Citation: Huan Chen, Donghui Hong, Kun Wan, Junjie Wang, Bo Niu, Yayun Zhang, Donghui Long. Urchin-like Nb₂O₅ hollow microspheres enabling efficient and selective photocatalytic C–C bond cleavage in lignin models under ambient conditions[J]. Chinese Chemical Letters, ;2022, 33(9): 4357-4362. doi: 10.1016/j.cclet.2021.11.084 shu

Urchin-like Nb₂O₅ hollow microspheres enabling efficient and selective photocatalytic C–C bond cleavage in lignin models under ambient conditions

Huan Chen ^{a, 1} ,
Donghui Hong ^{a, 1} ,
Kun Wan ^a ,
Junjie Wang ^a ,
Bo Niu ^a ,
Yayun Zhang ^{a, *,} ,
Donghui Long ^{a, b, *,}

a.
State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
b.
Shanghai Key Laboratory of Multiphase Materials Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

yy.zhang@ecust.edu.cn

longdh@mail.ecust.edu.cn

Received Date: 22 September 2021
Revised Date: 6 November 2021
Accepted Date: 28 November 2021
Available Online: 3 December 2021

Figures(4)

Selective cleavage of robust C−C bonds to harvest value-added aromatic oxygenates is an intriguing but challenging task in lignin depolymerization. Photocatalysis is a promising technology with the advantages of mild reaction conditions and strong sustainability. Herein, we show a novel urchin-like Nb₂O₅ hollow microsphere (U-Nb₂O₅ HM), prepared by one-pot hydrothermal method, are highly active and selective for C_α−C_β bond cleavage of lignin β-O-4 model compounds under mild conditions, achieving 94% substrate conversion and 96% C−C bond cleavage selectivity. Systematic experimental studies and density functional theory (DFT) calculations revealed that the superior performance of U-Nb₂O₅ HMs arises from more exposed active sites, more efficient free charge separation and the active (001) facet, which facilitates the activation of C_β−H bond of lignin models and generate key C_β radical intermediates by photogenerated holes, further inducing the C_α−C_β bond cleavage to produce aromatic oxygenates. This work could provide some suggestions for the fabrication of hierarchical photocatalysts in the lignin depolymerization system.
- Niobium oxide,
- Urchin-like hierarchical structure,
- Photocatalysis,
- β-O-4 Lignin model,
- C_β radical
1. [1]
  C. Xu, R.A. Arancon, J. Labidi, R. Luque, Chem. Soc. Rev. 43 (2014) 7485–7500. doi: 10.1039/C4CS00235K
2. [2]
  R. Rinaldi, R. Jastrzebski, M.T. Clough, et al., Angew. Chem. Int. Ed. 55 (2016) 8164–8215. doi: 10.1002/anie.201510351
3. [3]
  Y. Zhou, Y. Qian, J. Wang, X. Qiu, H. Zeng, Biomacromolecules 21 (2020) 3231–3241. doi: 10.1021/acs.biomac.0c00696
4. [4]
  K. Chen, X. Qiu, D. Yang, Y. Qian, Green Chem. 22 (2020) 6357–6371. doi: 10.1039/D0GC01505A
5. [5]
  J. Wang, Y. Qian, L. Li, X. Qiu, ChemSusChem 13 (2020) 4420–4427. doi: 10.1002/cssc.201903132
6. [6]
  H. Chen, K. Wan, F. Zheng, et al., Renew. Sustain. Energy Rev. 147 (2021) 111217. doi: 10.1016/j.rser.2021.111217
7. [7]
  C. Zhang, F. Wang, Acc. Chem. Res. 53 (2020) 470–484. doi: 10.1021/acs.accounts.9b00573
8. [8]
  M. Wang, F. Wang, Adv. Mater. 31 (2019) 1901866. doi: 10.1002/adma.201901866
9. [9]
  M.V. Galkin, J.S. Samec, ChemSusChem 9 (2016) 1544–1558. doi: 10.1002/cssc.201600237
10. [10]
  X. Liu, F.P. Bouxin, J. Fan, et al., ChemSusChem 13 (2020) 4296–4317. doi: 10.1002/cssc.202001213
11. [11]
  C. Li, X. Zhao, A. Wang, G.W. Huber, T. Zhang, Chem. Rev. 115 (2015) 11559–11624. doi: 10.1021/acs.chemrev.5b00155
12. [12]
  X. Wu, N. Luo, S. Xie, et al., Chem. Soc. Rev. 49 (2020) 6198–6223. doi: 10.1039/D0CS00314J
13. [13]
  P.J. Deuss, K. Barta, J.G. de Vries, Catal. Sci. Technol. 4 (2014) 1174–1196. doi: 10.1039/C3CY01058A
14. [14]
  P.J. Deuss, K. Barta, Coord. Chem. Rev. 306 (2016) 510–532. doi: 10.1016/j.ccr.2015.02.004
