Hydrogen electrode reaction: A complete kinetic description

Quaino, Paola; Chialvo, María R. Gennero de; Chialvo, Abel C.

doi:10.1016/j.electacta.2007.06.030

Cited by 78 publications

(100 citation statements)

References 27 publications

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“…Thus, there are many studies of the kinetic factors for polycrystalline platinum electrodes [26][27][28]. However, there are a few experimental studies on the kinetic factors of the deuterium evolution reaction (DER) [29].…”

Section: Introductionmentioning

confidence: 99%

Study of Deuterium Isotope Separation by PEFC

Shibuya

Matsushima

Ueda

2016

J. Electrochem. Soc.

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Hydrogen evolution and oxidation reactions were studied on a polycrystalline platinum electrode in 0.05 M D 2 SO 4 solution at 298 K by using a rotating disk electrode, focusing on the kinetic isotope effect on reactivity. The polarization measurements in the evolution reaction regime, on the one hand, revealed two Tafel regions: at low overpotentials close to the equilibrium potential, the Tafel slope was 0.039 V dec -1 , suggesting a Volmer-Tafel mechanism; and at potentials around 0.05 V or lower, a slope of 0.168 V dec -1 indicated that a transition to a Heyrovsky-Tafel mechanism occurred.In the oxidation reaction regime, on the other hand, a single Tafel slope of 0.055 V dec -1 was observed at potentials of 0.08 V or lower. Comparing between the deuterium and protium data for the kinetic factors supported the presence of an isotope effect, whereby the deuterium was more easily dissociated on the platinum electrode. The present kinetic result supported the deuterium separation of polymer electrolyte fuel cell (PEFC) in which the mixture gases of H 2 and D 2 were purged. The deuterium separation factor increased with increasing in the hydrogen utilization. This suggests a new isotope separation technique and also provides useful data for fuel cells.

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Section: Introductionmentioning

confidence: 99%

Study of Deuterium Isotope Separation by PEFC

Shibuya

Matsushima

Ueda

2016

J. Electrochem. Soc.

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“…The expressions for both the current density (j) and the surface coverage of the adsorbed hydrogen ( ) as a function of overpotential ( ) for the simultaneous occurrence of the three steps under a Frumkin type adsorption were derived previously [17]. For the present case the equations for j( ) can be written as, …”

Section: Hydrogen Oxidation Reactionmentioning

confidence: 99%

“…Nevertheless, it has been recently demonstrated that the usual analysis of the hor by this procedure can lead to errors in the interpretation of the kinetic results [14,17]. This is mainly due to the variation of the surface coverage ( ) of the adsorbed intermediate with the thickness of the diffusion layer at constant overpotential.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore the study of the aspects that govern the kinetics and the comprehension of the basic processes that occur during the reaction will produce advances in the design of new electrocatalysts, more efficient and cheaper. In this sense, studies carried out in our laboratory [14][15][16][17][18][19] in aqueous solution demonstrated that the hydrogen electrode reaction on platinum is preferentially verified through the Volmer-Tafel route at low overpotentials and that it is slowly changed to the Volmer-Heyrovsky route as the overpotential is increased. Nevertheless, it should be necessary to carry out basic kinetic studies in conditions similar to those corresponding to the operative cell.…”

Section: Introductionmentioning

confidence: 99%

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Kinetic Study of the Hydrogen Oxidation Reaction on Membrane Coated Electrodes. Part I: Theoretical Aspects

Marozzi¹,

Chialvo²,

Chialvo

2009

TOELECJ

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Abstract:A generalized theoretical analysis of the kinetics of the hydrogen oxidation reaction under the VolmerHeyrovsky-Tafel mechanism on an electrode covered by polymeric films is presented. The treatment includes the diffusion of the molecular hydrogen through the electrolyte solution, as well as through the different layers and interfaces. On the light of the resulting expressions, the applicability of the Levich-Koutecky diagrams for the determination of the kinetic current densities was critically analyzed.

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“…Adzic 10 and Chialvo 51,52 have both developed dual-pathway kinetic models that predict the existence of a shoulder or plateau in the HOR polarisation curves at low overpotentials, prior to a larger limiting current at higher overpotentials. These models were developed to fit data previously recorded by respectively), the Tafel step is independent of applied potential and the first plateau in the voltammograms is then the limiting current due to the Tafel-Volmer pathway.…”

Section: Hor Electrooxidation In [Demamentioning

confidence: 99%

Hydrogen Electrooxidation under Conditions of High Mass Transport in Room-Temperature Ionic Liquids and the Role of Underpotential-Deposited Hydrogen

Goodwin

Walsh

2016

J. Phys. Chem. C

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. (2016) Hydrogen electrooxidation under conditions of high mass transport in room-temperature ionic liquids and the role of underpotential-deposited hydrogen. Journal of Physical Chemistry C, 120 (21). pp. 11498-11507. ISSN 1932-7455 Access from the University of Nottingham repository: http://eprints.nottingham.ac.uk/33911/1/Article%20jp-2016-01592f.R2.pdf Copyright and reuse:The Nottingham ePrints service makes this work by researchers of the University of Nottingham available open access under the following conditions. This article is made available under the University of Nottingham End User licence and may be reused according to the conditions of the licence. For more details see: http://eprints.nottingham.ac.uk/end_user_agreement.pdf A note on versions:The version presented here may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the repository url above for details on accessing the published version and note that access may require a subscription. AbstractThe hydrogen oxidation reaction (HOR), an electrocatalytic reaction of fundamental and applied interest, was studied in the protic ionic liquid (PIL) diethylmethylammonium trifluoromethanesulfonate, [dema][TfO], at Pt electrodes using rotating disk electrode (RDE) and ultramicroelectrode (UME) voltammetry. A steady-state HOR current is observed during RDE voltammetry at overpotentials > 50 mV but an additional plateau is observed in the overpotential region 50-200 mV when using UMEs. The difference in voltammetric responses is attributed to higher rate of mass transport to the UME than to the RDE. Three models have been used to fit the experimental data. The first is a dual-pathway model, which assumes that the Tafel-Volmer and Heyrovsky-Volmer pathways are both active over the potential range of interest and no blockage of catalytic sites occurs during the reaction. The second is a dual-pathway model, which assumes that reaction intermediates block access of H 2 to catalytic sites. The third is based on the premise that underpotential-deposited hydrogen atoms (H upd ) can block adsorption and electrooxidation of H 2 at the Pt surface. While each model fits the polarisation curves reasonably well, detailed analysis suggests that the H updblocking model describes the responses better. To the best of our knowledge, this work is the first to demonstrate the advantages of UME voltammetry over RDE voltammetry for studying electrocatalytic reactions in PILs, and the first to show that H upd can inhibit an electrocatalytic reactions in an ionic liquid, a factor that may become important as the technological applications of these liquids increase.3

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Hydrogen electrode reaction: A complete kinetic description

Cited by 78 publications

References 27 publications

Study of Deuterium Isotope Separation by PEFC

Study of Deuterium Isotope Separation by PEFC

Kinetic Study of the Hydrogen Oxidation Reaction on Membrane Coated Electrodes. Part I: Theoretical Aspects

Hydrogen Electrooxidation under Conditions of High Mass Transport in Room-Temperature Ionic Liquids and the Role of Underpotential-Deposited Hydrogen

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