High-Nuclearity Copper Molecular Catalysts for Electrocatalytic CO-to-Acetate Conversion

Area of Science:

• Catalysis
• Nanomaterials Science
• Electrochemistry

Background:

• Metal nanoclusters (NCs) offer tunable structures and high metal nuclearity for catalysis.
• Ligand properties, active site accessibility, and atomic configuration influence NC catalytic behavior.

Purpose of the Study:

• To synthesize and evaluate ligand-modified copper nanoclusters (Cu NCs) for efficient CO electroreduction to acetate.
• To investigate the impact of ligand tuning on hydrophobicity, active site exposure, and catalytic performance.

Main Methods:

• Synthesis of a series of Cu NC-based catalysts with varied ligand properties.
• Tuning local hydrophobicity and balancing ligand coverage/active site exposure.
• Utilizing computation and operando spectroscopy to analyze catalytic mechanisms.

Main Results:

• Developed Cu NC catalysts for efficient electrosynthesis of acetate via CO electroreduction.
• Identified asymmetric Cu-Cu sites as crucial for CO binding strength and C-C coupling bifurcation.
• Achieved 86% acetate Faradaic efficiency and 29% energy efficiency with Cu13Nap catalyst.

Conclusions:

• Ligand modification of Cu NCs is a viable strategy for enhancing CO electroreduction to acetate.
• Catalyst design requires careful consideration of ligand properties, active site accessibility, and atomic configuration.
• The developed Cu NC catalysts significantly outperform previous NC-based catalysts for C2+ products.