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

图2

图3

图4

图5

图6

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

表2

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

表4

图7

表5

图8

参考文献 38

1	APPATURI J N, PULINGAM T, RAJABATHAR J R, et al. Acid-base bifunctional SBA-15 as an active and selective catalyst for synthesis of ethyl α-cyanocinnamate via Knoevenagel condensation[J]. Microporous and Mesoporous Materials, 2021, 320: 111091.
2	PATEL D, VITHALANI R, MODI C K. Highly efficient FeNP-embedded hybrid bifunctional reduced graphene oxide for Knoevenagel condensation with active methylene compounds[J]. New Journal of Chemistry, 2020, 44(7): 2868-2881.
3	陈琳, 谢蓉蓉, 关丽, 等. 苯并-α-吡喃酮类生物活性物质的合成[J]. 化工进展, 2014, 33(8): 2160-2164.
	CHEN Lin, XIE Rongrong, GUAN Li, et al. Synthesis of some biologically active coumarins[J]. Chemical Industry and Engineering Progress, 2014, 33(8): 2160-2164.
4	YANG Y, WANG D, JIANG P F, et al. Structure-induced Lewis-base Ga₄B₂O₉and its superior performance in Knoevenagel condensation reaction[J]. Molecular Catalysis, 2020, 490: 110914.
5	RUBAN S M, SATHISH C I, RAMADASS K, et al. Ordered mesoporous carbon nitrides with tuneable nitrogen contents and basicity for Knoevenagel condensation[J]. ChemCatChem, 2021, 13(1): 468-474.
6	高朋召, 吴迪, 郑航博, 等. 有机胺改性对ZIF-8催化Knoevenagel缩合反应活性的影响[J]. 湖南大学学报(自然科学版), 2020, 47(8): 124-132.
	GAO Pengzhao, WU Di, ZHENG Hangbo, et al. Effect of amine modification on catalytic activity of ZIF-8 in Knoevenagel condensation reaction[J]. Journal of Hunan University (Natural Sciences), 2020, 47(8): 124-132.
7	颜世强, 郭伟, 王文笙, 等. 锌-脯氨酸复合物催化的水相Knoevenagel缩合[J]. 有机化学, 2019, 39(5): 1469-1474.
	YAN Shiqiang, GUO Wei, WANG Wensheng, et al. Zinc-proline complex catalyzed Knoevenagel condensation in water[J]. Chinese Journal of Organic Chemistry, 2019, 39(5): 1469-1474.
8	ŞEN B, AKDERE E H, ŞAVK A, et al. A novel thiocarbamide functionalized graphene oxide supported bimetallic monodisperse Rh-Pt nanoparticles (RhPt/TC@GO NPs) for Knoevenagel condensation of aryl aldehydes together with malononitrile[J]. Applied Catalysis B: Environmental, 2018, 225: 148-153.
9	JOHARIAN M, MORSALI A, AZHDARI TEHRANI A, et al. Water-stable fluorinated metal–organic frameworks (F-MOFs) with hydrophobic properties as efficient and highly active heterogeneous catalysts in aqueous solution[J]. Green Chemistry, 2018, 20(23): 5336-5345.
10	BAHUGUNA A, KUMAR A, CHHABRA T, et al. Potassium-functionalized graphitic carbon nitride supported on reduced graphene oxide as a sustainable catalyst for Knoevenagel condensation[J]. ACS Applied Nano Materials, 2018, 1(12): 6711-6723.
11	李航, 付海, 班大明, 等. 蒙脱土负载KF催化Knoevenagel缩合反应[J]. 福建师范大学学报(自然科学版), 2019, 35(4): 37-43.
	LI Hang, FU Hai, BAN Daming, et al. Montmorillonite loading KF catalyzed Knoevenagel condensation reaction[J]. Journal of Fujian Normal University (Natural Science Edition), 2019, 35(4): 37-43.
12	李琳琳, 龚维, 付海, 等. 介孔分子筛KF-SBA-15的制备及其催化Knoevenagel反应[J]. 化学工业与工程, 2020, 37(3): 17-22.
	LI Linlin, GONG Wei, FU Hai，et al. Preparation of KF-SBA-15 and its catalytic Knoevenagel reaction[J]. Chemical Industry and Engineering, 2020, 37(3): 17-22.
13	TANGALE N P, SONAR S K, NIPHADKAR P S, et al. Hierarchical K/LTL zeolites: synthesis by alkali treatment, characterization and catalytic performance in Knoevenagel condensation reaction[J]. Journal of Industrial and Engineering Chemistry, 2016, 40: 128-136.
14	COTE A P, BENIN A I, OCKWIG N W, et al. Porous, crystalline, covalent organic frameworks[J]. Science, 2005, 310(5751): 1166-1170.
15	刘祎, 汪明旺, 吕宏凌, 等. 共价有机骨架聚合物功能膜制备方法的研究进展[J]. 化工进展, 2021, 40(8): 4360-4370.
	LIU Yi, WANG Mingwang, Hongling LYU, et al. Research progress in the preparation method of covalent organic framework polymers (COFs) functional membranes[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4360-4370.
16	张安睿, 艾玥洁. 共价有机框架(COFs)材料的结构控制及其在环境化学中的应用[J]. 化学进展, 2020, 32(10): 1564-1581.
	ZHANG Anrui, AI Yuejie. Structure control of covalent organic frameworks(COFs) and their applications in environmental chemistry[J]. Progress in Chemistry, 2020, 32(10): 1564-1581.
17	WU X C, WANG B W, YANG Z Q, et al. Novel imine-linked covalent organic frameworks: preparation, characterization and application[J]. Journal of Materials Chemistry A, 2019, 7(10): 5650-5655.
18	MONEHZADEH F, RAFIEE Z. Application of GO/COF as a novel, efficient and recoverable catalyst in the Knoevenagel reaction[J]. Applied Organometallic Chemistry, 2020, 34(6): e5631.
