Tip-Enhanced Raman Voltammetry: Coverage Dependence and Quantitative Modeling

Michael Mattei, Gyeongwon Kang, Guillaume Goubert, Dhabih V. Chulhai, George C Schatz, Lasse Jensen, Richard P. Van Duyne

Research output: Contribution to journalArticle

39 Citations (Scopus)

Abstract

Electrochemical atomic force microscopy tip-enhanced Raman spectroscopy (EC-AFM-TERS) was employed for the first time to observe nanoscale spatial variations in the formal potential, E0', of a surface-bound redox couple. TERS cyclic voltammograms (TERS CVs) of single Nile Blue (NB) molecules were acquired at different locations spaced 5-10 nm apart on an indium tin oxide (ITO) electrode. Analysis of TERS CVs at different coverages was used to verify the observation of single-molecule electrochemistry. The resulting TERS CVs were fit to the Laviron model for surface-bound electroactive species to quantitatively extract the formal potential E0' at each spatial location. Histograms of single-molecule E0' at each coverage indicate that the electrochemical behavior of the cationic oxidized species is less sensitive to local environment than the neutral reduced species. This information is not accessible using purely electrochemical methods or ensemble spectroelectrochemical measurements. We anticipate that quantitative modeling and measurement of site-specific electrochemistry with EC-AFM-TERS will have a profound impact on our understanding of the role of nanoscale electrode heterogeneity in applications such as electrocatalysis, biological electron transfer, and energy production and storage.

Original languageEnglish
Pages (from-to)590-596
Number of pages7
JournalNano Letters
Volume17
Issue number1
DOIs
Publication statusPublished - Jan 11 2017

Fingerprint

Voltammetry
Electrochemistry
electrochemistry
Molecules
Raman spectroscopy
Atomic force microscopy
atomic force microscopy
molecules
Electrocatalysis
Electrodes
electrodes
Tin oxides
histograms
indium oxides
Indium
tin oxides
electron transfer
electron energy
Electrons

Keywords

  • cyclic voltammetry
  • Laviron model
  • single-molecule electrochemistry
  • Tip-enhanced Raman spectroscopy (TERS)

ASJC Scopus subject areas

  • Bioengineering
  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Mechanical Engineering

Cite this

Mattei, M., Kang, G., Goubert, G., Chulhai, D. V., Schatz, G. C., Jensen, L., & Van Duyne, R. P. (2017). Tip-Enhanced Raman Voltammetry: Coverage Dependence and Quantitative Modeling. Nano Letters, 17(1), 590-596. https://doi.org/10.1021/acs.nanolett.6b04868

Tip-Enhanced Raman Voltammetry : Coverage Dependence and Quantitative Modeling. / Mattei, Michael; Kang, Gyeongwon; Goubert, Guillaume; Chulhai, Dhabih V.; Schatz, George C; Jensen, Lasse; Van Duyne, Richard P.

In: Nano Letters, Vol. 17, No. 1, 11.01.2017, p. 590-596.

Research output: Contribution to journalArticle

Mattei, M, Kang, G, Goubert, G, Chulhai, DV, Schatz, GC, Jensen, L & Van Duyne, RP 2017, 'Tip-Enhanced Raman Voltammetry: Coverage Dependence and Quantitative Modeling', Nano Letters, vol. 17, no. 1, pp. 590-596. https://doi.org/10.1021/acs.nanolett.6b04868
Mattei, Michael ; Kang, Gyeongwon ; Goubert, Guillaume ; Chulhai, Dhabih V. ; Schatz, George C ; Jensen, Lasse ; Van Duyne, Richard P. / Tip-Enhanced Raman Voltammetry : Coverage Dependence and Quantitative Modeling. In: Nano Letters. 2017 ; Vol. 17, No. 1. pp. 590-596.
@article{421ee2295afe4532a8525db3ed6394e3,
title = "Tip-Enhanced Raman Voltammetry: Coverage Dependence and Quantitative Modeling",
abstract = "Electrochemical atomic force microscopy tip-enhanced Raman spectroscopy (EC-AFM-TERS) was employed for the first time to observe nanoscale spatial variations in the formal potential, E0', of a surface-bound redox couple. TERS cyclic voltammograms (TERS CVs) of single Nile Blue (NB) molecules were acquired at different locations spaced 5-10 nm apart on an indium tin oxide (ITO) electrode. Analysis of TERS CVs at different coverages was used to verify the observation of single-molecule electrochemistry. The resulting TERS CVs were fit to the Laviron model for surface-bound electroactive species to quantitatively extract the formal potential E0' at each spatial location. Histograms of single-molecule E0' at each coverage indicate that the electrochemical behavior of the cationic oxidized species is less sensitive to local environment than the neutral reduced species. This information is not accessible using purely electrochemical methods or ensemble spectroelectrochemical measurements. We anticipate that quantitative modeling and measurement of site-specific electrochemistry with EC-AFM-TERS will have a profound impact on our understanding of the role of nanoscale electrode heterogeneity in applications such as electrocatalysis, biological electron transfer, and energy production and storage.",
keywords = "cyclic voltammetry, Laviron model, single-molecule electrochemistry, Tip-enhanced Raman spectroscopy (TERS)",
author = "Michael Mattei and Gyeongwon Kang and Guillaume Goubert and Chulhai, {Dhabih V.} and Schatz, {George C} and Lasse Jensen and {Van Duyne}, {Richard P.}",
year = "2017",
month = "1",
day = "11",
doi = "10.1021/acs.nanolett.6b04868",
language = "English",
volume = "17",
pages = "590--596",
journal = "Nano Letters",
issn = "1530-6984",
publisher = "American Chemical Society",
number = "1",

