Citation: Bu-Hang Zheng, Ji-Jie Ye, Hang Wang, Chuan-De Wu. Ni–O–Al mediated electronic modulation in hierarchical porous Ni-Al silicates for synergistic lignin depolymerization[J]. Chinese Chemical Letters, ;2026, 37(11): 112366. doi: 10.1016/j.cclet.2026.112366 shu

Ni–O–Al mediated electronic modulation in hierarchical porous Ni-Al silicates for synergistic lignin depolymerization

Bu-Hang Zheng ^a ,
Ji-Jie Ye ^a ,
Hang Wang ^{b, *,} ,
Chuan-De Wu ^{a, b, *,}

a.
State Key Laboratory of Silicon and Advanced Semiconductor Materials, Department of Chemistry, Zhejiang University, Hangzhou 310027, China
b.
Shandong Key Laboratory of Intelligent Energy Materials, School of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, China

hangwang@upc.edu.cn

cdwu@zju.edu.cn

Received Date: 29 August 2025
Revised Date: 27 December 2025
Accepted Date: 4 January 2026
Available Online: 5 January 2026

Figures(4)

Overcoming the challenge of efficient lignin depolymerization is central to the economic viability of lignocellulosic biorefining. While Ni-Al catalysts offer a promising alternative to noble metals for C–O bond hydrogenation, their practical application is limited by suboptimal activity and elusive depolymerization mechanisms. Herein, a hierarchical-porous Ni-Al silicate catalyst (PMS-96-r) is engineered, which delivers a 49 wt% lignin monomer yield from poplar sawdust through reductive catalytic fractionation (RCF) under mild conditions (220 ℃, 1 MPa H₂), while maintaining catalytic stability over five cycles. Characterizations and DFT calculations reveal that Al modulates the electronic properties of Ni via the Ni–O–Al structure, enhancing methoxy coordination and lowering the activation energy for β–O–4 cleavage. Moreover, molecular dynamics simulations reveal that the hierarchical porosity of PMS-96-r enhances lignin fragment diffusion through mesopores and enhances monomer transport via micropores, collectively shifting reaction equilibrium. This electronic-structural dual-engineering strategy establishes a mechanistic foundation for designing high-performance catalysts for sustainable lignin valorization.
- Reductive catalytic fractionation,
- Lignin depolymerization,
- Porous metal silicates,
- Poplar sawdust,
- Ni-Al silicate catalyst
1. [1]
  E.T.C. Vogt, B.M. Weckhuysen, Nature 629 (2024) 295–306. doi: 10.1038/s41586-024-07322-2
2. [2]
  Y. Liao, S.F. Koelewijn, G. Van den Bossche, et al., Science 367 (2020) 1385–1390. doi: 10.1126/science.aau1567
3. [3]
  N. Li, K. Yan, T. Rukkijakan, et al., Nature 630 (2024) 381–386. doi: 10.1038/s41586-024-07446-5
4. [4]
  S. Yu, L. Chen, Y. Xie, Q. Feng, C. Chen, Prog. Mater. Sci. 148 (2025) 101383. doi: 10.1016/j.pmatsci.2024.101383
5. [5]
