Citation: Xiao-Xue WU, Yan-Yan QI, Ying-Yi WANG, Li WANG, Gao-Mei TU, Yang-He FU, De-Li CHEN, Wei-Dong ZHU, Fu-Min ZHANG. Synthesis of Amines by Oxidative Coupling of Benzylamine over a Vanadium-Nitrogen Co-doped Porous Carbon Catalyst[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(6): 1049-1058. doi: 10.11862/CJIC.2022.112 shu

Synthesis of Amines by Oxidative Coupling of Benzylamine over a Vanadium-Nitrogen Co-doped Porous Carbon Catalyst

Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, China

Corresponding author: Fu-Min ZHANG, zhangfumin@zjnu.edu.cn
Received Date: 12 January 2022
Revised Date: 14 April 2022

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Synthesis of imine compounds via benzylamine oxidative coupling has become one of the most ideal methods due to its high atom economy and environmental friendliness. The key is to develop high - performance non-noble metal-based heterogeneous catalysts. In this work, a vanadium-nitrogen co-doped porous carbon (V-N-C) catalyst was prepared via high-temperature pyrolysis (900 ℃ for 2 h in an inert atmosphere) combined with acidleaching (1 mol·L^-1 HCl solution at 120 ℃ for 12 h) approach by using biomass chitosan as the sacrificial template, vanadium acetylacetonate as the source of metal vanadium, and ZnCl₂ as the pore-forming agent. Various characterization techniques including a high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) investigation were used to analyze the composition, structure, vanadium species size, content, and other physical and chemical properties of the catalyst, and its catalytic performance was evaluated in the oxidative cou-pling reaction of benzylamine. The characterization results showed that the specific surface area of the V-N-C catalyst was as high as 1 470 m²·g^-1, the pore volume was 1.06 cm³·g^-1, and the mass fraction of the vanadium species was 0.19% that were highly dispersed on the support likely in the form of single atoms (VN_x). In the oxidative selfcoupling reaction of benzylamine to the imine (reaction conditions: toluene as solvent, 110 ℃, 1.01×10⁵ Pa O₂, 12 h), the developed V-N-C exhibited excellent activity (99%), exclusive selectivity (99%), outperforming the homogeneous VO(acac)₂ and heterogeneous V₂O₅ catalysts. Moreover, V-N-C was repeatedly used 9 times without any decay in reactivity and stability. Furthermore, V-N-C presented excellent universality for a series of substrates containing different functional groups. Mechanism studies indicated that the reaction steps were involved in the initial formation of benzylimine and H₂O₂ intermediates by activating benzylamine and oxygen molecules, respectively, on the VN_x and defect sites of V-N-C, then benzylimine and benzylamine condensed to release an NH₃ molecule to gener-ate the target product imine.
- selective catalytic oxidation,
- heterogeneous catalysis,
- vanadium-nitrogen co-doped porous carbon,
- oxidative coupling
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