Abstract
X-ray photoelectron spectroscopy (XPS) is among the most powerful techniques to analyse structures of nitrogen-doped carbon materials. However, reported assignments of (1) graphitic nitrogen (N)/substitutional N, quaternary N (Q–N), or tertiary amine (T–N) and (2) pyrrolic N/secondary amine or T–N are questionable. Most reports assign peaks at ca. 401 eV as Q–N or graphitic N, whereas raw materials in most of those works contain neither counter anion nor halogen. Besides, the peak at ca. 400 eV has been assigned as pyrrolic N, but the presence of N–H is generally not confirmed. In this work, it was clarified that one of the reasons for the prevailing ambiguous assignments is the presence of N in heptagonal and pentagonal rings. The peaks at 400.1–401.2 eV were determined to be T–N, but not Q–N by analyzing graphitized polyimide (with the oxygen content of 0.01 at% or lower and the hydrogen content of 0 at%) using Raman spectroscopy, XPS, X-ray diffraction, total neutron scattering, elemental analysis, and molecular dynamics simulation. Besides, it was revealed that the peak at 400.1 eV originated from T–N on 5-membered rings or 7- and 5-membered rings, but not pyrrolic N because graphite including no hydrogen was used for analysis.
Graphical abstract
Similar content being viewed by others
References
Bianco A, Chen Y, Frackowiak E, Holzinger M, Koratkar N, Meunier V et al (2020) Carbon science perspective in 2020: current research and future challenges. Carbon 161:373–391
Guo D, Shibuya R, Akiba C, Saji S, Kondo T, Nakamura J (2016) Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science 351:361–365
Jeong HM, Lee JW, Shin WH, Choi YJ, Shin HJ, Kang JK et al (2011) Nitrogen-doped graphene for high-performance ultracapacitors and the importance of nitrogen-doped sites at basal planes. Nano Lett 11:2472–2477
Yasuda S, Yu L, Kim J, Murakoshi K (2013) Selective nitrogen doping in graphene for oxygen reduction reactions. Chem Commun 49:9627–9629
Wang H, Maiyalagan T, Wang X (2012) Review on recent progress in nitrogen-doped graphene: synthesis, characterization, and its potential applications. ACS Catal 2:781–794
Yamada Y, Gohda S, Abe K, Togo T, Shimano N, Sasaki T et al (2017) Carbon materials with controlled edge structures. Carbon 122:694–701
Artyushkova K (2020) Misconceptions in interpretation of nitrogen chemistry from X-ray photoelectron spectra. J Vac Sci Technol A 38:031002
Figueras M, Villar-Garcia IJ, Viñes F, Sousa C, Peña O’Shea VA, Illas F et al (2019) Correcting flaws in the assignment of nitrogen chemical environments in N-doped graphene. J Phys Chem C 123:11319–11327
Costa R, Morales-García A, Figueras M, Illas F (2021) Assigning XPS features in B, N-doped graphene: input from ab initio quantum chemical calculations. Phys Chem Chem Phys 23:1558–1665
Yamada Y, Kim J, Matsuo S, Sato S (2014) Nitrogen-containing graphene analyzed by X-ray photoelectron spectroscopy. Carbon 70:59–74
Yamada Y, Sato S (2015) Structural analysis of carbon materials by X-ray photoelectron spectroscopy using computational chemistry. Tanso 269:181–189
Yamada Y, Sato S (2020) Analysis of defective structures of carbon materials. Shokubai 62:47–53
Kato T, Yamada Y, Nishikawa Y, Ishikawa H, Sato S (2021) Carbonization mechanisms of polyimide: methodology to analyze carbon materials with nitrogen, oxygen, pentagons, and heptagons. Carbon 178:58–80
