Plasmon-Driven Chemistry in Ferri-/Ferrocyanide Gold Nanoparticle Oligomers: A SERS Study

Yue Qi; Vitor Brasiliense; Tyler W. Ueltschi; Ji Eun Park; Michael R. Wasielewski; George C. Schatz; Richard P. Van Duyne

doi:10.1021/jacs.0c05031

Plasmon-Driven Chemistry in Ferri-/Ferrocyanide Gold Nanoparticle Oligomers: A SERS Study

Yue Qi, Vitor Brasiliense, Tyler W. Ueltschi, Ji Eun Park, Michael R. Wasielewski, George C. Schatz^*, Richard P. Van Duyne

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

The plasmon-driven chemistry of ferri-/ferrocyanide ions inside surface-enhanced Raman spectroscopy (SERS) active hot spots associated with gold nanoparticle oligomers is studied with continuous wave (CW) pump-probe SERS. By comparing with solution-phase normal Raman spectra, the characteristic spectral variations observed upon 532 nm optical pumping can be attributed to an oxidation process that occurs on the surface species followed by desorption of the oxidized surface species from the gold nanoparticles. Interrogating the plasmon-driven processes over a wide range of temperatures reveals that neither process is purely driven by the thermal effects associated with the optical pumping, and the apparent activation energies of both steps are estimated based on semiquantitative SERS analysis. Our observation identifies a more detailed reaction pathway for this classic model system under considerably simplified reaction conditions, adding to the current mechanistic background for future plasmon-driven chemistry studies and applications.

Original language	English (US)
Pages (from-to)	13120-13129
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	142
Issue number	30
DOIs	https://doi.org/10.1021/jacs.0c05031
State	Published - Jul 29 2020

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.0c05031

Cite this

@article{c6cc6f0a102e4bd089d3446fca3203b4,

title = "Plasmon-Driven Chemistry in Ferri-/Ferrocyanide Gold Nanoparticle Oligomers: A SERS Study",

abstract = "The plasmon-driven chemistry of ferri-/ferrocyanide ions inside surface-enhanced Raman spectroscopy (SERS) active hot spots associated with gold nanoparticle oligomers is studied with continuous wave (CW) pump-probe SERS. By comparing with solution-phase normal Raman spectra, the characteristic spectral variations observed upon 532 nm optical pumping can be attributed to an oxidation process that occurs on the surface species followed by desorption of the oxidized surface species from the gold nanoparticles. Interrogating the plasmon-driven processes over a wide range of temperatures reveals that neither process is purely driven by the thermal effects associated with the optical pumping, and the apparent activation energies of both steps are estimated based on semiquantitative SERS analysis. Our observation identifies a more detailed reaction pathway for this classic model system under considerably simplified reaction conditions, adding to the current mechanistic background for future plasmon-driven chemistry studies and applications. ",

author = "Yue Qi and Vitor Brasiliense and Ueltschi, {Tyler W.} and Park, {Ji Eun} and Wasielewski, {Michael R.} and Schatz, {George C.} and {Van Duyne}, {Richard P.}",

note = "Funding Information: The authors acknowledge financial support from the National Science Foundation (NSF) Center for Chemical Innovation dedicated to Chemistry at the Space Time Limit Grant No. CHE-1414466, the Air Force Office of Scientific Research MURI (FA9550-14-1-0003), NSF Grant No. CHE-1807278, and the Department of Defense Vannevar Bush Faculty Fellowship program (N00014-17-1-3024) for experimental studies and NSF Grant No. CHE-1760537 for theory. Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = jul,

day = "29",

doi = "10.1021/jacs.0c05031",

language = "English (US)",

volume = "142",

pages = "13120--13129",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "30",

}

TY - JOUR

T1 - Plasmon-Driven Chemistry in Ferri-/Ferrocyanide Gold Nanoparticle Oligomers

T2 - A SERS Study

AU - Qi, Yue

AU - Brasiliense, Vitor

AU - Ueltschi, Tyler W.

AU - Park, Ji Eun

AU - Wasielewski, Michael R.

AU - Schatz, George C.

AU - Van Duyne, Richard P.

N1 - Funding Information: The authors acknowledge financial support from the National Science Foundation (NSF) Center for Chemical Innovation dedicated to Chemistry at the Space Time Limit Grant No. CHE-1414466, the Air Force Office of Scientific Research MURI (FA9550-14-1-0003), NSF Grant No. CHE-1807278, and the Department of Defense Vannevar Bush Faculty Fellowship program (N00014-17-1-3024) for experimental studies and NSF Grant No. CHE-1760537 for theory. Publisher Copyright: Copyright © 2020 American Chemical Society.

PY - 2020/7/29

Y1 - 2020/7/29

N2 - The plasmon-driven chemistry of ferri-/ferrocyanide ions inside surface-enhanced Raman spectroscopy (SERS) active hot spots associated with gold nanoparticle oligomers is studied with continuous wave (CW) pump-probe SERS. By comparing with solution-phase normal Raman spectra, the characteristic spectral variations observed upon 532 nm optical pumping can be attributed to an oxidation process that occurs on the surface species followed by desorption of the oxidized surface species from the gold nanoparticles. Interrogating the plasmon-driven processes over a wide range of temperatures reveals that neither process is purely driven by the thermal effects associated with the optical pumping, and the apparent activation energies of both steps are estimated based on semiquantitative SERS analysis. Our observation identifies a more detailed reaction pathway for this classic model system under considerably simplified reaction conditions, adding to the current mechanistic background for future plasmon-driven chemistry studies and applications.

AB - The plasmon-driven chemistry of ferri-/ferrocyanide ions inside surface-enhanced Raman spectroscopy (SERS) active hot spots associated with gold nanoparticle oligomers is studied with continuous wave (CW) pump-probe SERS. By comparing with solution-phase normal Raman spectra, the characteristic spectral variations observed upon 532 nm optical pumping can be attributed to an oxidation process that occurs on the surface species followed by desorption of the oxidized surface species from the gold nanoparticles. Interrogating the plasmon-driven processes over a wide range of temperatures reveals that neither process is purely driven by the thermal effects associated with the optical pumping, and the apparent activation energies of both steps are estimated based on semiquantitative SERS analysis. Our observation identifies a more detailed reaction pathway for this classic model system under considerably simplified reaction conditions, adding to the current mechanistic background for future plasmon-driven chemistry studies and applications.

UR - http://www.scopus.com/inward/record.url?scp=85089609010&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85089609010&partnerID=8YFLogxK

U2 - 10.1021/jacs.0c05031

DO - 10.1021/jacs.0c05031

M3 - Article

C2 - 32618467

AN - SCOPUS:85089609010

SN - 0002-7863

VL - 142

SP - 13120

EP - 13129

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 30

ER -

Plasmon-Driven Chemistry in Ferri-/Ferrocyanide Gold Nanoparticle Oligomers: A SERS Study

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this