Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study
Abstract
Nitrogen-doped graphene oxides (GO:N x) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH 2) 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:N x 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 sp 2 -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:N x . The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.
- Authors:
-
- Tamkang Univ., Taipei (Taiwan). Dept. of Physics
- Univ. of South Afric, Johannesburg (South Africa). Dept. of Physics
- Ulster Univ., Newtownabbey (United Kingdom). Engineering Research Inst.
- National Univ. of Kaohsiung (Taiwan). Dept. of Applied Physics
- National Synchrotron Radiation Research Center, Hsinchu (Taiwan)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source; Univ. of California, Santa Cruz, CA (United States). Dept. of Chemistry and Biochemistry
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1379732
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 7; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electronic properties and devices
Citation Formats
Chuang, Cheng-Hao, Ray, Sekhar C., Mazumder, Debarati, Sharma, Surbhi, Ganguly, Abhijit, Papakonstantinou, Pagona, Chiou, Jau-Wern, Tsai, Huang-Ming, Shiu, Hung-Wei, Chen, Chia-Hao, Lin, Hong-Ji, Guo, Jinghua, and Pong, Way-Faung. Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study. United States: N. p., 2017.
Web. doi:10.1038/srep42235.
Chuang, Cheng-Hao, Ray, Sekhar C., Mazumder, Debarati, Sharma, Surbhi, Ganguly, Abhijit, Papakonstantinou, Pagona, Chiou, Jau-Wern, Tsai, Huang-Ming, Shiu, Hung-Wei, Chen, Chia-Hao, Lin, Hong-Ji, Guo, Jinghua, & Pong, Way-Faung. Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study. United States. https://doi.org/10.1038/srep42235
Chuang, Cheng-Hao, Ray, Sekhar C., Mazumder, Debarati, Sharma, Surbhi, Ganguly, Abhijit, Papakonstantinou, Pagona, Chiou, Jau-Wern, Tsai, Huang-Ming, Shiu, Hung-Wei, Chen, Chia-Hao, Lin, Hong-Ji, Guo, Jinghua, and Pong, Way-Faung. Fri .
"Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study". United States. https://doi.org/10.1038/srep42235. https://www.osti.gov/servlets/purl/1379732.
@article{osti_1379732,
title = {Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study},
author = {Chuang, Cheng-Hao and Ray, Sekhar C. and Mazumder, Debarati and Sharma, Surbhi and Ganguly, Abhijit and Papakonstantinou, Pagona and Chiou, Jau-Wern and Tsai, Huang-Ming and Shiu, Hung-Wei and Chen, Chia-Hao and Lin, Hong-Ji and Guo, Jinghua and Pong, Way-Faung},
abstractNote = {Nitrogen-doped graphene oxides (GO:N x) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH 2) 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:N x 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 sp 2 -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:N x . The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.},
doi = {10.1038/srep42235},
journal = {Scientific Reports},
number = ,
volume = 7,
place = {United States},
year = {2017},
month = {2}
}
Web of Science
Works referenced in this record:
Substrate-induced bandgap opening in epitaxial graphene
journal, September 2007
- Zhou, S. Y.; Gweon, G. -H.; Fedorov, A. V.
- Nature Materials, Vol. 6, Issue 10
Light non-metallic atom (B, N, O and F)-doped graphene: a first-principles study
journal, November 2010
- Wu, M.; Cao, C.; Jiang, J. Z.
- Nanotechnology, Vol. 21, Issue 50
Raman Spectra of Graphite Oxide and Functionalized Graphene Sheets
journal, January 2008
- Kudin, Konstantin N.; Ozbas, Bulent; Schniepp, Hannes C.
- Nano Letters, Vol. 8, Issue 1
Oxygen-Containing Functional Groups on Single-Wall Carbon Nanotubes: NEXAFS and Vibrational Spectroscopic Studies
journal, October 2001
- Kuznetsova, Anya; Popova, Irene; Yates, John T.
- Journal of the American Chemical Society, Vol. 123, Issue 43
Nitrogen-Functionalized Graphene Nanoflakes (GNFs:N): Tunable Photoluminescence and Electronic Structures
journal, July 2012
- Chiou, J. W.; Ray, Sekhar C.; Peng, S. I.
