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Insights into pyrolysis behavior of polyacrylonitrile precursors using Py-GC/MS

Abstract

Pyrolysis process is a basic process to convert polyacrylonitrile (PAN)-based precursors fiber into PAN-based carbon fibers. Herein, pyrolysis behavior of pure PAN precursor and PAN precursor modified by transition metal Co and Fe was online analyzed. The effect of metal salts addition, pyrolysis temperature, and peroxidation on the formation of pyrolysis products were online analyzed via analytical pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). The results showed that the weight loss of Co-Fe/PAN-1 can be divided into two stages with the addition of transition metal Co and Fe, and it is contributed to the formation of C2H4N2, C4H8N2, C6H6N2, and C6H8N2 at the temperature range of 400 ℃–800 ℃. The number of pyrolysis products decreases, and CO2 is the main pyrolysis product after pre-oxidation of PAN-2 and Co-Fe/PAN-2. After carbonization, the formation of Co-Fe alloy was detected in Co-Fe/PAN-2@CNFs because of the addition of Co and Fe, and the specific surface area of Co-Fe/PAN-2@CNFs is 426 m2/g.

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Abbreviations

PAN-1:

PAN-1 was pre-oxidized in air at 280 ℃ for 2 h

PAN-2:

PAN-1 was pre-oxidized in air at 280 ℃ for 2 h

Co-Fe/PAN-1:

The precursor nanofiber film with the addition of metal salts dried at 60 °C in vacuum for 7 h

Co-Fe/PAN-2:

Co-Fe/PAN-2 was pre-oxidized in air at 280 ℃ for 2 h

PAN-2@CNFs:

PAN-2 is carbonized under N2 atmosphere at 800 ℃

Co-Fe/PAN-2@CNFs:

Co-Fe /PAN -2 is carbonized in N2 atmosphere at 800 ℃

Py-GC/MS:

Pyrolysis gas chromatography/mass spectrometry

TG:

Thermogravimetry

SEM:

Scanning electron microscopy

XRD:

X-ray diffraction

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Acknowledgements

The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (No. 31870570) and the Scientific Research Start-up Funding for Special Professor of Minjiang Scholars, Xiamen University.

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Contributions

Q.L and Z.Z. conceived and designed of the work. X.Y., D.X., and Z.L. cooperated on the experiment. F.L., D.W. (Duo Wang), and S.L. analyzed or interpreted the data. Q.L. wrote the manuscript. Z.Z. and D.W. (Dechao Wang) ensured funding for project contributed materials, and they are the corresponding author. D.W (Dechao Wang) Y.Y., C.M., and Z.L. helped to revise the manuscript. All authors have read and approved the manuscript.

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Correspondence to Dechao Wang or Zhifeng Zheng.

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This manuscript is not under consideration for publication and has not been published elsewhere in any medium including electronic journals and computer databases of a public nature. The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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Liu, Q., Yang, X., Xuan, D. et al. Insights into pyrolysis behavior of polyacrylonitrile precursors using Py-GC/MS. Chem. Pap. 75, 5297–5311 (2021). https://doi.org/10.1007/s11696-021-01714-8

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  • DOI: https://doi.org/10.1007/s11696-021-01714-8

Keywords

  • PAN-based precursor
  • Pyrolysis
  • Co and Fe modification
  • Temperature
  • Pre-oxidation