Citation: Li-Ying Wang, Jun-Jie Yu, Shuai Wang, Yang Liu, Ke-Xian Song, Ji-Pan Yu, Li-Yong Yuan, Zhi-Rong Liu, Wei-Qun Shi. Pyridine-based ionic sp² carbon-conjugated covalent organic frameworks for selective extraction of Pu(Ⅳ) from high-level liquid waste[J]. Chinese Chemical Letters, ;2025, 36(8): 110706. doi: 10.1016/j.cclet.2024.110706 shu

Pyridine-based ionic sp² carbon-conjugated covalent organic frameworks for selective extraction of Pu(Ⅳ) from high-level liquid waste

Li-Ying Wang ^{a, b, 1} ,
Jun-Jie Yu ^{a, 1} ,
Shuai Wang ^{a, c, 1} ,
Yang Liu ^a ,
Ke-Xian Song ^a ,
Ji-Pan Yu ^{a, *,} ,
Li-Yong Yuan ^{a, *,} ,
Zhi-Rong Liu ^{b, *,} ,
Wei-Qun Shi ^{a, d, *,}

a.
Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
b.
School of Nuclear Science and Engineering, East China University of Technology, Nanchang 330013, China
c.
School of Nuclear Technology and Chemistry & Biology, Hubei Key Laboratory of Radiation Chemistry and Functional Materials, Hubei University of Science and Technology, Xianning 437100, China
d.
School of Nuclear Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

yujipan@ihep.ac.cn

yuanly@ihep.ac.cn

199760011@ecut.edu.cn

shiwq@sjnu.edu.cn

Received Date: 29 September 2024
Revised Date: 26 November 2024
Accepted Date: 2 December 2024
Available Online: 2 December 2024

