

FOLLOWUS
a.State Key Laboratory of Precision and Intelligent Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China
b.School of Nuclear Science and Technology, University of Science and Technology of China, Hefei 230026, China
pstwmz@ustc.edu.cn (M.Z.W.)
xwge@ustc.edu.cn (X.W.G.)
Received:29 September 2024,
Revised:2024-10-25,
Accepted:27 October 2024,
Online First:17 January 2025,
Published:01 February 2025
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Yan, S.; Guo, Z. F.; Ge, Z. Q.; Zhang, B. Y.; Zhang, Y. R.; Li, Y. S.; Wang, M. Z.; Ge, X. W. Study on the radiation synthesis mechanism and the electrochemical property of polyaniline. Chinese J. Polym. Sci. 2025, 43, 328–340
Shuo Yan, Zi-Fang Guo, Zhi-Qing Ge, et al. Study on the Radiation Synthesis Mechanism and the Electrochemical Property of Polyaniline[J]. Chinese Journal of Polymer Science, 2025, 43(2): 328-340.
Yan, S.; Guo, Z. F.; Ge, Z. Q.; Zhang, B. Y.; Zhang, Y. R.; Li, Y. S.; Wang, M. Z.; Ge, X. W. Study on the radiation synthesis mechanism and the electrochemical property of polyaniline. Chinese J. Polym. Sci. 2025, 43, 328–340 DOI: 10.1007/s10118-025-3258-1.
Shuo Yan, Zi-Fang Guo, Zhi-Qing Ge, et al. Study on the Radiation Synthesis Mechanism and the Electrochemical Property of Polyaniline[J]. Chinese Journal of Polymer Science, 2025, 43(2): 328-340. DOI: 10.1007/s10118-025-3258-1.
Aniline in HNO
3
solution of pH
<
2.5 can be initiated directly to polymerize by γ-ray radiation at room temperature without the help of any additional chemical oxidants
thus providing a new route of clean and economical preparation of polyaniline with excellent electrochemical property.
As a highly promising conductive polymer material
the synthesis method
structure regulation
and performance improvement of polyaniline (PANI) are hot research topics. In this work
the radiation-induced polymerization of aniline in HNO
3
solution was successfully achieved at room temperature without the use of chemical oxidants. Through the analysis of the radiation chemical reactions of inorganic acids and nitrate salt solutions
the characterization of the intermediate free radicals in the irradiated systems
and the influence of the pH of the solutions on the polymerization activity and product morphologies
the radiation-induced polymerization mechanism of aniline is discussed in detail and proposed. Only at a condition of [HNO
3
]
>
[aniline
]
i.e.
pH
<
2.5
PANI can be successfully obtained under
γ
-ray radiation. The polymerization begins with the oxidation of aniline cations to aniline cation radicals by ·NO
3
generated by radiolysis reactions
and undergoes repeated three steps of monomer free radical recombination
deprotonation
and oxidation reaction of ·NO
3
thus forming a PANI macromolecule. In addition to the polymerization reaction
the aniline units are protonated and oxidized because of the strongly acidity and oxidation of the reaction system under
γ
-ray irradiation
which means th
at the molecular chain structure of the radiation-synthesized PANI can be regulated by pH
nitrate concentration
and irradiation conditions. Radiation-synthesized PANI has a moderate protonation and oxidation state
which can be used for the preparation of PANI supercapacitors with better electrochemical properties than those prepared by chemical oxidation under the same conditions. This work presents a new radiation-synthesis method and polymerization mechanism of PANI
which not only expands the application of radiation technique in the field of polymer synthesis
but also provides a new idea for the structural regulation and electrochemical property optimization of PANI.
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