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

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.