The effect of N and B doping on graphene and the adsorption and migration behavior of Pt atoms

Christopher Muhich, Jay Y. Westcott, Timothy C. Morris, Alan W. Weimer, Charles B. Musgrave

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Abstract

We utilize periodic density functional theory to study singly and triply N- and B-substituted graphene. We examine their doping mechanisms and effects on Pt atom adsorption and migration on graphene. We find a seemingly contradictory behavior between dopant type (n- vs p-type) and charge accumulation on the dopant atoms: the N atoms in both n-type singly N-doped graphene (NG) and p-type triply N-doped graphene (3NG) gain electron density while the B atoms in both singly (BG) and triply (3BG) B-doped graphene are p-type and lose electron density. This behavior arises from unequal charge sharing within C-B and C-N sp2 σ bonds and the requirement that the pz orbitals of N and B are singly occupied in order to maintain graphene's aromaticity. NG's N atom stabilizes Pt atom adsorption up to -0.39 eV (Eads = -1.86 eV) and by -0.13 eV even at distances 12.3 Å away from the N dopant. The Pt atom hopping energy barrier is lowered in graphene rings containing an NG N atom relative to undoped graphene, but the migration of a Pt atom over the N atom is unlikely due to a 1.0 eV barrier. 3NG's most stable Pt adsorption site (Eads= -2.86 eV) is the vacant C site at the center of 3NG's three N atoms and arises because of the formation of covalent bonds between Pt's d orbitals and the N atoms' three in-plane dangling sp2 orbitals. When a Pt atom adsorbs at a ring containing a pyridinic N, the strong N-Pt bonds trap the Pt atom, limiting its diffusion over the graphene sheet. The BG and 3BG structures bind Pt with a maximum adsorption energy of Eads= -2.16 eV and -5.30 eV, respectively. BG's high-lying B-C bonding orbitals allow the Pt atom to form strong σ bonds directly to the graphene sheet, while 3BG's B atoms donate electron density to the Pt atom creating an ionic bond between the negative Pt atom and the positive B atoms. These bonding mechanisms result in only short-range Pt stabilization and the B atoms having little influence on Pt atom migration outside B containing C rings; however, the depth and short-range nature of these energy wells funnel Pt atoms toward the B atoms and trap them there.

Original languageEnglish (US)
Pages (from-to)10523-10535
Number of pages13
JournalJournal of Physical Chemistry C
Volume117
Issue number20
DOIs
StatePublished - May 23 2013
Externally publishedYes

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Graphene
graphene
Doping (additives)
Adsorption
Atoms
adsorption
atoms
Carrier concentration
orbitals
rings
traps

ASJC Scopus subject areas

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

Cite this

The effect of N and B doping on graphene and the adsorption and migration behavior of Pt atoms. / Muhich, Christopher; Westcott, Jay Y.; Morris, Timothy C.; Weimer, Alan W.; Musgrave, Charles B.

In: Journal of Physical Chemistry C, Vol. 117, No. 20, 23.05.2013, p. 10523-10535.

Research output: Contribution to journalArticle

Muhich, Christopher ; Westcott, Jay Y. ; Morris, Timothy C. ; Weimer, Alan W. ; Musgrave, Charles B. / The effect of N and B doping on graphene and the adsorption and migration behavior of Pt atoms. In: Journal of Physical Chemistry C. 2013 ; Vol. 117, No. 20. pp. 10523-10535.
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abstract = "We utilize periodic density functional theory to study singly and triply N- and B-substituted graphene. We examine their doping mechanisms and effects on Pt atom adsorption and migration on graphene. We find a seemingly contradictory behavior between dopant type (n- vs p-type) and charge accumulation on the dopant atoms: the N atoms in both n-type singly N-doped graphene (NG) and p-type triply N-doped graphene (3NG) gain electron density while the B atoms in both singly (BG) and triply (3BG) B-doped graphene are p-type and lose electron density. This behavior arises from unequal charge sharing within C-B and C-N sp2 σ bonds and the requirement that the pz orbitals of N and B are singly occupied in order to maintain graphene's aromaticity. NG's N atom stabilizes Pt atom adsorption up to -0.39 eV (Eads = -1.86 eV) and by -0.13 eV even at distances 12.3 {\AA} away from the N dopant. The Pt atom hopping energy barrier is lowered in graphene rings containing an NG N atom relative to undoped graphene, but the migration of a Pt atom over the N atom is unlikely due to a 1.0 eV barrier. 3NG's most stable Pt adsorption site (Eads= -2.86 eV) is the vacant C site at the center of 3NG's three N atoms and arises because of the formation of covalent bonds between Pt's d orbitals and the N atoms' three in-plane dangling sp2 orbitals. When a Pt atom adsorbs at a ring containing a pyridinic N, the strong N-Pt bonds trap the Pt atom, limiting its diffusion over the graphene sheet. The BG and 3BG structures bind Pt with a maximum adsorption energy of Eads= -2.16 eV and -5.30 eV, respectively. BG's high-lying B-C bonding orbitals allow the Pt atom to form strong σ bonds directly to the graphene sheet, while 3BG's B atoms donate electron density to the Pt atom creating an ionic bond between the negative Pt atom and the positive B atoms. These bonding mechanisms result in only short-range Pt stabilization and the B atoms having little influence on Pt atom migration outside B containing C rings; however, the depth and short-range nature of these energy wells funnel Pt atoms toward the B atoms and trap them there.",
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AU - Musgrave, Charles B.