- The Journal of Physical Chemistry C, Vol. 116, Issue 30
Blue Photoluminescence from Chemically Derived Graphene Oxide
journal, January 2010
- Eda, Goki; Lin, Yun-Yue; Mattevi, Cecilia
- Advanced Materials, Vol. 22, Issue 4, p. 505-509
Product or sum: comparative tests of Voigt, and product or sum of Gaussian and Lorentzian functions in the fitting of synthetic Voigt-based X-ray photoelectron spectra
journal, January 2007
- Hesse, R.; Streubel, P.; Szargan, R.
- Surface and Interface Analysis, Vol. 39, Issue 5
Band structure information and resonant inelastic soft X-ray scattering in broad band solids
journal, October 2000
- Eisebitt, S.; Eberhardt, W.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 110-111
Photoemission studies of graphite high-energy conduction-band and valence-band states using soft-x-ray synchrotron radiation excitation
journal, December 1977
- Bianconi, A.; Hagström, S. B. M.; Bachrach, R. Z.
- Physical Review B, Vol. 16, Issue 12
Identification of the nitrogen species on N-doped graphene layers and Pt/NG composite catalyst for direct methanol fuel cell
journal, January 2010
- Zhang, Le-Sheng; Liang, Xian-Qing; Song, Wei-Guo
- Physical Chemistry Chemical Physics, Vol. 12, Issue 38
Imaging local electronic corrugations and doped regions in graphene
journal, June 2011
- Schultz, Brian J.; Patridge, Christopher J.; Lee, Vincent
- Nature Communications, Vol. 2, Issue 1
Electronic properties of a‐CNx thin films: An x-ray-absorption and photoemission spectroscopy study
journal, August 2005
- Ray, S. C.; Pao, C. W.; Chiou, J. W.
- Journal of Applied Physics, Vol. 98, Issue 3
Electronic band structure of graphene from resonant soft x-ray spectroscopy: The role of core-hole effects
journal, December 2012
- Zhang, L.; Schwertfager, N.; Cheiwchanchamnangij, T.
- Physical Review B, Vol. 86, Issue 24
Pyridinic N doped graphene: synthesis, electronic structure, and electrocatalytic property
journal, January 2011
- Luo, Zhiqiang; Lim, Sanhua; Tian, Zhiqun
- Journal of Materials Chemistry, Vol. 21, Issue 22
Enhanced Electrocatalytic Activity of Pt Subnanoclusters on Graphene Nanosheet Surface
journal, June 2009
- Yoo, EunJoo; Okata, Tatsuhiro; Akita, Tornoki
- Nano Letters, Vol. 9, Issue 6
Evaluation of Solution-Processed Reduced Graphene Oxide Films as Transparent Conductors
journal, February 2008
- Becerril, Héctor A.; Mao, Jie; Liu, Zunfeng
- ACS Nano, Vol. 2, Issue 3
Molecular Doping of Graphene
journal, January 2008
- Wehling, T. O.; Novoselov, K. S.; Morozov, S. V.
- Nano Letters, Vol. 8, Issue 1
Resonant inelastic soft X-ray scattering spectra at the nitrogen and carbon K-edges of poly(pyridine-2,5-diyl)
journal, June 1999
- Magnuson, M.; Yang, L.; Guo, J. -H.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 101-103
High resolution X-ray emission spectroscopy of water and its assignment based on two structural motifs
journal, March 2010
- Tokushima, Takashi; Harada, Yoshihisa; Horikawa, Yuka
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 177, Issue 2-3
Simultaneous Nitrogen Doping and Reduction of Graphene Oxide
journal, November 2009
- Li, Xiaolin; Wang, Hailiang; Robinson, Joshua T.
- Journal of the American Chemical Society, Vol. 131, Issue 43
Atomic oxygen functionalization of double walled C nanotubes
journal, September 2009
- Larciprete, R.; Gardonio, S.; Petaccia, L.
