Inter-Atomic Synergy on Single-Atom Alloy Promotes Cyclohexanone Oxime Electrosynthesis.

Area of Science:

• Electrochemistry
• Materials Science
• Catalysis

Background:

• Traditional synthesis of cyclohexanone oxime is energy-intensive and hazardous.
• Existing electrosynthesis methods face challenges with intermediate over-reduction and inefficient C─N coupling.

Purpose of the Study:

• To develop a sustainable and efficient electrosynthesis route for cyclohexanone oxime.
• To investigate a novel single-atom alloy catalyst for improved activity and selectivity.

Main Methods:

• Electrosynthesis using a Fe1Bi single-atom alloy (SAA) catalyst.
• In situ electrochemical spectroscopic measurements.
• Density functional theory (DFT) calculations.
• Techno-economic analysis using flow electrolyzer data.

Main Results:

• The Fe1Bi SAA catalyst achieved 70.9% Faradaic efficiency and a yield rate of 0.94 mmol cm⁻² h⁻¹ for cyclohexanone oxime.
• Identified a synergistic mechanism involving Fe activating cyclohexanone and Bi reducing nitrite to hydroxylamine.
• Demonstrated the potential economic viability of the process.

Conclusions:

• The Fe-Bi atomic interfaces in the SAA catalyst enable cooperative catalysis for efficient C─N coupling.
• This work offers atomic-level insights into electrosynthesis of organonitrogen compounds.
• The developed method presents a sustainable alternative to conventional industrial processes.