19	APPATURI J N, RATTI R, PHOON B L, et al. A review of the recent progress on heterogeneous catalysts for Knoevenagel condensation[J]. Dalton Transactions, 2021, 50(13): 4445-4469.
20	QI S C, WU J K, LU J, et al. Underlying mechanism of CO₂ adsorption onto conjugated azacyclo-copolymers: N-doped adsorbents capture CO₂ chiefly through acid–base interaction?[J]. Journal of Materials Chemistry A, 2019, 7(30): 17842-17853.
21	焦莉, 徐金妹, 张秋亚, 等. 氨基修饰片状氮化碳的制备及光催化性能[J]. 化工进展, 2020, 39(5): 1866-1874.
	JIAO Li, XU Jinmei, ZHANG Qiuya, et al. Preparation and photocatalytic activity of amino-modified sheet-like carbon nitride[J]. Chemical Industry and Engineering Progress, 2020, 39(5): 1866-1874.
22	WANG Z Z, LYU P, HU Y, et al. Thermal degradation study of intumescent flame retardants by TG and FTIR: melamine phosphate and its mixture with pentaerythritol[J]. Journal of Analytical and Applied Pyrolysis, 2009, 86(1): 207-214.
23	HU X W, LONG Y, FAN M Y, et al. Two-dimensional covalent organic frameworks as self-template derived nitrogen-doped carbon nanosheets for eco-friendly metal-free catalysis[J]. Applied Catalysis B: Environmental, 2019, 244: 25-35.
24	BHUNIA M K, MELISSEN S, PARIDA M R, et al. Dendritic tip-on polytriazine-based carbon nitride photocatalyst with high hydrogen evolution activity[J]. Chemistry of Materials, 2015, 27(24): 8237-8247.
25	WANG H F, WANG C Y, YANG Y F, et al. H₃PW₁₂O₄₀/mpg-C₃N₄ as an efficient and reusable bifunctional catalyst in one-pot oxidation–Knoevenagel condensation tandem reaction[J]. Catalysis Science & Technology, 2017, 7(2): 405-417.
26	LIU H H, CHEN D L, WANG Z Q, et al. Microwave-assisted molten-salt rapid synthesis of isotype triazine-/heptazine based g-C₃N₄ heterojunctions with highly enhanced photocatalytic hydrogen evolution performance[J]. Applied Catalysis B: Environmental, 2017, 203: 300-313.
27	HUA S X, QU D, AN L, et al. Highly efficient p-type Cu₃P/n-type g-C₃N₄ photocatalyst through Z-scheme charge transfer route[J]. Applied Catalysis B: Environmental, 2019, 240: 253-261.
28	CHAUDHARY M, SINGH L, REKHA P, et al. Adsorption of uranium from aqueous solution as well as seawater conditions by nitrogen-enriched nanoporous polytriazine[J]. Chemical Engineering Journal, 2019, 378: 122236.
29	ZHAO Y L, ZHAO Y, QIU J K, et al. Facile grafting of imidazolium salt in covalent organic frameworks with enhanced catalytic activity for CO₂ fixation and the Knoevenagel reaction[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(50): 18413-18419.
30	HAO W J, CHEN D, LI Y S, et al. Facile synthesis of porphyrin based covalent organic frameworks via an A₂B₂ monomer for highly efficient heterogeneous catalysis[J]. Chemistry of Materials, 2019, 31(19): 8100-8105.
31	HU J Y, ZANCA F, MCMANUS G J, et al. Catalyst-enabled in situ linkage reduction in imine covalent organic frameworks[J]. ACS Applied Materials & Interfaces, 2021, 13(18): 21740-21747.
32	RAHMATI E, RAFIEE Z. Synthesis of Co-MOF/COF nanocomposite: application as a powerful and recoverable catalyst in the Knoevenagel reaction[J]. Journal of Porous Materials, 2021, 28(1): 19-27.
33	RAFIEE Z. Fabrication of efficient Zn-MOF/COF catalyst for the Knoevenagel condensation reaction[J]. Journal of the Iranian Chemical Society, 2021, 18(10): 2657-2664.
34	SAKTHIVEL B, DHAKSHINAMOORTHY A. Chitosan as a reusable solid base catalyst for Knoevenagel condensation reaction[J]. Journal of Colloid and Interface Science, 2017, 485: 75-80.
35	XUE B, ZHU J G, LIU N, et al. Facile functionalization of graphene oxide with ethylenediamine as a solid base catalyst for Knoevenagel condensation reaction[J]. Catalysis Communications, 2015, 64: 105-109.
36	RAJABI F, FAYYAZ F, LUQUE R. Cytosine-functionalized SBA-15 mesoporous nanomaterials: synthesis, characterization and catalytic applications[J]. Microporous and Mesoporous Materials, 2017, 253: 64-70.
37	LUAN Y, QI Y, GAO H Y, et al. A general post-synthetic modification approach of amino-tagged metal–organic frameworks to access efficient catalysts for the Knoevenagel condensation reaction[J]. Journal of Materials Chemistry A, 2015, 3(33): 17320-17331.
38	ZHANG L N, WANG H, SHEN W Z, et al. Controlled synthesis of graphitic carbon nitride and its catalytic properties in Knoevenagel condensations[J]. Journal of Catalysis, 2016, 344: 293-302.

