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Microscopic Insights into the Chlorine Evolution Reaction on RuO2(110): a Mechanistic Ab Initio Atomistic Thermodynamics Study

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Abstract

The frequently discussed mechanisms for the chlorine evolution reaction (CER)—Volmer–Tafel, Volmer–Heyrovsky, and Krishtalik—are assessed for the case of RuO2 within a mechanistic ab initio thermodynamics approach, employing the concept of Gibbs energy loss. The CER over the fully O-covered RuO2(110) surface, the stable surface configuration under CER conditions, is shown to proceed via the Volmer–Heyrovsky mechanism, i.e., the adsorption and discharge of the chloride ion are followed by the direct recombination of this surface species with a chloride ion from the electrolyte solution. The weak adsorption of the chloride ion on the fully O-covered RuO2(110) surface constitutes the elementary reaction step with highest Gibbs energy loss which has its origin in a too strong ruthenium–oxygen bond. Therefore, the activity of the model catalyst RuO2(110) can be enhanced by weakening the surface metal–oxygen bond such as realized with a monolayer of PtO2 coated on RuO2(110).

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Acknowledgments

K.E. acknowledges financial support by Fonds Chemischer Industrie (FCI) via a PhD scholarship. Franziska Hess is acknowledged for providing figures of ball and stick models of the stoichiometric and fully O-covered RuO2(110) surface. H.O. was supported by the LOEWE program STORE_E within the Laboratory of Materials Research at the JLU. T.J. acknowledges support from the European Research Council (ERC) through the ERC-Starting Grant THEOFUN.

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Authors and Affiliations

  1. Physical Chemistry Department, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 58, 35392, Giessen, Germany

    Kai S. Exner & Herbert Over

  2. Institute of Electrochemistry, Ulm University, Albert-Einstein-Allee 47, 89069, Ulm, Germany

    Josef Anton & Timo Jacob

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  1. Kai S. Exner
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  2. Josef Anton
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Correspondence to Herbert Over.

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Exner, K.S., Anton, J., Jacob, T. et al. Microscopic Insights into the Chlorine Evolution Reaction on RuO2(110): a Mechanistic Ab Initio Atomistic Thermodynamics Study. Electrocatalysis 6, 163–172 (2015). https://doi.org/10.1007/s12678-014-0220-3

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  • DOI: https://doi.org/10.1007/s12678-014-0220-3

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