  G. Zhang, L. Ma, Y. Dong, Y. Fang, X. Kong, Fuel 333 (2023) 126400. doi: 10.1016/j.fuel.2022.126400
6. [6]
  M.M. Abu-Omar, K. Barta, G.T. Beckham, et al., Energy Environ. Sci. 14 (2021) 262–292. doi: 10.1039/d0ee02870c
7. [7]
  Z. Sun, B. Fridrich, A. de Santi, S. Elangovan, K. Barta, Chem. Rev. 118 (2018) 614–678. doi: 10.1021/acs.chemrev.7b00588
8. [8]
  Y.M. Questell-Santiago, M.V. Galkin, K. Barta, J.S. Luterbacher, Nat. Rev. Chem. 4 (2020) 311–330. doi: 10.1038/s41570-020-0187-y
9. [9]
  X. Li, R. Ma, X. Gao, et al., Adv. Sci. 11 (2024) 2310202. doi: 10.1002/advs.202310202
10. [10]
  L. Ma, G. Zhang, S. Dou, Y. Dong, X. Kong, Int. J. Biol. Macromol. 269 (2024) 132156. doi: 10.1016/j.ijbiomac.2024.132156
11. [11]
  M.S. Webber, J. Watson, J. Zhu, et al., Nat. Mater. 23 (2024) 1622–1638. doi: 10.1038/s41563-024-02024-6
12. [12]
  L. Ma, G. Zhang, Y. Dong, et al., J. Environ. Chem. Eng. 11 (2023) 110215. doi: 10.1016/j.jece.2023.110215
13. [13]
  G. Zhang, L. Ma, Y. Dong, S. Dou, X. Kong, J. Colloid. Interface Sci. 647 (2023) 188–200. doi: 10.1016/j.jcis.2023.05.139
14. [14]
  R. Rinaldi, R. Jastrzebski, M.T. Clough, et al., Angew. Chem. Int. Ed. 55 (2016) 8164–8215. doi: 10.1002/anie.201510351
15. [15]
  W. Deng, Y. Feng, J. Fu, et al., Green Energy Environ. 8 (2023) 10–114. doi: 10.1016/j.gee.2022.07.003
16. [16]
  C. Mondelli, G. Gözaydın, N. Yan, J. Pérez-Ramírez, Chem. Soc. Rev. 49 (2020) 3764–3782. doi: 10.1039/d0cs00130a
17. [17]
  D.M. Alonso, S.G. Wettstein, J.A. Dumesic, Chem. Soc. Rev. 41 (2012) 8075–8098. doi: 10.1039/c2cs35188a
18. [18]
  C. Li, X. Zhao, A. Wang, G.W. Huber, T. Zhang, Chem. Rev. 115 (2015) 11559–11624. doi: 10.1021/acs.chemrev.5b00155
19. [19]
  W. Schutyser, T. Renders, S. Van den Bosch, et al., Chem. Soc. Rev. 47 (2018) 852–908. doi: 10.1039/c7cs00566k
20. [20]
  Z. Shen, C. Shi, F. Liu, et al., Adv. Sci. 11 (2024) 2306693. doi: 10.1002/advs.202306693
21. [21]
  A.J. Ragauskas, G.T. Beckham, M.J. Biddy, et al., Science 344 (2014) 1246843. doi: 10.1126/science.1246843
22. [22]
  C. Zhang, F. Wang, Acc. Chem. Res. 53 (2020) 470–484. doi: 10.1021/acs.accounts.9b00573
23. [23]
  Y. Jing, L. Dong, Y. Guo, X. Liu, Y. Wang, ChemSusChem 13 (2020) 4181–4198. doi: 10.1002/cssc.201903174
24. [24]
  C. Liu, H. Wang, A.M. Karim, J. Sun, Y. Wang, Chem. Soc. Rev. 43 (2014) 7594–7623. doi: 10.1039/C3CS60414D
25. [25]
  L. Yin, M. Feng, T. Li, et al., Chem. Eng. J. 488 (2024) 150811. doi: 10.1016/j.cej.2024.150811
26. [26]
  S. Wang, X. Li, R. Ma, G. Song, Acc. Chem. Res. 58 (2025) 529–542. doi: 10.1021/acs.accounts.4c00644
27. [27]
  S. Wang, X. Li, C. Fu, H. Li, G. Song, ACS Catal. 14 (2024) 3565–3574. doi: 10.1021/acscatal.3c05461
28. [28]
