Citation: Jingting He, Man Dong, Yang Zhao, Jianxia Gu, Chunyi Sun, Dongxu Cui, Xiaohui Yao, Fanfei Meng, Chunjing Tao, Xinlong Wang, Zhongmin Su. Single atoms anchored on zirconium-organic cage for efficient carbon dioxide photoreduction[J]. Chinese Chemical Letters, ;2026, 37(1): 111253. doi: 10.1016/j.cclet.2025.111253 shu

Single atoms anchored on zirconium-organic cage for efficient carbon dioxide photoreduction

Jingting He ^{a, 1} ,
Man Dong ^{b, 1} ,
Yang Zhao ^b ,
Jianxia Gu ^b ,
Chunyi Sun ^{b, *,} ,
Dongxu Cui ^b ,
Xiaohui Yao ^b ,
Fanfei Meng ^a ,
Chunjing Tao ^b ,
Xinlong Wang ^{b, *,} ,
Zhongmin Su ^{a, *,}

a.
School of Materials Science and Engineering, Changchun University of Science and Technology, Changchun 130022, China
b.
Key Laboratory of Polyoxometalate Science of Ministry of Education, Northeast Normal University, Changchun 130024, China

suncy009@nenu.edu.cn

wangxl824@nenu.edu.cn

zmsu@nenu.edu.cn

Received Date: 5 December 2024
Revised Date: 26 February 2025
Accepted Date: 22 April 2025
Available Online: 22 April 2025

Figures(5)

