First principles study of morphology, doping level, and water solvation effects on the catalytic mechanism of nitrogen-doped graphene in the oxygen reduction reaction

Dohyun Kwak, Abhishek Khetan, Seunghyo Noh, Heinz Pitsch, Byungchan Han

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

By using first principles DFT calculations, we reveal oxygen reduction reaction mechanisms in N-doped graphene (N-Gr). Considering both the morphology and the concentration of dopant N atoms in bulk and edge N-Gr forms, we calculate the energies of a large number of N-Gr model systems to cover a wide range of possible N-Gr structures and determine the most stable N-Gr forms. In agreement with experiments, our DFT calculations suggest that doping levels in stable N-Gr forms are limited to less than approximately 30 at.% N, above which the hexagonal graphene framework is broken. The ground state structures of bulk and edge N-Gr forms are found to differ depending on the doping level and poisoning of the edge bonds. Oxygen reduction reaction mechanisms are evaluated by using Gibbs free-energy diagrams with and without water solvation. Our results indicate that N doping significantly alters the catalytic properties of pure graphene and that dilutely doped bulk N-Gr forms are the most active.

Original languageEnglish
Pages (from-to)2662-2670
Number of pages9
JournalChemCatChem
Volume6
Issue number9
DOIs
Publication statusPublished - 2014 Jan 1

Fingerprint

Graphite
Solvation
Graphene
solvation
graphene
Nitrogen
Doping (additives)
Oxygen
nitrogen
Water
oxygen
water
Discrete Fourier transforms
poisoning
Gibbs free energy
Ground state
diagrams
Atoms
ground state

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

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abstract = "By using first principles DFT calculations, we reveal oxygen reduction reaction mechanisms in N-doped graphene (N-Gr). Considering both the morphology and the concentration of dopant N atoms in bulk and edge N-Gr forms, we calculate the energies of a large number of N-Gr model systems to cover a wide range of possible N-Gr structures and determine the most stable N-Gr forms. In agreement with experiments, our DFT calculations suggest that doping levels in stable N-Gr forms are limited to less than approximately 30 at.{\%} N, above which the hexagonal graphene framework is broken. The ground state structures of bulk and edge N-Gr forms are found to differ depending on the doping level and poisoning of the edge bonds. Oxygen reduction reaction mechanisms are evaluated by using Gibbs free-energy diagrams with and without water solvation. Our results indicate that N doping significantly alters the catalytic properties of pure graphene and that dilutely doped bulk N-Gr forms are the most active.",
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First principles study of morphology, doping level, and water solvation effects on the catalytic mechanism of nitrogen-doped graphene in the oxygen reduction reaction. / Kwak, Dohyun; Khetan, Abhishek; Noh, Seunghyo; Pitsch, Heinz; Han, Byungchan.

In: ChemCatChem, Vol. 6, No. 9, 01.01.2014, p. 2662-2670.

Research output: Contribution to journalArticle

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