Constructing Cu-C Bonds in a Graphdiyne-Regulated Cu Single-Atom Electrocatalyst for CO₂ Reduction to CH₄

Area of Science:

• Catalysis
• Materials Science
• Electrochemistry

Background:

• Controlling reaction intermediates is key for selective electrocatalytic CO2 to CH4 conversion.
• Metal-carbon (M-C) bonds are vital for tuning multi-electron reactions but difficult to construct in nanomaterials.

Purpose of the Study:

• To design and synthesize a catalyst with a Cu-C bond for enhanced electrocatalytic CO2 reduction to CH4.
• To investigate the role of the Cu-C bond in controlling reaction intermediates and improving selectivity.

Main Methods:

• In situ anchoring of Copper Single Atoms (Cu SAs) onto graphdiyne (GDY).
• In situ Raman spectroelectrochemistry to monitor intermediates.
• Density Functional Theory (DFT) calculations to understand reaction pathways.

Main Results:

• Successfully constructed a Cu-C bond (Cu-C(GDY)) in Cu SAs/GDY.
• The Cu-C bond promotes the formation of *OCHO intermediates over *COOH during CO2 reduction.
• Enhanced charge transfer and a more facile pathway to CH4 were observed.

Conclusions:

• Constructing Cu-C bonds in Cu SAs/GDY is an effective strategy to control reaction intermediates.
• This approach significantly boosts the catalytic performance for CO2 to CH4 conversion.
• Provides atomic-level insights for improving CO2 reduction selectivity.