DOI

The oxygen reduction reaction (ORR) is the key operating process that determines the efficiency of energy storage and conversion devices; however, due to sluggish kinetics, it requires a catalyst. In recent years, the trial-and-error approach for the catalyst development has been gradually replaced by the rational design based on theoretical predictions of catalytic activity, which includes the use of so-called descriptors, i.e., certain properties of the catalyst that correlate with the electrocatalytic activity of the material and can be evaluated relatively easily. To assess the applicability of different ORR activity descriptors to a variety of possible catalytic centers of doped graphene (impurity atoms, vacancies, and their combination), here, we consider different graphene imperfections by treating them within the same formalism using the following known descriptors: spin density at the impurity center, molecular orbital descriptor Ediff, charge redistribution in graphene caused by the imperfection, and charge redistribution under electrode polarization. To link the catalytic activity to the electronic properties of graphene, we calculated the partial electron density of states (PDOS) related to the reaction site at the Fermi level and local density of states for the reaction center, which are directly related to the electron transfer rate during the ORR. We found their reasonable correlation with PDOS. This fact indicates that descriptors based on the quantum theory are generally the most promising ones for reactivity predictions.

Original languageEnglish
Pages (from-to)6038-6053
Number of pages16
JournalJournal of Physical Chemistry C
Volume124
Issue number11
Early online date27 Feb 2020
DOIs
StatePublished - 19 Mar 2020

    Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Surfaces, Coatings and Films
  • Physical and Theoretical Chemistry

    Research areas

  • Electrolytic reduction, electronic properties, Graphene, Molecular orbitals, Oxygen, Oxygen reduction reaction, Quantum theory, Reaction kinetics, DESIGN PRINCIPLES, CHEMICAL-VAPOR-DEPOSITION, LARGE-SCALE GROWTH, FUEL-CELLS, TOTAL-ENERGY CALCULATIONS, HETEROATOM-DOPED GRAPHENE, CARBON NANOTUBES, MONOLAYER GRAPHENE, NITROGEN, METAL

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