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

Youngsoo Kim, Andrew J. Wilson, Prashant 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

Hot electrons
Nanoparticles
Catalysis
Electron tunneling
Self assembled monolayers
Anions
Negative ions
Chemical activation
Ligands
Wire
Kinetics
Electrons

Keywords

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

ASJC Scopus subject areas

  • Catalysis

Cite this

The Nature of Plasmonically Assisted Hot-Electron Transfer in a Donor-Bridge-Acceptor Complex. / Kim, Youngsoo; Wilson, Andrew J.; Jain, Prashant.

In: ACS Catalysis, Vol. 7, No. 7, 07.07.2017, p. 4360-4365.

Research output: Contribution to journalArticle

@article{2ac883aec8f449aa98bf5e97b18a2f64,
title = "The Nature of Plasmonically Assisted Hot-Electron Transfer in a Donor-Bridge-Acceptor Complex",
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 {\AA}. 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.",
keywords = "LSPR, Marcus theory, artificial photosynthesis, nanoparticle, photocatalysis, plasmon resonance, plasmonic catalysis, self-assembled monolayer",
author = "Youngsoo Kim and Wilson, {Andrew J.} and Prashant Jain",
year = "2017",
month = "7",
day = "7",
doi = "10.1021/acscatal.7b01318",
language = "English (US)",
volume = "7",
pages = "4360--4365",
journal = "ACS Catalysis",
issn = "2155-5435",
publisher = "American Chemical Society",
number = "7",

}

TY - JOUR

T1 - The Nature of Plasmonically Assisted Hot-Electron Transfer in a Donor-Bridge-Acceptor Complex

AU - Kim, Youngsoo

AU - Wilson, Andrew J.

AU - Jain, Prashant

PY - 2017/7/7

Y1 - 2017/7/7

N2 - 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.

AB - 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.

KW - LSPR

KW - Marcus theory

KW - artificial photosynthesis

KW - nanoparticle

KW - photocatalysis

KW - plasmon resonance

KW - plasmonic catalysis

KW - self-assembled monolayer

UR - http://www.scopus.com/inward/record.url?scp=85024911078&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85024911078&partnerID=8YFLogxK

U2 - 10.1021/acscatal.7b01318

DO - 10.1021/acscatal.7b01318

M3 - Article

AN - SCOPUS:85024911078

VL - 7

SP - 4360

EP - 4365

JO - ACS Catalysis

JF - ACS Catalysis

SN - 2155-5435

IS - 7

ER -