Atomically precise alkynyl-protected Ag₁₉Cu₂ nanoclusters: synthesis, structure analysis, and electrocatalytic CO₂...

Area of Science:

• Nanomaterials Chemistry
• Catalysis
• Electrochemistry

Background:

• Electrochemical CO₂ reduction (eCO₂RR) is crucial for sustainable energy.
• Atomically precise metal nanoclusters offer tunable properties for catalysis.
• Bimetallic nanoclusters present unique opportunities for enhanced catalytic performance.

Purpose of the Study:

• To synthesize and characterize a novel bimetallic nanocluster, Ag₁₉Cu₂.
• To investigate the electrocatalytic performance of Ag₁₉Cu₂ for CO₂ reduction.
• To elucidate the structure-performance relationship at the atomic level.

Main Methods:

• Synthesis of Ag₁₉Cu₂(C extunderscore Ar^F)₁₂(PPh₃)₆Cl₆ nanoclusters.
• Single-crystal X-ray diffraction (SC-XRD) for structural analysis.
• Electrochemical CO₂ reduction reaction (eCO₂RR) measurements.
• Density functional theory (DFT) calculations.

Main Results:

• Ag₁₉Cu₂ is a superatomic cluster with 2 free valence electrons and a defined metal core structure.
• Achieved high CO faradaic efficiency (95.26%) and current density (257.2 mA cm^-2) at -1.3 V for eCO₂RR.
• Demonstrated robust long-term stability over 14 hours of continuous operation.
• DFT revealed ligand shedding from the Ag₄ unit exposes active sites, enhancing CO selectivity.

Conclusions:

• Ag₁₉Cu₂ nanoclusters exhibit excellent catalytic activity and selectivity for CO production in eCO₂RR.
• The study highlights the importance of atomic-level structural control in designing efficient catalysts.
• This work contributes to the development of alkynyl-protected bimetallic nanoclusters for catalytic applications.