Jansen RJJ, Bekkum HV (1995) XPS of nitrogen-containing functional groups on activated carbon. Carbon 33:1021–1027
Inagaki M, Toyoda M, Soneda Y, Morishita T (2018) Nitrogen-doped carbon materials. Carbon 132:104–140
Konno H, Nakahashi T, Inagaki M (1997) State analysis of nitrogen in carbon film derived from polyimide kapton. Carbon 35:669–674
Yoon SJ, Kim S, Kim DK, Yu DM, Hempelmann R, Hong YT et al (2020) Nitrogen-doping through two-step pyrolysis of polyacrylonitrile on graphite felts for vanadium redox flow batteries. Energy Fuels 34:5052–5059
Furuyado M, Zaini MAA, Aikawa M, Amano Y, Machida M (2010) Adsorption of Cd(II) on activated carbon fiber prepared from polyacrylonitrile (PAN). J Environ Chem 20:379–384
Kumar B, Asadi M, Pisasale D, Sinha-Ray S, Rosen BA, Haasch R et al (2013) Renewable and metal-free carbon nanofiber catalysts for carbon dioxide reduction. Nat Commun 4:1–8
Koch RJ, Weser M, Zhao W, Viñes F, Gotterbarm K, Kozlov SM, Höfert O, Ostler M, Papp C, Gebhardt J, Steinrück HP, Görling A, Seyller T (2012) Growth and electronic structure of nitrogen-doped graphene on Ni(111). Phys Rev B 86:075401
Bertoti I, Mohai M, Laszlo K (2015) Surface modification of graphene and graphite by nitrogen plasma: determination of chemical state alterations and assignments by quantitative X-ray photoelectron spectroscopy. Carbon 84:185–196
Yamada Y, Suzuki Y, Yasuda H, Uchizawa S, Hirose-Takai K, Sato Y et al (2014) Functionalized graphene sheets coordinating metal cations. Carbon 75:81–94
Yamada Y, Miyauchi M, Kim J, Takai KH, Sato Y, Suenaga K et al (2011) Exfoliated graphene ligands stabilizing copper cations. Carbon 49:3375–3378
Yamada Y, Matsuo S, Abe K, Kubo S, Sato S (2016) Selective doping of nitrogen into carbon materials without catalysts. J Mater Sci 51:8900–8915. https://doi.org/10.1007/s10853-016-0142-y
Yamada Y, Tanaka H, Kubo S, Sato S, Unveiling bonding states and roles of edges in nitrogen-doped graphene nanoribbon by X-ray photoelectron spectroscopy (submitted for publication)
Yamada Y, Yasuda H, Murota K, Nakamura M, Sodesawa T, Sato S (2013) Analysis of heat-treated graphite oxide by X-ray photoelectron spectroscopy. J Mater Sci 48:8171–8198. https://doi.org/10.1007/s10853-013-7630-0
Bellafont NP, Mañeru DR, Illas F (2014) Identifying atomic sites in N-doped pristine and defective graphene from ab initio core level binding energies. Carbon 76:155–164
Gohda S, Yamada Y, Murata M, Saito M, Kanazawa S, Ono H et al (2020) Bottom-up synthesis of highly soluble carbon materials. J Mater Sci 55:11808–11828. https://doi.org/10.1007/s10853-020-04813-1
Gohda S, Saito M, Yamada Y, Kanazawa S, Ono H, Sato S (2021) Carbonization of phloroglucinol promoted by heteropoly acids. J Mater Sci 56:2944–2960. https://doi.org/10.1007/s10853-020-05393-w
Senda T, Yamada Y, Morimoto M, Nono N, Sogabe T, Kubo S et al (2019) Analyses of oxidation process for isotropic pitch-based carbon fiber using model compounds. Carbon 142:311–326
Kim J, Yamada Y, Suzuki Y, Ciston J, Sato S (2014) Pyrolysis of epoxidized fullerenes analyzed by spectroscopies. J Phys Chem C 118:7076–7084
Fujimoto A, Yamada Y, Koinuma M, Sato S (2016) Origins of sp3C peaks in C1s X-ray photoelectron spectra of carbon materials. Anal Chem 88:6110–6114
Kim J, Han JW, Yamada Y (2021) Heptagons in the basal plane of graphene nanoflakes analyzed by simulated X-ray photoelectron spectroscopy. ACS Omega 6:2389–2395
