In Situ Nanoscale Redox Mapping Using Tip-Enhanced Raman Spectroscopy

Electrochemical atomic force microscopy tip-enhanced Raman spectroscopy (EC-AFM-TERS) was used for the first time to spatially resolve local heterogeneity in redox behavior on an electrode surface in situ and at the nanoscale. A structurally well-defined Au(111) nanoplate located on a polycrystalline ITO substrate was studied to examine nanoscale redox contrast across the two electrode materials. By monitoring the TERS intensity of adsorbed Nile Blue (NB) molecules on the electrode surface, TERS maps were acquired with different applied potentials. The EC-TERS maps showed a spatial contrast in TERS intensity between Au and ITO. TERS line scans near the edge of a 20 nm-thick Au nanoplate demonstrated a spatial resolution of 81 nm under an applied potential of -0.1 V vs Ag/AgCl. The intensities from the TERS maps at various applied potentials followed Nernstian behavior, and a formal potential (E ^0′ ) map was constructed by fitting the TERS intensity at each pixel to the Nernst equation. Clear nanoscale spatial contrast between the Au and ITO regions was observed in the E ^0′ map. In addition, statistical analysis of the E ^0′ map identified a statistically significant 4 mV difference in E ^0′ on Au vs ITO. Electrochemical heterogeneity was also evident in the E ^0′ distribution, as a bimodal distribution was observed in E ^0′ on polycrystalline ITO, but not on gold. A direct comparison between an AFM friction image and the E ^0′ map resolved the electrochemical behavior of individual ITO grains with a spatial resolution of ∼40 nm. The variation in E ^0′ was attributed to different local surface charges on the ITO grains. Such site-specific electrochemical information with nanoscale spatial and few mV voltage resolutions is not available using ensemble spectroelectrochemical methods. We expect that in situ redox mapping at the nanoscale using EC-AFM-TERS will have a crucial impact on understanding the role of nanoscale surface features in applications such as electrocatalysis.