Tip-Enhanced Raman Voltammetry: Coverage Dependence and Quantitative Modeling
作者： Michael Mattei , Gyeongwon Kang , Guillaume Goubert , Dhabih V. Chulhai , George C. Schatz
DOI: 10.1021/ACS.NANOLETT.6B04868
关键词: Redox 、 Analytical chemistry 、 Electrode 、 Molecule 、 Electrochemistry 、 Nile blue 、 Materials science 、 Indium tin oxide 、 Raman spectroscopy 、 Voltammetry
摘要: Electrochemical atomic force microscopy tip-enhanced Raman spectroscopy (EC-AFM-TERS) was employed for the first time to observe nanoscale spatial variations in formal potential, E0′, of a surface-bound redox couple. TERS cyclic voltammograms (TERS CVs) single Nile Blue (NB) molecules were acquired at different locations spaced 5–10 nm apart on an indium tin oxide (ITO) electrode. Analysis CVs coverages used verify observation single-molecule electrochemistry. The resulting fit Laviron model electroactive species quantitatively extract potential E0′ each location. Histograms coverage indicate that electrochemical behavior cationic oxidized is less sensitive local environment than neutral reduced species. This information not accessible using purely methods or ensemble spectroelectrochemical measurements. We anticipate qua...
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