Efficient Catalytic Hydrogenation of Nitroaromatic Using Cobalt Single-atom Derived from Metal-organic Framework

doi:10.6023/A23080374

Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (12): 1701-1707.DOI: 10.6023/A23080374 Previous Articles Next Articles

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金属-有机骨架衍生的Co单原子高效催化硝基芳烃氢化还原

刘健^a, 欧金花^a^,^*(), 李泽平^a, 蒋婧怡^a, 梁荣涛^a, 张文杰^a, 刘开建^a^,^*(), 韩瑜^b^,^c^,^*()

a 湖南工学院材料科学与工程学院衡阳 421002
b 大连理工大学建设工程学部大连 116024
c 辽宁省建设科学研究院有限责任公司沈阳 110005

投稿日期:2023-08-10 发布日期:2023-12-01
基金资助:
国家自然科学基金青年项目(22202067); 湖南省自然科学基金项目(2023JJ30206); 湖南省教育厅科学研究项目(22A0620); 湖南省大学生创新创业项目(S202311528006); 湖南省大学生创新创业项目(S202311528102X); 湖湘青年科技创新人才项目(2020RC3055); 湖南工学院材料科学与工程学科开放课题项目(KFA23001)

Efficient Catalytic Hydrogenation of Nitroaromatic Using Cobalt Single-atom Derived from Metal-organic Framework

Jian Liu^a, Jinhua Ou^a(), Zeping Li^a, jingyi Jiang^a, Rongtao Liang^a, Wenjie Zhang^a, kaijian Liu^a(), Yu Han^b^,^c()

a School of Materials Science and Engineering, Hunan Institute of Technology, Hengyang 421002, China
b Faculty of Infrastructure Engineering, Dalian University of Technology, Dalian 116024, China
c Liaoning Province Building Science Research Institute Co. Ltd, Shenyang 110005, China

Received:2023-08-10 Published:2023-12-01
Contact: *E-mail: Oujinhua98@126.com;kjl1982@126.com;hanyu2010@mail.dlut.edu.cn
Supported by:
National Natural Science Foundation of China(22202067); Hunan Provincial Natural Science Foundation of China(2023JJ30206); Research Foundation of Education Bureau of Hunan Province, China(22A0620); National Students’ project for innovation and entrepreneurship training program(S202311528006); National Students’ project for innovation and entrepreneurship training program(S202311528102X); Hunan Young Scientific and Technological Innovative Talents(2020RC3055); Open Project Fund of Materials Science and Engineering of Hunan Institute of Technology(KFA23001)

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Abstract

Aromatic amines and their derivatives are widely used as important active intermediates in drugs, dyes and herbicides. Therefore, the development of highly efficient, low-cost, and highly selective catalysts for the hydrogenation of nitroaromatic hydrocarbons is desirable. In this study, Zn-Co metal-organic framework (MOF) materials were synthesized with Zn²⁺/Co²⁺ as the metal source and 2-methylimidazole as an organic ligand at room temperature. Then, a Co catalyst (Co-N-C) was prepared by in-situ pyrolysis using the Zn-Co MOF as a sacrificial template under a nitrogen atmosphere. Aromatic nitro compounds can be selectively converted to the corresponding aromatic amines using ethanol as solvent, hydrazine hydrate as a hydrogen source, and Co-N-C as catalyst. The Co-N-C synthesized by pyrolysis at 1000 ℃ possesses the best catalytic activity. The effects of solvent and reaction time and the amount of Co-N-C, ethanol, and hydrazine hydrate on the catalytic system were investigated. The catalytic effect was the best when 5 mg Co-N-C, 4 mL ethanol, and 4 mmol hydrazine hydrate were added to the system, and the yield of aniline reached 100% after 10 h. Thirty-one different types of nitro-aromatic compounds, including ortho-, meta-, and para-substituted nitroaromatics with electron-donating or electron-withdrawing substituents, nitrobenzene derivatives with other reducible functional groups, and heterocyclic and polycyclic aromatic compounds, were obtained in high yields under this system, which has a wide substrate scope. In addition, the flutamide and nilutamide derivatives and aminoglutethimide were prepared in excellent yields using the Co-N-C catalytic system. The feasibility of the Co-N-C catalytic system was demonstrated using a gram-scale reaction. Cycling and anti-leaching experiments demonstrated that the Co-N-C material has excellent stability and anti-leaching properties, and acts as a reusable heterogeneous catalyst, which can be easily separated and collected by centrifugation. In addition, two reaction mechanisms of direct reduction and condensation reduction of nitro-aromatics using a Co-N-C catalyzed system were proposed by testing the reaction process. This research provides an efficient, simple, and green method for the hydrogenation reduction of nitroaromatics.

