Wilhelm, Florian; Schmickler, Wolfgang; Spohr, Eckhard:
Proton transfer to charged platinum electrodes. A molecular dynamics trajectory study
2010
In: Journal of physics : a journal recognized by the European Physical Society, Condensed matter, Jg. 22 (2010), Heft 17, S. 175001
Artikel/Aufsatz in Zeitschrift2010Chemie
Fakultät für Chemie
Titel:
Proton transfer to charged platinum electrodes. A molecular dynamics trajectory study
Autor(in):
Wilhelm, Florian; Schmickler, Wolfgang; Spohr, EckhardLSF
Erscheinungsjahr
2010
WWW URL
WWW URL
Erschienen in:
Titel:
Journal of physics : a journal recognized by the European Physical Society, Condensed matter
in:
Jg. 22 (2010), Heft 17, S. 175001
ISSN:
Signatur der UB

Abstract:

A recently developed empirical valence bond (EVB) model for proton transfer on Pt(111) electrodes (Wilhelm et al 2008 J. Phys. Chem. C 112 10814) has been applied in molecular dynamics (MD) simulations of a water film in contact with a charged Pt surface. A total of seven negative surface charge densities σ between − 7.5 and − 18.9 µC cm − 2 were investigated. For each value of σ, between 30 and 84 initial conditions of a solvated proton within a water slab were sampled, and the trajectories were integrated until discharge of a proton occurred on the charged surfaces. We have calculated the mean rates for discharge and for adsorption of solvated protons within the adsorbed water layer in contact with the metal electrode as a function of surface charge density. For the less negative values of σ we observe a Tafel-like exponential increase of discharge rate with decreasing σ. At the more negative values this exponential increase levels off and the discharge process is apparently transport limited. Mechanistically, the Tafel regime corresponds to a stepwise proton transfer: first, a proton is transferred from the bulk into the contact water layer, which is followed by transfer of a proton to the charged surface and concomitant discharge. At the more negative surface charge densities the proton transfer into the contact water layer and the transfer of another proton to the surface and its discharge occur almost simultaneously.