Citation: Danfeng Zhao, Jing Lin, Rushuo Li, Liang Chu, Zhaokun Wang, Xiubing Huang, Ge Wang. Constructing frustrated Lewis pairs on porous Ce-based metal-organic frameworks with improved dicyclopentadiene hydrogenation activity[J]. Chinese Chemical Letters, ;2025, 36(7): 110172. doi: 10.1016/j.cclet.2024.110172 shu

Constructing frustrated Lewis pairs on porous Ce-based metal-organic frameworks with improved dicyclopentadiene hydrogenation activity

Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China

xiubinghuang@ustb.edu.cn

gewang@ustb.edu.cn

Received Date: 7 May 2024
Revised Date: 11 June 2024
Accepted Date: 24 June 2024
Available Online: 24 June 2024

Figures(6)

The construction of frustrated Lewis acid-base pairs (FLPs) in porous systems is very important for the field of industrial hydrogenation catalysis, but there is still a great challenge. Based on the Ce³⁺/Ce⁴⁺ redox pairs and abundant defects in porous Ce-based metal-organic frameworks (Ce-MOFs), FLP sites consisting of ligand-defective Ce sites (Lewis acid, LA) and neighboring terminal O sites (Lewis base, LB) were constructed in situ by a simple vacuum thermal activation method in lamellar Ce-UiO-66-F. Defects/oxygen vacancies in the Ce-MOFs structure result in the difference in the electron cloud density between Ce and O, which is suitable for HH hetero-cleavage and H-transfer in the dicyclopentadiene (DCPD) hydrogenation process. Particularly, Ce-UiO-66-F-200 achieved 96.9% conversion of DCPD and 97.8% selectivity of 8, 9-dihydrodicyclopentadiene (8, 9-DHDCPD) at 100 ℃ under 2 MPa H2 for 10 h, which is 9.4 times higher than 10.2% conversion of DCPD over the unactivated Ce-UiO-66-F. This research promotes the understanding of solid MOFs-based porous FLPs for H₂ activation, and encourages the in-depth investigation of surface solid FLPs to the whole material FLPs.
- Ce-based metal−organic framework,
- Frustrated Lewis pairs,
- Hydrogen activation,
- Thermocatalytic hydrogenation
1. [1]
  W. Gao, S. Liu, G. Sun, et al., Small 19 (2023) 2300956.
2. [2]
  K. Chang, Y. Dong, X. Xu, Chem. Comm. 55 (2019) 12777–12780. doi: 10.1039/c9cc06676d
3. [3]
  L. Zhang, Z. Chen, Z. Liu, et al., Nat. Commun. 12 (2021) 6574.
4. [4]
  G.J. Kubas, Science 314 (2006) 1096–1097. doi: 10.1126/science.1135430
5. [5]
  G.C. Welch, R.R.S. Juan, J.D. Masuda, et al., Science 314 (2006) 1124–1126. doi: 10.1126/science.1134230
6. [6]
  S. Zhang, Z.Q. Huang, Y. Ma, et al., Nat. Commun. 8 (2017) 15266.
7. [7]
  Z.Q. Huang, L.P. Liu, S. Qi, et al., ACS Catal. 8 (2018) 546–554. doi: 10.1021/acscatal.7b02732
8. [8]
  Y. Ma, S. Zhang, C.R. Chang, et al., Chem. Soc. Rev. 47 (2018) 5541–5553. doi: 10.1039/c7cs00691h
9. [9]
  A.R. Jupp, D.W. Stephan, Trends Chem. 1 (2019) 35–48.
10. [10]
  J. Lam, K.M. Szkop, E. Mosaferi, et al., Chem. Soc. Rev. 48 (2019) 3592–3612. doi: 10.1039/c8cs00277k
11. [11]
  D.W. Stephan, Acc. Chem. Res. 48 (2015) 306–316. doi: 10.1021/ar500375j
12. [12]
  D.W. Stephan, Chem 6 (2020) 1520–1526.
13. [13]
  Y. Zhang, P.C. Lan, K. Martin, et al., Chem. Catal. 2 (2022) 439–457.
14. [14]
  A. Dai, S. Li, T. Wang, et al., Chin. Chem. Lett. 34 (2023) 107559.