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In the current era marked by energy shortages, the advancement of nuclear energy stands as an inevitable progression. The reprocessing of spent nuclear fuel plays a crucial role in determining the sustainability of nuclear energy as a viable energy source. Among these processes, the separation and recovery of Pu(Ⅳ) from high-level liquid waste (HLLW) hold paramount significance in terms of safety and strategic implications. Herein, this work focused on the synthesis of two acid- and radiation-resistant pyridine-based sp²c-COFs (COF-IHEP3 and COF-IHEP4), followed by the creation of two pyridine-based ionized sp²c-COFs named COF-IHEP3-CH₃NO₃ and COF-IHEP4-CH₃NO₃ through post-modification. These materials have potential anion exchange capacity for the selective separation of Pu(Ⅳ) in highly acidic conditions. Notably, in 8 mol/L nitric acid solution, COF-IHEP3-CH₃NO₃ demonstrated the capability to eliminate plutonium within 20 min in 98% removal efficiency with a K_d value of 2450 mL/g. Experimental and theoretical analysis suggest that the ionized sp²c-COFs exhibit exceptional stability, selectivity, and prevention of secondary contamination towards Pu(Ⅳ) in the presence of multiple ions environments. In short, this work provides an appropriate anion exchange strategy to design ionic sp²c-COFs as a promising platform for Pu(Ⅳ) recovery from HLLW.
- Covalent organic framework,
- Highly acidic conditions,
- High-level liquid waste,
- Anion exchange,
- Pu(Ⅳ)
1. [1]
  O. Usman, O. Ozkan, G.N. Ike, J. Clean. Prod. 451 (2024) 142070.
2. [2]
  M.F. Bashir, B.L. Ma, A. Sharif, et al., Technol. Soc. 75 (2023) 102385. doi: 10.1016/j.techsoc.2023.102385
3. [3]
  J. Veliscek-Carolan, J. Hazard. Mater. 318 (2016) 266–281. doi: 10.1016/j.jhazmat.2016.07.027
4. [4]
  M. Salvatores, Nucl. Eng. Des. 235 (2005) 805–816. doi: 10.1016/j.nucengdes.2004.10.009
5. [5]
  D. von Hippel, P. Hayes, J. Kang, et al., Energy Policy 39 (2011) 6867–6881.
6. [6]
  A. Paulillo, J.M. Dodds, S.J. Palethorpe, et al., Sustain. Mater. Technol. 28 (2021) e00278.
7. [7]
  C.Y. Liu, J.H. Lan, Q.B. Yan, et al., Chin. Chem. Lett. 33 (2022) 3561–3564. doi: 10.3390/ma15103561
8. [8]
  V. Gilinsky, Foreign Aff. 57 (1978) 374. doi: 10.2307/20040120
9. [9]
  D.X. Feng, M.C. Ji, H.Q. Liao, et al., Environ. Res. 216 (2023) 114677.
10. [10]
  N. Vigier, S. Grandjean, B. Arab-Chapelet, et al., J. Alloys Compd. 444–445 (2007) 594–597. doi: 10.1016/j.jallcom.2007.01.057
11. [11]
  X.B. Li, Q.Y. Wu, C.Z. Wang, et al., Chin. Chem. Lett. 35 (2024) 109359.
12. [12]
  C. Berger, C. Marie, D. Guillaumont, et al., Inorg. Chem. 59 (2020) 1823–1834. doi: 10.1021/acs.inorgchem.9b03024
13. [13]
  A. Rout, K. Chatterjee, K.A. Venkatesan, et al., Sep. Purif. Technol. 159 (2016) 43–49.
14. [14]
  S. Sharma, S. Panja, A. Bhattacharyya, et al., Dalton Trans. 45 (2016) 7737–7747.
15. [15]
  B. Sreenivasulu, C.V.S. Brahmananda Rao, A. Suresh, et al., J. Radioanal. Nucl. Chem. 331 (2022) 3623–3632. doi: 10.1007/s10967-022-08451-6
16. [16]
  Y.M. Chen, C.Z. Wang, L. Zhang, et al., J. Mol. Liq. 386 (2023) 122404.
17. [17]
  A. Kaya, J. Shirahashi, et al., J. Nucl. Sci. Technol. 4 (1967) 289–292.
18. [18]
  J.G. Pribyl, K.M.L. Taylor-Pashow, T.C. Shehee, et al., ACS Omega 3 (2018) 8181–8189. doi: 10.1021/acsomega.8b01057
19. [19]
  P. Zhao, J.D. Begg, M. Zavarin, et al., Environ. Sci. Technol. 50 (2016) 6948–6956. doi: 10.1021/acs.est.6b00605
20. [20]
  B. Rao, X.Y. Ma, K. Q, et al., Chem. Eng. J. 431 (2022) 134169.
21. [21]
  Z. Wang, M.C. Liu, L. Wang, et al., Molecules 27 (2022) 3110. doi: 10.3390/molecules27103110
22. [22]
  H.D. Zhang, S. Wang, J.P. Yu, et al., Chem. Eng. J. 463 (2023) 142408.
23. [23]
  S.C. Zhong, Y. Wang, T. Bo, et al., Chem. Eng. J. 455 (2023) 140523.
24. [24]
  Y. Wang, J.H. Lan, X.F. Yang, et al., Adv. Funct. Mater. 32 (2022) 2205222.
25. [25]
  X.W. Liu, A.R. Zhang, R. Ma, et al., Chin. Chem. Lett. 33 (2022) 3549–3555.
26. [26]
  B.Y. Zhang, L.L. Chen, Z.N. Zhang, et al., Adv. Sci. 9 (2022) 2105912.
27. [27]
  L.Y. Xiao, Z.L. Wang, J.Q. Guan, Adv. Funct. Mater. 34 (2024) 2310195.
28. [28]
  W.R. Cui, C.R. Zhang, R.H. Xu, et al., ACS EST Water 1 (2021) 440–448. doi: 10.1021/acsestwater.0c00176
29. [29]
  P.F. Dong, X.Y. Xu, R.G. Luo, et al., J. Am. Chem. Soc. 145 (2023) 15473–15481. doi: 10.1021/jacs.3c03897
30. [30]
  H. Hu, C.L. Song, D. Wang, et al., Chin. Chem. Lett. 34 (2023) 107770.
31. [31]
  C. Liu, C. Jia, S.X. Gan, et al., Chin. Chem. Lett. 35 (2024) 109750.
