Atomically Precise [Cu₂₃H₄(SC₇H₇)₁₈(PPh₃)₆] Nanocluster: Structural Integration of Johnson Solids through a Cu(0)...

Area of Science:

• Nanomaterials Science
• Catalysis
• Electrochemistry

Background:

• Copper nanoclusters (NCs) show promise in catalysis, but instability of Cu(0) limits applications.
• Existing systems often rely on less effective Cu(I)-based NCs, restricting catalytic performance.
• Developing stable Cu(0)-based NCs is crucial for advancing catalytic applications.

Purpose of the Study:

• To synthesize a stable copper nanocluster (NC) containing a Cu(0) core.
• To investigate the catalytic performance of the novel Cu(0)-containing NC in electrochemical CO2 reduction.
• To elucidate the structural and electronic factors governing the NC's stability and product selectivity.

Main Methods:

• Synthesis of a novel [Cu23H4(SC7H7)18(PPh3)6] nanocluster with a Cu(0) core.
• Electrochemical CO2 reduction experiments to assess catalytic activity and selectivity.
• Density functional theory (DFT) calculations to validate experimental findings and analyze reaction mechanisms.

Main Results:

• A stable Cu(0)-containing NC was successfully synthesized, protected by Cu(I) units, thiolate ligands, and hydrides.
• The NC demonstrated exceptional structural stability and consistent catalytic performance in electrochemical CO2 reduction.
• The NC exhibited high selectivity for formic acid (HCOOH) production over time.
• DFT calculations confirmed HCOOH as the preferred product due to favorable electronic and geometric structures.

Conclusions:

• A robust synthetic strategy yields stable Cu(0)-containing NCs, overcoming previous limitations.
• The novel NC architecture provides enhanced stability and catalytic efficiency for CO2 reduction.
• The findings highlight the potential of precisely engineered Cu(0) NCs for selective electrocatalytic applications, outperforming Cu(I) counterparts.