  T. Renders, S. Van den Bosch, T. Vangeel, et al., ACS Sustain. Chem. Eng. 4 (2016) 6894–6904. doi: 10.1021/acssuschemeng.6b01844
29. [29]
  L. Chen, L. Pan, A.P. van Muyden, et al., Cell Rep. Phys. Sci. 2 (2021) 100567. doi: 10.1016/j.xcrp.2021.100567
30. [30]
  S. Van den Bosch, W. Schutyser, R. Vanholme, et al., Energy Environ. Sci. 8 (2015) 1748–1763. doi: 10.1039/C5EE00204D
31. [31]
  W. Jiang, Q. Li, M. Cao, et al., ACS Catal. 15 (2025) 2595–2606. doi: 10.1021/acscatal.4c07113
32. [32]
  S. Wang, K. Zhang, H. Li, L.P. Xiao, G. Song, Nat. Commun. 12 (2021) 416. doi: 10.1038/s41467-020-20684-1
33. [33]
  J. Zhu, F. Chen, Z. Zhang, et al., ACS Sustain. Chem. Eng. 7 (2019) 12955–12963. doi: 10.1021/acssuschemeng.9b02005
34. [34]
  J. He, C. Zhao, J.A. Lercher, J. Am. Chem. Soc. 134 (2012) 20768–20775. doi: 10.1021/ja309915e
35. [35]
  R. Ma, W. Hao, X. Ma, Y. Tian, Y. Li, Angew. Chem. Int. Ed. 53 (2014) 7310–7315. doi: 10.1002/anie.201402752
36. [36]
  X. Kong, C. Liu, Y. Fan, W. Xu, R. Xiao, ACS Sustain. Chem. Eng. 10 (2022) 495–507. doi: 10.1021/acssuschemeng.1c06830
37. [37]
  S. De, J. Zhang, R. Luque, N. Yan, Energy Environ. Sci. 9 (2016) 3314–3347. doi: 10.1039/C6EE02002J
38. [38]
  Z.Q. Liu, Y.Y. Yu, Y.J. Liu, et al., ACS Catal. 14 (2024) 2115–2126. doi: 10.1021/acscatal.3c04721
39. [39]
  Q. Wang, L.P. Xiao, Y.H. Lv, et al., ACS Catal. 12 (2022) 11899–11909. doi: 10.1021/acscatal.2c02955
40. [40]
  X. Wang, R. Rinaldi, Catal. Today 269 (2016) 48–55. doi: 10.1504/IJMIC.2016.074298
41. [41]
  S. Van den Bosch, T. Renders, S. Kennis, et al., Green Chem. 19 (2017) 3313–3326. doi: 10.1039/C7GC01324H
42. [42]
  X. Lu, H. Guo, J. Chen, et al., ChemSusChem 15 (2022) e202200099. doi: 10.1002/cssc.202200099
43. [43]
  X. Si, J. Chen, F. Lu, et al., ACS Sustain. Chem. Eng. 7 (2019) 19034–19041. doi: 10.1021/acssuschemeng.9b04746
44. [44]
  X. Yang, F. Geng, Z. Yang, et al., ACS Sustain. Chem. Eng. 12 (2024) 13816–13825. doi: 10.1021/acssuschemeng.4c03808
45. [45]
  P. Chen, Q. Zhang, R. Shu, et al., Bioresour. Technol. 226 (2017) 125–131. doi: 10.1016/j.biortech.2016.12.030
46. [46]
  C. Zhang, L. Wang, C.D. Wu, Dalton Trans. 52 (2023) 8834–8849. doi: 10.1039/d3dt01020a
47. [47]
  M.E. Davis, Nature 417 (2002) 813–821. doi: 10.1038/nature00785
48. [48]
  Q. Song, F. Wang, J. Cai, et al., Energy Environ. Sci. 6 (2013) 994. doi: 10.1039/c2ee23741e
49. [49]
  S. Qiu, M. Wang, Y. Fang, T. Tan, Sustain. Energ. Fuels 4 (2020) 5588–5594. doi: 10.1039/d0se01118e
50. [50]
  H.N. Pham, A.E. Anderson, R.L. Johnson, et al., ACS Catal. 5 (2015) 4546–4555. doi: 10.1021/acscatal.5b00329
51. [51]
  B.R. Silveira De Araujo, J.A. Onrubia-Calvo, G. Pétaud, et al., ChemCatChem 15 (2023) e202300071. doi: 10.1002/cctc.202300071
52. [52]
  J. Ye, J. Tang, Y.J. Zhao, C.D. Wu, Inorg. Chem. 59 (2020) 767–776. doi: 10.1021/acs.inorgchem.9b03039
