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



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,*()   

  1. 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 Liua, Jinhua Oua(), Zeping Lia, jingyi Jianga, Rongtao Lianga, Wenjie Zhanga, kaijian Liua(), Yu Hanb,c()   

  1. 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:;;
  • 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)

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