Key words: single-atom catalyst, Co-N-C, nitroaromatics, hydrogenation

Cite this article

Jian Liu, Jinhua Ou, Zeping Li, jingyi Jiang, Rongtao Liang, Wenjie Zhang, kaijian Liu, Yu Han. Efficient Catalytic Hydrogenation of Nitroaromatic Using Cobalt Single-atom Derived from Metal-organic Framework[J]. Acta Chimica Sinica, 2023, 81(12): 1701-1707.

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Entry	Cat.	Solvent	Time/h	Con./%	Yield^b/%
1	ZIF-8	EtOH	5	9	2
2	ZIF-67	EtOH	5	48	9
3	Zn-Co MOF	EtOH	5	50	11
4	Co-N-C-900	EtOH	5	100	61
5	Co-N-C-1000	EtOH	5	100	72
6	Co-N-C-1100	EtOH	5	100	65
7	N-C-1000	EtOH	5	N.R.	N.R.
8	Co@N-C-1000	EtOH	5	39	25
9	Co-N-C-1000	DMSO	5	10	6
10	Co-N-C-1000	DMF	5	8	4
11	Co-N-C-1000	MeCN	5	32	27
12	Co-N-C-1000	THF	5	65	60
13	Co-N-C-1000	NMP	5	40	29
14	Co-N-C-1000	DCE	5	8	2
15	Co-N-C-1000	EtOH	8	100	89
16	Co-N-C-1000	EtOH	10	100	100
17^c	Co-N-C-1000	EtOH	10	94	59
18^d	Co-N-C-1000	EtOH	10	90	68
19^e	Co-N-C-1000	EtOH	10	95	37
20^f	Co-N-C-1000	EtOH	10	100	70
21^g	Co-N-C-1000	EtOH	10	100	100
22^h	Co-N-C-1000	EtOH	4	100	100

Entry	Cat.	Solvent	Time/h	Con./%	Yield^b/%
1	ZIF-8	EtOH	5	9	2
2	ZIF-67	EtOH	5	48	9
3	Zn-Co MOF	EtOH	5	50	11
4	Co-N-C-900	EtOH	5	100	61
5	Co-N-C-1000	EtOH	5	100	72
6	Co-N-C-1100	EtOH	5	100	65
7	N-C-1000	EtOH	5	N.R.	N.R.
8	Co@N-C-1000	EtOH	5	39	25
9	Co-N-C-1000	DMSO	5	10	6
10	Co-N-C-1000	DMF	5	8	4
11	Co-N-C-1000	MeCN	5	32	27
12	Co-N-C-1000	THF	5	65	60
13	Co-N-C-1000	NMP	5	40	29
14	Co-N-C-1000	DCE	5	8	2
15	Co-N-C-1000	EtOH	8	100	89
16	Co-N-C-1000	EtOH	10	100	100
17^c	Co-N-C-1000	EtOH	10	94	59
18^d	Co-N-C-1000	EtOH	10	90	68
19^e	Co-N-C-1000	EtOH	10	95	37
20^f	Co-N-C-1000	EtOH	10	100	70
21^g	Co-N-C-1000	EtOH	10	100	100
22^h	Co-N-C-1000	EtOH	4	100	100

金属-有机骨架衍生的Co单原子高效催化硝基芳烃氢化还原

Efficient Catalytic Hydrogenation of Nitroaromatic Using Cobalt Single-atom Derived from Metal-organic Framework

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