- Carbon, Vol. 47, Issue 11
Resonant C Kα X-ray emission of some carbon allotropes and organic compounds
journal, October 2000
- Guo, Jinghua; Nordgren, Joseph
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 110-111
Graphite Oxide as a Photocatalyst for Hydrogen Production from Water
journal, June 2010
- Yeh, Te-Fu; Syu, Jhih-Ming; Cheng, Ching
- Advanced Functional Materials, Vol. 20, Issue 14
A comparative study of the electronic structures of oxygen- and chlorine-treated nitrogenated carbon nanotubes by x-ray absorption and scanning photoelectron microscopy
journal, November 2007
- Ray, S. C.; Pao, C. W.; Tsai, H. M.
- Applied Physics Letters, Vol. 91, Issue 20
Disorder Induced Localized States in Graphene
journal, January 2006
- Pereira, Vitor M.; Guinea, F.; Lopes dos Santos, J. M. B.
- Physical Review Letters, Vol. 96, Issue 3
Nonlinear bandgap opening behavior of BN co-doped graphene
journal, October 2016
- Wang, Bo-Yao; Wang, Hsiaotsu; Chen, Ling-Yen
- Carbon, Vol. 107
Gate-Tunable Dirac Point of Molecular Doped Graphene
journal, January 2016
- Solís-Fernández, Pablo; Okada, Susumu; Sato, Tohru
- ACS Nano, Vol. 10, Issue 2
Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy
journal, October 2015
- Wang, Y. F.; Singh, Shashi B.; Limaye, Mukta V.
- Scientific Reports, Vol. 5, Issue 1
A Chemical Route to Graphene for Device Applications
journal, November 2007
- Gilje, Scott; Han, Song; Wang, Minsheng
- Nano Letters, Vol. 7, Issue 11, p. 3394-3398
Structure of nitrogenated amorphous carbon films from NEXAFS
journal, January 2002
- Bhattacharyya, Somnath; Lübbe, M.; Bressler, P. R.
- Diamond and Related Materials, Vol. 11, Issue 1
From Point Defects in Graphene to Two-Dimensional Amorphous Carbon
journal, March 2011
- Kotakoski, J.; Krasheninnikov, A. V.; Kaiser, U.
- Physical Review Letters, Vol. 106, Issue 10
Band Gap Engineering of Chemical Vapor Deposited Graphene by in Situ BN Doping
journal, January 2013
- Chang, Cheng-Kai; Kataria, Satender; Kuo, Chun-Chiang
- ACS Nano, Vol. 7, Issue 2
X-ray absorption spectroscopy of graphite oxide
journal, June 2008
- Jeong, H.-K.; Noh, H.-J.; Kim, J.-Y.
- EPL (Europhysics Letters), Vol. 82, Issue 6, Article No. 67004
Chemical bonding in carbon nitride films studied by X-ray spectroscopies
journal, September 2001
- Zheng, W.
- Diamond and Related Materials, Vol. 10, Issue 9-10
High-throughput solution processing of large-scale graphene
journal, November 2008
- Tung, Vincent C.; Allen, Matthew J.; Yang, Yang
- Nature Nanotechnology, Vol. 4, Issue 1
Electronic structure of nitrogen-carbon alloys determined by photoelectron spectroscopy
journal, January 1998
- Souto, S.; Pickholz, M.; dos Santos, M. C.
- Physical Review B, Vol. 57, Issue 4
Electrochemically Exfoliated Graphene and Graphene Oxide for Energy Storage and Electrochemistry Applications
journal, October 2015
- Ambrosi, Adriano; Pumera, Martin
- Chemistry - A European Journal, Vol. 22, Issue 1
X-ray photoelectron spectroscopy of graphitic carbon nanomaterials doped with heteroatoms
journal, January 2015
- Susi, Toma; Pichler, Thomas; Ayala, Paola
- Beilstein Journal of Nanotechnology, Vol. 6
Excitons and Resonant Inelastic X-Ray Scattering in Graphite
journal, April 1997
- van Veenendaal, Michel; Carra, Paolo
- Physical Review Letters, Vol. 78, Issue 14
Valence and conduction band offsets at amorphous hexagonal boron nitride interfaces with silicon network dielectrics
journal, March 2014
- King, Sean W.; Paquette, Michelle M.; Otto, Joseph W.
