Dynamic structural engineering of ferrocene-functionalized Ag₂₀ nanoclusters for enhanced CO₂ electroreduction...

Area of Science:

• Nanomaterials Science
• Catalysis
• Organometallic Chemistry

Background:

• Hybrid catalysts combining organometallic motifs and metal nanoclusters offer tunable active sites.
• Silver nanoclusters are promising for catalysis but require precise structural control.

Purpose of the Study:

• To synthesize and characterize a novel silver nanocluster, Ag20-Fc, with a unique sandwich-like architecture.
• To investigate the structure-activity relationship of Ag20-Fc in electrocatalytic CO2 reduction.
• To elucidate the mechanism behind the enhanced catalytic performance.

Main Methods:

• Cooperative coordination synthesis using thiacalix[4]arene (TC4A) and ferrocenylacetylene ligands.
• Electrospray ionization mass spectrometry (ESI-MS) for structural analysis in solution.
• Electrocatalytic CO2 reduction experiments and Density Functional Theory (DFT) calculations.

Main Results:

• A sandwich-type Ag20-Fc nanocluster with a tunable structure was synthesized.
• Ag20-Fc demonstrated excellent electrocatalytic CO2 reduction to CO with >98% Faradaic efficiency and 24h stability.
• DFT calculations revealed that ferrocenyl group hybridization enhances catalytic activity by lowering the *COOH intermediate formation barrier.

Conclusions:

• The Ag20-Fc nanocluster represents a significant advancement in hybrid catalyst design for CO2 electroreduction.
• Ligand engineering and understanding the electronic structure are crucial for optimizing nanocluster catalysts.
• This work provides a pathway for developing highly efficient and stable catalysts for carbon utilization.