Cation Effects on the Adsorbed Intermediates of CO₂ Electroreduction Are Systematic and Predictable

Area of Science:

• Electrochemistry
• Computational Chemistry
• Materials Science

Background:

• The electrode-electrolyte interface significantly influences CO2 electroreduction.
• Understanding cation effects is crucial for optimizing electrocatalysis.

Purpose of the Study:

• To investigate systematic cation effects on CO2 reduction intermediates.
• To predict cation impacts on electrocatalytic activity and selectivity.

Main Methods:

• Density Functional Theory (DFT) calculations were employed.
• Investigated K+, Na+, and Mg2+ interactions with CO2 reduction intermediates.
• Analyzed effects on Au, Ag, Cu, and Pd catalytic surfaces.

Main Results:

• Cation effects on intermediates can be stabilizing or destabilizing.
• Systematic trends in cation influence were observed.
• Stabilization of the *COOH intermediate was consistently achieved on weak-binding metals.

Conclusions:

• Cation effects on CO2 electroreduction intermediates are predictable.
• This predictability can guide the design of improved electrocatalysts.
• Enhanced activation of weak-binding metals for CO2 to CO conversion was demonstrated.