Surface Nanostructure Effects on Dopamine Adsorption and Electrochemistry on Glassy Carbon Electrodes

Dopamine (DA) adsorption and electron-transfer kinetics are strongly sensitive to the structure and composition of carbon electrodes. Activation of carbon surfaces is a popular method to improve DA detection, but the role of carbon structural features on DA behavior remains uncertain. Herein, we use scanning electrochemical cell microscopy (SECCM) for local anodization of glassy carbon (GC) electrodes in acid media followed by electrochemical imaging of DA adsorption and electrochemistry covering both unmodified and anodized GC regions of the same electrode. Electrochemical measurements of adsorbed DA involve the delivery of DA from the SECCM meniscus (30 μM) for 1 s periods followed by voltammetric analysis at a reasonable sweep rate (47 V s^-1). This general approach reduces effects from interelectrode variability and allows for considerable numbers of measurements and statistical analysis of electrochemical data sets. Localized electrode activity is correlated to surface structure and chemistry by a range of characterization techniques. Anodization enhances DA electron-transfer kinetics and provides more sites for adsorption (higher specific surface area). A consequence is that adsorption takes longer to approach completion on the anodized surface. In fact, normalizing DA surface coverage by the electrochemical surface area (ECSA) reveals that adsorption is less extensive on anodized surfaces compared to as-prepared GC on the same time scale. Thus, ECSA, which has often been overlooked when calculating DA surface coverage on carbon electrodes, even where different activation methods would be expected to result in different surface roughness and nanostructure, is an important consideration. Lower graphitic and higher oxygen content on anodized GC also suggest that oxygen-containing functional groups do not necessarily enhance DA adsorption and may have the opposite effect. This work further demonstrates SECCM as a powerful technique for revealing surface structure-function relationships and correlations at heterogeneous electrodes.