Tailoring the facet distribution on copper with chloride

Area of Science:

• Surface Science
• Electrochemistry
• Materials Science

Background:

• Electrocatalytic reactions are highly dependent on the catalyst's surface structure.
• Understanding the relationship between surface geometry and catalytic performance is crucial for designing efficient catalysts.
• Existing methods for characterizing active surface sites are limited.

Purpose of the Study:

• To develop a simple methodology for tuning and quantifying surface structure on copper catalysts.
• To establish a correlation between active surface sites and their geometric configurations.
• To provide a tool for assessing structure-electrocatalytic performance relationships.

Main Methods:

• Tuning copper facet distribution via electrochemical oxidation/reduction in chloride solutions.
• Quantifying facet contributions using voltammetric lead (Pb) underpotential deposition (UPD).
• Combining experimental data with density functional theory (DFT) calculations to analyze chloride's ligand effect.

Main Results:

• A method to tailor the distribution and ratio of facets on copper surfaces was successfully demonstrated.
• Voltammetric Pb UPD was used to decouple and identify contributions from different copper facets.
• Chloride adsorption was found to preferentially occur on the (310) facet, influencing facet distribution and promoting specific domain growth.

Conclusions:

• The study provides a valuable tool for correlating active sites with specific copper geometries in electrocatalysis.
• The developed methodology allows for selective tailoring of copper facet distribution, essential for designing well-defined nanostructured catalysts.
• This work advances the understanding of structure-performance relationships in electrocatalysis.