Temperature-dependent kinetic studies of the chlorine evolution reaction over RuO2(110) model electrodes

I. Sohrabnejad-Eskan, A. Goryachev, K.S. Exner, L.A. Kibler, E.J.M. Hensen, J.P. Hofmann, H. Over

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Ultrathin single-crystalline RuO 2(110) films supported on Ru(0001) are employed as model electrodes to extract kinetic information about the industrially important chlorine evolution reaction (CER) in a 5M concentrated NaCl solution under well-defined electrochemical conditions and variable temperatures. A combination of chronoamperometry (CA) and online electrochemical mass spectrometry (OLEMS) experiments provides insight into the selectivity issue: At pH = 0.9, the CER dominates over oxygen evolution, whereas at pH = 3.5, oxygen evolution and other parasitic side reactions contribute mostly to the total current density. From temperature-dependent CA data for pH = 0.9, we determine the apparent free activation energy of the CER over RuO 2(110) to be 0.91 eV, which compares reasonably well with the theoretical value of 0.79 eV derived from first-principles microkinetics. The experimentally determined apparent free activation energy of 0.91 eV is considered as a benchmark for assessing future improved theoretical modeling from first principles.

Original languageEnglish
Pages (from-to)2403–2411
Number of pages9
JournalACS Catalysis
Issue number4
Publication statusPublished - 7 Apr 2017


  • RuO
  • apparent free activation energy
  • chlor-alkali electrolysis
  • chlorine evolution reaction (CER)
  • oxygen evolution reaction (OER)
  • selectivity


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