15. [15]
  D. Zhao, X. Li, K. Zhang, et al., Coord. Chem. Rev. 487 (2023) 215159.
16. [16]
  Q. Liu, Y. Li, Y. Fan, et al., J. Mater. Chem. A 8 (2020) 11442–11447. doi: 10.1039/d0ta01845g
17. [17]
  Y. Zhong, P. Liao, J. Kang, et al., J. Am. Chem. Soc. 145 (2023) 4659–4666. doi: 10.1021/jacs.2c12590
18. [18]
  Z. Niu, W.D.B. Gunatilleke, Q. Sun, et al., Chem 4 (2018) 2587–2599.
19. [19]
  Z. Niu, W. Zhang, P.C. Lan, et al., Angew. Chem. Int. Ed. 58 (2019) 7420–7424. doi: 10.1002/anie.201903763
20. [20]
  Y. Zhang, S. Chen, A.M. Al-Enizi, et al., Angew. Chem. Int. Ed. 135 (2023) e202213399.
21. [21]
  J. Zhang, Y. Shao, Y. Li, et al., Chin. Chem. Lett. 29 (2018) 1226–1232.
22. [22]
  Z.M. Xu, Z. Hu, Y. Huang, et al., J. Am. Chem. Soc. 145 (2023) 14994–15000. doi: 10.1021/jacs.3c04929
23. [23]
  Y. Liang, Z. Zhang, X. Su, et al., Angew. Chem. Int. Ed. 135 (2023) e202309030.
24. [24]
  S. Shyshkanov, T.N. Nguyen, F.M. Ebrahim, et al., Angew. Chem. Int. Ed. 58 (2019) 5371–5375. doi: 10.1002/anie.201901171
25. [25]
  S. Shyshkanov, T.N. Nguyen, A. Chidambaram, et al., Chem. Comm. 55 (2019) 10964–10967. doi: 10.1039/c9cc04374h
26. [26]
  J. Ye, J.K. Johnson, ACS Catal. 5 (2015) 6219–6229. doi: 10.1021/acscatal.5b01191
27. [27]
  J. Ye, J.K. Johnson, ACS Catal. 5 (2015) 2921–2928. doi: 10.1021/acscatal.5b00396
28. [28]
  J. Jia, C. Qian, Y. Dong, et al., Chem. Soc. Rev. 46 (2017) 4631–4644.
29. [29]
  L. Wang, T. Yan, R. Song, et al., Angew. Chem. Int. Ed. 58 (2019) 9501–9505. doi: 10.1002/anie.201904568
30. [30]
  K. Werner, X. Weng, F. Calaza, et al., J. Am. Chem. Soc. 139 (2017) 17608–17616. doi: 10.1021/jacs.7b10021
31. [31]
  L. Li, W. Liu, R. Chen, et al., Angew. Chem. Int. Ed. 61 (2022) e202214490.
32. [32]
  X. Huang, K. Zhang, B. Peng, et al., ACS Catal. 11 (2021) 9618–9678. doi: 10.1021/acscatal.1c02443
33. [33]
  D. Yang, Y. Xu, K. Pan, et al., Chin. Chem. Lett. 33 (2022) 378–384.
34. [34]
  Y. Guo, Z. Liu, F. Zhang, et al., ChemCatChem 13 (2021) 874–881. doi: 10.1002/cctc.202001531
35. [35]
  Ü. Kökçam-Demir, A. Goldman, L. Esrafili, et al., Chem. Soc. Rev. 49 (2020) 2751–2798. doi: 10.1039/c9cs00609e
36. [36]
  Y. Liang, C. Li, L. Chen, et al., Chin. Chem. Lett. 32 (2021) 787–790.
37. [37]
  X. Sun, K. Yuan, Y. Zhang, J. Rare Earths 38 (2020) 801–818.
38. [38]
  M. Lammert, M.T. Wharmby, S. Smolders, et al., Chem. Comm. 51 (2015) 12578–12581.
39. [39]
  M. Lammert, C. Glißmann, H. Reinsch, et al., Cryst. Growth Des. 17 (2017) 1125–1131. doi: 10.1021/acs.cgd.6b01512
40. [40]
  S. Dai, E. Montero-Lanzuela, A. Tissot, et al., Chem. Sci. 14 (2023) 3451–3461. doi: 10.1039/d2sc05161c
41. [41]
  S. Dai, F. Nouar, S. Zhang, et al., Angew. Chem. Int. Ed. 133 (2021) 4328–4334. doi: 10.1002/ange.202014184
42. [42]
  G. Huang, Y. Wang, T. Liu, Chin. Chem. Lett. 30 (2019) 2309–2312.
43. [43]
  H.G. Jin, M. Wang, J.X. Wen, et al., ACS Appl. Mater. Interfaces 13 (2021) 3899–3910. doi: 10.1021/acsami.0c18899
44. [44]
  J.P. Vizuet, M.L. Mortensen, A.L. Lewis, et al., J. Am. Chem. Soc. 143 (2021) 17995–18000. doi: 10.1021/jacs.1c10493
45. [45]
  A. Cadiau, Y. Belmabkhout, K. Adil, et al., Science 356 (2017) 731–735. doi: 10.1126/science.aam8310