}

TY - JOUR

T1 - Tip-Enhanced Raman Voltammetry

T2 - Coverage Dependence and Quantitative Modeling

AU - Mattei, Michael

AU - Kang, Gyeongwon

AU - Goubert, Guillaume

AU - Chulhai, Dhabih V.

AU - Schatz, George C

AU - Jensen, Lasse

AU - Van Duyne, Richard P.

PY - 2017/1/11

Y1 - 2017/1/11

N2 - Electrochemical atomic force microscopy tip-enhanced Raman spectroscopy (EC-AFM-TERS) was employed for the first time to observe nanoscale spatial variations in the formal potential, E0', of a surface-bound redox couple. TERS cyclic voltammograms (TERS CVs) of single Nile Blue (NB) molecules were acquired at different locations spaced 5-10 nm apart on an indium tin oxide (ITO) electrode. Analysis of TERS CVs at different coverages was used to verify the observation of single-molecule electrochemistry. The resulting TERS CVs were fit to the Laviron model for surface-bound electroactive species to quantitatively extract the formal potential E0' at each spatial location. Histograms of single-molecule E0' at each coverage indicate that the electrochemical behavior of the cationic oxidized species is less sensitive to local environment than the neutral reduced species. This information is not accessible using purely electrochemical methods or ensemble spectroelectrochemical measurements. We anticipate that quantitative modeling and measurement of site-specific electrochemistry with EC-AFM-TERS will have a profound impact on our understanding of the role of nanoscale electrode heterogeneity in applications such as electrocatalysis, biological electron transfer, and energy production and storage.

AB - Electrochemical atomic force microscopy tip-enhanced Raman spectroscopy (EC-AFM-TERS) was employed for the first time to observe nanoscale spatial variations in the formal potential, E0', of a surface-bound redox couple. TERS cyclic voltammograms (TERS CVs) of single Nile Blue (NB) molecules were acquired at different locations spaced 5-10 nm apart on an indium tin oxide (ITO) electrode. Analysis of TERS CVs at different coverages was used to verify the observation of single-molecule electrochemistry. The resulting TERS CVs were fit to the Laviron model for surface-bound electroactive species to quantitatively extract the formal potential E0' at each spatial location. Histograms of single-molecule E0' at each coverage indicate that the electrochemical behavior of the cationic oxidized species is less sensitive to local environment than the neutral reduced species. This information is not accessible using purely electrochemical methods or ensemble spectroelectrochemical measurements. We anticipate that quantitative modeling and measurement of site-specific electrochemistry with EC-AFM-TERS will have a profound impact on our understanding of the role of nanoscale electrode heterogeneity in applications such as electrocatalysis, biological electron transfer, and energy production and storage.

KW - cyclic voltammetry

KW - Laviron model

KW - single-molecule electrochemistry

KW - Tip-enhanced Raman spectroscopy (TERS)

UR - http://www.scopus.com/inward/record.url?scp=85019850974&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85019850974&partnerID=8YFLogxK

U2 - 10.1021/acs.nanolett.6b04868

DO - 10.1021/acs.nanolett.6b04868

M3 - Article

C2 - 27936805

AN - SCOPUS:85019850974

VL - 17

SP - 590

EP - 596

JO - Nano Letters

JF - Nano Letters

SN - 1530-6984

IS - 1

ER -