53. [53]
  Y.Y. Liu, C.D. Wu, Inorg. Chem. 63 (2024) 1166–1174. doi: 10.1021/acs.inorgchem.3c03554
54. [54]
  C. Zhang, X.K. Shi, C.D. Wu, Inorg. Chem. 61 (2022) 16786–16793. doi: 10.1021/acs.inorgchem.2c02624
55. [55]
  H. Li, G.Z. Chen, C.D. Wu, Dalton Trans. 52 (2023) 17219–17228. doi: 10.1039/d3dt03002d
56. [56]
  Z. Liu, C.D. Wu, Appl. Catal. A 685 (2024) 119901. doi: 10.1016/j.apcata.2024.119901
57. [57]
  C. Wang, W. Fang, Z. Liu, et al., Nat. Nanotechnol. 17 (2022) 714–720. doi: 10.1038/s41565-022-01154-9
58. [58]
  S.S. Wong, R. Shu, J. Zhang, H. Liu, N. Yan, Chem. Soc. Rev. 49 (2020) 5510–5560. doi: 10.1039/d0cs00134a
59. [59]
  Y. Li, Y. Yu, Y. Lou, et al., Angew. Chem. Int. Ed. 62 (2023) e202307116. doi: 10.1002/anie.202307116
60. [60]
  J. Ma, D. Le, N. Yan, Chem 9 (2023) 2869–2880. doi: 10.1016/j.chempr.2023.05.030
61. [61]
  M.Y. Liu, Z.H. Zhang, X.Q. Wang, et al., Green Energy Environ. 10 (2025) 161–172. doi: 10.1117/12.3070788
62. [62]
  I. Vande Walle, N. Van Camp, L. Van de Casteele, K. Verheyen, R. Lemeur, Biomass Bioenerg. 31 (2007) 276–283. doi: 10.1016/j.biombioe.2007.01.002
63. [63]
  N. Ohtsu, M. Oku, T. Shishido, K. Wagatsuma, Appl. Surf. Sci. 253 (2007) 8713–8717. doi: 10.1016/j.apsusc.2007.04.049
64. [64]
  A.N. Mansour, C.A. Melendres, Surf. Sci. Spectra 3 (1994) 271–278. doi: 10.1116/1.1247756
65. [65]
  Y.Y. Liu, G.P. Zhan, C.D. Wu, Chem. Commun. 57 (2021) 6185–6188. doi: 10.1039/d1cc01797g
66. [66]
  Q. Hou, M. Zhen, L. Liu, et al., Appl. Catal. B 224 (2018) 183–193. doi: 10.1016/j.apcatb.2017.09.049
67. [67]
  G. Meng, W. Lan, L. Zhang, et al., J. Am. Chem. Soc. 145 (2023) 12884–12893. doi: 10.1021/jacs.3c04028
68. [68]
  S. Su, L.P. Xiao, X. Chen, et al., ChemSusChem 15 (2022) e202200365. doi: 10.1002/cssc.202200365
69. [69]
  V. Ranaware, D. Verma, R. Insyani, et al., Green Chem. 21 (2019) 1021–1042. doi: 10.1039/c8gc03623c
70. [70]
  X. Dou, W. Li, C. Zhu, X. Jiang, Appl. Catal. B 287 (2021) 119975. doi: 10.1016/j.apcatb.2021.119975
71. [71]
  K. Wu, J. Wang, Y. Zhu, et al., Ind. Eng. Chem. Res. 58 (2019) 12602–12610. doi: 10.1021/acs.iecr.9b01807
72. [72]
  Z. Liu, H. Li, X. Gao, et al., Nat. Commun. 13 (2022) 4716. doi: 10.1038/s41467-022-32451-5
73. [73]
  N.D. Yilmazer, M.F. Fellah, I. Onal, Appl. Surf. Sci. 256 (2010) 5088–5093. doi: 10.1016/j.apsusc.2010.03.067
74. [74]
  H. Xu, W. Chu, W. Sun, C. Jiang, Z. Liu, RSC Adv. 6 (2016) 96545–96553. doi: 10.1039/C6RA14009B
75. [75]
  Q. Xu, Q. Wang, L.P. Xiao, et al., J. Mater. Chem. A 11 (2023) 23809–23820. doi: 10.1039/d3ta04927b
76. [76]
  H. Li, G. Song, ACS Catal. 10 (2020) 12229–12238. doi: 10.1021/acscatal.0c02339
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