Molecular-Level Decoding of Electron Transfer Dynamics in Metal Nanoclusters

Area of Science:

• Nanoscale Science and Technology
• Physical Chemistry
• Materials Science

Background:

• Understanding electron transfer (ET) in metal nanoclusters (NCs) is crucial for their application in chemistry, biology, and energy.
• Metal NCs bridge the gap between atoms and nanoparticles, exhibiting unique quantum confinement effects influencing ET.
• Investigating ET in metal NCs connects molecular ET theories with those for larger nanoparticles.

Purpose of the Study:

• To summarize systematic studies on ET processes in metal NCs.
• To demonstrate the applicability of Marcus theory to metal NC ET dynamics.
• To propose molecular engineering strategies for regulating ET kinetics in metal NC systems.

Main Methods:

• Systematic experimental and theoretical studies of electron transfer in metal nanoclusters.
• Application of Marcus theory to describe the rate dependence on driving force.
• Development of molecular engineering strategies for controlling ET kinetics.

Main Results:

• Metal NC ET dynamics are accurately described by Marcus theory, showing a bell-shaped rate dependence on driving force.
• Three strategies (Rehm-Weller/Marcus regime switching, parameter tuning, proton-coupled ET) are proposed for ET regulation.
• Unique 'molecule-like' ET in NCs, due to discrete energy levels, enables faster and more programmable proton-coupled ET.

Conclusions:

• Metal NCs exhibit distinct ET behaviors, facilitating faster and more controlled charge transfer processes.
• Mechanistic insights into NC ET kinetics can advance applications in luminophores, sensing, and catalysis (OER, CO2RR).
• This work promotes quantitative structure-ET-application correlations and refines nanoscale charge transfer theories for rational NC design.