The Nature of Plasmonically Assisted Hot-Electron Transfer in a Donor-Bridge-Acceptor Complex

Youngsoo Kim, Andrew J. Wilson, Prashant K. Jain

Research output: Contribution to journalArticle

Abstract

This work provides a mechanistic understanding of hot-electron-based catalysis on Au nanoparticles (NPs) induced under plasmonic excitation. Plasmon excitation-induced hot-electron transfer from an Au NP (donor) to a ferricyanide anion (acceptor) was studied as a function of the donor-acceptor distance set by a thiolate-based self-assembled monolayer (SAM). Hot-electron-transfer rates and activation barrier heights were measured as a function of the donor-acceptor distance, up to 20 Å. Hot-electron transfer was found to be longer range than anticipated. The distance-dependent kinetics reveal that the hot-electron transfer takes place via multistep hopping in a "wire-like" manner across the insulating ligands, quite unlike the tunneling-dominated electron transfer known to take place across SAMs in the absence of plasmonic excitation. Field-assisted electron hopping may play a crucial role in hot-electron extraction and catalysis involving plasmon-excited NPs.

Original languageEnglish (US)
Pages (from-to)4360-4365
Number of pages6
JournalACS Catalysis
Volume7
Issue number7
DOIs
StatePublished - Jul 7 2017

    Fingerprint

Keywords

  • LSPR
  • Marcus theory
  • artificial photosynthesis
  • nanoparticle
  • photocatalysis
  • plasmon resonance
  • plasmonic catalysis
  • self-assembled monolayer

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this