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N2 - We utilize periodic density functional theory to study singly and triply N- and B-substituted graphene. We examine their doping mechanisms and effects on Pt atom adsorption and migration on graphene. We find a seemingly contradictory behavior between dopant type (n- vs p-type) and charge accumulation on the dopant atoms: the N atoms in both n-type singly N-doped graphene (NG) and p-type triply N-doped graphene (3NG) gain electron density while the B atoms in both singly (BG) and triply (3BG) B-doped graphene are p-type and lose electron density. This behavior arises from unequal charge sharing within C-B and C-N sp2 σ bonds and the requirement that the pz orbitals of N and B are singly occupied in order to maintain graphene's aromaticity. NG's N atom stabilizes Pt atom adsorption up to -0.39 eV (Eads = -1.86 eV) and by -0.13 eV even at distances 12.3 Å away from the N dopant. The Pt atom hopping energy barrier is lowered in graphene rings containing an NG N atom relative to undoped graphene, but the migration of a Pt atom over the N atom is unlikely due to a 1.0 eV barrier. 3NG's most stable Pt adsorption site (Eads= -2.86 eV) is the vacant C site at the center of 3NG's three N atoms and arises because of the formation of covalent bonds between Pt's d orbitals and the N atoms' three in-plane dangling sp2 orbitals. When a Pt atom adsorbs at a ring containing a pyridinic N, the strong N-Pt bonds trap the Pt atom, limiting its diffusion over the graphene sheet. The BG and 3BG structures bind Pt with a maximum adsorption energy of Eads= -2.16 eV and -5.30 eV, respectively. BG's high-lying B-C bonding orbitals allow the Pt atom to form strong σ bonds directly to the graphene sheet, while 3BG's B atoms donate electron density to the Pt atom creating an ionic bond between the negative Pt atom and the positive B atoms. These bonding mechanisms result in only short-range Pt stabilization and the B atoms having little influence on Pt atom migration outside B containing C rings; however, the depth and short-range nature of these energy wells funnel Pt atoms toward the B atoms and trap them there.

AB - We utilize periodic density functional theory to study singly and triply N- and B-substituted graphene. We examine their doping mechanisms and effects on Pt atom adsorption and migration on graphene. We find a seemingly contradictory behavior between dopant type (n- vs p-type) and charge accumulation on the dopant atoms: the N atoms in both n-type singly N-doped graphene (NG) and p-type triply N-doped graphene (3NG) gain electron density while the B atoms in both singly (BG) and triply (3BG) B-doped graphene are p-type and lose electron density. This behavior arises from unequal charge sharing within C-B and C-N sp2 σ bonds and the requirement that the pz orbitals of N and B are singly occupied in order to maintain graphene's aromaticity. NG's N atom stabilizes Pt atom adsorption up to -0.39 eV (Eads = -1.86 eV) and by -0.13 eV even at distances 12.3 Å away from the N dopant. The Pt atom hopping energy barrier is lowered in graphene rings containing an NG N atom relative to undoped graphene, but the migration of a Pt atom over the N atom is unlikely due to a 1.0 eV barrier. 3NG's most stable Pt adsorption site (Eads= -2.86 eV) is the vacant C site at the center of 3NG's three N atoms and arises because of the formation of covalent bonds between Pt's d orbitals and the N atoms' three in-plane dangling sp2 orbitals. When a Pt atom adsorbs at a ring containing a pyridinic N, the strong N-Pt bonds trap the Pt atom, limiting its diffusion over the graphene sheet. The BG and 3BG structures bind Pt with a maximum adsorption energy of Eads= -2.16 eV and -5.30 eV, respectively. BG's high-lying B-C bonding orbitals allow the Pt atom to form strong σ bonds directly to the graphene sheet, while 3BG's B atoms donate electron density to the Pt atom creating an ionic bond between the negative Pt atom and the positive B atoms. These bonding mechanisms result in only short-range Pt stabilization and the B atoms having little influence on Pt atom migration outside B containing C rings; however, the depth and short-range nature of these energy wells funnel Pt atoms toward the B atoms and trap them there.

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