Oxide electrodes ionic transfer reactions

In more general terms, the operation of electrochemical cells may be understood on the basis that each electrode represents a medium for the electron interchange concomitant to oxidation—reduction processes. These reactions may involve electron transfer (i) between ions of different valence states in immediate proximity close to the electrode surface, (ii) through the decomposition of the solvent into ionic species,... 

It is worth noting that, as far as they are less than several nanometers thick, the passive films are subject to the quantum mechanical tunneling of electrons. Electron transfer at passive metal electrodes, hence, easily occurs no matter whether the passive film is an insulator or a semiconductor. By contrast, no ionic tunneling is expected to occur across the passive film even if it is extremely thin. The thin passive film is thus a barrier to the ionic transfer but not to the electronic transfer. Redox reactions involving only electron transfer are therefore allowed to occur at passive film-covered metal electrodes just like at metal electrodes with no surface film. It is also noticed, as mentioned earlier, that the interface between the passive film and the solution is equivalent to the interface between the solid metal oxide and the solution, and hence that the interfacial potential is independent of the electrode potential of the passive metal as long as the interface is in the state of band edge pinning. 

Electrode reactions involve charge transfer as a fundamental step, wherein a neutral species is converted into an ion, or an ion is converted into a neutral species. Both reactions thus involve electron transfer. At the cathode, the charge transfer reaction involves the conversion of an oxygen molecule into oxide ions. The electrodes in solid state electrochemical devices may either be purely electronic conductors, or may exhibit both ionic and electronic conductivity (the so-called mixed ionic electronic conduction, MIEC). In addition, the electrodes may be either single phase or composite, two-phase. For the purposes of illustration, in what follows we will examine the overall cathode reaction in a system with a single phase, purely electronically conducting electrode. 

Although IL electrolytes provide partial selectivity, the primary selectivity of an IL-electrochemical sensor comes from the redox properties of the analyte observed using amperometric methods, wherein the electrical current generated by reaction of an analyte at an electrode at a fixed or variable potential is measured [22]. We have shown redox chemistry that occurs only in ILs and can be exploited to enhance sensor performance [202], As shown in Fig. 2.16, we discovered that at platinum electrode in [NTf2]-based ionic liquids (ILs), facile methane electro-oxidation is observed suggesting a unique catalytic Pt-INTfj] interface for electron-transfer reaction of methane at room temperature. Little methane electro-oxidation signals are observed in ILs with other anions. In this experiment, an oxygen reduction process... 

Electrodes may be classified into the following two categories as shown in Fig. 4-3 one is the electronic electrode at which the transfer of electrons takes place, and the other is the ionic electrode at which the transfer of ions takes place. The electronic electrode corresponds, for instance, to the case in which the transfer of redox electrons in reduction-oxidation reactions, such as Fe = Fe + e,occurs and the ionic electrode corresponds to the case in which the transfer of ions, such as Fe , , = Fe, occiirs across the electrode interface. Usually, the former is found with insoluble electrodes such as platinum electrodes in aqueous solution containing redox particles and the latter is found with soluble metal electrodes such as iron and nickel. In practice, both electron transfer and ion transfer can take place simultaneously across the electrode interface. 

A solid oxide fuel cell (SOFC) consists of two electrodes anode and cathode, with a ceramic electrolyte between that transfers oxygen ions. A SOFC typically operates at a temperature between 700 and 1000 °C. at which temperature the ceramic electrolyte begins to exhibit sufficient ionic conductivity. This high operating temperature also accelerates electrochemical reactions therefore, a SOFC does not require precious metal catalysts to promote the reactions. More abundant materials such as nickel have sufficient catalytic activity to be used as SOFC electrodes. In addition, the SOFC is more fuel-flexible than other types of fuel cells, and reforming of hydrocarbon fuels can be performed inside the cell. This allows use of conventional hydrocarbon fuels in a SOFC without an external reformer. 

In addition to being able to catalyze the dissociation of O2. the material used for the cathode must be electronically conductive in the presence of air at high temperature, a property found primarily in noble metals and electronically conductive oxides. Ionic conductivity is also desirable for extending the reaction zone well into the electrode since the ions must ultimately be transferred to the electrolyte. Since precious metals are prohibitively expensive when used in quantities sufficient for providing electronic conductivity, essentially all SOFC prototypes use perovskite-based cathodes, with the most common material being a Sr-doped LaMnOs (LSM). In most cases, the cathode is a composite of the electronically conductive ceramic and an ionically conductive oxide, often the same material used in the electrolyte. 

The limited reversibility of some electrode reactions might require consideration of consumable (cheap) ionic liquids in the anode compartment for technical applications and commercial electroplating. For example, the electrochemical oxidation of oxalate delivers carbon dioxide, hydride could be oxidized to hydrogen, halides to the halogen or trihalide salt in the case of iodide ionic liquids and so on. Since ionic liquids can readily form biphasic systems an alternative may be to have the anodic reaction in an immiscible solvent. In that case a common ion would be needed that can be transferred from one phase to the other. 

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