Plasmonic Hot Electron-Mediated Hydrodehalogenation Kinetics on Nanostructured Ag Electrodes

Area of Science:

• Surface chemistry
• Nanomaterials science
• Photochemistry

Background:

• Plasmon-mediated chemical reactions (PMCRs) are a rapidly developing field.
• Understanding and controlling the kinetics of PMCRs, particularly those involving hot carriers, remains a challenge.
• Silver nanoparticle-modified electrodes offer a platform for studying these phenomena.

Purpose of the Study:

• To investigate the influence of electrode potential, laser wavelength, and power on PMCR kinetics.
• To probe hot electron behavior using 8-bromoadenine (8BrAd) as a model molecule.
• To elucidate the mechanism of modulating PMCR efficiency at electrochemical interfaces.

Main Methods:

• Utilized in situ electrochemical surface-enhanced Raman spectroscopy (EC-SERS) to monitor reactions.
• Employed density functional theory (DFT) calculations for theoretical insights.
• Investigated the C-Br bond cleavage in 8BrAd mediated by plasmonic hot electrons.

Main Results:

• Demonstrated that applied potentials and laser light can effectively modulate the energy of plasmon relaxation-generated hot electrons.
• Established a correlation between hot electron energy levels and PMCR efficiency.
• Identified a mechanism for promoting PMCRs by optimizing the energy matching of hot electrons.

Conclusions:

• The energy of hot electrons from plasmon relaxation is tunable via electrochemical potential and laser irradiation.
• This tunability provides a pathway to enhance the efficiency of PMCRs.
• The findings offer valuable guidance for designing efficient surface plasmon resonance photoelectrochemical reactions on nanostructured metal electrodes.