Oxygen reduction reaction kinetic parameters

Anastasijevic NA, Vesovic V, Adzic RR. Determination of the kinetic parameters of the oxygen reduction reaction using the rotating ring-disk electrode part I. Theory J Electroanal Chem Interfacial Electrochem 1987 229 305-16. 

TABLE 4.2.7 Kinetic Parameters for the Oxygen Reduction Reaction in Acid and Alkaline Solutions... 

Fouda-Onana F, Bah S, Savadogo O (2009) Palladium-copper alloys as catalysts fra the oxygen reduction reaction in an acidic media I Correlation between the ORR kinetic parameters and intrinsic physical properties of the alloys. J Electroanal Chem 636(1-2) 1-9... 

More recently, Wang et al. [28] derived an intrinsic kinetic equation for the four-electron (4e ) oxygen reduction reaction (ORR) in acidic media, by using free energies of activation and adsorption as the kinetic parameters, which were obtained through fitting experimental ORR data from a Pt(lll) rotating disk electrode (RDE). Their kinetic model consists of four essential elementary reactions (1) a dissociative adsorption (DA) (2) a reductive adsorption (RA), which yields two reaction intermediates, O and OH (3) a reductive transition (RT) from O to OH and (4) a reductive desorption (RD) of OH, as shown below [28] (Reproduced with permission from [28]). 

Anastasijevic, N., Vesovic, V. and Adzic, R. (1987). Determination of the Kinetic Parameters of the Oxygen Reduction Reaction Using the Rotating Ring-disk Electrode Part 1. Theory, J. Electroanal Chem., 229, pp. 305-316. 

Pathways, mechanisms, and corresponding kinetic parameters of the ORR have been discussed in the section Electrocatalysis of the Oxygen Reduction Reaction at Platinum. In a highly simplified picture, derived originally on the basis of a series of experimental studies by Damjanovic and coworkers (Damjanovic, 1992 Gatrell and MacDougall, 2003 Sepa et al., 1981,1987), it was proposed that the rate-determining reaction step is the initial adsorption. 

Parirni NS, Umasankar Y, Atanassov P, Ramasamy RP. Electrochemical kinetic and mechanistic parameters of laccase-catalyzed oxygen reduction reaction. ACS Catal 2012 2 38-44. 

The reverse reaction, dissolved O2 reduction in alkaline and acid solutions, was also studied [117, 118]. The reduction was found to be highly inhibited, probably due to the lack of adsorption sites for oxygen and/or reduced intermediates. The reaction is hypothesized to proceed mainly at sp3-sites the non-diamond sp2 carbon was deactivated by anodic prepolarization. The kinetic parameters were found as a = 0.24, k° = 7 10-5 cm s-1 in alkaline medium. It is significant that, owing to its high overvoltage, the dissolved O2 reduction does not interfere with other reactions, which thus can be studied on diamond electrodes without air removal from the cell this could be advantageous in certain types of analytical applications. 

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. 

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