Citation: Yin-Hua Zhu, Yong-Qi Ji, Jian-Bo Yang, Xin-Ying Xiang, Hua Mei, Yan Xu. Giant 28-nuclear water cluster-intercalated polyoxometalate-based photocatalyst with bandgap modulation for efficient CO₂ photoconversion[J]. Chinese Chemical Letters, ;2026, 37(9): 111412. doi: 10.1016/j.cclet.2025.111412 shu

Giant 28-nuclear water cluster-intercalated polyoxometalate-based photocatalyst with bandgap modulation for efficient CO₂ photoconversion

College of Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211816, China

meihua@njtech.edu.cn

yanxu@njtech.edu.cn

Received Date: 29 March 2025
Revised Date: 26 May 2025
Accepted Date: 6 June 2025
Available Online: 6 June 2025

Figures(5)

Guest molecule intercalation is an effective strategy for engineering electron structures and enhancing photocatalytic CO₂ reduction. Our designed charge-transfer system incorporates 28 nuclear H₂O molecules as electron mediators within the POM-based photocatalyst, enabling efficient electron transport pathways. Comparative analysis of synthesized isostructural catalysts shows water-intercalated Na₇[Co₂(H₂O)₈(H₁₁CoP₈Mo₁₂O₆₂)]·44H₂O (abbr. compound 1) achieves exceptional CO₂ reduction activity (21,347.4 µmol g^-1 h^-1), outperforming anhydrous (C₄H₁₄N₂)₄[Co₂(H₁₀CoP₈Mo₁₂O₆₂)]·4H₂O (abbr. compound 2) by 68%. This work demonstrates that water intercalation simultaneously optimizes band structure and improves material stability, providing a novel paradigm for advanced photocatalytic system design.
- Reduced polyoxometalate-based catalyst,
- Photocatalytic CO₂ reduction,
- Water intercalation,
- Band gap regulation,
- Heterogeneous catalyst
1. [1]
  R. Paul, R. Das, N. Das, et al., Angew. Chem. Int. Ed. 62 (2023) e202311304. doi: 10.1002/anie.202311304
2. [2]
  R. Paul, A. Boruah, R. Das, et al., Small 20 (2023) 2305307.
3. [3]
  R. Das, R. Paul, A. Parui, et al., J. Am. Chem. Soc. 145 (2022) 422–435.
4. [4]
  Y. Xie, Z. Fang, L. Li, H. Yang, T.F. Liu, ACS Appl. Mater. Interfaces 11 (2019) 27017–27023. doi: 10.1021/acsami.9b09436
5. [5]
  H. Yu, E. Haviv, R. Neumann, Angew. Chem. Int. Ed. 59 (2020) 6219–6223. doi: 10.1002/anie.201915733
6. [6]
  N. Li, J. Liu, B.X. Dong, Y.Q. Lan, Angew. Chem. Int. Ed. 59 (2020) 20779–20793. doi: 10.1002/anie.202008054
7. [7]
  M. Zhang, P. Huang, J.P. Liao, et al., Angew. Chem. Int. Ed. 135 (2023) e202311999. doi: 10.1002/ange.202311999
8. [8]
  Y. Zhao, X. Xu, K. Zhang, et al., ACS Catal. 14 (2024) 3556–3564. doi: 10.1021/acscatal.3c05648
9. [9]
  X. Sun, L. Sun, G. Li, et al., Angew. Chem. Int. Ed. 61 (2022) e202207677. doi: 10.1002/anie.202207677
10. [10]
  Q. Li, J.N. Chang, Z. Wang, et al., J. Am. Chem. Soc. 145 (2023) 23167–23175. doi: 10.1021/jacs.3c07471
11. [11]
  S. Yan, S. Ouyang, H. Xu, et al., J. Mater. Chem. A 4 (2016) 15126–15133. doi: 10.1039/C6TA04620G
12. [12]
  L.L. Liu, Z.Y. Xu, P. Yi, et al., Chem. Sci. 15 (2024) 16977–16986. doi: 10.1039/d4sc04634j
13. [13]
  Y.H. Zhu, J.B. Yang, X.M. Liu, et al., Dalton Trans. 51 (2022) 3502–3511. doi: 10.1039/d1dt04348j
14. [14]
  Y.H. Zhu, J.B. Yang, P.F. Yan, et al., J. Mater. Chem. A 12 (2024) 5340–5347. doi: 10.1039/d3ta06964h
15. [15]
  S. Li, Y. Peng, C. Hu, Z. Chen, Appl. Catal. B 279 (2020) 119401. doi: 10.1016/j.apcatb.2020.119401
16. [16]
  W. Lyu, Y. Liu, J. Zhou, et al., Angew. Chem. Int. Ed. 135 (2023) e202310733. doi: 10.1002/ange.202310733
17. [17]
  J.N. Li, Z.Y. Du, N.F. Li, et al., Dalton Trans. 50 (2021) 9137–9143. doi: 10.1039/d1dt00809a
18. [18]
  J. Du, Y. Ma, X. Xin, et al., Chem. Eng. J. 398 (2020) 125518. doi: 10.1016/j.cej.2020.125518
19. [19]
  S.L. Xie, J. Liu, L.Z. Dong, et al., Chem. Sci. 10 (2019) 185–190. doi: 10.1039/c8sc03471k
20. [20]
