NH—	—NH₂	π-π* 卫星峰
35.96	3.71	5.10	55.23		48.23	39.24	6.72	5.81

表1 COF-MC中元素及不同种类氮质量分数

元素质量分数/%					不同种类氮质量分数/%
C	O	S	N		—N $? ????$	—NH—	—NH₂	π-π* 卫星峰
35.96	3.71	5.10	55.23		48.23	39.24	6.72	5.81

表2 催化剂及底物比对Knoevenagel缩合反应的影响

序号

催化剂

n(苯甲醛)∶n(丙二腈)

转化率

选择性

TOF×10^-3

/mol·g^-1·h^-1

表3 催化剂用量对Knoevenagel 缩合反应的影响

序号	催化剂用量/mg	转化率/%	选择性/%	TOF $×$ 10^-3/mol·g^-1·h^-1
1	50	100	>99.9	100
2	40	100	>99.9	125
3	30	99	>99.9	163
4	20	98	>99.9	242
5	10	80	>99.9	402

表3 催化剂用量对Knoevenagel 缩合反应的影响

序号	催化剂用量/mg	转化率/%	选择性/%	TOF $×$ 10^-3/mol·g^-1·h^-1
1	50	100	>99.9	100
2	40	100	>99.9	125
3	30	99	>99.9	163
4	20	98	>99.9	242
5	10	80	>99.9	402

表4 反应温度及时间对苯甲醛与丙二腈Knoevenagel缩合反应的影响

序号	温度/℃	时间/h	转化率/%	选择性/%	TOF×10^-3/mol·g^-1·h^-1
1	60	2	79	>99.9	196
2	70	2	95	>99.9	238
3	80	2	98	>99.9	244
4	90	2	99	>99.9	248
5	80	0.5	61	>99.9	610
6	80	1	75	>99.9	375
7	80	1.5	94	>99.9	313
8	80	2.5	98	>99.9	196

图7 COF-MC催化剂的稳定性考察

表5 与已报道的苯甲醛和丙二腈 Knoevenagel 缩合反应催化剂比较

序号	催化剂	溶剂	温度/℃	时间/h	产率/%	TOF×10^-3/mol·g^-1·h^-1	参考文献
1	COF-MC	无	80	2	98	244	本文
2	COF-HNU14	无	25	5	99	50	［29］
3	A₂B₂-Pro-COF	甲苯/H₂O	60	3	81	27	［30］
4	COF-366-R	甲苯	60	6	81	25	［31］
5	GO/COF	无	室温	1/6	98	392	［18］
6	Co-MOF/COF	无	25	1/6	93	372	［32］
7	Zn-MOF/COF	无	25	1/6	99	396	［33］
8	NC-700	H₂O/乙醇	40	1	> 99	50	［23］
9	壳聚糖	乙醇	40	6	> 99	7	［34］
10	N-GO-1.00	CH₃CN	40	4	96.5	24	［35］
11	Cyt@SBA-15	乙醇	室温	1	99	99	［36］
12	UiO-66-NH-RNH₂	甲苯	室温	2	97	46	［37］

图8 COF-MC催化Knoevenagel缩合反应的机理

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