Sustainable Electrosynthesis of Cyclohexanone Oxime through Nitrate Reduction on a Zn-Cu Alloy Catalyst.
ACS Catal
; 14(5): 3287-3297, 2024 Mar 01.
Article
em En
| MEDLINE
| ID: mdl-38449527
ABSTRACT
Cyclohexanone oxime is an important precursor for Nylon-6 and is typically synthesized via the nucleophilic addition-elimination of hydroxylamine with cyclohexanone. Current technologies for hydroxylamine production are, however, not environment-friendly due to the requirement of harsh reaction conditions. Here, we report an electrochemical method for the one-pot synthesis of cyclohexanone oxime under ambient conditions with aqueous nitrate as the nitrogen source. A series of Zn-Cu alloy catalysts are developed to drive the electrochemical reduction of nitrate, where the hydroxylamine intermediate formed in the electroreduction process can undergo a chemical reaction with the cyclohexanone present in the electrolyte to produce the corresponding oxime. The best performance is achieved on a Zn93Cu7 electrocatalyst with a 97% yield and a 27% Faradaic efficiency for cyclohexanone oxime at 100 mA/cm2. By analyzing the catalytic activities/selectivities of the different Zn-Cu alloys and conducting in-depth mechanistic studies via in situ Raman spectroscopy and theoretical calculations, we demonstrate that the adsorption of nitrogen species plays a central role in catalytic performance. Overall, this work provides an attractive strategy to build the C-N bond in oxime and drive organic synthesis through electrochemical nitrate reduction, while highlighting the importance of controlling surface adsorption for product selectivity in electrosynthesis.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
ACS Catal
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
Reino Unido
País de publicação:
Estados Unidos