Electron oxide electrodes

The. more tightly held an electron is. the more difficult it is to remove, hence the higher the electrode potential necessary to remove it. Make the reasonable hypothesis that the electron removed in a one-electron oxidation comes from the highest occupied orbital. HOMO. Using SHMO. determine the HOMO for ben7 ene, biphenyl, and naphthalene. 

Metal oxide electrodes have been coated with a monolayer of this same diaminosilane (Table 3, No. 5) by contacting the electrodes with a benzene solution of the silane at room temperature (30). Electroactive moieties attached to such silane-treated electrodes undergo electron-transfer reactions with the underlying metal oxide (31). Dye molecules attached to sdylated electrodes absorb light coincident with the absorption spectmm of the dye, which is a first step toward simple production of photoelectrochemical devices (32) (see Photovoltaic cells). 

To exploit the energy produced in this reaction, the half reactions are separated. The oxidation reaction is carried out at a zinc electrode (Zn Zir + 2 electrons) and the reduction reaction is carried out at a copper electrode (Cu"" + 2 electrons Cu metal). Electrons flow through a metal wire from the oxidizing electrode (anode) to the reducing electrode (cathode), creating electric current that can be harnessed, for example, to light a tungsten bulb. 

Dry cells (batteries) and fuel cells are the main chemical electricity sources. Diy cells consist of two electrodes, made of different metals, placed into a solid electrolyte. The latter facilitates an oxidation process and a flow of electrons between electrodes, directly converting chemical energy into electricity. Various metal combinations in electrodes determine different characteristics of the dry cells. For example, nickel-cadmium cells have low output but can work for several years. On the other hand, silver-zinc cells are more powerful but with a much shorter life span. Therefore, the use of a particular type of dry cell is determined by the spacecraft mission profile. Usually these are the short missions with low electricity consumption. Diy cells are simple and reliable, since they lack moving parts. Their major drawbacks are... 

The underlying theory may be simplified as follows. Polarography is concerned with electrode reactions at the indicator or micro-electrode, i.e. with reactions involving a transfer of electrons between the electrode and the components of the solution. These components are called oxidants when they can accept electrons, and reductants when they can lose electrons. The electrode is a cathode when a reduction can take place at its surface, and an anode when oxidation occurs at its surface. During the reduction of an oxidant at the cathode, electrons leave the electrode with the formation of an equivalent amount of the reductant in solution ... 

Tetrabutylammonium [bismuth(III) bis(phthalocyanine)] undergoes a one-electron oxidation (dichloromethane, U = IV, platinum electrode, several days) to give bismuth bis(phthalocyanine).167... 

In the other examples, the electrode materials are not involved in the reactions chemically, but constitute the source [sink] of electrons. Such electrodes are called nonconsumable. The term inert electrodes sometimes used is unfortunate insofar as the electrode itself is by no means inert rather, it has a strong catalytic effect on the electrode reaction. For reactions occurring at such electrodes, the terms oxidation- reduction... 

Nakabayashi, S., Yagi, 1., Sugiyama, N., Tamura, K. and Uosaki, K. (1997) Reaction pathway of four-electron oxidation of formaldehyde on platinum electrode as observed by in situ optical spectroscopy. Surf. Sci., 386, 82-88. 

After the electrolysis for 5 h at —0.15 V with the bubbling of O2 into W, the amount of CO2 produced was found to be 1.6 x 10 moles. A photoabsorption spectrum of the NB after electrolysis gave a peak at 780 nm. The peak was identical with that of the one electron oxidation product of DMFC, DMFC, which had been prepared coulometrically by using a column electrode with glassy carbon fiber working electrode [40]. This fact indicates that the electrolysis product was DMFC. The DMFC produced by the electrolysis was estimated to be 3.08 x 10 moles. 