46. [46]
  M.S. Christian, K.J. Fritzsching, J.A. Harvey, et al., JACS Au 2 (2022) 1889–1898. doi: 10.1021/jacsau.2c00259
47. [47]
  S. Rojas-Buzo, P. Concepción, J.L. Olloqui-Sariego, et al., ACS Appl. Mater. Interfaces 13 (2021) 31021–31030. doi: 10.1021/acsami.1c07496
48. [48]
  S. Rojas-Buzo, D. Salusso, F. Bonino, et al., Mater. Today Chem. 27 (2023) 101337.
49. [49]
  D. Jia, J. Zhao, Z. Tao, et al., Carbon 184 (2021) 855–863.
50. [50]
  C. Wu, X. Chen, J. Liang, et al., Chem. Eng. J. 462 (2023) 142141.
51. [51]
  G.C. Shearer, S. Forselv, S. Chavan, et al., Top. Catal. 56 (2013) 770–782. doi: 10.1007/s11244-013-0027-0
52. [52]
  X. Feng, H.S. Jena, C. Krishnaraj, et al., J. Am. Chem. Soc. 143 (2021) 21511–21518. doi: 10.1021/jacs.1c05357
53. [53]
  S. Rojas-Buzo, B. Bohigues, D. Salusso, et al., ACS Catal. 13 (2023) 9171–9180. doi: 10.1021/acscatal.3c00502
54. [54]
  B. Choudhury, A. Choudhury, Mater. Chem. Phys. 131 (2012) 666–671.
55. [55]
  T. Islamoglu, D. Ray, P. Li, et al., Inorg. Chem. 57 (2018) 13246–13251. doi: 10.1021/acs.inorgchem.8b01748
56. [56]
  S. Smolders, K.A. Lomachenko, B. Bueken, et al., ChemPhysChem 19 (2018) 373–378. doi: 10.1002/cphc.201700967
57. [57]
  X. Kan, G. Zhang, J. Ma, et al., Adv. Funct. Mater. 34 (2024) 2312044.
58. [58]
  K.A. Lomachenko, J. Jacobsen, A.L. Bugaev, et al., J. Am. Chem. Soc. 140 (2018) 17379–17383. doi: 10.1021/jacs.8b10343
59. [59]
  M. Ronda-Lloret, I. Pellicer-Carreño, A. Grau-Atienza, et al., Adv. Funct. Mater. 31 (2021) 2102582.
60. [60]
  P. Ji, T. Drake, A. Murakami, et al., J. Am. Chem. Soc. 140 (2018) 10553–10561. doi: 10.1021/jacs.8b05765
61. [61]
  C. Atzori, K.A. Lomachenko, J. Jacobsen, et al., Dalton Trans. 49 (2020) 5794–5797. doi: 10.1039/d0dt01023e
1. [1]
  Tao Ban , Xi-Yang Yu , Hai-Kuo Tian , Zheng-Qing Huang , Chun-Ran Chang . One-step conversion of methane and formaldehyde to ethanol over SA-FLP dual-active-site catalysts: A DFT study. Chinese Chemical Letters, 2024, 35(4): 108549-. doi: 10.1016/j.cclet.2023.108549
2. [2]
  Mianfeng Li , Haozhi Wang , Zijun Yang , Zexiang Yin , Yuan Liu , Yingmei Bian , Yang Wang , Xuerong Zheng , Yida Deng . Synergistic enhancement of alkaline hydrogen evolution reaction by role of Ni-Fe LDH introducing frustrated Lewis pairs via vacancy-engineered. Chinese Chemical Letters, 2025, 36(3): 110199-. doi: 10.1016/j.cclet.2024.110199
3. [3]
  Jinyuan Cui , Tingting Yang , Teng Xu , Jin Lin , Kunlong Liu , Pengxin Liu . Hydrogen spillover enhances the selective hydrogenation of α,β-unsaturated aldehydes on the Cu-O-Ce interface. Chinese Journal of Structural Chemistry, 2025, 44(1): 100438-100438. doi: 10.1016/j.cjsc.2024.100438
4. [4]
  Yinyin Xu , Yuanyuan Li , Jingbo Feng , Chen Wang , Yan Zhang , Yukun Wang , Xiuwen Cheng . Covalent organic frameworks doped with manganese-metal organic framework for peroxymonosulfate activation. Chinese Chemical Letters, 2024, 35(4): 108838-. doi: 10.1016/j.cclet.2023.108838
5. [5]
