Oxygen reduction parameters

Neyerlin KC, Gu W, Jome J, Gasteiger HA. 2006. Determination of catalyst unique parameters for the oxygen reduction reaction in a PEMFC. J Electrochem Soc 153 A1955-A1963. 

Wang JX, Markovic NM, Adzic RR. 2004. Kinetic analysis of oxygen reduction on Pt(ll 1) in acid solutions Intrinsic kinetic parameters and anion adsorption effects. J Phys Chem B 108 ... 

It is important to compare the catalytic properties of Prussian blue with known hydrogen peroxide transducers. Table 13.2 presents the catalytic parameters, which are of major importance for analytical chemistry selectivity and catalytic activity. It is seen that platinum, which is still considered as the universal transducer, possesses rather low catalytic activity in both H202 oxidation and reduction. Moreover, it is nearly impossible to measure hydrogen peroxide by its reduction on platinum, because the rate of oxygen reduction is ten times higher. The situation is drastically improved in case of enzyme peroxidase electrodes. However, the absolute records of both catalytic activity... 

In practice, in all fuel cells that involve the utilization of 02 from air (Section 13.4.5), the oxygen reduction reaction [Eqs. (13.4) and (13.24)] is always rate determining for terrestrial applications. One can seejust how important it is to attempt to develop electrocatalysts for the cathodes of fuel cells on which the enhanced current density is high and Tafel slope is low and the efficiency of energy conversion, therefore, maximal. The direct relation of the mechanism of oxygen reduction and the associated Tafel parameters to the economics of electricity production and transportation is thus clearly seen. 

The mass-transport-limited current density for oxygen reduction is independent of the kinetic parameters for this reaction rather it depends on factors such as the concentration and the diffusion coefficient of oxygen in the medium. It depends oh the rate of flow of the liquid in a pipe or around a sailing ship or a structure immersed in a river. 

Several surface oxygen species have been postulated based on kinetic parameters, stable intermediates, and in situ observations during oxygen reduction or evolution. As in the case of hydrogen, platinum is the most well-studied electrocatalyst. Optical measurements (122-126) show that a freshly developed oxygen layer on platinum behaves reversibly up to 0.95 V. However, rapid aging yields an irreversibly bound layer. Chemisorption of OH is assumed to occur in this potential region (123,124,127,128) formed by z. + + H- + e (27)... 

The actual mechanism for oxygen reduction may involve more complicated steps and usually includes competitive adsorption of multiple species and multiple reaction pathways. Figure 18.4 shows the different competing pathways for the ORR. Under these circumstances, a generalized extension of the model presented earlier can be used, provided the experimental parameters such as... 

Other competing cathodic reactions can occur, and these cause an increase in zinc usage which adversely affects the process efficiency. Examples of these are hydrogen gas evolution or oxygen reduction. Other metal cations or impurities that load into the organic may also be reduced depending on the processing parameters and the electrochemical nature of the impurities. 

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