Citation: Junchen Peng, Zhongyuan Guo, Dandan Dong, Yusheng Lu, Bao Wang, Fangjie Lu, Chaofeng Huang, Bin Dai. Cu⁰/Cu^δ⁺ site construction and its catalytic role in acetylene hydrochlorination[J]. Chinese Chemical Letters, ;2025, 36(8): 111208. doi: 10.1016/j.cclet.2025.111208 shu

Cu⁰/Cu^δ⁺ site construction and its catalytic role in acetylene hydrochlorination

School of Chemistry and Chemical Engineering/State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, Shihezi University, Shihezi 832000, China

luyusheng@shzu.edu.cn

cf.huang@shzu.edu.cn

db_tea@shzu.edu.cn

Received Date: 7 January 2025
Revised Date: 14 April 2025
Accepted Date: 14 April 2025
Available Online: 15 April 2025

Figures(4)

In view of the dearth of active components and the unsatisfactory dispersion of Cu-based catalysts, it is imperative to undertake a detailed investigation of catalysts with enhanced catalytic performance. In order to achieve a balance between the catalytic activity and stability in the reaction process, a series of P-atom doped Cu⁰/Cu^δ+ binary Cu-based catalysts were prepared by means of heteroatom introduction and heat treatment. The introduction of P enhanced the stability of Cu during heat treatment, thereby inhibiting the excessive agglomeration of Cu. The structure of the Cu⁰/Cu^δ+ binary catalyst was modified through heat treatment and HCl activation, and the relationship between its structure and catalytic activity was subsequently investigated. The activation process of HCl facilitated the conversion of the Cu⁰ state to the Cu-Cl state and augmented the valence state of Cu. The valence modulation of the Cu site by HCl during the reaction prevented the over-reduction of the Cu site by acetylene and enhanced the stability of the catalyst. The 3Cu/5CuP/AC-800 catalyst was operated for 50 h without significant deactivation under the reaction conditions of T = 180 ℃, V(HCl)/V(C₂H₂) = 1.15 and GHSV(C₂H₂) = 180 h^-1. This design strategy provides a novel reference point for further studies of CuCl₂ based catalysts for acetylene hydrochlorination.
- Acetylene hydrochlorination,
- P-atom doped,
- Cu⁰/Cu^δ+ binary catalyst,
- HCl activation,
- Heat treatment
1. [1]
  X. Wang, W. Chen, X. Lei, et al., Coord. Chem. Rev. 500 (2024) 215541.
2. [2]
  B. Wang, Z. Jiang, T. Wang, et al., ACS Catal. 11 (2021) 11016–11028. doi: 10.1021/acscatal.1c01921
3. [3]
  R. Lin, A.P. Amrute, J. Perez-Ramirez, Chem. Rev. 117 (2017) 4182–4247. doi: 10.1021/acs.chemrev.6b00551
4. [4]
  S.K. Kaiser, A.H. Clark, L. Cartocci, et al., Small 17 (2021) e2004599. doi: 10.1002/smll.202004599
5. [5]
  G. Malta, S.A. Kondrat, S.J. Freakley, et al., Science 355 (2017) 1399–1403. doi: 10.1126/science.aal3439
6. [6]
  Y. Yue, B. Wang, J. Huang, et al., ACS Appl. Mater. Inter. 16 (2024) 16106–16119. doi: 10.1021/acsami.3c18532
7. [7]
  S. Ali, L. Wang, H. Yan, et al., Appl. Organomet. Chem. 38 (2024) e7681.
8. [8]
  B. Wang, Y. Yue, C. Jin, et al., Appl. Catal. B: Environ. 272 (2020) 118944.
9. [9]
  Y. Fan, H. Xu, G. Gao, et al., Nat. Commun. 15 (2024) 6035.
10. [10]
  B. Wang, Y. Yue, S. Wang, et al., Chem. Commun. 56 (2020) 10722–10725. doi: 10.1039/d0cc04382f
11. [11]
  S.K. Kaiser, R. Lin, F. Krumeich, et al., Angew. Chem. Int. Ed. 58 (2019) 12297–12304. doi: 10.1002/anie.201906916
12. [12]
  H. Shao, Y. Lu, H. Meng, et al., Ind. Eng. Chem. Res. 63 (2024) 11320–11333. doi: 10.1021/acs.iecr.4c00167
13. [13]
  L. Yao, H. Zhang, Y. Li, et al., New J. Chem. 46 (2022) 3738–3746. doi: 10.1039/d1nj05120b
14. [14]
  J. Zeng, J. Zhao, ChemistrySelect 7 (2022) e202104535.
15. [15]
  L. Song, L. Liu, M. Zhu, et al., Chin. J. Chem. Eng. 45 (2022) 32–40.
16. [16]
