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.

It is fundamentally interesting to study the photoelectrochemical properties of complex oxides for applications in photovoltaics and photocatalysis. In this paper, we study the band gap (E g ) and energetics of the conduction band (CB) and valence band (VB) for films of zinc stannate (Zn 2 SnO 4 ) nanoparticles (ca. 25 nm) of the inverse-spinel structure prepared by the hydrothermal method. UV-vis spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemistry, and photoelectrochemistry were used to study the films. The fundamental E g for Zn 2 SnO 4 is proposed to be 3.6-3.7 eV with a directforbidden transition. The position of the CB was approximated from the flat band potential, E fb , measured by the photocurrent onset potential. In aqueous and nonaqueous solutions the E fb of n-Zn 2 SnO 4 was found to be more positive than TiO 2 anatase in the electrochemical scale. In aqueous solutions E fb of Zn 2 SnO 4 was found to follow a 59 mV/pH slope with E fb extrapolated at pH 0 of 0.08 V vs NHE. In acetonitrile solutions that simulate the electrolyte for dye-sensitized solar cells (DSCs) the E fb of Zn 2 SnO 4 was found to be strongly dependent on electrolyte composition and more positive than TiO 2 vs the I -/I 3 couple. The reverse trend observed for the open-circuit voltage in certain DSC electrolytes is explained in terms of the higher rates of electron-triiodide recombination of TiO 2 despite the lower position of the Zn 2 SnO 4 CB in the vacuum scale.

A new constant-distance imaging method based on the relationship between tip impedance and tip-substrate separation has been developed for the scanning electrochemical microscope. The tip impedance is monitored by application of a high-frequency ac voltage bias between the tip and auxiliary electrode. The high-frequency ac current is easily separated from the dc-level faradaic electrochemistry with a simple RC filter, which allows impedance measurements during feedback or generation/collection experiments. By employing a piezo-based feedback controller, we are able to maintain the impedance at a constant value and, thus, maintain a constant tip-substrate separation. Application of the method to feedback and generation/collection experiments with tip electrodes as small as 2 microm is presented.

We describe a method to detect individual semiconducting nanoparticles (NPs) using the photoelectrochemical (PEC) current measured at an ultramicroelectrode (UME). We use photooxidation of MeOH by TiO2 NPs as a model system of photocatalysis in solution. NPs suspended in MeOH under constant illumination produce valence-band holes that oxidize MeOH. The electrons are collected at the UME, and the current-versus-time data show discrete current changes that are assigned to particle-by-particle interactions of the NPs with the UME. The stepwise changes in the photocurrent denote irreversible attachment of NPs to Pt UMEs (<30 μm diameter). We found that accumulation of electrons in the conduction band by the NPs is not enough to explain the stochastic PEC currents. We propose that the observed anodic steps have a PEC nature and are due to photooxidation of MeOH by the NPs at the electrode surface.

Oxygen evolution electrocatalysts in acidic media were studied by scanning electrochemical microscopy (SECM) in the substrate generation-tip collection (SG-TC) imaging mode with a 100 microm diam tip. Pure IrO2 and Sn(1-x)Ir(x)O2 combinatorial mixtures were prepared by a sol-gel route to form arrays of electrocatalyst spots. The experimental setup has been developed to optimize screening of electrocatalyst libraries under conditions where the entire array is capable of the oxygen evolution reaction (OER). The activity of individual spots was determined by reducing the interference from the reaction products of neighboring spots diffusing to the tip over the spot of interest. A gold layer deposited on the external wall of the SECM tip was used as a tip shield. In this study the shield was kept at a constant potential to reduce oxygen under mass transfer controlled conditions. The tip shield consumes oxygen coming from the neighbor spots in the array and enables the tip to correctly detect the activity of the spot below the tip. Simulations and experimental results are shown, demonstrating the effectiveness of the tip shield with the SG-TC setup in determining the properties of the composite materials and imaging arrays.