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Origins of peaks of graphitic and pyrrolic nitrogen in N1s X-ray photoelectron spectra of carbon materials: quaternary nitrogen, tertiary amine, or secondary amine?

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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.

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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).

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Authors and Affiliations

  1. Graduate School of Engineering, Chiba University, 1-33 Yayoi, Inage, Chiba, 263-8522, Japan

    Tomofumi Kato, Yasuhiro Yamada, Hayato Sato & Satoshi Sato

  2. Kaneka Corporation, 5-1-1 Torikainishi, Settsu, Osaka, 566-0072, Japan

    Yasushi Nishikawa

  3. Institute of Materials Structure Science, High Energy Accelerator Research Organization, 203-1 Shirakata, Tokai-mura, Naka-gun, Ibaraki, 319-1106, Japan

    Toshiya Otomo

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  1. Tomofumi Kato
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Correspondence to Yasuhiro Yamada.

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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

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