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@article{Kucernak:2016:10.1021/acs.jpcc.6b00011,
author = {Kucernak, ARJ and Zalitis, CM},
doi = {10.1021/acs.jpcc.6b00011},
journal = {Journal of Physical Chemistry C},
pages = {10721--10745},
title = {General Models for the Electrochemical Hydrogen Oxidation and Hydrogen Evolution Reactions – Theoretical Derivation and Experimental Results Under Near Mass-Transport Free Conditions},
url = {http://dx.doi.org/10.1021/acs.jpcc.6b00011},
volume = {120},
year = {2016}
}

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TY  - JOUR
AB  - 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 parame
AU  - Kucernak,ARJ
AU  - Zalitis,CM
DO  - 10.1021/acs.jpcc.6b00011
EP  - 10745
PY  - 2016///
SN  - 1932-7455
SP  - 10721
TI  - General Models for the Electrochemical Hydrogen Oxidation and Hydrogen Evolution Reactions – Theoretical Derivation and Experimental Results Under Near Mass-Transport Free Conditions
T2  - Journal of Physical Chemistry C
UR  - http://dx.doi.org/10.1021/acs.jpcc.6b00011
UR  - http://hdl.handle.net/10044/1/31392
VL  - 120
ER  -

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