DFT study of stabilization effects on N-doped graphene for ORR catalysis

Mateusz Reda*, Heine Anton Hansen, Tejs Vegge

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

Noble metal free catalysts, such as N-doped graphene, have drawn a lot of attention as a promising replacement for platinum in low temperature fuel cells. Computational prediction of catalytic activity requires accurate description of the oxygen reduction reaction (ORR) intermediates adsorption energies. Two stabilizing effects, immanently present in experimental ORR setups with basal plane N-doped graphene catalyst, are studied systematically by means of density functional theory. Distant nitrogen with no adsorbates on neighboring carbon atoms selectively stabilizes *O and *O2 adsorbates. Water solvation stabilizes all ORR intermediates, having a greater impact on *O and *O2, than on *OH and *OOH, in contrast to metal and oxide catalysts. Synergistic stabilization of *O caused by both effects reaches remarkably a high value of 1.5 eV for nitrogen concentrations above 4.2% N. Such a strong effect is explained by a high reactivity of *O and *O2, which possess empty O(sp) states. At 6.25% N, the reaction environment is found to comprise *O and free nitrogen spectators. Finally, strong *O solvation is found to be present in a broader class of systems, comprising all materials where the ORR occurs on a 2nd row element. Including at least a single explicit water layer is paramount to achieve the correct description of the ORR intermediates adsorption energies on these materials.
Original languageEnglish
JournalCatalysis Today
Volume312
Pages (from-to)118-125
Number of pages8
ISSN0920-5861
DOIs
Publication statusPublished - 2018

Keywords

  • Oxygen reduction reaction
  • Density functional theory
  • N-doped graphene
  • Explicit solvation

Cite this

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title = "DFT study of stabilization effects on N-doped graphene for ORR catalysis",
abstract = "Noble metal free catalysts, such as N-doped graphene, have drawn a lot of attention as a promising replacement for platinum in low temperature fuel cells. Computational prediction of catalytic activity requires accurate description of the oxygen reduction reaction (ORR) intermediates adsorption energies. Two stabilizing effects, immanently present in experimental ORR setups with basal plane N-doped graphene catalyst, are studied systematically by means of density functional theory. Distant nitrogen with no adsorbates on neighboring carbon atoms selectively stabilizes *O and *O2 adsorbates. Water solvation stabilizes all ORR intermediates, having a greater impact on *O and *O2, than on *OH and *OOH, in contrast to metal and oxide catalysts. Synergistic stabilization of *O caused by both effects reaches remarkably a high value of 1.5 eV for nitrogen concentrations above 4.2{\%} N. Such a strong effect is explained by a high reactivity of *O and *O2, which possess empty O(sp) states. At 6.25{\%} N, the reaction environment is found to comprise *O and free nitrogen spectators. Finally, strong *O solvation is found to be present in a broader class of systems, comprising all materials where the ORR occurs on a 2nd row element. Including at least a single explicit water layer is paramount to achieve the correct description of the ORR intermediates adsorption energies on these materials.",
keywords = "Oxygen reduction reaction, Density functional theory, N-doped graphene, Explicit solvation",
author = "Mateusz Reda and Hansen, {Heine Anton} and Tejs Vegge",
year = "2018",
doi = "10.1016/j.cattod.2018.02.015",
language = "English",
volume = "312",
pages = "118--125",
journal = "Catalysis Today",
issn = "0920-5861",
publisher = "Elsevier",

}

DFT study of stabilization effects on N-doped graphene for ORR catalysis. / Reda, Mateusz; Hansen, Heine Anton; Vegge, Tejs.

In: Catalysis Today, Vol. 312, 2018, p. 118-125.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - DFT study of stabilization effects on N-doped graphene for ORR catalysis

AU - Reda, Mateusz

AU - Hansen, Heine Anton

AU - Vegge, Tejs

PY - 2018

Y1 - 2018

N2 - Noble metal free catalysts, such as N-doped graphene, have drawn a lot of attention as a promising replacement for platinum in low temperature fuel cells. Computational prediction of catalytic activity requires accurate description of the oxygen reduction reaction (ORR) intermediates adsorption energies. Two stabilizing effects, immanently present in experimental ORR setups with basal plane N-doped graphene catalyst, are studied systematically by means of density functional theory. Distant nitrogen with no adsorbates on neighboring carbon atoms selectively stabilizes *O and *O2 adsorbates. Water solvation stabilizes all ORR intermediates, having a greater impact on *O and *O2, than on *OH and *OOH, in contrast to metal and oxide catalysts. Synergistic stabilization of *O caused by both effects reaches remarkably a high value of 1.5 eV for nitrogen concentrations above 4.2% N. Such a strong effect is explained by a high reactivity of *O and *O2, which possess empty O(sp) states. At 6.25% N, the reaction environment is found to comprise *O and free nitrogen spectators. Finally, strong *O solvation is found to be present in a broader class of systems, comprising all materials where the ORR occurs on a 2nd row element. Including at least a single explicit water layer is paramount to achieve the correct description of the ORR intermediates adsorption energies on these materials.

AB - Noble metal free catalysts, such as N-doped graphene, have drawn a lot of attention as a promising replacement for platinum in low temperature fuel cells. Computational prediction of catalytic activity requires accurate description of the oxygen reduction reaction (ORR) intermediates adsorption energies. Two stabilizing effects, immanently present in experimental ORR setups with basal plane N-doped graphene catalyst, are studied systematically by means of density functional theory. Distant nitrogen with no adsorbates on neighboring carbon atoms selectively stabilizes *O and *O2 adsorbates. Water solvation stabilizes all ORR intermediates, having a greater impact on *O and *O2, than on *OH and *OOH, in contrast to metal and oxide catalysts. Synergistic stabilization of *O caused by both effects reaches remarkably a high value of 1.5 eV for nitrogen concentrations above 4.2% N. Such a strong effect is explained by a high reactivity of *O and *O2, which possess empty O(sp) states. At 6.25% N, the reaction environment is found to comprise *O and free nitrogen spectators. Finally, strong *O solvation is found to be present in a broader class of systems, comprising all materials where the ORR occurs on a 2nd row element. Including at least a single explicit water layer is paramount to achieve the correct description of the ORR intermediates adsorption energies on these materials.

KW - Oxygen reduction reaction

KW - Density functional theory

KW - N-doped graphene

KW - Explicit solvation

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DO - 10.1016/j.cattod.2018.02.015

M3 - Journal article

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EP - 125

JO - Catalysis Today

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SN - 0920-5861

ER -