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

doi:10.1016/S1872-2067(24)60115-4

Abstract

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.

Key words: Co-based electrocatalyst, Sulfur-vacancies, Electrocatalysis, Electroreduction coupling

Dianke Xie, Tianyi Yang, Chongyang Ma, Chung-Li Dong, Shuangyin Wang, Yuqin Zou. Highly selective electrosynthesis of imines via electroreduction coupling of nitroarenes with aryl aldehydes on Co₉S₈ with positively charged sulfur vacancies[J]. Chinese Journal of Catalysis, 2024, 65: 206-216.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60115-4

https://www.cjcatal.com/EN/Y2024/V65/I10/206

Figures/Tables 8

Scheme 1. Schematic comparison of the thermodynamic and electrochemical strategy for imines production.

Fig. 1. Physical characterization of Co9S8 and Co9S8-Vs. (a) XRD patterns; high-resolution XPS spectra of Co 2p (b) and S 2p (c); (d) EPR spectra; (e) normalized Co K-edge XANES spectra; (f) corresponding FT-EXAFS spectra of Co9S8 and Co9S8-Vs.

Fig. 2. The electrochemical performance and activation characterization. (a) LSV curves of Co9S8 and Co9S8-Vs at a scan rate of 10 mV s?1 in the electrolyte with and without different substrates. (b) Selectivity and conversion over Co9S8 and Co9S8-Vs within 2 h at 0 VRHE. Potential-dependent selectivity of product and conversion of Ph-NO2 over Co9S8 (c) and Co9S8-Vs (d) within 2 h at +0.2 to ?0.4 VRHE. Coulomb-dependent evolution of each product over Co9S8 (e) and Co9S8-Vs (f).

Fig. 3. The adsorption behaviors of organic substrate on electrocatalytic. OCP curves of Co9S8 and Co9S8-Vs in the electrolyte when Ph-NO2 (a) and Ph-CHO (b) were injected. EQCM curves of Co9S8 and Co9S8-Vs when Ph-NO2 (c) and Ph-CHO (d) were injected. (e) Scheme of sulfur vacancies regulating the surface micro-environment of Co9S8-Vs catalyst.

Fig. 4. Unveiling the reaction pathway by in situ infrared spectroscopy. (a) In situ infrared spectroscopy of Co9S8-Vs electrode; (b) Detailed diagram of in situ infrared spectroscopy; (c) Schematic of the proposed reaction pathway (the numbering of the highlighted purple bonds in the schematic corresponds to the numbering in Fig. 4(b)).

Fig. 5. Quantum mechanics density functional theory calculations. (a) Computational energy profile of optimized intermediates on Co9S8 (440) and Co9S8-Vs (440); (b) Calculated Ph-NH2 and Ph-N=CH-Ph desorption energy; (c) Time-dependent conversion of Ph-NO2 over Co9S8 and Co9S8-Vs in an electrolyte containing Ph-NO2 only and both Ph-NO2 and Ph-CHO.

Scheme 2. Substrate scope of electroreduction coupling of nitroarenes with aryl aldehydes over the Co9S8-Vs cathode. Nitroarenes substrates (0.1 mmol), aryl aldehydes substrates (0.5 mmol), Ti-supported Co9S8-Vs (working area: 1 cm2), the electrolyte was a mixture of 1 mol L?1 KOH and ethanol with a volume ratio of 1:1 (10 mL), room temperature, 0 VRHE. The con. and sel. were determined by gas chromatography-mass spectrometry.

Scheme 3. The gram-scale reaction and Late-stage functionalization. (a) The gram-scale reaction of the electroreduction coupling of nitrobenzene with benzaldehyde over the Co9S8-Vs cathode. Late-stage functionalization: (b) Aza Diels-Alder reaction of the imine; (c) Mannich-type addition and cyclization via imine with trimethylsilyl enolates.

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

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