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］

[1]	储甜甜, 刘润竹, 杜高华, 马嘉浩, 张孝阿, 王成忠, 张军营. 有机胍催化脱氢型RTV硅橡胶的制备和可降解性能[J]. 化工进展, 2023, 42(7): 3664-3673.
[2]	李佳, 樊星, 陈莉, 李坚. 硝酸生产尾气中NO _x 和N₂O联合脱除技术研究进展[J]. 化工进展, 2023, 42(7): 3770-3779.
[3]	于姗, 段元刚, 张怡欣, 唐春, 付梦瑶, 黄靖元, 周莹. 分步法分解硫化氢制氢和硫黄催化剂研究进展[J]. 化工进展, 2023, 42(7): 3780-3790.
[4]	俞俊楠, 俞建峰, 程洋, 齐一搏, 化春键, 蒋毅. 基于深度学习的变宽度浓度梯度芯片性能预测[J]. 化工进展, 2023, 42(7): 3383-3393.
[5]	汪嘉欣, 潘勇, 熊欣怡, 万晓月, 王建超. 甲苯一步催化硝化制备二硝基甲苯反应过程及危险性[J]. 化工进展, 2023, 42(7): 3420-3430.
[6]	韩恒文, 韩伟, 李明丰. 烯烃水合反应工艺与催化剂研究进展[J]. 化工进展, 2023, 42(7): 3489-3500.
[7]	冯江涵, 宋钫. 阴离子交换膜电解池的研究进展[J]. 化工进展, 2023, 42(7): 3501-3509.
[8]	王蕴青, 杨国锐, 延卫. 过渡金属磷化物的改性方法及其在电化学析氢中的应用[J]. 化工进展, 2023, 42(7): 3532-3549.
[9]	于志庆, 黄文斌, 王晓晗, 邓开鑫, 魏强, 周亚松, 姜鹏. B掺杂Al₂O₃@C负载CoMo型加氢脱硫催化剂性能[J]. 化工进展, 2023, 42(7): 3550-3560.
[10]	龚鹏程, 严群, 陈锦富, 温俊宇, 苏晓洁. 铁酸钴复合碳纳米管活化过硫酸盐降解铬黑T的性能及机理[J]. 化工进展, 2023, 42(7): 3572-3581.
[11]	王达锐, 孙洪敏, 薛明伟, 王一棪, 刘威, 杨为民. 微波法高效合成全结晶ZSM-5分子筛催化剂及其催化性能[J]. 化工进展, 2023, 42(7): 3582-3588.
[12]	蒋博龙, 崔艳艳, 史顺杰, 常嘉城, 姜楠, 谭伟强. 过渡金属Co₃O₄/ZnO-ZIF氧还原催化剂Co/Zn-ZIF模板法制备及其产电性能[J]. 化工进展, 2023, 42(6): 3066-3076.
[13]	杨家添, 唐金铭, 梁恣荣, 黎胤宏, 胡华宇, 陈渊. 新型淀粉基高吸水树脂抑尘剂的制备及其应用[J]. 化工进展, 2023, 42(6): 3187-3196.
[14]	吴锋振, 刘志炜, 谢文杰, 游雅婷, 赖柔琼, 陈燕丹, 林冠烽, 卢贝丽. 生物质基铁/氮共掺杂多孔炭的制备及其活化过一硫酸盐催化降解罗丹明B[J]. 化工进展, 2023, 42(6): 3292-3301.
[15]	陈怡欣, 甄摇摇, 陈瑞浩, 吴继伟, 潘丽美, 姚翀, 罗杰, 卢春山, 丰枫, 王清涛, 张群峰, 李小年. 铂基纳米催化剂的制备及在加氢领域的进展[J]. 化工进展, 2023, 42(6): 2904-2915.