Sustainable Electrosynthesis of Cyclohexanone Oxime through Nitrate Reduction on a Zn-Cu Alloy Catalyst.

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.

Recent research progress on building C-N bonds via electrochemical NOx reduction.

The release of NOx species (such as nitrate, nitrite and nitric oxide) into water and the atmosphere due to human being's agricultural and industrial activities has caused a series of environmental problems, including accumulation of toxic pollutants that are dangerous to humans and animals, acid rain, the greenhouse effect and disturbance of the global nitrogen cycle balance. Electrosynthesis of organonitrogen compounds with NOx species as the nitrogen source offers a sustainable strategy to upgrade the waste NOx into value-added organic products under ambient conditions. The electrochemical reduction of NOx species can generate surface-adsorbed intermediates such as hydroxylamine, which are usually strong nucleophiles and can undergo nucleophilic attack to carbonyl groups to build C-N bonds and generate organonitrogen compounds such as amine, oxime, amide and amino acid. This mini-review summarizes the most recent progress in building C-N bonds via the in situ generation of nucleophilic intermediates from electrochemical NOx reduction, and highlights some important strategies in facilitating the reaction rates and selectivities towards the C-N coupling products. In particular, the preparation of high-performance electrocatalysts (e.g., nano-/atomic-scale catalysts, single-atom catalysts, alloy catalysts), selection of nucleophilic intermediates, novel design of reactors and understanding the surface adsorption process are highlighted. A few key challenges and knowledge gaps are discussed, and some promising research directions are also proposed for future advances in electrochemical C-N coupling.