General Models for the Electrochemical Hydrogen Oxidation and Hydrogen Evolution Reactions – Theoretical Derivation and Experimental Results Under Near Mass-Transport Free Conditions
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Published version
Accepted version
Author(s)
Kucernak, ARJ
Zalitis, CM
Type
Journal Article
Abstract
Full derivations of Heyrovsky-Volmer (HV), Tafel-Volmer(TV), Heyrovsky-Tafel(HT), and Heyrovsky-Tafel-Volmer(HTV) mechanisms under steady state conditions are provided utilising a new theoretical framework which allows better understanding of the each of the mechanistic currents and part currents. Simple and easily implemented equations are presented, which provide both the hydrogen coverage and electrochemical current as a function of overpotential and relevant kinetic parameters. It is shown how these responses are governed by a set of dimensionless parameters associated with the ratio of electrokinetic parameters. For each of the different mechanisms, an “atlas” of Hads coverage with overpotential and corresponding current density is provided, allowing an understanding of all possible responses depending on the dimensionless parameters. Analysis of these mechanisms provides the limiting reaction orders of the exchange current density for protons and bimolecular hydrogen for each of the different mechanisms, as well as the possible Tafel slopes as a function of the molecular symmetry factor, . Only the HV mechanism is influenced by pH whereas the TV,HT, and HTV mechanisms are not. The cases where the equations simplify to limiting forms are discussed. Analysis of the exchange current density from experimental data is discussed, and it is shown that fitting the linear region around the equilibrium potential underestimates the true exchange current density for all of the mechanisms studied. Furthermore, estimates of exchange current density via back-extrapolation from large overpotentials is also shown to be highly inaccurate. Analysis of Tafel slopes is discussed along with the mechanistic information which can and cannot be determined. The new models are used to simultaneously fit sixteen experimental responses of Pt/C electrodes in acid towards the her/hor as a function of , pH, p(H2), and temperature, using a consistent set of electrokinetic parameters. Examples of implementation of the equations as both computable document format and Excel spreadsheets are provided.
Date Issued
2016-04-19
Date Acceptance
2016-04-19
Citation
Journal of Physical Chemistry C, 2016, 120 (20), pp.10721-10745
ISSN
1932-7455
Publisher
American Chemical Society
Start Page
10721
End Page
10745
Journal / Book Title
Journal of Physical Chemistry C
Volume
120
Issue
20
Copyright Statement
This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
License URL
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Grant Number
EP/J016454/1
EP/M023508/1
Subjects
Physical Chemistry
09 Engineering
03 Chemical Sciences
10 Technology
Publication Status
Published