  L. Wang, D.W. Bahnemann, L. Bian, et al., Angew. Chem. Int. Ed. 58 (2019) 8103–8108. doi: 10.1002/anie.201903027
21. [21]
  R. Wang, J. Liu, L.Z. Dong, et al., CCS Chem. 5 (2023) 2237–2250. doi: 10.31635/ccschem.022.202202316
22. [22]
  Z.Y. Du, Y.Z. Yu, N.F. Li, et al., Sustain. Energy Fuels 5 (2021) 3876–3883. doi: 10.1039/d1se00804h
23. [23]
  A. Xia, J. Zheng, Q. Zhang, et al., Chem. Eng. J. 496 (2024) 154381. doi: 10.1016/j.cej.2024.154381
24. [24]
  Y. Zhao, Z. Shao, Y. Cui, et al., Small 19 (2023) 2300398. doi: 10.1002/smll.202300398
25. [25]
  Y. Benseghir, A. Solé-Daura, P. Mialane, et al., ACS Catal. 12 (2021) 453–464.
26. [26]
  L. Wang, T. Yang, B. Feng, et al., Chin. J. Catal. 54 (2023) 265–277. doi: 10.1016/S1872-2067(23)64546-2
27. [27]
  H. Tang, F. Xiong, Y. Jiang, et al., Nano Energy 58 (2019) 347–354. doi: 10.1016/j.nanoen.2019.01.053
28. [28]
  Y.S. Xia, M. Tang, L. Zhang, et al., Nat. Commun. 13 (2022) 2964. doi: 10.1038/s41467-022-30676-y
29. [29]
  J. Zou, S. Wu, Y. Lin, et al., Environ. Sci. Technol. 58 (2024) 14895–14905. doi: 10.1021/acs.est.4c03869
30. [30]
  G. Chen, Y. Ji, X. Shi, et al., Chem. Eng. J. 496 (2024) 154261. doi: 10.1016/j.cej.2024.154261
31. [31]
  S. Biswas, F.A. Rahimi, R.K. Saravanan, et al., Chem. Sci. 15 (2024) 16259. doi: 10.1039/d4sc03163f
32. [32]
  Y. Wang, Z. Qin, M.J. Buehler, Z. Xu, Nat. Commun. 7 (2016) 12854. doi: 10.1038/ncomms12854
33. [33]
  L. Li, S. Xu, E.A. Carter, Chem. Mater. 32 (2020) 10678–10687. doi: 10.1021/acs.chemmater.0c03891
34. [34]
  X. Yu, C.C. Zhao, J.X. Gu, et al., Inorg. Chem. 60 (2021) 7364–7371. doi: 10.1021/acs.inorgchem.1c00499
35. [35]
  O. Oulhakem, B. Rezki, M. Belaiche, et al., J. Catal. 427 (2023) 115109. doi: 10.1016/j.jcat.2023.115109
36. [36]
  J. Du, Z.L. Lang, Y.Y. Ma, et al., Chem. Sci. 11 (2020) 3007–3015. doi: 10.1039/c9sc05392a
37. [37]
  Y. Feng, F. Fu, L. Zeng, et al., Angew. Chem. Int. Ed. 63 (2024) e202317341. doi: 10.1002/anie.202317341
38. [38]
  Q. Mi, Y. Ping, Y. Li, et al., J. Am. Chem. Soc. 134 (2012) 18318–18324. doi: 10.1021/ja3067622
39. [39]
  C. Dai, L. Zhong, W. Wu, et al., Solar RRL 6 (2022) 2100872. doi: 10.1002/solr.202100872
40. [40]
  X.Y. Dao, W.Y. Sun, Inorg. Chem. Front. 8 (2021) 3178–3204. doi: 10.1039/d1qi00411e
41. [41]
  M. Dong, Y. Tian, J.X. Gu, et al., Inorg. Chem. Front. 10 (2023) 1279–1285. doi: 10.1039/d2qi02366k
42. [42]
  L. Bian, L. Liang, Y. Fan, et al., J. Colloid Interface Sci. 671 (2024) 543–552. doi: 10.1016/j.jcis.2024.05.190
43. [43]
  H. Tao, T. Jia, L. Zhang, et al., J. Colloid Interface Sci. 655 (2024) 909–919. doi: 10.1016/j.jcis.2023.11.072
44. [44]
  T. Jia, L. Wang, Z. Zhu, et al., Chin. Chem. Lett. 35 (2024) 108692. doi: 10.1016/j.cclet.2023.108692
45. [45]
  N. Wang, J. Huang, L. Chen, et al., Chem. Eng. J. 486 (2024) 150273. doi: 10.1016/j.cej.2024.150273
46. [46]
  Z. Jiang, K. Tong, Z. Li, H. Tao, M. Zhu, Angew. Chem. Int. Ed. 64 (2025) e2025007.
47. [47]
  H. Dong, F.M. Zhang, Chin. J. Struct. Chem. 43 (2024) 100307.
48. [48]
  J. Ning, J. Huang, Y. Liu, et al., Chin. J. Struct. Chem. 43 (2024) 100453.
49. [49]
  J. Ma, L. Li, Y. Zhang, J. Qian, X. Wang, Chin. J. Struct. Chem. 43 (2024) 100466.
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2. [2]
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沈阳化工大学材料科学与工程学院沈阳 110142

Giant 28-nuclear water cluster-intercalated polyoxometalate-based photocatalyst with bandgap modulation for efficient CO2 photoconversion

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通讯作者: 陈斌, bchen63@163.com

Giant 28-nuclear water cluster-intercalated polyoxometalate-based photocatalyst with bandgap modulation for efficient CO₂ photoconversion