Probing Redox Reactions at the Nanoscale with Electrochemical Tip-Enhanced Raman Spectroscopy

Dmitry Kurouski, Michael Mattei, Richard P Van Duyne*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

126 Scopus citations

Abstract

A fundamental understanding of electrochemical processes at the nanoscale is crucial to solving problems in research areas as diverse as electrocatalysis, energy storage, biological electron transfer, and plasmon-driven chemistry. However, there is currently no technique capable of directly providing chemical information about molecules undergoing heterogeneous charge transfer at the nanoscale. Tip-enhanced Raman spectroscopy (TERS) uniquely offers subnanometer spatial resolution and single-molecule sensitivity, making it the ideal tool for studying nanoscale electrochemical processes with high chemical specificity. In this work, we demonstrate the first electrochemical TERS (EC-TERS) study of the nanoscale redox behavior of Nile Blue (NB), and compare these results with conventional cyclic voltammetry (CV). We successfully monitor the disappearance of the 591 cm-1 band of NB upon reduction and its reversible reappearance upon oxidation during the CV. Interestingly, we observe a negative shift of more than 100 mV in the onset of the potential response of the TERS intensity of the 591 cm-1 band, compared to the onset of faradaic current in the CV. We hypothesize that perturbation of the electrical double-layer by the TERS tip locally alters the effective potential experienced by NB molecules in the tip-sample junction. However, we demonstrate that the tip has no effect on the local charge transfer kinetics. Additionally, we observe step-like behavior in some TERS voltammograms corresponding to reduction and oxidation of single or few NB molecules. We also show that the coverage of NB is nonuniform across the ITO surface. We conclude with a discussion of methods to overcome the perturbation of the double-layer and general considerations for using TERS to study nanoscale electrochemical processes.

Original languageEnglish (US)
Pages (from-to)7956-7962
Number of pages7
JournalNano Letters
Volume15
Issue number12
DOIs
StatePublished - Dec 9 2015

Keywords

  • Cyclic Voltammetry (CV)
  • Nanoscale Electrochemistry
  • Tip-Enhanced Raman Spectroscopy (TERS)

ASJC Scopus subject areas

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

Fingerprint Dive into the research topics of 'Probing Redox Reactions at the Nanoscale with Electrochemical Tip-Enhanced Raman Spectroscopy'. Together they form a unique fingerprint.

Cite this