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Full Free Energy Diagram of an Electrocatalytic Reaction over a Single‐Crystalline Model Electrode
Author(s) -
Exner Kai S.,
SohrabnejadEskan Iman,
Anton Josef,
Jacob Timo,
Over Herbert
Publication year - 2017
Publication title -
chemelectrochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.182
H-Index - 59
ISSN - 2196-0216
DOI - 10.1002/celc.201700687
Subject(s) - tafel equation , electrolysis , thermodynamics , gibbs free energy , oxygen evolution , ab initio , electrocatalyst , electrode , electrolysis of water , chemistry , pourbaix diagram , materials science , electrochemistry , physics , electrolyte , organic chemistry
A long‐term aim of chemical kinetics is to gain detailed information on the full free energy diagram along the reaction coordinate of electrocatalytic processes such as those encountered in fuel cells, batteries, and industrial electrolysis. We present here a universal approach to construct the free energy landscape of an electrocatalyzed reaction over a single‐crystalline model electrode without relying on full kinetics from first principles, a highly computer‐resource‐demanding approach. The free energies of the transition states are determined by a dedicated evaluation scheme of experimental Tafel plots, whereas ab initio thermodynamics calculations provide the free energies of the reaction intermediates. We exemplified this approach with the chlorine and oxygen evolution reactions over a well‐defined RuO 2 (110) model electrode, both reactions constitute large‐scale industrial processes.