Molecular-Level Engineering of Organic-Modified Cu(100) for Tailored Selectivity in CO₂ Electroreduction

Area of Science:

• Materials Science
• Electrochemistry
• Computational Chemistry

Background:

• Interfacial molecular engineering is an emerging strategy for tuning electrocatalyst performance.
• Metal-based electrocatalysts, particularly copper, are crucial for CO2 electroreduction.

Purpose of the Study:

• To investigate how organic modifiers (2-aminoacetaldehyde and glycine) influence the electronic properties and catalytic selectivity of Cu(100) for CO2 electroreduction.
• To elucidate the mechanistic pathways governing CO2 activation and product formation under molecular modification.

Main Methods:

• First-principles calculations were employed to model the adsorption of organic modifiers on Cu(100) surfaces.
• Density functional theory (DFT) was used to analyze electronic structure changes and reaction pathways.

Main Results:

• Organic modifiers stabilize CO2 intermediates via hydrogen bonding and redistribute electronic density on the Cu surface, enhancing CO2 activation.
• 2-aminoacetaldehyde promotes synergistic dual-site coordination, shifting selectivity from methane to methanol.
• Distinct C-C coupling pathways were identified, with 2-aminoacetaldehyde favoring *CHO-*CHO dimerization and glycine promoting *CO-*CHO coupling.
• The hydrogen evolution reaction (HER) was effectively suppressed.

Conclusions:

• Molecular engineering at the interface provides a rational design strategy for advanced CO2 electroreduction catalysts.
• The study establishes a mechanistic framework linking interfacial structure, electronic modulation, and catalytic selectivity.
• This approach offers a pathway to design highly selective and efficient copper-based electrocatalysts for CO2 conversion.