Oxide electrodes optically transparent

Figure 33.1a illustrates the idea of the smart window. In this device a layer of electrochromic material and a layer of a transparent ion-conducting electrolyte are sandwiched between two optically transparent electrodes (OTEs). Indium-doped tin oxide on glass is used most commonly as the OTE. This material has very low... 

A regenerative photogalvanic cell with oxidative quenching (Fig. 5.58b) is based, for example, on the Fe3+-Ru(bpy)2+ system. In contrast to the iron-thionine cell, the homogeneous photoredox process takes place near the (optically transparent) cathode. The photoexcited Ru(bpy)2+ ion reduces Fe3+ and the formed Ru(bpy)3+ and Fe2+ are converted at the opposite electrodes to the initial state. 

Figure 5.10 Redox titration of the Ni-C EPR signal in D. gigas hydrogenase, in the presence of mediators under partial pressure of H2. (A) Titration monitored by EPR spectroscopy (data from Cammack et al. 1982, 1987).The data points were obtained by removing samples from a vessel as shown in Fig. 5.8. Data NiA signal A NiC signal. (B) Titration monitored by FTIR spectroscopy (data from De Lacey et al. 1997).The spectra were recorded directly in a sealed optically transparent thin-layer electrode cell. Note that the oxidized and reduced species, which are undetectable by EPR, can be measured. Data o I946cm (NiB state) 1914+ 1934cm (NiSR state) A 1952cm (NiA state) 1940cm (NiR state).

In situ UV-visible spectroscopy monitors the energy of electrons within the analyte. While, strictly speaking, all materials change their UV-visible spectrum in accompaniment with electrode reactions (they are said to be electrochromic), the majority of these changes are not discernible by the human eye, and therefore may not be useful to the analyst. Electrodes must be optically transparent for in situ work, with the most commonly used being a thin film of the semiconductor, indium-tin oxide, on glass. 

To learn how to lest if an optically transparent electrode made of indium-tin oxide (ITO) is dirty or over-reduced, and therefore unsuitable for electroanalyses, Just by visual examination. 

Optically transparent electrodes. In situ spectroelectrochemistry was discussed in the previous chapter. The most common materials for constructing optically transparent electrodes for use in such analyses are thin films of semiconducting oxide deposited on to glass. Such materials are readily available commercially. 

Indium-tin oxide (ITO) Tin-doped indium oxide, used as a thin solid film on glass when constructing optically transparent electrodes. 

ECDs operate in the diffuse reflectance mode and the basic requirements for their functionality are (i) a primary electrochromic electrode (e.g. a polymer electrode) deposited on a substrate which is both optically transparent and electrically conducting (generally indium-tin-oxide(ITO)-... 

The electrochemical approach discussed here relies on a number of special properties of indium tin-oxide (ITO) electrodes, which had been used in particular for spectroelectrochemistry since ITO is optically transparent and can be fabricated on glass [28, 29]. The first important attribute of ITO is the ability to access potentials up to about 1.4 V (all potentials versus SSCE) in neutral solution [29]. Second, ITO electrodes do not adsorb DNA appreciably [30], which could be anticipated from the ability of metal oxides to adsorb cationic proteins [31] polyanionic nucleic acids were therefore not expected to adsorb. This property makes ITO quite different from carbon, which allows access to relatively high potentials but strongly adsorbs DNA [32]. Third, the direct oxidation of guanine at ITO is extremely slow, even... 

To assess the electrochromic response of the bipyridinium dications embedded into multilayers of 7, we envisaged the possibility of assembling these films on optically transparent platinum electrodes.27d f Specifically, we deposited an ultrathin platinum him on an indium-tin oxide substrate and then immersed the resulting assembly into a chloroform/methanol (2 1, v/v) solution of 7. As observed with the gold electrodes (Fig. 7.5), the corresponding cyclic voltammograms show waves for the reversible reduction of the bipyridinium dications with a significant increase in 2p with the immersion time. In fact, is 0.8,1.5, and 3.1 nmol/cm2 after immersion times of 1, 6, and 72 h, respectively. Furthermore, the correlation between ip and v is linear after 1 h and deviates from linearity after 6 and 72 h. Thus, the bisthiol 7 can indeed form multiple electroactive layers also on platinum substrates. 