- Applied Physics Letters, Vol. 104, Issue 10
Efficient Reduction of Graphite Oxide by Sodium Borohydride and Its Effect on Electrical Conductance
journal, June 2009
- Shin, Hyeon‐Jin; Kim, Ki Kang; Benayad, Anass
- Advanced Functional Materials, Vol. 19, Issue 12
Graphene Oxide Dispersions in Organic Solvents
journal, October 2008
- Paredes, J. I.; Villar-Rodil, S.; Martínez-Alonso, A.
- Langmuir, Vol. 24, Issue 19
X-ray absorption spectroscopy (XAS) study of dip deposited a-C:H(OH) thin films
journal, August 2004
- Ray, S. C.; Tsai, H. M.; Chiou, J. W.
- Journal of Physics: Condensed Matter, Vol. 16, Issue 32
Angle-resolved soft-x-ray fluorescence and absorption study of graphite
journal, October 1994
- Skytt, P.; Glans, P.; Mancini, D. C.
- Physical Review B, Vol. 50, Issue 15
Synthesis of nitrogen doped graphene from graphene oxide within an ammonia flame for high performance supercapacitors
journal, January 2014
- Li, Delong; Yu, Chaozhi; Wang, Miaosheng
- RSC Adv., Vol. 4, Issue 98
Spatially Resolved Raman Spectroscopy of Single- and Few-Layer Graphene
journal, February 2007
- Graf, D.; Molitor, F.; Ensslin, K.
- Nano Letters, Vol. 7, Issue 2, p. 238-242
Probing disorder and charged impurities in graphene by Raman spectroscopy
journal, September 2009
- Casiraghi, Cinzia
- physica status solidi (RRL) - Rapid Research Letters, Vol. 3, Issue 6
Probing the Graphite Band Structure with Resonant Soft-X-Ray Fluorescence
journal, February 1995
- Carlisle, J. A.; Shirley, Eric L.; Hudson, E. A.
- Physical Review Letters, Vol. 74, Issue 7
Electronic structure study of Li+/OH− modified single-walled carbon nanotubes by soft-x-ray absorption and resonant emission spectroscopy
journal, May 2010
- Zhong, Jun; Song, Li; Chiou, Jauwern
- Applied Physics Letters, Vol. 96, Issue 21
The Impact of Functionalization on the Stability, Work Function, and Photoluminescence of Reduced Graphene Oxide
journal, January 2013
- Kumar, Priyank V.; Bernardi, Marco; Grossman, Jeffrey C.
- ACS Nano, Vol. 7, Issue 2, p. 1638-1645
The Structure of Graphite Oxide: Investigation of Its Surface Chemical Groups
journal, May 2010
- Lee, D. W.; De Los Santos V., L.; Seo, J. W.
- The Journal of Physical Chemistry B, Vol. 114, Issue 17
Preparation of Graphitic Oxide
journal, March 1958
- Hummers, William S.; Offeman, Richard E.
- Journal of the American Chemical Society, Vol. 80, Issue 6, p. 1339-1339
The rise of graphene
journal, March 2007
- Geim, A. K.; Novoselov, K. S.
- Nature Materials, Vol. 6, Issue 3, p. 183-191
Graphene oxide: A promising nanomaterial for energy and environmental applications
journal, September 2015
- Li, Fen; Jiang, Xue; Zhao, Jijun
- Nano Energy, Vol. 16
Nitrogen-doped graphene and its electrochemical applications
journal, January 2010
- Shao, Yuyan; Zhang, Sheng; Engelhard, Mark H.
- Journal of Materials Chemistry, Vol. 20, Issue 35
Nitrogen K-edge X-ray absorption near edge structure (XANES) spectra of purine-containing nucleotides in aqueous solution
journal, August 2014
- Shimada, Hiroyuki; Fukao, Taishi; Minami, Hirotake
- The Journal of Chemical Physics, Vol. 141, Issue 5
Electronic structure of carbon nitride thin films studied by X-ray spectroscopy techniques
journal, January 2005
- Hellgren, Niklas; Guo, Jinghua; Luo, Yi
- Thin Solid Films, Vol. 471, Issue 1-2
Large-area ultrathin films of reduced graphene oxide as a transparent and flexible electronic material
journal, April 2008
- Eda, Goki; Fanchini, Giovanni; Chhowalla, Manish
- Nature Nanotechnology, Vol. 3, Issue 5, p. 270-274
Core-level photoemission from graphite
journal, September 2000
- Prince, K. C.; Ulrych, I.; Peloi, M.
