Thermochemical and electrochemical stability of ruthenium oxides: A DFT perspective

Kimika Teorikoa Seminar

Ruthenium oxides are used in some important catalytic processes such as the chlorine evolution reaction and oxygen evolution reaction. These reactions are central in the chloralkali process, water electrolyzers and the thermocatalytic Sumitomo process. Since Ru oxides are not particularly abundant in the Earth’s crust, it is essential to understand the factors that affect their catalytic performance and durability. DFT coupled with thermodynamic models can serve as a guide or support to experiments. However, accurately assessing the thermochemistry of oxides, gas-phase species, and reaction intermediates is challenging for DFT. In this talk, I will analyze the formation energies of RuO x using several exchange-correlation functionals. I will show a correlation between the DFT errors and the number of O atoms in the oxides and provide a simple method to correct these errors. The corrections bring DFT energy estimations close to experimental results and allow for the elaboration of accurate phase diagrams.

Aguado-Ruiz, I.; Urrego-Ortiz, R.; Calle-Vallejo, F. A Computational View on the
Thermochemical and Electrochemical Stability of Ruthenium Oxides. Journal of
Materials Chemistry A 2025, 13 (17), 12482–12491. https://doi.org/10.1039/d4ta09213a.