Ru/NiPOx高效电催化醛还原胺化反应的研究

doi:10.6023/A24020054

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Ru/NiPO_x高效电催化醛还原胺化反应的研究

刘浩^#, 徐旭莉^#, 郭勇, 刘晓晖^*, 王艳芹

华东理工大学化学与分子工程学院工业催化研究所上海市功能性材料化学重点实验室上海 200237

投稿日期:2024-02-17
基金资助:
国家自然科学基金(Nos. 21872050, 22072042 and 21403065)以及国家重点研发计划(No. 2022YFC3902500)资助.

Efficient Electro-catalytic Reductive Amination of Aldehyde over Ru Deposited on Nickel Phosphate

Liu, Hao, Xu, Xuli, Guo, Yong, Liu, Xiaohui^*, Wang, Yanqin

Shanghai Key Laboratory of Functional Materials Chemistry, Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science of Technology, Shanghai, 200237, P. R. China

Received:2024-02-17
Contact: * E-mail: xhliu@ecust.edu.cn
About author:# These authors contributed equally to this work
Supported by:
National Natural Science Foundation of China (Nos. 21872050, 22072042 and 21403065) and National Key Research and Development Program of China (No. 2022YFC3902500).

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摘要/Abstract

电催化还原胺化是一种环境友好且可持续的合成胺途径. 在本文中,我们建立了一个以2Ru/NiPOx为阴极催化苯甲醛和环己胺电化学还原胺化反应的体系,该体系可以高效获得95.1%的N-苄基环己胺产率,以及64.7%的法拉第效率,其中活化DMSO还原胺化与DMSO自身反应之间具有相匹配的活性是实现定向氢转移还原胺化的关键. 最后,通过漫反射红外傅里叶变换光谱(DRIFTS)表征、自由基捕获实验和DMSO-D6同位素标记实验探索了反应的机理.

关键词: 电催化还原胺化, N-苄基环己胺, Ru基催化剂, 磷酸镍, 自由基反应

Electro-catalytic reductive amination is an environmentally friendly and sustainable route to synthesize amines. In this paper, we prepared 2Ru/NiPO_x catalysts using nickel phosphate as a carrier impregnated and loaded with 2 wt% Ru and used them for the electrochemical reductive amination of benzaldehyde and cyclohexylamine. The reaction was carried out with tetrabutylammonium bromide (TBAB) as electrolyte and dimethyl sulfoxide (DMSO) as both H donor and solvent. 2Ru/NiPOx catalysts were used as the cathode in an undivided cell to produce N-benzylcyclohexylamine in 95.1% yield with a Faraday efficiency of 64.7%. The Faraday efficiency starts to decrease when the loading of Ru exceeds 2 wt%, which is due to the fact that the excess Ru accelerates the self-reaction of DMSO, thus decreasing the Faraday efficiency. EIS results showed that NiPO_x supported Ru particles could significantly improve the electron transfer rate during the reductive amination reaction. The CV test showed that -4 V was the optimal potential for the 2Ru/NiPOx catalyst as the cathodic electrocatalytic reduction of amination, and the paired anodic reaction was the oxidation of DMSO. The DRIFT results showed that the activation of DMSO by 2Ru/NiPOx was weaker than that of the other Ru-based catalysts, resulting in a high Faraday efficiency. The C=N adsorbed on 2Ru/NiPO_x had a higher electron cloud density, which was favorable for the attack of N by the H⁺ generated from water splitting, thus promoting the reductive amination. The free radical trapping experiments proved that free radicals are involved in the reaction process. Isotope labeling experiments confirmed that DMSO is the H atom donor of the radical intermediate. Therefore, a possible reaction mechanism was deduced: the spontaneously generated imine was adsorbed on the surface of the 2Ru/NiPOx catalyst at the cathode, and then attacked by H⁺ and electrons to generate a free radical, which seized H from DMSO to generate N-benzylcyclohexylamine and DMSO radical, and finally, the DMSO radical could get H⁺ and electrons at the cathode to regenerate DMSO.

Key words: electrocatalytic reductive amination, N-benzylcyclohexylamine, Ru-based catalyst, nickel phosphate, free radical reaction

引用此文

刘浩, 徐旭莉, 郭勇, 刘晓晖, 王艳芹. Ru/NiPO_x高效电催化醛还原胺化反应的研究[J]. 化学学报, doi: 10.6023/A24020054.

Liu, Hao, Xu, Xuli, Guo, Yong, Liu, Xiaohui, Wang, Yanqin. Efficient Electro-catalytic Reductive Amination of Aldehyde over Ru Deposited on Nickel Phosphate[J]. Acta Chimica Sinica, doi: 10.6023/A24020054.

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Ru/NiPO_x高效电催化醛还原胺化反应的研究

Efficient Electro-catalytic Reductive Amination of Aldehyde over Ru Deposited on Nickel Phosphate

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