Ligand-Dependent Intracluster Interactions in Electrochemical CO₂ Reduction Using Cu₁₄ Nanoclusters

Area of Science:

• Materials Science
• Electrochemistry
• Catalysis

Background:

• Electrochemical CO2 reduction (CO2RR) converts CO2 into valuable products.
• Copper nanoclusters (Cu NCs) are promising catalysts for CO2RR.
• The role of protective ligands in Cu NC performance is not well understood.

Purpose of the Study:

• To investigate the influence of different thiolate ligands on the stability and CO2RR performance of Cu14 nanoclusters.
• To understand how ligand structure affects electrochemical stability and product selectivity.
• To provide insights for designing improved Cu NC catalysts.

Main Methods:

• Synthesis of Cu14 nanoclusters with different thiolate ligands (2-phenylethanethiolate and cyclohexanethiolate).
• Electrochemical characterization of catalyst stability and CO2RR performance.
• Analysis of product selectivity, particularly for formic acid.

Main Results:

• Different thiolate ligands substantially affect the electrochemical stability of Cu14 NCs during CO2RR.
• Cu14 NCs protected by 2-phenylethanethiolate showed enhanced stability.
• The 2-phenylethanethiolate-protected Cu14 NCs achieved higher selectivity (≈40%) for formic acid production compared to the cyclohexanethiolate-protected ones.

Conclusions:

• Ligand choice is critical for enhancing the stability and selectivity of copper nanoclusters in CO2RR.
• Tailoring ligands can optimize Cu NCs for efficient electrochemical CO2 conversion.
• These findings are vital for developing robust and selective catalysts for CO2 utilization.