Integration of single-atom catalysts (SACs) onto metal-organic frameworks (MOFs) with porous channels has garnered significant interest in the field of CO₂ reduction. However, MOFs are usually bulky can impede the diffusion of intermediates with substrates and maximizing catalytic site utilization remains a challenge. In this study, we utilized firstly the post-synthetic single-atom chelation sites on zirconium-based metal-organic cages (Zr-MOCs) to anchor cobalt (Co) atom to synthesize single-dispersible ZrT-1-NH₂-IS-Co molecular cages for CO₂ photoreduction. Experimental results demonstrate that ZrT-1-NH₂-IS-Co exhibits impressive catalytic performance, achieving syngas yields of up to 30.9 mmol g^-1 h^-1, ranking among the highest values of reported crystalline porous catalysts. Mechanistic insights reveal the newly introduced metal serving as the catalytic site and *COOH acts as a crucial intermediate in the CO₂ reduction process. Furthermore, the successful synthesis of ZrT-1-NH₂-IS-Ni and ZrT-1-NH₂-IS-Mn show the universality of the modification strategies, with their CO₂ catalytic activity surpassing that of ZrT-1-NH₂.
- Single-atom catalysts,
- Zirconium-based metal-organic cages,
- Single-dispersible,
- Photocatalytic CO₂ reduction,
- CO₂-to-syngas conversion
1. [1]
  E.V. Kondratenko, G. Mul, J. Baltrusaitis, G.O. Larrazabal, J. Perez-Ramirez, Energy Environ. Sci. 6 (2013) 3112–3135. doi: 10.1039/c3ee41272e
2. [2]
  J.H. Zhang, Y.C. Wang, H.J. Wang, D.C. Zhong, T.B. Lu, Chin. Chem. Lett. 33 (2022) 2065–2068.
3. [3]
  A.A. Zhang, R. Wang, H.B. Huang, T.F. Liu, R. Cao, Chin. Chem. Lett. 34 (2023) 107311.
4. [4]
  S. You, Y. Dong, B. Hou, et al., J. Mater. Chem. C 11 (2023) 7389–7396. doi: 10.1039/d3tc00775h
5. [5]
  Y.W. Hou, M. Dong, J.T. He, et al., Inorg. Chem. Front. 10 (2023) 5098–5110. doi: 10.1039/d3qi00596h
6. [6]
  D. Wang, J.J. Mao, C.C. Zhang, et al., eScience 3 (2023) 100119.
7. [7]
  J. Gu, X. Zhao, Y. Sun, et al., J. Mater. Chem. A 8 (2020) 16616–16623. doi: 10.1039/d0ta04595k
8. [8]
  Y. Zhang, B. Xia, J. Ran, K. Davey, S.Z. Qiao, Adv. Energy Mater. 10 (2020) 1903879.
9. [9]
  M. Zhang, M. Lu, M.Y. Yang, et al., eScience 3 (2023) 100116.
10. [10]
  X. Jiao, K. Zheng, Z. Hu, Y. Sun, Y. Xie, ACS Cent. Sci. 6 (2020) 653–660. doi: 10.1021/acscentsci.0c00325
11. [11]
  R. Li, C. Zhang, K. You, et al., Chin. Chem. Lett. 34 (2023) 108801.
12. [12]
  M. Dong, J. Zhou, J. Zhong, et al., Adv. Funct. Mater. 32 (2022) 2110136.
13. [13]
  S. Guo, X. Qi, H. Zhou, et al., J. Mater. Chem. A 8 (2020) 11712–11718. doi: 10.1039/d0ta00205d
14. [14]
  Y. Zhang, Y. Liu, H. Li, G. Bai, X. Lan, Chem. Eng. J. 489 (2024) 151479.
15. [15]
  P. Dong, Y. Wang, A. Zhang, et al., ACS Catal. 11 (2021) 13266–13279. doi: 10.1021/acscatal.1c03441
16. [16]
  Y. Wang, P. Dong, K. Zhu, et al., Chem. Eng. J. 446 (2022) 136883.
17. [17]
  J. Wang, X. Ge, W.Q. Yin, X.Z. Wang, Y. Wu, Inorg. Chem. 63 (2024) 9307–9314. doi: 10.1021/acs.inorgchem.4c01144
18. [18]
  X. Ge, D. Xie, R.f. Cheng, et al., Precis. Chem. 1 (2023) 153–160. doi: 10.1021/prechem.2c00006
19. [19]
  X. Ge, D. Zhou, J. Wang, et al., Chem. Eng. J. 481 (2024) 148587.
20. [20]
  H.H. Wong, M.Z. Sun, T. Wu, et al., eScience 4 (2024) 100140.
21. [21]
  Y. Wei, M. Zhang, R. Zou, Q. Xu, Chem. Rev. 120 (2020) 12089–12174. doi: 10.1021/acs.chemrev.9b00757
22. [22]
  X. Liang, S.F. Ji, Y.J. Chen, D.S. Wang, iScience 25 (2022) 104177.
23. [23]
  X. Qi, R. Zhong, M. Chen, et al., ACS Catal. 11 (2021) 7241–7248. doi: 10.1021/acscatal.1c01974
24. [24]
  Y. Fang, J.A. Powell, E. Li, et al., Chem. Soc. Rev. 48 (2019) 4707–4730. doi: 10.1039/c9cs00091g
25. [25]
  W. Liu, R. Yin, X. Xu, et al., Adv. Sci. 6 (2019) 1802373.
26. [26]
  B.A. Johnson, S. Ott, Chem. Sci. 11 (2020) 7468–7478. doi: 10.1039/d0sc02601h
27. [27]
  Y. An, L. Wang, W. Jiang, et al., Polyoxometalates 2 (2023) 9140030. doi: 10.26599/pom.2023.9140030
28. [28]
  G.L. Liu, Z.F. Ju, D.Q. Yuan, M.C. Hong, Inorg. Chem. 52 (2013) 13815–13817. doi: 10.1021/ic402428m
29. [29]
  E.S.M. El-Sayed, Y. Di Yuan, D. Zhao, D. Yuan, Acc. Chem. Res. 55 (2022) 1546–1560. doi: 10.1021/acs.accounts.1c00654
30. [30]
  J. Jiao, C. Tan, Z. Li, et al., J. Am. Chem. Soc. 140 (2018) 2251–2259. doi: 10.1021/jacs.7b11679
31. [31]
  Y. Fang, Z. Xiao, J. Li, et al., Angew. Chem. Int. Ed. 57 (2018) 5283–5287. doi: 10.1002/anie.201712372
32. [32]
  D. Nam, J. Huh, J. Lee, et al., Chem. Sci. 8 (2017) 7765–7771.
33. [33]
  A. Dey, J. Pradhan, S. Biswas, et al., Angew. Chem. Int. Ed. 63 (2024) e202315596.
34. [34]
  D.X. Cui, Y. Geng, J.N. Kou, et al., Nat. Commun. 13 (2022) 4011.
35. [35]
  Z. Xia, L. Wang, Q. Zhang, F. Li, L. Xu, Polyoxometalates 1 (2022) 9140001. doi: 10.26599/pom.2022.9140001
36. [36]
  J. Wang, K. Sun, D. Wang, et al., ACS Catal. 13 (2023) 8760–8769. doi: 10.1021/acscatal.3c01003
37. [37]
  Y.L. Dong, H.R. Liu, S.M. Wang, G.W. Guan, Q.Y. Yang, ACS Catal. 13 (2023) 2547–2554. doi: 10.1021/acscatal.2c04588
38. [38]
  Q.Y. Wu, Z.W. Yang, Z.W. Wang, W.L. Wang, Proc. Natl. Acad. Sci. U. S. A. 120 (2023) e2219923120.
39. [39]
  M. Dong, Y. Tian, J. Gu, et al., Inorg. Chem. Front. 10 (2023) 1279–1285. doi: 10.1039/d2qi02366k
40. [40]
  S. Saha, G. Das, J. Thote, R. Banerjee, J. Am. Chem. Soc. 136 (2014) 14845–14851. doi: 10.1021/ja509019k
41. [41]
  K.F. Li, X.Q. An, K.H. Park, M. Khraisheh, J.W. Tang, Catal. Today 224 (2014) 3–12.
42. [42]
  M. Dong, W. Li, J. Zhou, et al., Chin. J. Chem. 40 (2022) 2678–2684. doi: 10.1002/cjoc.202200046
43. [43]
  Z. Fu, X. Wang, A. Gardner, et al., Chem. Sci. 11 (2020) 543–550. doi: 10.1039/c9sc03800k
44. [44]
  Z. Wang, J. Yang, J. Cao, et al., ACS Nano 14 (2020) 6164–6172. doi: 10.1021/acsnano.0c02162
45. [45]
  X. Yao, K. Chen, L.Q. Qiu, Z.W. Yang, L.N. He, Chem. Mater. 33 (2021) 8863–8872. doi: 10.1021/acs.chemmater.1c03136
46. [46]
  X. Yu, C. Zhao, J. Gu, et al., Inorg. Chem. 60 (2021) 7364–7371. doi: 10.1021/acs.inorgchem.1c00499
47. [47]
  J. Li, Q. Zhang, L. Zhang, et al., Catal. Sci. Technol. 12 (2022) 3343–3355. doi: 10.1039/d2cy00403h
48. [48]
  S. Yao, L. Chang, G. Guo, et al., Inorg. Chem. 61 (2022) 13058–13066. doi: 10.1021/acs.inorgchem.2c01359
49. [49]
  R. Paul, R. Das, N. Das, et al., Angew. Chem. Int. Ed. 62 (2023) e202311304.
50. [50]
  P.M.M. Stanley, A.Y.Y. Su, V. Ramm, et al., Adv. Mater. 35 (2023) 2207380.
51. [51]
  M. Dong, Q. Pan, F. Meng, et al., J. Colloid Interface Sci. 662 (2024) 807–813.
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