Oxygen Electrochemistry

Tarasevich, M. R.; Sadkowski, A.; Yeager, Ernest

doi:10.1007/978-1-4613-3584-9_6

Cited by 297 publications

(195 citation statements)

References 188 publications

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“…The perovskite structure ABO3−δ has been chosen for many systematic studies of catalytic activity [25,[46][47][48][49][50], including oxygen reduction and evolution (i.e., oxygen electrocatalysis) [14,22,[25][26][27][28][51][52][53][54][55]. The key idea of this section is a demonstration of both intentional and unintentional effects of chemical substitution or changes in stoichiometry on the activity for oxygen reduction ( Figure 2).…”

Section: Effect Of Chemical Substitution On Activitymentioning

confidence: 99%

Perovskite Electrocatalysts for the Oxygen Reduction Reaction in Alkaline Media

Risch

2017

Catalysts

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Abstract:Oxygen reduction is considered a key reaction for electrochemical energy conversion but slow kinetics hamper application in fuel cells and metal-air batteries. In this review, the prospect of perovskite oxides for the oxygen reduction reaction (ORR) in alkaline media is reviewed with respect to fundamental insight into activity and possible mechanisms. For gaining these insights, special emphasis is placed on highly crystalline perovskite films that have only recently become available for electrochemical interrogation. The prospects for applications are evaluated based on recent progress in the synthesis of perovskite nanoparticles. The review concludes with the current understanding of oxygen reduction on perovskite oxides and a perspective on opportunities for future fundamental and applied research.

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Section: Effect Of Chemical Substitution On Activitymentioning

confidence: 99%

Perovskite Electrocatalysts for the Oxygen Reduction Reaction in Alkaline Media

Risch

2017

Catalysts

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“…It is accepted that the reduction can occur by a number of pathways, see Figure 1. 7,8 The direct 4e − reduction pathway is envisaged to result from mechanisms where there is cleavage of the O-O bond early in the reaction sequence, while the alternative pathways involve 2e…”

mentioning

confidence: 99%

Voltammetric Studies of the Mechanism of the Oxygen Reduction in Alkaline Media at the Spinels Co₃O₄and NiCo₂O₄

Sönmez

Thompson

Price

et al. 2016

J. Electrochem. Soc.

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The mechanism of O 2 reduction at the spinels, Co 3 O 4 and NiCo 2 O 4 , in KOH electrolyte is probed using voltammetry at rotating disc and rotating ring-disc electrodes by examination of the rotation rate dependent limiting currents. The analysis shows that the products and mechanisms at the two spinels are quite different. At the cobalt spinel, a substantial amount of the 2e − reduction product, H 2 O 2 , is formed while at NiCo 2 O 4 the 4e − reduction strongly predominates. In terms of both the overpotential for reduction and its limiting current density, the mixed spinel is a substantially better electrocatalyst. It is proposed that the differences arise from an enhanced rate of O-O bond cleavage early in the reduction process at NiCo 2 O 4 .

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“…t) dependent variable t) step-size in numerical solution technique local current density due to reaction j, A/cm 2 exchange current density due to reaction j at reference concentrations, A/cm 2 total current density, A/cm 2 diffusion limiting current density, mA/cm 2 current density in the absence of mass transfer effects (see Eq. [33]), mA/cm 2 identity matrix total current, mA limiting current, mA diffusion limiting current, mA equilibrium constant for homogeneous reaction in the bulk solution backward rate constant for homogeneous reaction forward rate constant for homogeneous reaction rate constant for non-charge-transfer reaction at electrode surface number of charge transfer reactions at electrode surface number of reactions at the electrode flux of species i, mol/cm2s Levenberg-Marquardt approximation to the Hessian number of species in the solution number of electrons transferred in reaction j P P~ q~ q There are several reasons for the current interest in the electrochemical behavior of pyrite and other sulfide minerals (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17). Among these reasons are the use of metal sulfides in high energy batteries (1), solar energy applications (2-4), the need to treat low grade and complex sulfide ores by direct leaching (5)(6)(7)(8), the possibility of direct electrowinning of metals from sulfide ores (9), and the need to desulfurize coal (10)(11).…”

