2004
DOI: 10.1039/b402695k
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Hydrogen diffusion effects on the kinetics of the hydrogen electrode reaction. Part I. Theoretical aspects

Abstract: The effect of the hydrogen diffusion on the hydrogen electrode reaction has been studied and rigorous kinetic expressions for the Tafel-Heyrovsky-Volmer mechanism has been derived. The analysis of the dependences of the current density ( j) on overpotential (Z), particularly oriented to the hydrogen oxidation reaction (hor), leads to the following main results: (i) in the Tafel-Volmer (TV) route, the current density reaches a maximum value ( j max ) less or equal to the limiting diffusion current density (j L … Show more

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Cited by 60 publications
(84 citation statements)
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“…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%
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“…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%
“…In this context, for the case in which the hor takes place preferably through the VolmerTafel route, a maximum value of the current density j max will be obtained when , which can be less or equal to j L depending on the values of parameters j L , v T e and e (Equations 7a-8 in reference 16). Moreover, for the Heyrovsky-Volmer route j max will be equal to j L when , regardless of the values of all the parameters [14][15][16]. In the case of the simultaneous occurrence of the three steps, depending on the relative values of the different parameters, j( ) can exhibit a first zone at low determined by the Tafel step and then a gradual increase in the contribution of the Heyrovsky step, which finally becomes preponderant [14,16].…”
Section: Analysis Of Equation (20)mentioning
confidence: 99%
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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%