title: Interrogation of surfaces for the quantification of adsorbed species on electrodes: oxygen on gold and platinum in neutral media.
abstract: We introduce a new in situ electrochemical technique based on the scanning electrochemical microscope (SECM) operating in a transient feedback mode for the detection and direct quantification of adsorbed species on the surface of electrodes. A SECM tip generates a titrant from a reversible redox mediator that reacts chemically with an electrogenerated or chemically adsorbed species at a substrate of about the same size as the tip, which is positioned at a short distance from it (ca.1 microm). The reaction between the titrant and the adsorbate provides a transient positive feedback loop until the adsorbate is consumed completely. The sensing mechanism is provided by the contrast between positive and negative feedback, which allows a direct quantification of the charge neutralized at the substrate. The proposed technique allows quantification of the adsorbed species generated at the substrate at a given potential under open circuit conditions, a feature not attainable with conventional electrochemical methods. Moreover, the feedback mode allows the tip to be both the titrant generator and detector, simplifying notably the experimental setup. The surface interrogation technique we introduce was tested for the quantification of electrogenerated oxides (adsorbed oxygen species) on gold and platinum electrodes at neutral pH in phosphate and TRIS buffers and with two different mediator systems. Good agreement is found with cyclic voltammetry at the substrate and with previous results in the literature, but we also find evidence for the formation of "incipient oxides" which are not revealed by conventional voltammetry. The mode of operation of the technique is supported by digital simulations, which show good agreement with the experimental results.
authors.affiliation: Center for Electrochemistry, Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712, USA.
authors.forename: Joaquín
authors.initials: J
authors.lastname: Rodríguez-López
authors.forename: Mario A
authors.initials: MA
authors.lastname: Alpuche-Avilés
authors.forename: Allen J
authors.initials: AJ
authors.lastname: Bard