Kim J, Yamada Y, Kawai M, Tanabe T, Sato S (2015) Spectral change of simulated X-ray photoelectron spectroscopy from graphene to fullerene. J Mater Sci 50:6739–6747. https://doi.org/10.1007/s10853-015-9229-0
Diana N, Yamada Y, Gohda S, Ono H, Kubo S, Sato S (2021) Carbon materials with high pentagon density. J Mater Sci 56:2912–2943
Kim J, Lee N, Nodo M, Min YH, Noh SH, Kim N et al (2018) Distinguishing zigzag and armchair edges on graphene nanoribbons by X-ray photoelectron and Raman spectroscopies. ACS Omega 3:17789–17796
Yamada Y, Kawai M, Yorimitsu H, Otsuka S, Takanashi M, Sato S (2018) Carbon materials with zigzag and armchair edges. ACS Appl Mater Interfaces 10:40710–40739
Kowalik M, Ashraf C, Damirchi B, Akbarian D, Rajabpour S, Duin ACTV (2019) Atomistic scale analysis of the carbonization process for C/H/O/N based polymers with the ReaxFF reactive force field. J Phys Chem B 123:5357–5367
Gaussian 09, Revision A.02, Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR et al (2009) Gaussian 09, revision E.01. Gaussian Inc, Wallingford, CT
ReaxFF 2016, SCM, Theoretical chemistry, Vrije Universiteit, Amsterdam, The Netherlands, http://www.scm.com
Huang PY, Vargas CSR, van der Zande AM, Whitney WS, Levendorf MP, Kevek JW et al (2011) Grains and grain boundaries in single-layer graphene atomic patchwork quilts. Nature 469:389–392
Kudin KN, Ozbas B, Schniepp HC, Prudhomme RK, Aksay IA, Car R (2008) Raman spectra of graphite oxide and functionalized graphene sheets. Nano Lett 8:36–41
Eckmann A, Felten A, Mishchenko A, Britnell L, Krupke R, Novoselov KS et al (2012) Probing the nature of defects in graphene by Raman spectroscopy. Nano Lett 12:3925–3930
Hatori H, Yamada Y, Shiraishi M, Yoshihara M, Kimura T (1996) The mechanism of polyimide pyrolysis in the early stage. Carbon 34:201–208
Herraiz M, Dubois M, Batisse N, Hajjar-Garreau S, Simon L (2018) Large-scale synthesis of fluorinated graphene by rapid thermal exfoliation of highly fluorinated graphite. Dalton Trans 47:4596–4606
Yamada Y, Murota K, Fujita R, Kim J, Watanabe A, Nakamura M, Sato S, Hata K, Peter E, Ciston J, Song C, Kim K, Regan W, Gannett W, Zettl Z (2014) Subnanometer vacancy defects introduced on graphene by oxygen gas. J Am Chem Soc 136:2232–2235
Sasaki T, Yamada Y, Sato S (2018) Quantitative analysis of zigzag and armchair edges on carbon materials with and without pentagons using infrared spectroscopy. Anal Chem 90:10724–10731
Acknowledgements
This work was supported by JSPS KAKENHI Grant Number JP21K04773. The neutron experiment at the Materials and Life Science Experimental Facility of the J-PARC was performed under a user program (Proposal No. 2018BF2104).
Funding
This study was funded by JSPS KAKENHI (Grant Number JP21K04773). Yasuhiro Yamada has received research grants from JSPS (Grant Number JP21K04773).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they do not have any conflict of interest
Additional information
Handling Editor: Christopher Blanford.
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Kato, T., Yamada, Y., Nishikawa, Y. et al. Origins of peaks of graphitic and pyrrolic nitrogen in N1s X-ray photoelectron spectra of carbon materials: quaternary nitrogen, tertiary amine, or secondary amine?. J Mater Sci 56, 15798–15811 (2021). https://doi.org/10.1007/s10853-021-06283-5
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-021-06283-5