title: Full Kinetics from First Principles of the Chlorine Evolution Reaction over a RuO2 (110) Model Electrode.
abstract: Current progress in modern electrocatalysis research is spurred by theory, frequently based on ab initio thermodynamics, where the stable reaction intermediates at the electrode surface are identified, while the actual energy barriers are ignored. This approach is popular in that a simple tool is available for searching for promising electrode materials. However, thermodynamics alone may be misleading to assess the catalytic activity of an electrochemical reaction as we exemplify with the chlorine evolution reaction (CER) over a RuO2 (110) model electrode. The full procedure is introduced, starting from the stable reaction intermediates, computing the energy barriers, and finally performing microkinetic simulations, all performed under the influence of the solvent and the electrode potential. Full kinetics from first-principles allows the rate-determining step in the CER to be identified and the experimentally observed change in the Tafel slope to be explained.
authors.affiliation: Physikalisch-Chemisches Institut, Justus-Liebig-Universität, Heinrich-Buff-Ring 17, 35392, Gießen, Germany.
authors.forename: Kai S
authors.initials: KS
authors.lastname: Exner
authors.affiliation: Institut für Elektrochemie, Universität Ulm, Albert-Einstein-Allee 47, 89069, Ulm, Germany.|Helmholtz-Institut-Ulm (HIU), Helmholtzstrasse 11, 89081, Ulm, Germany.
authors.forename: Josef
authors.initials: J
authors.lastname: Anton
authors.affiliation: Institut für Elektrochemie, Universität Ulm, Albert-Einstein-Allee 47, 89069, Ulm, Germany.|Helmholtz-Institut-Ulm (HIU), Helmholtzstrasse 11, 89081, Ulm, Germany.
authors.forename: Timo
authors.initials: T
authors.lastname: Jacob
authors.affiliation: Physikalisch-Chemisches Institut, Justus-Liebig-Universität, Heinrich-Buff-Ring 17, 35392, Gießen, Germany. herbert.over@phys.chemie.uni-giessen.de.
authors.forename: Herbert
authors.initials: H
authors.lastname: Over
keywords: chlorine evolution; density functional calculations; electrocatalysis; reaction kinetics; ruthenium dioxide