Citation: Linqi Cheng, Jie Yu, Xupeng Zhang, Dongxue Lv, Heng-Guo Wang. Tuning bimetallic sites in phthalocyanine-based π-d conjugated metal–organic framework cathode for wide-temperature (−20~60 ℃) potassium-organic batteries[J]. Chinese Chemical Letters, ;2026, 37(10): 111601. doi: 10.1016/j.cclet.2025.111601 shu

Tuning bimetallic sites in phthalocyanine-based π-d conjugated metal–organic framework cathode for wide-temperature (−20~60 ℃) potassium-organic batteries

Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education Faculty of Chemistry, Northeast Normal University, Changchun 130024, China

wanghg061@nenu.edu.cn

Received Date: 4 June 2025
Revised Date: 8 July 2025
Accepted Date: 17 July 2025
Available Online: 17 July 2025

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The orbital differentiation of transition metal ions demonstrates a critical role in modulating the structure and properties of two-dimensional π-d conjugated metal-organic frameworks (2D c-MOFs), which is possible to achieve the high-capacity and high-voltage features in rechargeable metal-ion batteries. Herein, we propose and demonstrate the strategy of coordination chemistry with different transition metal ions to construct metal phthalocyanine-based 2D c-MOFs (NiPc-8O-Cu, NiPc-8O-Ni and CuPc-8O-Cu) with different central and peripheral metal-coordination redox-active sites, which were discussed for the first time as the advanced cathode materials for potassium-ion batteries (PIBs). Benefiting from the low-spin state and the closed-shell d-orbital of central metal, NiPc-8O-Cu has higher electron/ion conductivity and stronger electron delocalization, demonstrating fascinating electrochemical performance, including a high reversible specific capacity (194 mAh/g at 0.2 A/g) and a well long-term cycling performance (over 3000 cycles at 5.0 A/g). It is worth noting that NiPc-8O-Cu can also showcase the good cycle performance at wide-temperature (−20~60 ℃). These findings provide a general guideline for the development of high-performance 2D c-MOFs as electrode materials for metal-ion batteries by engineering "inside and outside" active-site strategy.
- π-d conjugated metal–organic frameworks,
- Tuning bimetallic sites,
- Potassium-ion batteries,
- Low-spin state,
- Ions co-storage mechanism
1. [1]
  G. Zhu, X. Tian, H.C. Tai, et al., Nature 596 (2021) 525. doi: 10.1038/s41586-021-03757-z
2. [2]
  A.M. Desaulty, D.M. Climent, G. Lefebvre, et al., Nat. Commun. 13 (2022) 4172. doi: 10.1038/s41467-022-31850-y
3. [3]
  X. Zhou, Q. Liu, C. Jiang, et al., Angew. Chem. Int. Ed. 59 (2020) 3802–3832. doi: 10.1002/anie.201814294
4. [4]
  A. Masias, J. Marcicki, W.A. Paxton, ACS Energy Lett. 6 (2021) 621–630. doi: 10.1021/acsenergylett.0c02584
5. [5]
  G. Chang, Y. Zhao, L. Dong, et al., J. Mater. Chem. A 8 (2020) 4996. doi: 10.1039/c9ta12169b
6. [6]
  C. Fang, Y. Huang, W. Zhang, et al., Adv. Energy Mater. 6 (2016) 1501727. doi: 10.1002/aenm.201501727
7. [7]
  G. Zeng, B. Liu, U. Ali, et al., Appl. Catal. B: Environ. 351 (2024) 123996. doi: 10.1016/j.apcatb.2024.123996
8. [8]
  X. Qiu, B. Zhang, Y. Xu, et al., Green Chem. 24 (2022) 2506. doi: 10.1039/d1gc04784a
9. [9]
  H. Zhang, X. Liu, T. Ji, et al., Chin. Chem. Lett. 37 (2026) 110790. doi: 10.1016/j.cclet.2024.110790
10. [10]
  Y. Fang, G.Y. Zhu, N.N. Zhu, et al., J. Energy Chem. 105 (2025) 312–325. doi: 10.1016/j.jechem.2025.01.062
11. [11]
  Y.F. Chen, Y. Fang, N.N. Zhu, et al., Angew. Chem. Int. Ed. 64 (2025) e20242464.
12. [12]
  L. Fan, R. Ma, Q. Zhang, X. Jia, B. Lu, Angew. Chem. Int. Ed. 58 (2019) 10500–10505. doi: 10.1002/anie.201904258
13. [13]
  L.F. Zhao, Z. Hu, W.H. Lai, et al., Adv. Energy Mater. 11 (2021) 2002704. doi: 10.1002/aenm.202002704
14. [14]
  X. Min, J. Xiao, M. Fang, et al., Energy Environ. Sci. 14 (2021) 2186. doi: 10.1039/d0ee02917c