  X. Dong, G. Liu, Z. Chen, et al., Chin. J. Catal. 46 (2023) 137–147.
17. [17]
  M. Zhang, H. Zhang, F. Li, et al., Catal. Sci. Technol. 12 (2022) 4255–4265. doi: 10.1039/d2cy00786j
18. [18]
  M. Zhang, L. Wang, H. Yan, et al., J. Mater. Res. Technol. 13 (2021) 2055–2065.
19. [19]
  L. Dang, L. Wang, H. Yan, et al., Microporous Mesoporous Mater. 377 (2024) 113204.
20. [20]
  B. Wang, C. Jin, S. Shao, et al., Green Energy Environ. 8 (2022) 1128–1140.
21. [21]
  L. Yang, H. Zhang, L. Li, et al., ACS Sustain. Chem. Eng. 11 (2023) 1666–1677. doi: 10.1021/acssuschemeng.2c05381
22. [22]
  L. Yang, L. Li, J. Li, et al., Ind. Eng. Chem. Res. 63 (2024) 12394–12402. doi: 10.1021/acs.iecr.4c00863
23. [23]
  F. Feng, C. Jin, S. Wang, et al., Appl. Catal. A: Gen. 661 (2023) 119238.
24. [24]
  H. Meng, Y. Yang, T. Shen, et al., Nat. Commun. 14 (2023) 7980.
25. [25]
  S. Ning, H. Ou, Y. Li, et al., Angew. Chem. Int. Ed. 62 (2023) e202302253.
26. [26]
  Z. Zhang, H. Tian, H. Jiao, et al., J. Mater. Chem. A 12 (2024) 1218–1232.
27. [27]
  Z. Zhang, X. Wang, H. Tian, et al., J. Colloid Interface Sci. 661 (2024) 966–976.
28. [28]
  J. Huang, T. Ding, K. Ma, et al., ChemCatChem 10 (2018) 3862–3871. doi: 10.1002/cctc.201800421
29. [29]
  Y. Yue, S. Wang, Q. Zhou, et al., ACS Catal. 13 (2023) 9777–9791. doi: 10.1021/acscatal.3c01527
30. [30]
  F. Guo, K. Peng, S. Liang, et al., Energy 180 (2019) 584–593.
31. [31]
  B. Wang, T. Zhang, L. Li, et al., Chem. Eng. J. 480 (2024) 148323.
32. [32]
  T. Jia, L. Wang, Z. Zhu, et al., Chin. Chem. Lett. 35 (2024) 108692.
33. [33]
  S. Kuang, M. Li, X. Chen, et al., Chin. Chem. Lett. 34 (2023) 108013.
34. [34]
  R. Chen, S. Chen, L. Wang, et al., Adv. Mater. 36 (2024) e2304713.
35. [35]
  H. Tian, Z. Zhang, H. Fang, et al., Appl. Catal. B: Environ. Energy 351 (2024) 124001.
36. [36]
  T. Wang, Z. Jiang, Q. Tang, et al., Commun. Chem. 5 (2022) 2.
37. [37]
  S.K. Kaiser, R. Lin, S. Mitchell, et al., Chem. Sci. 10 (2019) 359–369. doi: 10.1039/c8sc03186j
38. [38]
  K.J. Lee, S. Choi, S. Park, et al., Chem. Mater. 28 (2016) 4403–4408. doi: 10.1021/acs.chemmater.6b01459
39. [39]
  Y. Zheng, K. Chen, K. Jiang, et al., J. Energy Storage 56 (2022) 105995.
40. [40]
  Z. Guo, W. Peng, J. Li, et al., New J. Chem. 47 (2023) 14019–14029. doi: 10.1039/d3nj01710a
41. [41]
  H. Li, F. Wang, W. Cai, et al., Catal. Sci. Technol. 5 (2015) 5174–5184.
42. [42]
  F. Li, X. Wang, P. Zhang, et al., Chin. J. Chem. Eng. 59 (2023) 193–199.
43. [43]
  W. Zheng, J. Yang, H. Chen, et al., Adv. Funct. Mater. 30 (2019) 1907658.
44. [44]
  X. Hai, S. Xi, M. Sharon, et al., Nat. Nanotechnol. 17 (2022) 174–181. doi: 10.1038/s41565-021-01022-y
45. [45]
  J. Wang, C. Liu, J. Li, et al., Appl. Catal. B: Environ. Energy 207 (2017) 316–325. doi: 10.1021/acsomega.6b00342
46. [46]
  D. Faust Akl, G. Giannakakis, A. Ruiz-Ferrando, et al., Adv. Mater. 35 (2023) 2211464.
47. [47]
  W. Li, C. Min, F. Tan, et al., ACS Nano 13 (2019) 3177–3187. doi: 10.1021/acsnano.8b08692
48. [48]
  S. Ma, Z. Han, K. Leng, et al., Small 16 (2020) e2001384.
49. [49]
  S. Zhang, Z. Zhang, Y. Si, et al., ACS Nano 15 (2021) 15238–15248. doi: 10.1021/acsnano.1c05834
50. [50]
  L. Wang, C. Zhu, M. Xu, et al., J. Am. Chem. Soc. 143 (2021) 18854–18858. doi: 10.1021/jacs.1c09498
51. [51]
  S. Chao, Q. Guan, W. Li, J. Catal. 330 (2015) 273–279.
52. [52]
  F. Wan, S. Chao, Q. Guan, et al., Catal. Commun. 101 (2017) 120–124.
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沈阳化工大学材料科学与工程学院沈阳 110142

Cu0/Cuδ+ site construction and its catalytic role in acetylene hydrochlorination

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通讯作者: 陈斌, bchen63@163.com

Cu⁰/Cu^δ⁺ site construction and its catalytic role in acetylene hydrochlorination