Citation: Hui Bian, Xinyi Yuan, Nan Zhang, Zhuo Xu, Juhong Lian, Ruibin Jiang, Junqing Yan, Deng Li, Shengzhong (Frank) Liu. Correlating vacancy-defect density with CO₂ activation for promoted CO₂ methanation over CsPbBr₃ photocatalyst[J]. Chinese Chemical Letters, ;2025, 36(7): 111034. doi: 10.1016/j.cclet.2025.111034 shu

Correlating vacancy-defect density with CO₂ activation for promoted CO₂ methanation over CsPbBr₃ photocatalyst

Hui Bian ^{a, b} ,
Xinyi Yuan ^a ,
Nan Zhang ^b ,
Zhuo Xu ^b ,
Juhong Lian ^c ,
Ruibin Jiang ^b ,
Junqing Yan ^{b, *,} ,
Deng Li ^{b, *,} ,
Shengzhong (Frank) Liu ^{b, d, *,}

a.
School of Science, Xi’an University of Posts and Telecommunications, Xi’an 710119, China
b.
Key Laboratory of Applied Surface and Colloid Chemistry, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710119, China
c.
College of Chemistry and Materials Science, Weinan Normal University, Weinan 714099, China
d.
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

junqingyan@snnu.edu.cn

dengli@snnu.edu.cn

liusz@snnu.edu.cn

Received Date: 1 January 2025
Revised Date: 27 February 2025
Accepted Date: 4 March 2025
Available Online: 5 March 2025

Figures(4)

