Highly selective electrosynthesis of imines via electroreduction coupling of nitroarenes with aryl aldehydes on Co9S8 with positively charged sulfur vacancies

IF 15.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis Pub Date : 2024-10-01 DOI:10.1016/S1872-2067(24)60115-4

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Abstract

The electrocatalytic synthesis of imines through the reductive imination of nitroarenes with aldehydes is a facile, environmentally friendly, and valuable process. In this study, high selectivity electrosynthesis of imines was realized through the electrocatalytic C-N coupling reaction between nitroarenes and aryl aldehydes on Co₉S₈ nanoflowers with rich sulfur vacancies (Co₉S₈-V_s). Comparative experiments revealed that positively charged sulfur vacancies play a pivotal role in boosting catalytic selectivity towards imines. Electron-deficient sulfur vacancies intensified the adsorption of negatively charged Ph-NO₂, thereby enhancing the conversion rate of the electrochemical nitrobenzene-reduction reaction (eNB-RR). Simultaneously, sulfur vacancies augmented the adsorption capability of negatively charged Ph-CHO, enriching Ph-CHO species at the electrode interface and expediting the Schiff base condensation reaction rate. The experimental results show that the reaction conditions can satisfy the different nitroarenes and aryl aldehydes in the electrocatalytic aqueous-phase system under mild conditions to obtain the corresponding imine products in high selectivity. This study provides a facile and environmentally friendly pathway for future electrocatalytic synthesis of imine.

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在带正电荷硫空位的 Co9S8 上通过硝基烯烃与芳基醛的电还原偶联高选择性地电合成亚胺

通过硝基烯烃与醛的还原亚胺化反应电催化合成亚胺是一种简便、环保和有价值的工艺。本研究通过在富含硫空位的 Co9S8 纳米流体（Co9S8-Vs）上进行硝基烯烃与芳基醛的电催化 C-N 偶联反应，实现了亚胺的高选择性电合成。对比实验表明，带正电荷的硫空位在提高对亚胺的催化选择性方面起着关键作用。缺电子的硫空位增强了对带负电的 Ph-NO2 的吸附，从而提高了电化学硝基苯还原反应（eNB-RR）的转化率。同时，硫空位增强了带负电荷的 Ph-CHO 的吸附能力，使 Ph-CHO 物种在电极界面富集，加快了希夫碱缩合反应的速率。实验结果表明，在电催化水相体系中，反应条件可以满足不同硝基烯烃和芳基醛在温和条件下以高选择性得到相应的亚胺产物。这项研究为今后电催化合成亚胺提供了一条简便、环保的途径。

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来源期刊

Chinese Journal of Catalysis 工程技术-工程：化工

CiteScore

25.80

自引率

10.30%

发文量

235

审稿时长

1.2 months

期刊介绍： The journal covers a broad scope, encompassing new trends in catalysis for applications in energy production, environmental protection, and the preparation of materials, petroleum chemicals, and fine chemicals. It explores the scientific foundation for preparing and activating catalysts of commercial interest, emphasizing representative models.The focus includes spectroscopic methods for structural characterization, especially in situ techniques, as well as new theoretical methods with practical impact in catalysis and catalytic reactions.The journal delves into the relationship between homogeneous and heterogeneous catalysis and includes theoretical studies on the structure and reactivity of catalysts.Additionally, contributions on photocatalysis, biocatalysis, surface science, and catalysis-related chemical kinetics are welcomed.