A Heterodimeric Cluster-Based Pair Catalyst for Electrochemical Synthesis of Cyclohexanone Oxime

Area of Science:

• Materials Science
• Catalysis
• Electrochemistry

Background:

• Heterogeneous catalysts function as complex chemical ecosystems with distinct functional units.
• Designing catalysts with multiple active sites is crucial for enhancing catalytic performance.
• Atomically precise metal clusters offer tunable properties for catalytic applications.

Purpose of the Study:

• To develop a novel dinuclear heterogeneous catalyst for the electrochemical synthesis of cyclohexanone oxime.
• To investigate the catalytic mechanism at the interface of two distinct molecular clusters.
• To demonstrate a strategy for designing advanced catalysts with improved selectivity and conversion.

Main Methods:

• Synthesis of an atomically precise Ag4Pd2(SR)8 cluster and a polyoxotitanium Ti4O2(TBC[4])2(iPrO)4 cluster.
• Assembly of the two clusters into a heterodimeric catalyst via bridging sulfur.
• Electrochemical characterization and reaction pathway analysis for cyclohexanone oxime synthesis.

Main Results:

• The heterodimeric catalyst features a unique Ti-S-metal interface (metal = Pd, Ag).
• The catalyst demonstrated high performance in the electrochemical synthesis of cyclohexanone oxime.
• A proposed mechanism involves nitrate deoxygenation, nitrite reduction, and subsequent coupling with cyclohexanone.

Conclusions:

• A novel dinuclear catalyst was successfully synthesized by combining molecularly precise silver-palladium and polyoxotitanium clusters.
• The catalyst's unique interface facilitates selective nitrogen source recognition and efficient cyclohexanone oxime production.
• This work presents a viable strategy for designing multifunctional heterogeneous catalysts for enhanced chemical synthesis.