15. [15]
  Y. Hu, W. Tang, Q. Yu, et al., Adv. Funct. Mater. 30 (2020) 2000675. doi: 10.1002/adfm.202000675
16. [16]
  Z. Chen, Y. Wu, X. Liu, et al., J. Energy Chem. 81 (2023) 462–471. doi: 10.1016/j.jechem.2023.02.050
17. [17]
  H. Li, Q. Ma, Y. Yuan, et al., Adv. Funct. Mater. 34 (2024) 2301987. doi: 10.1002/adfm.202301987
18. [18]
  T. Li, Y. Wang, Q. Zhou, et al., J. Mater. Sci. Technol. 158 (2023) 86–95. doi: 10.1117/12.2672855
19. [19]
  M. Yang, X. Zeng, M. Xie, et al., J. Am. Chem. Soc. 10 (2024) 6753–6762. doi: 10.1021/jacs.3c13113
20. [20]
  H. Xue, H. Zhu, J. Huang, Chin. Chem. Lett. 34 (2023) 107134. doi: 10.1016/j.cclet.2022.01.027
21. [21]
  X. Li, J. Wang, F. Xue, et al., Angew. Chem. Int. Ed. 60 (2021) 2534–2540. doi: 10.1002/anie.202012947
22. [22]
  P. Apostol, S.M. Gali, A. Su, et al., J. Am. Chem. Soc. 145 (2023) 24669–24677.
23. [23]
  X. Su, Z. Zhong, X. Yan, et al., J. Am. Chem. Soc. 146 (2024) 9036–9044. doi: 10.1021/jacs.3c13985
24. [24]
  C. Huang, W. Sun, Y. Jin, et al., Angew. Chem. Int. Ed. 63 (2024) e202313591. doi: 10.1002/anie.202313591
25. [25]
  M. Qi, L. Cheng, H.G. Wang, et al., Adv. Mater. 36 (2024) 2401878. doi: 10.1002/adma.202401878
26. [26]
  L. Wang, N. Liu, X. Zhao, et al., Chem. Sci. 15 (2024) 2133–2140. doi: 10.1039/d3sc05023h
27. [27]
  K. Fan, J. Li, Y. Xu, et al., J. Am. Chem. Soc. 145 (2023) 12682–12690. doi: 10.1021/jacs.3c02378
28. [28]
  M. Yang, Y. Wang, Y.F. Huang, et al., Angew. Chem. Int. Ed. 64 (2025) e202421008. doi: 10.1002/anie.202421008
29. [29]
  L. Jiang, L. Lin, Z. Wang, et al., J. Am. Chem. Soc. 146 (2024) 22930–22936. doi: 10.1021/jacs.4c07945
30. [30]
  J. Geng, Y. Ni, Z. Zhu, et al., J. Am. Chem. Soc. 145 (2023) 1564–1571. doi: 10.1021/jacs.2c08273
31. [31]
  L. Cheng, M. Qi, J. Yu, et al., Angew. Chem. Int. Ed. 63 (2024) e202405239. doi: 10.1002/anie.202405239
32. [32]
  P. Bao, L. Cheng, X. Yan, et al., Angew. Chem. Int. Ed. 63 (2024) e202405168. doi: 10.1002/anie.202405168
33. [33]
  H.G. Wang, H. Wang, Z. Si, et al., Angew. Chem. Int. Ed. 58 (2019) 10204– 10208. doi: 10.1002/anie.201904242
34. [34]
  H.G. Wang, Q. Li, Q. Wu, et al., Adv. Energy Mater. 11 (2021) 2100381. doi: 10.1002/aenm.202100381
35. [35]
  Z. Meng, A. Aykanat, K.A. Mirica, J. Am. Chem. Soc. 141 (2019) 2046–2053. doi: 10.1021/jacs.8b11257
36. [36]
  L. Cheng, L. Chen, J. Yu, et al., J. Colloid Interf. Sci. 663 (2024) 656–664. doi: 10.1016/j.jcis.2024.02.178
37. [37]
  J. Zhao, M. Zhou, J. Chen, et al., Chem. Eng. J. 425 (2021) 131630. doi: 10.1016/j.cej.2021.131630
38. [38]
  H.G. Wang, Q. Wu, L. Cheng, et al., Energy Storage Mater. 52 (2022) 495–513. doi: 10.1016/j.ensm.2022.08.022
39. [39]
  H. Pan, Y. Ren, Q. Wang, et al., Coordin. Chem. Rev. 527 (2025) 216404. doi: 10.1016/j.ccr.2024.216404
40. [40]
  L. Cheng, X. Yan, J. Yu, et al., Adv. Mater. 37 (2025) 2411625. doi: 10.1002/adma.202411625
41. [41]
  Y.H. Zhong, Y. Wang, S.Y. Zhao, et al., Adv. Funct. Mater. 34 (2024) 2316199. doi: 10.1002/adfm.202316199
42. [42]
  Y. Ni, L. Lin, Y. Shang, et al., Angew. Chem. Int. Ed. 60 (2021) 16937–16941. doi: 10.1002/anie.202104494
43. [43]
  X. Zhou, S. Xiao, D. Yang, et al., Angew. Chem. Int. Ed. 63 (2024) e202409255. doi: 10.1002/anie.202409255
44. [44]
  Y. Chen, Q. Zhu, K. Fan, et al., Angew. Chem. Int. Ed. 60 (2021) 18769–18776. doi: 10.1002/anie.202106055
45. [45]
  J. Chen, H. Yin, Q. Xue, et al., Adv. Funct. Mater. 34 (2024) 2411362. doi: 10.1002/adfm.202411362
46. [46]
  X.T. Zhao, J.Z. Guo, W.L. Li, et al., Chin. Chem. Lett. 35 (2024) 108715. doi: 10.1016/j.cclet.2023.108715
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2. [2]
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3. [3]
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4. [4]
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