Metal-defect pairs for near-stoichiometric electrocatalytic C-N coupling

Area of Science:

• Catalysis
• Electrochemistry
• Materials Science

Background:

• Aqueous electrochemical reductive cross-coupling reactions (ERCR) require efficient catalysts.
• Existing geminal-site catalysts (GSCs) lack scalable synthetic routes for single-site variants.

Purpose of the Study:

• To develop a novel synthetic strategy for GSCs with metal-defect catalytic pairs (M-D GSCs).
• To demonstrate the efficacy of M-D GSCs in high-concentration ERCR reactions.

Main Methods:

• A defect-accompanying strategy involving pyrolysis of metal-citrate complexes was employed.
• In-situ and ex-situ characterizations were used to analyze catalyst formation.
• An innovative cathodic oxime-alkali process was developed for product synthesis.

Main Results:

• Fe-D GSCs were successfully synthesized, converting metal-citrate complexes into metal-defect catalytic pairs.
• High concentrations (0.5 M) of nitrites and cyclohexanone were converted to cyclohexanone oximes with near-stoichiometric yields (91.3% Faradaic efficiency).
• The cathodic oxime-alkali process yielded high-purity sodium hydroxide and cyclohexanone oximes.

Conclusions:

• The developed M-D GSC synthesis strategy is effective for creating advanced catalytic materials.
• M-D GSCs show significant potential for high-concentration ERCR, enabling efficient synthesis of valuable chemicals.
• This work advances the field of electrocatalysis for sustainable chemical production.