Bi-modified Ni3S2 promotes selective nitrite-to-hydroxylamine reduction for cyclohexanone oxime synthesis
Dingkun Yao1, Rui Yu1, Sijia Liu1
1The Key Laboratory of Functional Molecular Solids, Ministry of Education, The Key Laboratory of Electrochemical Clean Energy of Anhui Higher Education Institutes, College of Chemistry and Materials Science, Anhui Normal University, Wuhu, 241002, P. R. China. qing.qin@ahnu.edu.cn.
Chemical Communications (Cambridge, England)
|July 6, 2026
Summary
Bismuth-modified Nickel sulfide (Ni3S2) efficiently converts nitrite to cyclohexanone oxime in water. This process offers a sustainable route to caprolactam precursors, crucial for nylon production.
Area of Science:
- Electrochemistry
- Materials Science
- Organic Synthesis
Background:
- Caprolactam is a key precursor for nylon-6 production.
- Current synthesis methods often involve harsh conditions or hazardous intermediates.
- Developing sustainable and efficient catalytic routes is essential for green chemistry.
Purpose of the Study:
- To develop a novel electrocatalyst for ambient aqueous nitrite reduction oximation.
- To investigate the role of bismuth modification on Nickel sulfide (Ni3S2) performance.
- To establish a sustainable pathway for cyclohexanone oxime synthesis, a caprolactam precursor.
Main Methods:
- Electrochemical synthesis and characterization of Bi-modified Ni3S2.
- Aqueous phase reduction oximation of nitrite to cyclohexanone oxime.
- Analysis of reaction intermediates and product selectivity using spectroscopic techniques.
- Electrocatalytic performance evaluation including Faradaic efficiency and yield.
Main Results:
- Bi-modified Ni3S2 demonstrated high activity for ambient aqueous nitrite reduction oximation.
- Achieved a Faradaic efficiency of 52.78% and a yield of 0.42 mmol h-1 cm-2.
- Bismuth modification regulated the electronic structure of Ni3S2 and interfacial water behavior.
- The catalyst promoted selective NH2OH-mediated nitrogen-organic coupling.
Conclusions:
- Bi-modified Ni3S2 is a promising electrocatalyst for sustainable cyclohexanone oxime production.
- The catalyst design offers a greener alternative for caprolactam precursor synthesis.
- Understanding the electronic and interfacial effects of Bi modification provides insights for future catalyst development.
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