Electrochemistry of Atomically Precise Metal Nanoclusters

Area of Science:

• Nanomaterials Science
• Electrochemistry
• Catalysis

Background:

• Thiolate-protected metal nanoclusters bridge the bulk and molecular limits, exhibiting quantum confinement effects.
• Recent advances allow for the synthesis of atomically precise gold nanoclusters (e.g., Au25(SR)18) with defined molecular formulas.
• These nanoclusters possess unique size-dependent electrochemical, optical, and catalytic properties.

Purpose of the Study:

• To highlight recent advances in the electrochemistry of atomically precise metal nanoclusters.
• To discuss their applications in electrocatalysis and electrochemical sensing.
• To focus on gold-based nanoclusters due to limited progress in other metal nanoclusters.

Main Methods:

• Voltammetry for investigating electronic structure (HOMO-LUMO gap).
• Density functional theory (DFT) calculations for predicting atomic and electronic structures.
• Heteroatom-doping and metal-doping strategies to modify properties.

Main Results:

• A decreasing HOMO-LUMO gap with increasing nanocluster size was observed, correlating with optical gap changes.
• Heteroatom-doping and metal-doping (e.g., Pt, Pd) significantly alter electronic structures and optical spectra.
• Doped nanoclusters may exhibit Jahn-Teller distortion and modified redox potentials.

Conclusions:

• Atomically precise metal nanoclusters offer tunable electrochemical and optical properties.
• Their well-defined structures are advantageous for electrocatalysis, enabling tailored binding and redox potentials.
• These nanoclusters provide a powerful platform for developing highly active and selective nanocatalysts for water splitting, CO2 conversion, and sensing.