32. [32]
  E.B. Zhou, X. Zhang, L. Zhu, et al., Adv. Funct. Mater. 33 (2023) 2213667.
33. [33]
  J. Li, X.C. Jing, Q.Q. Li, et al., Chem. Soc. Rev. 49 (2020) 3565–3604. doi: 10.1039/d0cs00017e
34. [34]
  F. Liu, C.J. Wang, C. Liu, et al., Appl. Phys. Lett. 119 (2021) 211905.
35. [35]
  M.X. Wu, Y.W. Yang, Chin. Chem. Lett. 28 (2017) 1135–1143.
36. [36]
  L.Y. Ou, Z.L. Xue, B. Li, et al., Chin. Chem. Lett. (2024) 110294.
37. [37]
  H.M. Wang, H.M. Ding, X.S. Meng, et al., Chin. Chem. Lett. 27 (2016) 1376–1382.
38. [38]
  H.M. El-Kaderi, J.R. Hunt, J.L. Mendoza-Cortés, et al., Science 316 (2007) 268–272. doi: 10.1126/science.1139915
39. [39]
  A.P. Côté, A.I. Benin, N.W. Ockwig, et al., Science 310 (2005) 1166–1170. doi: 10.1126/science.1120411
40. [40]
  T. Li, Y. Pan, B.B. Shao, et al., Adv. Funct. Mater. 33 (2023) 2304990.
41. [41]
  F.J. Uribe-Romo, J.R. Hunt, H. Furukawa, et al., J. Am. Chem. Soc. 131 (2009) 4570–4571. doi: 10.1021/ja8096256
42. [42]
  E.Q. Jin, J. Li, K.Y. Geng, et al., Nat. Commun. 9 (2018) 4143.
43. [43]
  P.H. Zhang, Z.F. Wang, S. Wang, et al., Angew. Chem. Int. Ed. 61 (2022) e202213247.
44. [44]
  S.C. Wei, F. Zhang, W.B. Zhang, et al., J. Am. Chem. Soc. 141 (2019) 14272–14279. doi: 10.1021/jacs.9b06219
45. [45]
  E.Q. Jin, M. Asada, Q. Xu, et al., Science 357 (2017) 673–676. doi: 10.1126/science.aan0202
46. [46]
  A. Acharjya, P. Pachfule, J. Roeser, et al., Chem. Int. Ed. 58 (2019) 14865–14870. doi: 10.1002/anie.201905886
47. [47]
  S.C. Zhong, Y. Wang, M.S. Xie, et al., Chin. Chem. Lett. 36 (2025) 110312.
48. [48]
  F.L. Zhang, H.M. Hao, X.Y. Dong, et al., Appl. Catal. B: Environ. 305 (2022) 121027.
49. [49]
  F.L. Zhang, X.Y. Ma, X.Y. Dong, et al., Chem. Eng. J. 451 (2023) 138802.
50. [50]
  F.L. Zhang, Y.X. Wang, H.X. Zhao, et al., ACS Appl. Mater. Interfaces 16 (2024) 8772–8782. doi: 10.1021/acsami.3c16838
51. [51]
  Z.L. Li, H. Li, X.Y. Guan, et al., J. Am. Chem. Soc. 139 (2017) 17771–17774. doi: 10.1021/jacs.7b11283
52. [52]
  K.C. Sole, M.B. Mooiman, E. Hardwick, Sep. Purif. Rev. 47 (2018) 159–178.
53. [53]
  J. van Deventer, Solvent Extr. Ion Exch. 29 (2011) 695–718. doi: 10.1080/07366299.2011.595626
54. [54]
  M.V. Ryzhinsky, A.V. Stepanov, J. Radioanal. Nucl. Chem. 147 (1991) 27–32.
55. [55]
  S.A. Ansari, P.K. Mohapatra, V.K. Manchanda, J. Hazard. Mater. 161 (2009) 1323–1329.
56. [56]
  G.E. Fryxell, Y.H. Lin, S. Fiskum, et al., Environ. Sci. Technol. 39 (2005) 1324–1331. doi: 10.1021/es049201j
57. [57]
  S. Chappa, A.K. Singha Deb, Sk.M. Ali, et al., J. Phys. Chem. B 120 (2016) 2942–2950. doi: 10.1021/acs.jpcb.5b11293
58. [58]
  M. Kaur, H.J. Zhang, L. Martin, et al., Environ. Sci. Technol. 47 (2013) 11942–11959. doi: 10.1021/es402205q
59. [59]
  R.M. Tinnacher, J.D. Begg, H. Mason, et al., Environ. Sci. Technol. 49 (2015) 2776–2785. doi: 10.1021/es505120s
60. [60]
  L.P. Xiong, K. Lv, M. Gu, et al., Chem. Eng. J. 355 (2019) 159–169.
61. [61]
  S.Q. Xu, Z.Q. Liao, A. Dianat, et al., Angew. Chem. 134 (2022) e202202492.
62. [62]
  Q.Y. Guo, H.Y. Ji, L. Yang, et al., Chin. Chem. Lett. 33 (2022) 2621–2624.
63. [63]
  D.L. Pastoetter, S.Q. Xu, M. Borrelli, et al., Angew. Chem. Int. Ed. 59 (2020) 23620–23625. doi: 10.1002/anie.202010398
64. [64]
  X.Y. Wang, J.Y. Yang, X.S. Shi, et al., Small 18 (2022) 2107108.
65. [65]
  Y. Liang, M. Xia, Q.H. Yu, et al., Adv. Compos. Hybrid Mater. 5 (2022) 184–194. doi: 10.1007/s42114-021-00311-3
66. [66]
  M.H. Liu, Q. Xu, G.F. Zeng, Angew. Chem. Int. Ed. 63 (2024) e202404886.
67. [67]
  S. Chatterjee, J.M. Peterson, A.J. Casella, et al., Inorg. Chem. 59 (2020) 6826–6838. doi: 10.1021/acs.inorgchem.0c00199
68. [68]
  H.B. Li, G.A. Ye, X.R. Wang, et al., J. Nucl. Radiochem. 32 (2010) 65–69.
69. [69]
  R. Bu, L. Zhang, X.Y. Liu, et al., ACS Appl. Mater. Interfaces 13 (2021) 26431–26440. doi: 10.1021/acsami.1c01791
70. [70]
  X.D. Gong, Q. Tian, J.B. Li, et al., Appl. Surf. Sci. 615 (2023) 156307.
71. [71]
  G. Schreckenbach, T. Ziegler, J. Phys. Chem. 99 (1995) 606–611. doi: 10.1021/j100002a024
72. [72]
  A. Schäfer, A. Klamt, D. Sattel, et al., Phys. Chem. Chem. Phys. 2 (2000) 2187–2193.
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Pyridine-based ionic sp2 carbon-conjugated covalent organic frameworks for selective extraction of Pu(Ⅳ) from high-level liquid waste

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Pyridine-based ionic sp² carbon-conjugated covalent organic frameworks for selective extraction of Pu(Ⅳ) from high-level liquid waste