15. [15]
  H. Liu, H. Li, N. Luo, F. Wang, ACS Catal. 10 (2019) 632–643.
16. [16]
  S. Gazi, W.K. Hung Ng, R. Ganguly, et al., Chem. Sci. 6 (2015) 7130–7142. doi: 10.1039/C5SC02923F
17. [17]
  Y. Wang, Y. Liu, J. He, Y. Zhang, Sci. Bull. 64 (2019) 1658–1666. doi: 10.1016/j.scib.2019.09.003
18. [18]
  Y. Wang, J. He, Y. Zhang, CCS Chem. 2 (2020) 107–117. doi: 10.31635/ccschem.020.201900076
19. [19]
  R.A. Rani, A.S. Zoolfakar, J.Z. Ou, et al., Sens. Actuators B 176 (2013) 149–156. doi: 10.1016/j.snb.2012.09.028
20. [20]
  C.J. Zhang, S.J. Kim, M. Ghidiu, et al., Adv. Funct. Mater. 26 (2016) 4143–4151. doi: 10.1002/adfm.201600682
21. [21]
  K. Su, H. Liu, Z. Gao, P. Fornasiero, F. Wang, Adv. Sci. 8 (2021) 2003156. doi: 10.1002/advs.202003156
22. [22]
  Y. Zhao, C. Eley, J. Hu, et al., Angew. Chem. Int. Ed. 51 (2012) 3846–3849. doi: 10.1002/anie.201108580
23. [23]
  R. Song, H. Chi, Q. Ma, et al., J. Am. Chem. Soc. 143 (2021) 13664–13674. doi: 10.1021/jacs.1c05008
24. [24]
  K. Su, H. Liu, B. Zeng, et al., ACS Catal. 10 (2019) 1324–1333.
25. [25]
  F. Hashemzadeh, A. Gaffarinejad, R. Rahimi, J. Hazard. Mater. 286 (2015) 64–74. doi: 10.1016/j.jhazmat.2014.12.038
26. [26]
  H. Zhang, Q. Wu, C. Guo, Y. Wu, T. Wu, ACS Sustain. Chem. Eng. 5 (2017) 3517–3523. doi: 10.1021/acssuschemeng.7b00231
27. [27]
  J. Chen, H. Wang, G. Huang, et al., J. Alloy. Compd. 728 (2017) 19–28. doi: 10.1016/j.jallcom.2017.08.266
28. [28]
  H. Li, Z. Bian, J. Zhu, et al., J. Am. Chem. Soc. 129 (2007) 8406–8407. doi: 10.1021/ja072191c
29. [29]
  J. Yu, H. Yu, H. Guo, M. Li, S. Mann, Small 4 (2008) 87–91. doi: 10.1002/smll.200700738
30. [30]
  T. Xiong, F. Dong, Z. Wu, RSC Adv. 4 (2014) 56307–56312. doi: 10.1039/C4RA10786A
31. [31]
  T. Su, R. Peng, Z.D. Hood, et al., ChemSusChem 11 (2018) 688–699. doi: 10.1002/cssc.201702317
32. [32]
  Y. Wu, X. Fan, Y. Chen, et al., J. Mater. Chem. A 7 (2019) 20813–20823. doi: 10.1039/C9TA07320E
33. [33]
  S. Zhang, G. Liu, W. Qiao, J. Wang, L. Ling, J. Colloid Interface Sci. 562 (2020) 193–203. doi: 10.1016/j.jcis.2019.12.015
34. [34]
  W. Zhao, W. Zhao, G. Zhu, et al., Dalton Trans. 45 (2016) 3888–3894. doi: 10.1039/C5DT04578A
35. [35]
  M. Li, X. He, Y. Zeng, et al., Chem. Sci. 6 (2015) 6799–6805. doi: 10.1039/C5SC03249K
36. [36]
  H. Yan, Q. Shen, Y. Sun, et al., ACS Catal. 11 (2021) 6371–6383. doi: 10.1021/acscatal.1c01566
37. [37]
  J. Chen, H. Wang, Z. Zhang, et al., J. Mater. Chem. A 7 (2019) 5493–5503. doi: 10.1039/C8TA12118D
38. [38]
  H. Cui, G. Zhu, Y. Xie, et al., J. Mater. Chem. A 3 (2015) 11830–11837. doi: 10.1039/C5TA01544H
39. [39]
  C. Yang, Z. Wang, T. Lin, et al., J. Am. Chem. Soc. 135 (2013) 17831–17838. doi: 10.1021/ja4076748
40. [40]
  G. Zhu, T. Lin, X. Lv, et al., J. Mater. Chem. A 1 (2013) 9650–9653. doi: 10.1039/c3ta11782k
41. [41]
  L. Ma, H. Zhou, X. Kong, Z. Li, H. Duan, ACS Sustain. Chem. Eng. 9 (2021) 1932–1940. doi: 10.1021/acssuschemeng.0c08612
42. [42]
  T. Cui, L. Ma, S. Wang, et al., J. Am. Chem. Soc. 143 (2021) 9429–9439. doi: 10.1021/jacs.1c02328
43. [43]
  H. Liu, H. Li, J. Lu, et al., ACS Catal. 8 (2018) 4761–4771. doi: 10.1021/acscatal.8b00022
44. [44]
  F. Su, S.C. Mathew, G. Lipner, et al., J. Am. Chem. Soc. 132 (2010) 16299–16301. doi: 10.1021/ja102866p
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沈阳化工大学材料科学与工程学院沈阳 110142

Urchin-like Nb2O5 hollow microspheres enabling efficient and selective photocatalytic C–C bond cleavage in lignin models under ambient conditions

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通讯作者: 陈斌, bchen63@163.com

Urchin-like Nb₂O₅ hollow microspheres enabling efficient and selective photocatalytic C–C bond cleavage in lignin models under ambient conditions