Alloy composition cell reaction

For the study of the electrocatalytic reduction of oxygen and oxidation of methanol, our approach to the preparation of catalysts by two-phase protocol " provides a better controllability over size, composition or surface properties in comparison with traditional approaches such as coprecipitation, deposition-precipitation, and impregnation. " The electrocatalytic activities were studied in both acidic and alkaline electrolytes. This chapter summarizes some of these recent results, which have provided us with further information for assessing gold-based alloy catalysts for fuel cell reactions. 

As in the nickel-cadmium cell, the electrolyte is concentrated potassium hydroxide. Depending on the metal alloy used, the emf has a value usually in the range 1.32-1.35 V, which turns out to be almost the same as that of the nickcl-cadmium cell. Note that the electrolyte composition is completely invariant during cycling. Unlike the situation with the nickel-cadmium cell, water is not involved in the cell reaction. 

Cell Alloy composition Current- generating reaction -AZ ... 

Figure 3.7 Combination of a bulk metal electrode and an alloy electrode. The alloy is shown as a layer deposited on a substrate. The cell reaction is the transformation of one mole of pure metal into the alloy of composition A Bj. ...

In the alloy Ag Au, silver is the electronegative component (the less noble one) and gold is the electropositive component (the more noble one). The electrolyte in the given example was a special glass with Ag ion conductivity. The glass was melted on the silver electrode. The electrolyte fihn had a thickness of 0.1 mm and the resistance was of the order of 2000 Q. The cell reaction was described in the previous chapter. The electrode process (Eq. (3.31)) consisted of the transfer of metal atoms from the pure Ag into the alloy environment Agjj AUj, keeping the alloy composition constant. Eqs. (3.33)-(3.37) could then be applied to calculate the partial molar functions of the Ag Au, system. 

The alkaline cell has an open-circuit voltage of 1.5 V that can deliver 150 Wh/kg and 460 Wh/1. The reactions have fast kinetics and can deliver full capacity, even at high-rate discharges. Since its introduction in 1959, there has been a steady increase in performance of the alkaline cell as new materials and cell components were incorporated into the structure. The present alkaline cell designs are based on the use of nanostructured electrolytic manganese dioxide, a thinner polymer gasket seal with sealant to increase internal volume and improve shelf Ufe. Mercury has been eliminated by using new zinc alloy compositions. These improvements have resulted in about a 40 % improvement in performance over the same-size cells produced in 1959. 

FIGURE 39 Corrosion. Corrosion is the process of gradual deterioration of metals and alloys as a result of their interaction with the environment. The corrosion process is a reversal of metallurgical processes, whereby metals are recovered from the minerals in which they occur in nature (a). It is an electrolytic process, brought about by the passage of electric currents. Any metal or alloy contains sites in which there are slight local compositional differences. When such compositional differences are exposed to a humid or wet environment, extremely small electrolytic cells as the one shown in (b) are created in each cell, an electric current drives the otherwise nonspontaneous corrosion reactions. In a surface undergoing corrosion there are millions of electrolytic cells. 

Over the past 35 years, much has been learned about the electrooxidation of methanol on the surface of noble metals and metal alloys, in particular platinum and ruthenium [2, 4, 6, 7]. Significant overpotential losses occur in the reaction due to poisoning of the alloy catalyst surface by carbon monoxide. Yet, Pt-based metal alloys are still the most popular catalyst materials in the development of new fuel cell electrocatalysts, based on the expectation that a more CO-tolerant methanol catalyst will be developed. The vast ternary composition space beyond Pt-Ru catalysts has not been adequately explored. This section demonstrates how the ternary space can be explored using the high-throughput, electrocatalyst workflow described above. 

Bimetallic Pt-Sn catalysts are useful commercially, e.g., for hydrocarbon conversion reactions. In many catalysts, Pt-Sn alloys are formed and play an important role in the catalysis. This is particularly true in recent reports of highly selective oxidative dehydrogenation of alkanes [37]. In addition, Pt-Sn alloys have been investigated as electrocatalysts for fuel cells and may have applications as gas sensors. Characterization of the composition and geometric structure of single-crystal Pt-Sn alloy surfaces is important for developing improved correlations of structure with activity and/or selectivity of Pt-Sn catalysts and electrocatalysts. 

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