Section: Evaluation Of Electrochemical Parameters From Polarization Dmentioning

confidence: 99%

Analysis of Electrokinetic Data by Parameter Estimation and Model Discrimination Technqiues

Adanuvor

White

1988

J. Electrochem. Soc.

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An alternative approach to classical methods of electrochemical data analysis is presented. This alternative method is based on nonlinear parameter estimation and model discrimination techniques. The method is used to obtain the relevant kineuc ana transport parameters and to elucidate the kinetic mechanism of 02 reduction at carbon and silver electrodes in alkaline electrolytes.Conventional methods for electrochemical data analysis generally tend to focus on a narrow range of the kinetic expressions describing the electrochemical process, such as the Tafel or the linear segments of typical polarization curves. Focus on these sections of the polarization curves produces a set of parameter values which electrochemists have traditionally used to elucidate the mechanisms of electrochemical reactions. However, in most instances, the linear and Tafel segments of these curves are distorted by diffusion processes, the reverse reaction in the neighborhood of the equilibrium potential, and coupling effects of other reactions. Therefore, parameters estimated from the Tafel or linear regions of the polarization curves, especially for complex electrode reaction systems, may not reflect the true values of the parameters of the electrode reactions under consideration. For instance, where the electrode reaction is relatively fast, the Tafel segment may be so short as to create difficulty in accurately estimating the parameters. On the other hand, for slow electrode reactions, the polarization curves can have several Tafel segments with transition regions, where the reaction from one segment could be coupled with that in another segment. McIntyre (1) noted the coupling effect of a regenerative process of a heterogeneous catalytic electrode reaction over the complete potential range in which the electroactive species was reduced and recommended that the coupling effect be taken into account if kinetic parameters characteristic of the charge-transfer reaction are to be obtained. On the other hand, the linear region extends only a few millivolts beyond the equilibrium or open-circuit potential. As pointed out by Nagy et al. (2), measurements at such low overpotentials are often hampered by signal-to-noise ratio problems, and extrapolation from the linear to higher overpotential range as commonly done in electrochemical studies is generally questionable.Most kinetic models, in addition to relating the overall process and the component steps to the potential driving force and to the concentrations of reactants, products, and * Electrochemical Society Active Member.intermediates, must also take into account the transport O f reacting species, intermediates, and products to and from the electrode surface. Furthermore, consideration of homogeneous reactions in the solution and heterogeneous non-charge transfer reactions at the electrode surface increases the complexity of the system of model equations needed to evaluate the kinetic parameters. This system of model equations is normally described by a set of differential equatio...

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Oxygen Electrochemistry

Cited by 297 publications

References 188 publications

Perovskite Electrocatalysts for the Oxygen Reduction Reaction in Alkaline Media

Perovskite Electrocatalysts for the Oxygen Reduction Reaction in Alkaline Media

Voltammetric Studies of the Mechanism of the Oxygen Reduction in Alkaline Media at the Spinels Co₃O₄and NiCo₂O₄

Analysis of Electrokinetic Data by Parameter Estimation and Model Discrimination Technqiues

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Oxygen Electrochemistry

Cited by 297 publications

References 188 publications

Perovskite Electrocatalysts for the Oxygen Reduction Reaction in Alkaline Media

Perovskite Electrocatalysts for the Oxygen Reduction Reaction in Alkaline Media

Voltammetric Studies of the Mechanism of the Oxygen Reduction in Alkaline Media at the Spinels Co3O4and NiCo2O4

Analysis of Electrokinetic Data by Parameter Estimation and Model Discrimination Technqiues

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Voltammetric Studies of the Mechanism of the Oxygen Reduction in Alkaline Media at the Spinels Co₃O₄and NiCo₂O₄