In a typical spectroelectrochemical measurement, an optically transparent electrode (OTE) is used and the UV/vis absorption spectrum (or absorbance) of the substance participating in the reaction is measured. Various types of OTE exist, for example (i) a plate (glass, quartz or plastic) coated either with an optically transparent vapor-deposited metal (Pt or Au) film or with an optically transparent conductive tin oxide film (Fig. 5.26), and (ii) a fine micromesh (40-800 wires/cm) of electrically conductive material (Pt or Au). The electrochemical cell may be either a thin-layer cell with a solution-layer thickness of less than 0.2 mm (Fig. 9.2(a)) or a cell with a solution layer of conventional thickness ( 1 cm, Fig. 9.2(b)). The advantage of the thin-layer cell is that the electrolysis is complete within a short time ( 30 s). On the other hand, the cell with conventional solution thickness has the advantage that mass transport in the solution near the electrode surface can be treated mathematically by the theory of semi-infinite linear diffusion. 

The development of electrodes that exhibit optical transparency has enabled spectral observations to be made directly through the electrode simultaneously with electrochemical perturbations [19-21]. These electrodes typically consist of a very thin film of conductive material such as Pt, Au, carbon, or a semiconductor such as doped tin oxide that is deposited on a glass or quartz substrate. Miniature metal screens, minigrid electrodes in which the presence of very small holes (6-40 fim) lends transparency, have also been used. Optically transparent electrodes (OTE) and the cells that incorporate them are discussed in Chapters 9 and 11. 

Figure 3.16A shows spectra of o-tolidine in an optically transparent thin-layer electrode (OTTLE) for a series of applied potentials. Curve a was recorded after application of +0.800 V, which caused complete oxidation of o-tolidine ([0]/[R] > 1000). Curve g was recorded after application of +0.400 V, causing complete reduction ([0]/[R] < 0.001). The intermediate spectra correspond to intermediate values of Eapplied. Since the absorbance at 438 nm reflects the amount of o-tolidine in the oxidized form via Beer s law, the ratio [0]/[RJ that corresponds to each value of Eapplied can be calculated from the spectra by Equation 3.18. 

Delta Technologies 13960 N. 47th St. Stillwater, MN 55802-1234 Indium oxide optically transparent electrodes on glass and quartz... 

Methods. All solutions were prepared to be ImM Cytochrome c, 0.1mM DCIP, 0.10M alkali halide, and 0.10M phosphate buffer at pH 7.0 or pD 7.0. The DCIP served as a mediator-titrant for coupling the Cytochrome c with the electrode potential. E° values were measured using a previously described spectropotentiostatic technique using an optically transparent thin-layer electrode (OTTLE) (7,11,12). This method involved incrementally converting the cytochrome from its fully oxidized to fully reduced state by a series of applied potentials. For each potential a spectrum was recorded after equilibrium was attained. The formal redox potential was obtained from a Nernst plot. The n value... 

Photoexcitation of n-type semiconductors renders the surface highly activated toward electron transfer reactions. Capture of the photogenerated oxidizing equivalent (hole) by an adsorbed oxidizable organic molecule initiates a redox sequence which ultimately produces unique oxidation products. Furthermore, specific one electron routes can be observed on such irradiated surfaces. The irradiated semiconductor employed as a single crystalline electrode, as an amorphous powder, or as an optically transparent colloid, thus acts as both a reaction template and as a directed electron acceptor. Recent examples from our laboratory will be presented to illustrate the control of oxidative cleavage reactions which can be achieved with these heterogeneous photocatalysts. 

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