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Fabrication of Melamine/Tb\begin{document}$ ^{\textbf{3+}} $\end{document}-Intercalated Polydiacetylene Nanosheets and Their Thermochromic Reversibility Test

Qing Wang Gang Wang Xia-yun Huang Dao-yong Chen

王青, 王刚, 黄霞芸, 陈道勇. 三聚氰胺/Tb\begin{document}$ ^{\bf{3+}} $\end{document}插层的聚二炔纳米片的制备及其热致变色可逆性研究 测试[J]. 机械工程学报, 2020, 33(3): 357-364. doi: 10.1063/1674-0068/cjcp1907143
引用本文: 王青, 王刚, 黄霞芸, 陈道勇.

三聚氰胺/Tb

\begin{document}$ ^{\bf{3+}} $\end{document}

插层的聚二炔纳米片的制备及其热致变色可逆性研究 测试

[J]. 机械工程学报, 2020, 33(3): 357-364. doi: 10.1063/1674-0068/cjcp1907143
Qing Wang, Gang Wang, Xia-yun Huang, Dao-yong Chen. Fabrication of Melamine/Tb\begin{document}$ ^{\textbf{3+}} $\end{document}-Intercalated Polydiacetylene Nanosheets and Their Thermochromic Reversibility Test[J]. JOURNAL OF MECHANICAL ENGINEERING, 2020, 33(3): 357-364. doi: 10.1063/1674-0068/cjcp1907143
Citation: Qing Wang, Gang Wang, Xia-yun Huang, Dao-yong Chen. Fabrication of Melamine/Tb\begin{document}$ ^{\textbf{3+}} $\end{document}-Intercalated Polydiacetylene Nanosheets and Their Thermochromic Reversibility Test[J]. JOURNAL OF MECHANICAL ENGINEERING, 2020, 33(3): 357-364. doi: 10.1063/1674-0068/cjcp1907143

Fabrication of Melamine/Tb\begin{document}$ ^{\textbf{3+}} $\end{document}-Intercalated Polydiacetylene Nanosheets and Their Thermochromic Reversibility Test

doi: 10.1063/1674-0068/cjcp1907143
  • 摘要: 聚二炔(PDA)是一类具有层状结构的共轭聚合物.在插层过程中,客体组分可插入PDA的层间,形成插层结构.在这些结构中,一部分插层复合物具有近乎完美的组装结构,并展现出完全可逆的热致变色特性.迄今为止,已报到的具有近乎完美组装结构的PDA复合物中仅成功插入了单个客体组分.本文选择其一侧的羧基可与Tb\begin{document}$ ^{3+} $\end{document}离子或三聚氰胺(MAs)作用的10,12-二十五烷二炔酸(PCDA)作为单体.当PCDA,MA和Tb\begin{document}$ ^{3+} $\end{document}投料摩尔比为3:267:1时,虽然体系中存在大大过量的MA,仅有Tb$ ^{3+} $离子插入了PDA层间,该复合物具有近乎完美插层结构,表现出完全可逆的热致变色特性.当PCDA,MA和Tb$ ^{3+} $投料摩尔比为3:267:0.6时,此时Tb$ ^{3+} $和MAs都插入了PDA的层间,该复合物存在近乎完美的结构区域和一些不完美的缺陷区域(例如:MA插层区域以及区域-区域边界处).因此,其仅表现出部分可逆的热致变色特性.其近乎完美的结构区域中的共轭主链仍能可逆地恢复至其初始构象,而缺陷区域的共轭主链则很难可逆地恢复至其初始构象.

     

  • Scheme 1.  Illustration of the preparation procedure of Tb$ ^{3+} $-intercalated PCDA and MA/Tb$ ^{3+} $-intercalated PCDA nano- sheet. The PCDA-MA-Tb$ ^{3+} $ coassemblies were firstly prepared. After annealed at 68 $ ^{\circ} $C for 6 h, the coassemblies were re- organized to Tb$ ^{3+} $-intercalated or MA/Tb$ ^{3+} $-intercalated PCDA depending on the amount of PCDA, MA, and Tb$ ^{3+} $ ion added. In the MA/Tb$ ^{3+} $-intercalated PCDA, there existed Tb$ ^{3+} $-intercalated and MA-intercalated domains.

    Figure  1.  (a) DSC curve of pure PCDA and Tb$ ^{3+} $-intercalated PCDA, (b) TEM image of Tb$ ^{3+} $-intercalated PCDA nanosheets, and (c) distribution of hydrodynamic diameter ($ D_ \rm{h} $) of Tb$ ^{3+} $-intercalated PCDA nanosheets. The feeding molar ratio of PCDA, MA, and Tb$ ^{3+} $ ion is 3:267:1.

    Figure  2.  (a) XRD patterns of MA-intercalated PCDA, Tb$ ^{3+} $-intercalated PCDA and MA/Tb$ ^{3+} $-intercalated PCDA, (b) TEM image of MA/Tb$ ^{3+} $-intercalated PCDA nanosheets, (c) distribution of hydrodynamic diameter ($ D_ \rm{h} $) of MA/Tb$ ^{3+} $-intercalated PCDA nanosheet, and (d) DSC curve of PCDA, Tb$ ^{3+} $-intercalated PCDA and MA/Tb$ ^{3+} $-intercalated PCDA. The feeding molar ratio of PCDA, MA, and Tb$ ^{3+} $ ion is 3:267:0.6.

    Figure  3.  (a) UV-Vis spectra of Tb$ ^{3+} $-intercalated poly-PCDA nanosheet suspension at different temperatures. The abrupt shift of $ \lambda_{ \rm{max}} $ to ca. 550 nm occurred at 80 $ ^{\circ} $C. The dashed line represents the spectrum of the suspension after cooling to 25 $ ^{\circ} $C from 90 $ ^{\circ} $C, indicating the complete reversibility of nanosheet suspension. (b) Colorimetric response (CR) of Tb$ ^{3+} $-intercalated poly-PCDA nanosheet suspension demonstrated its completely reversible thermochromism. The red nanosheet suspension at 90 $ ^{\circ} $C could fully return to the initial blue color when it was cooled to 25 $ ^{\circ} $C during the 20th heating-cooling cycles. (c) UV-Vis spectra of MA/Tb$ ^{3+} $-intercalated poly-PCDA nanosheet suspension during the 1st heating-cooling cycle between 25 $ ^{\circ} $C and 90 $ ^{\circ} $C. (d) CR of nanosheet suspension demonstrated its partial thermochromic reversibility. The red nanosheet suspension at 90 $ ^{\circ} $C yielded to purple color when it was cooled to 25 $ ^{\circ} $C at the 1st heating-cooling cycle. During the 2nd$ - $10th heating-cooling cycles, the suspension alternately switched between purple and red color.

    S1.   Elemental analysis and ICP-AES results of Tb3+-intercalated PCDA and MA/Tb3+-intercalated PCDA nanosheet

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出版历程
  • 收稿日期:  2019-07-26
  • 录用日期:  2019-08-30
  • 发布日期:  2020-03-17

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