Citation: Xiang-Hao Han, Jia-Qi Chu, Wen-Zhuang Wang, Qiao-Yan Qi, Xin Zhao. A two-step solvothermal procedure to improve crystallinity of covalent organic frameworks and achieve scale-up preparation[J]. Chinese Chemical Letters, ;2022, 33(5): 2464-2468. doi: 10.1016/j.cclet.2021.11.066 shu

A two-step solvothermal procedure to improve crystallinity of covalent organic frameworks and achieve scale-up preparation

Xiang-Hao Han ^a ,
Jia-Qi Chu ^{a, b} ,
Wen-Zhuang Wang ^a ,
Qiao-Yan Qi ^a ,
Xin Zhao ^{a, *,}

a.
Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China
b.
Shanghai Normal University, Shanghai 200234, China

xzhao@sioc.ac.cn

Received Date: 21 September 2021
Revised Date: 17 November 2021
Accepted Date: 23 November 2021
Available Online: 27 November 2021

Figures(5)

Covalent organic frameworks (COFs), as a novel class of functional polymers, exhibit versatile applications due to their crystalline porous structures and conjugated skeletons. However, synthesis of COFs with high crystallinity still faces great challenges, especially for scale-up preparation. Herein we report a two-step solvothermal process to improve crystallinity of COFs. The first step focuses on polycondensation of monomers with no need for optimizing crystallization conditions. In the second step, appropriate solvothermal conditions are used to facilitate crystallization of the COFs through defects correction and structural repairing. Furthermore, this strategy could also be applicable to scale-up synthesis of high quality COFs, which lays a foundation for their practical applications.
- Covalent organic frameworks,
- Synthesis,
- Solvothermal condensation,
- High crystallinity,
- Scale-up preparation
1. [1]
  P.J. Waller, F. Gandara, O.M. Yaghi, Acc. Chem. Res.48 (2015) 3053–3063. doi: 10.1021/acs.accounts.5b00369
2. [2]
  B. Gui, G. Lin, H. Ding, et al., Acc. Chem. Res. 53 (2020) 2225–2234. doi: 10.1021/acs.accounts.0c00357
3. [3]
  Y. Li, W. Chen, G. Xing, D. Jiang, L. Chen, Chem. Soc. Rev. 49 (2020) 2852–2868. doi: 10.1039/d0cs00199f
4. [4]
  X. Guan, F. Chen, Q. Fang, S. Qiu, Chem. Soc. Rev. 49 (2020) 1357–1384. doi: 10.1039/c9cs00911f
5. [5]
  M.S. Lohse, T. Bein, Adv. Funct. Mater. 28 (2018) 1705553. doi: 10.1002/adfm.201705553
6. [6]
  Y. Song, Q. Sun, B. Aguila, S. Ma, Adv. Sci. 6 (2019) 1801410. doi: 10.1002/advs.201801410
7. [7]
  J. Li, X. Jing, Q. Li, et al., Chem. Soc. Rev. 49 (2020) 3565–3604. doi: 10.1039/d0cs00017e
8. [8]
  W.K. Haug, E.M. Moscarello, E.R. Wolfson, P.L. McGrier, Chem. Soc. Rev. 49 (2020) 839–864. doi: 10.1039/c9cs00807a
9. [9]
  M.X. Wu, Y.W. Yang, Chin. Chem. Lett. 28 (2017) 1135–1143.
10. [10]
  S. Tao, D. Jiang, CCS Chem. 3 (2021) 2003–2024. doi: 10.31635/ccschem.020.202000491
11. [11]
  A.P. Côté, A.I. Benin, N.W. Ockwig, et al., Science 310 (2005) 1166–1170. doi: 10.1126/science.1120411
12. [12]
  X.H. Han, Q.Y. Qi, Z.B. Zhou, X. Zhao, Chin. J. Chem. 38 (2020) 1676–1680. doi: 10.1002/cjoc.202000317
13. [13]
  N.L. Campbell, R. Clowes, L.K. Ritchie, A.I. Cooper, Chem. Mater. 21 (2009) 204–206. doi: 10.1021/cm802981m
14. [14]
  B.P. Biswal, S. Chandra, S. Kandambeth, et al., J. Am. Chem. Soc. 135 (2013) 5328–5331. doi: 10.1021/ja4017842
15. [15]
  Y. Peng, W.K. Wong, Z. Hu, et al., Chem. Mater. 28 (2016) 5095–5101. doi: 10.1021/acs.chemmater.6b01954
16. [16]
  S.Y. Ding, X.H. Cui, J. Feng, G. Lu, W. Wang, Chem. Commun. 53 (2017) 11956–11959. doi: 10.1039/C7CC05779B
17. [17]
  J.L. Segura, M.J. Mancheno, F. Zamora, Chem. Soc. Rev. 45 (2016) 5635–5671.
18. [18]
  Y. Jin, Y. Hu, M. Ortiz, et al., Chem. Soc. Rev. 49 (2020) 4637–4666. doi: 10.1039/c9cs00879a
19. [19]
  Q. Gao, L. Bai, Y. Zeng, et al., Chem. Eur. J. 21 (2015) 16818–16822. doi: 10.1002/chem.201503053
20. [20]
  E. Vitaku, W.R. Dichtel, J. Am. Chem. Soc. 139 (2017) 12911–12914. doi: 10.1021/jacs.7b06913
21. [21]
  T. Ma, E.A. Kapustin, S.X. Yin, et al., Science 361 (2018) 48–52. doi: 10.1126/science.aat7679
22. [22]
  J. Hu, S.K. Gupta, J. Ozdemir, M.H. Beyzavi, ACS Appl. Nano Mater. 3 (2020) 6239–6269. doi: 10.1021/acsanm.0c01327
23. [23]
  B.J. Smith, A.C. Overholts, N. Hwang, W.R. Dichtel, Chem. Commun. 52 (2016) 3690–3693. doi: 10.1039/C5CC10221A
24. [24]
  W. Kong, W. Jia, R. Wang, et al., Chem. Commun. 55 (2019) 75–78. doi: 10.1039/c8cc08590k
25. [25]
  J. Tan, S. Namuangruk, W. Kong, et al., Angew. Chem. Int. Ed. 55 (2016) 13979–13984. doi: 10.1002/anie.201606155
26. [26]
  W. Huang, Y. Jiang, X. Li, et al., ACS Appl. Mater. Interfaces 5 (2013) 8845–8849. doi: 10.1021/am402649g
27. [27]
  N. Liu, L. Shi, X. Han, et al., Chin. Chem. Lett. 31 (2020) 386–390.
28. [28]
  Z.F. Pang, T.Y. Zhou, R.R. Liang, Q.Y. Qi, X. Zhao, Chem. Sci. 8 (2017) 3866–3870. doi: 10.1039/C6SC05673C
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