Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and EmissionSpectroscopy Study

CH Chuang, SC Ray, D Mazumder, S Sharma, A Ganguly, Pagona Papakonstantinou, JW Chiou, HM Tsai, HW Shiu, CH Chen, HJ Lin, J Guo, WF Pong

Research output: Contribution to journalArticle

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Abstract

Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.
LanguageEnglish
Pages42235
JournalScientific Reports
Volume7
DOIs
Publication statusPublished - 10 Feb 2017

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Chemical modification
X ray absorption
Oxides
Nitrogen
Valence bands
Inelastic scattering
Photoelectron spectroscopy
X ray scattering
Atoms
Substitution reactions
Carbon Monoxide
X ray spectroscopy
Fermi level
Functional groups
Urea
Carbon
Doping (additives)
Oxygen
Electrons

Keywords

  • nitrogen doped reduced graphene oxide
  • X-ray Absorption spectroscopy (XANES)
  • X ray emission spectroscopy
  • valence-band photoemission spectroscopy (VB-PES)
  • resonant inelastic X-ray scattering (RIXS).

Cite this

Chuang, CH ; Ray, SC ; Mazumder, D ; Sharma, S ; Ganguly, A ; Papakonstantinou, Pagona ; Chiou, JW ; Tsai, HM ; Shiu, HW ; Chen, CH ; Lin, HJ ; Guo, J ; Pong, WF. / Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and EmissionSpectroscopy Study. In: Scientific Reports. 2017 ; Vol. 7. pp. 42235.
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abstract = "Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at{\%}), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at{\%}) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.",
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Chuang, CH, Ray, SC, Mazumder, D, Sharma, S, Ganguly, A, Papakonstantinou, P, Chiou, JW, Tsai, HM, Shiu, HW, Chen, CH, Lin, HJ, Guo, J & Pong, WF 2017, 'Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and EmissionSpectroscopy Study', Scientific Reports, vol. 7, pp. 42235. https://doi.org/10.1038/srep42235

Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and EmissionSpectroscopy Study. / Chuang, CH; Ray, SC; Mazumder, D; Sharma, S; Ganguly, A; Papakonstantinou, Pagona; Chiou, JW; Tsai, HM; Shiu, HW; Chen, CH; Lin, HJ; Guo, J; Pong, WF.

In: Scientific Reports, Vol. 7, 10.02.2017, p. 42235.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and EmissionSpectroscopy Study

AU - Chuang, CH

AU - Ray, SC

AU - Mazumder, D

AU - Sharma, S

AU - Ganguly, A

AU - Papakonstantinou, Pagona

AU - Chiou, JW

AU - Tsai, HM

AU - Shiu, HW

AU - Chen, CH

AU - Lin, HJ

AU - Guo, J

AU - Pong, WF

PY - 2017/2/10

Y1 - 2017/2/10

N2 - Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.

AB - Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.

KW - nitrogen doped reduced graphene oxide

KW - X-ray Absorption spectroscopy (XANES)

KW - X ray emission spectroscopy

KW - valence-band photoemission spectroscopy (VB-PES)

KW - resonant inelastic X-ray scattering (RIXS).

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DO - 10.1038/srep42235

M3 - Article

VL - 7

SP - 42235

JO - Scientific Reports

T2 - Scientific Reports

JF - Scientific Reports

SN - 2045-2322

ER -