Fichter and Kern O first reported that uric acid could be electrochemically oxidized. The reaction was studied at a lead oxide electrode but without control of the anode potential. Under such uncontrolled conditions these workers found that in lithium carbonate solution at 40-60 °C a yield of approximately 70% of allantoin was obtained. In sulfuric acid solution a 63% yield of urea was obtained. A complete material balance was not obtained nor were any mechanistic details developed. In 1962 Smith and Elving 2) reported that uric acid gave a voltammetric oxidation peak at a wax-impregnated spectroscopic graphite electrode. Subsequently, Struck and Elving 3> examined the products of this oxidation and reported that in 1 M HOAc complete electrochemical oxidation required about 2.2 electrons per molecule of uric acid. The products formed were 0.25 mole C02,0.25 mole of allantoin or an allantoin precursor, 0.75 mole of urea, 0.3 mole of parabanic acid and 0.30 mole of alloxan per mole of uric acid oxidized. On the basis of these products a scheme was developed whereby uric acid (I, Fig. 1) is oxidized in a primary 2e process to a shortlived dicarbonium ion (Ha, lib, Fig. 1) which, being unstable, under-... 

Very recently a new kind of electrocatalyst has been propounded using the dinuclear quinone-containing complex of ruthenium (25).492,493 Controlled-potential electrolysis of the complex at 1.70 V vs. Ag AgCl in H20 + CF3CH2OH evolves dioxygen with a current efficiency of 91% (21 turnovers). The turnover number of 02 evolution increases up to 33,500 when the electrolysis is carried out in water (pH 4.0) with an indium-tin oxide(ITO) electrode to which the complex is bound. It has been suggested that the four-electron oxidation of water is achieved by redox reactions of not only the two Run/Ruin couples, but also the two semiquinone/quinone couples of the molecule. 

I. Taniguchi, K. Watanabe, M. Tominaga, and F.M. Hawkridge, Direct electron transfer of horse heart myoglobin at an indium oxide electrode. J. Electroanal. Chem. 333, 331-338 (1992). 

M. Tominaga, T. Kumagai, S. Takita, and I. Taniguchi, Effect of surface hydrophilicity of an indium oxide electrode on direct electron transfer of myoglobins. Chem. Lett. 10, 1771-1774 (1993). 

The only difference between the active oxidizing and a ferric porphyrin hydroxide complex is two electrons (scheme 4). Indeed, the electrochemical oxidation of hydroxy ferric tetra-mesitylporphyrin shows two reversible one-electron oxidations (40), and, in principle, use of water and an electrode should allow development of a system capable of catalytically oxidizing hydrocarbons. 

Further reaction of Ph3P+ and Hg contributes the second ET for the overall two-electron oxidation. This was studied in detail for oxidations of tetraphenyllead, tetraethyllead and tetramethyllead at mercury electrodes in dichloromethane. The rationale of the mechanisms proposed above is based on the following observations122. 

An alternative electrochemical method has recently been used to obtain the standard potentials of a series of 31 PhO /PhO- redox couples (13). This method uses conventional cyclic voltammetry, and it is based on the CV s obtained on alkaline solutions of the phenols. The observed CV s are completely irreversible and simply show a wave corresponding to the one-electron oxidation of PhO-. The irreversibility is due to the rapid homogeneous decay of the PhO radicals produced, such that no reverse wave can be detected. It is well known that PhO radicals decay with second-order kinetics and rate constants close to the diffusion-controlled limit. If the mechanism of the electrochemical oxidation of PhO- consists of diffusion-limited transfer of the electron from PhO- to the electrode and the second-order decay of the PhO radicals, the following equation describes the scan-rate dependence of the peak potential ... 

Y. Cao, Thin metal-oxide layer as stable electron-injecting electrode for light emitting diodes, PCTInt. Appl., WO 2000022683, pp. 37, (2000). 

As mentioned, DPV is particularly useful to determine accurately the formal electrode potentials of partially overlapping consecutive electron transfers. For instance, Figure 40 compares the cyclic voltammogram of a species which undergoes two closely spaced one-electron oxidations with the relative differential-pulse voltammogram. As seen in DPV the two processes are well separated. 

Table 6 Formal electrode potential (V vs. SCE, at 25° C) for the one-electron oxidation of a few substituted ferrocenes. Dichloromethane solution [NBu4][CIO4] supporting electrolyte...

Table 8 Formal electrode potentials ( V, vs. SCE), and relative separation (V), for the two one-electron oxidations of a few diferrocenyl molecules...

As illustrated in Figure 45, this dianion undergoes two successive one-electron oxidations, the first of which is clearly chemically reversible, whereas the second is affected by electrode adsorption phenomena.81... 

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