Constructing vacancy-decorated metal halide perovskites (MHPs) have emerged as promising pathway to enhance photocatalytic activity and selectivity for solar CO₂ reduction. However, the controllable construction of vacancy defects is still challenging, and our understanding of the roles of these defects, particularly their effects on the adsorption activation of surface reaction molecules, is still insufficient. Herein, we elaborately designed and synthesized adjustable Br vacancies in CsPbBr₃ catalysts by manipulating the dissolution and recrystallization speed of precursors during the ball milling process using solvents with gradient polarities. We found that the Br vacancies could promote the charge separation, while having slight influence on the band structure of CsPbBr₃. More importantly, temperature-programmed desorption results combined with theoretical calculations revealed that Br vacancies can significantly enhance the adsorption of CO₂ and CO on the surface, specifically increasing the adsorption strength between CO and the active sites. This finding provides a substantial opportunity for achieving high activity and selectivity in photocatalytic CO₂ methanation. Accordingly, a high rate of CO₂ photoreduction to CH₄ up to 17.94 ± 0.81 µmol g^-1 h^-1 along with superior selectivity of 95.8% were acquired for CsPbBr₃HX featuring with the richest Br vacancy defects, which is 18.9-fold compared that of CsPbBr₃CAN with the lowest Br vacancy defects. This investigation deepens insights into action mechanism of defects on halide perovskites catalysts, offering a novel strategy for the high-effective conversion of CO₂ into valuable products.
- Defect density,
- CO₂ adsorption,
- Perovskite,
- Polarity,
- Photocatalysis
1. [1]
  Z. Jiang, X. Xu, Y. Ma, et al., Nature 586 (2020) 549–554. doi: 10.1038/s41586-020-2738-2
2. [2]
  X. Jiang, J. Huang, Z. Bi, et al., Adv. Mater. 34 (2022) 2109330.
3. [3]
  Y. Li, Y. Lei, H. Wang, et al., Nano-Micro Lett. 15 (2023) 128.
4. [4]
  Z. Dai, N.P. Padture, Nat. Energy 8 (2023) 1319–1327. doi: 10.1038/s41560-023-01378-6
5. [5]
  Y. Zou, S. Li, D. Zheng, et al., Sci. China Chem. 67 (2024) 2215–2223. doi: 10.1007/s11426-024-2076-3
6. [6]
  Y. Jiang, J.F. Liao, H.Y. Chen, et al., Chem 6 (2020) 766–780.
7. [7]
  Y. Wang, H. Huang, Z. Zhang, et al., Appl. Catal. B 282 (2021) 119570.
8. [8]
  H. Arandiyan, S.S. Mofarah, C.C. Sorrell, et al., Chem. Soc. Rev. 50 (2021) 10116–10211. doi: 10.1039/d0cs00639d
9. [9]
  G. Li, Z. Su, L. Canil, et al., Science 379 (2023) 399–403.
10. [10]
  J. Liu, Z. Liu, J. Ren, et al., Adv. Funct. Mater. 35 (2025) 2420239. doi: 10.1002/adfm.202420239
11. [11]
  C. Wang, Z. Xie, Y. Wang, et al., Adv. Sci. 11 (2024) 2402471.
12. [12]
  Y. Wang, H. Fan, X. Liu, et al., J. Alloys Compd. 945 (2023) 169197.
13. [13]
  J. Wu, X. Li, W. Shi, et al., Angew. Chem. Int. Ed. 57 (2018) 8719–8723. doi: 10.1002/anie.201803514
14. [14]
  J. Liu, S. Zhang, D. Qu, et al., Nano-Micro Lett. 17 (2024) 24.
15. [15]
  X. Wang, K. Li, J. He, et al., Nano Energy 78 (2020)105388.
16. [16]
  Y. Dong, K. Li, W. Luo, et al., Angew. Chem. Int. Ed. 59 (2020) 12931–12937. doi: 10.1002/anie.202002939
17. [17]
  Z. He, Q. Tang, X. Liu, et al., Energy Fuels 35 (2021) 15005–15009. doi: 10.1021/acs.energyfuels.1c01482
18. [18]
  J. Pi, X. Jia, Z. Long, et al., Adv. Energy Mater. 12 (2022) 2202074.
19. [19]
  Y. Jiang, J.F. Liao, H.Y. Chen, et al., Chem 6 (2020) 766–780.
20. [20]
  J. San Martin, N. Dang, E. Raulerson, et al., Angew. Chem. Int. Ed. 61 (2022) e202205572.
21. [21]
  Q. Wang, G. Zhang, W. Xing, et al., Angew. Chem. Int. Ed. 62 (2023) e202307930.
22. [22]
  J. Liu, H. Liang, B. Wei, et al., Small Struct. 4 (2023) 2200379.
23. [23]
  J.N. Yang, Y. Song, J.S. Yao, et al., J. Am. Chem. Soc. 142 (2020) 2956–2967. doi: 10.1021/jacs.9b11719
24. [24]
  M. Li, Y. Zhao, J. Guo, et al., Nano-Micro Lett. 15 (2023) 119. doi: 10.32014/2023.2518-170x.304
25. [25]
  L. Song, Q. Zhang, S. Ullah, et al., J. Mater. Chem. C 11 (2023) 4526–4535. doi: 10.1039/d3tc00406f
26. [26]
  Y. Wang, Q. Zhou, Y. Zhu, et al., Appl. Catal. B 294 (2021) 120236.
27. [27]
  Y. Li, C. Wang, M. Song, et al., Appl. Catal. B 243 (2019) 760–770.
28. [28]
  L. Wang, B. Zhu, J. Zhang, et al., Matter 5 (2022) 4187–4211.
29. [29]
  B.N. Choi, J.Y. Seo, Z. An, et al., Chem. Eng. J. 430 (2022) 132807.
30. [30]
  B. He, P. Xiao, S. Wan, et al., Angew. Chem. Int. Ed. 62 (2023) e202313172.
31. [31]
  H. Bian, T. Liu, D. Li, et al., Chem. Eng. J. 435 (2022) 135071.
32. [32]
  X. Yue, L. Cheng, J. Fan, et al., Appl. Catal. B 304 (2022) 120979.
33. [33]
  W. Yan, Y. Zhang, Y. Bi, Angew. Chem. Int. Ed. 63 (2024) e202316459.
34. [34]
  Q. Ren, Y. He, H. Wang, et al., Research 6 (2023) 0244.
35. [35]
  X. Yan, C. Duan, S. Yu, et al., J. CO₂ Util. 79 (2024) 102648.
36. [36]
  S. Cheng, Z. Sun, K.H. Lim, et al., Appl. Catal. B 343 (2024) 123583.
37. [37]
  N.H. Kwon, J. Park, X. Jin, et al., ACS Nano 17 (2023) 23732–23745. doi: 10.1021/acsnano.3c07566
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Correlating vacancy-defect density with CO2 activation for promoted CO2 methanation over CsPbBr3 photocatalyst

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通讯作者: 陈斌, bchen63@163.com

Correlating vacancy-defect density with CO₂ activation for promoted CO₂ methanation over CsPbBr₃ photocatalyst