- Physical Review B, Vol. 62, Issue 11
Change of Structural Behaviors of Organo-Silane Exposed Graphene Nanoflakes
journal, April 2010
- Pao, C. W.; Ray, S. C.; Tsai, H. M.
- The Journal of Physical Chemistry C, Vol. 114, Issue 18
Graphene Oxidation: Thickness-Dependent Etching and Strong Chemical Doping
journal, July 2008
- Liu, Li; Ryu, Sunmin; Tomasik, Michelle R.
- Nano Letters, Vol. 8, Issue 7
Electronic and atomic structure of amorphous carbon
journal, February 1987
- Robertson, J.; O’Reilly, E. P.
- Physical Review B, Vol. 35, Issue 6, p. 2946-2957
Solution-Processable Graphene Oxide as an Efficient Hole Transport Layer in Polymer Solar Cells
journal, June 2010
- Li, Shao-Sian; Tu, Kun-Hua; Lin, Chih-Cheng
- ACS Nano, Vol. 4, Issue 6, p. 3169-3174
Nitrogen and Sulfur Dual-Doped Reduced Graphene Oxide: Synergistic Effect of Dopants Towards Oxygen Reduction Reaction
journal, May 2015
- Bag, Sourav; Mondal, Bodhisatwa; Das, Ashok Kumar
- Electrochimica Acta, Vol. 163
The Effect of Thermal Reduction on the Photoluminescence and Electronic Structures of Graphene Oxides
journal, April 2014
- Chuang, C. -H.; Wang, Y. -F.; Shao, Y. -C.
- Scientific Reports, Vol. 4, Issue 1
Works referencing / citing this record:
Simultaneous Improvement of Photovoltaic Performance and Stability by In Situ Formation of 2D Perovskite at (FAPbI 3 ) 0.88 (CsPbBr 3 ) 0.12 /CuSCN Interface
journal, January 2018
- Chen, Jiangzhao; Seo, Ja-Young; Park, Nam-Gyu
- Advanced Energy Materials, Vol. 8, Issue 12
Influence of surface chemistry on optical, chemical and electronic properties of blue luminescent carbon dots
journal, January 2019
- Ren, Jian; Weber, Fabian; Weigert, Florian
- Nanoscale, Vol. 11, Issue 4
The electrochemical corrosion of an air thermally-treated carbon fiber cloth electrocatalyst with outstanding oxygen evolution activity under alkaline conditions
journal, January 2019
- Wu, Tianxing; Han, Miaomiao; Zhu, Xiaoguang
- Chemical Communications, Vol. 55, Issue 16
Polyacrylate grafted graphene oxide nanocomposites for biomedical applications
journal, February 2020
- Ganya, Elison S.; Soin, Navneet; Moloi, Sabata J.
- Journal of Applied Physics, Vol. 127, Issue 5
Breakdown of water super-permeation in electrically insulating graphene oxide films: role of dual interlayer spacing
journal, June 2018
- Kavitha, Maheshwari Kavirajan; Sakorikar, Tushar; Vayalamkuzhi, Pramitha
- Nanotechnology, Vol. 29, Issue 32
Modified fermi level in strontium nanoparticles decorated reduced graphene oxide for wide concentration detection of nitrogen dioxide at room temperature
journal, March 2019
- Mukherjee, Anwesha; Jaidev, Leela R.; Chatterjee, Kaushik
- Materials Research Express, Vol. 6, Issue 6
Influence of surface chemistry on optical, chemical and electronic properties of blue luminescent carbon dots
text, January 2019
- Ren, Jian; Weber, Fabian; Weigert, Florian
- Freie Universität Berlin