  Liangji Chen , Zhen Yuan , Fudong Feng , Xin Zhou , Zhile Xiong , Wuji Wei , Hao Zhang , Banglin Chen , Shengchang Xiang , Zhangjing Zhang . A hydrogen-bonded organic framework containing fluorescent carbazole and responsive pyridyl units for sensing organic acids. Chinese Chemical Letters, 2024, 35(9): 109344-. doi: 10.1016/j.cclet.2023.109344
6. [6]
  Jianing He , Xiao Wang , Zijian Wang , Ruize Jiang , Ke Wang , Rui Zhang , Huilin Wang , Baokang Geng , Hongyi Gao , Shuyan Song , Hongjie Zhang . Investigation on Cu promotion effect on Ce-based solid solution-anchored Rh single atoms for three-way catalysis. Chinese Chemical Letters, 2025, 36(2): 109640-. doi: 10.1016/j.cclet.2024.109640
7. [7]
  Mengmeng Ao , Jian Wei , Chuan-Shu He , Heng Zhang , Zhaokun Xiong , Yonghui Song , Bo Lai . Insight into the activation of peroxymonosulfate by N-doped copper-based carbon for efficient degradation of organic pollutants: Synergy of nonradicals. Chinese Chemical Letters, 2025, 36(1): 109882-. doi: 10.1016/j.cclet.2024.109882
8. [8]
  Meirong HAN , Xiaoyang WEI , Sisi FENG , Yuting BAI . A zinc-based metal-organic framework for fluorescence detection of trace Cu²⁺. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1603-1614. doi: 10.11862/CJIC.20240150
9. [9]
  Wenbiao Zhang , Bolong Yang , Zhonghua Xiang . Atomically dispersed Cu-based metal-organic framework directly for alkaline polymer electrolyte fuel cells. Chinese Chemical Letters, 2025, 36(2): 109630-. doi: 10.1016/j.cclet.2024.109630
10. [10]
  Tengjia Ni , Xianbiao Hou , Huanlei Wang , Lei Chu , Shuixing Dai , Minghua Huang . Controllable defect engineering based on cobalt metal-organic framework for boosting oxygen evolution reaction. Chinese Journal of Structural Chemistry, 2024, 43(1): 100210-100210. doi: 10.1016/j.cjsc.2023.100210
11. [11]
  Xin Chen , Meng Zhao , Yan-Yuan Jia . Stable Eu(III)-based metal-organic framework for fluorescence sensing of benzaldehyde and its analogues. Chinese Journal of Structural Chemistry, 2025, 44(3): 100445-100445. doi: 10.1016/j.cjsc.2024.100445
12. [12]
  Zixuan Zhu , Xianjin Shi , Yongfang Rao , Yu Huang . Recent progress of MgO-based materials in CO₂ adsorption and conversion: Modification methods, reaction condition, and CO₂ hydrogenation. Chinese Chemical Letters, 2024, 35(5): 108954-. doi: 10.1016/j.cclet.2023.108954
13. [13]
  Shiqi Xu , Zi Ye , Shuang Shang , Fengge Wang , Huan Zhang , Lianguo Chen , Hao Lin , Chen Chen , Fang Hua , Chong-Jing Zhang . Pairs of thiol-substituted 1,2,4-triazole-based isomeric covalent inhibitors with tunable reactivity and selectivity. Chinese Chemical Letters, 2024, 35(7): 109034-. doi: 10.1016/j.cclet.2023.109034
14. [14]
  Rongxin Zhu , Shengsheng Yu , Xuanzong Yang , Ruyu Zhu , Hui Liu , Kaikai Niu , Lingbao Xing . Construction of pyrene-based hydrogen-bonded organic frameworks as photocatalysts for photooxidation of styrene in water. Chinese Chemical Letters, 2024, 35(10): 109539-. doi: 10.1016/j.cclet.2024.109539
15. [15]
  Yuxin Wang , Zhengxuan Song , Yutao Liu , Yang Chen , Jinping Li , Libo Li , Jia Yao . Methyl functionalization of trimesic acid in copper-based metal-organic framework for ammonia colorimetric sensing at high relative humidity. Chinese Chemical Letters, 2024, 35(6): 108779-. doi: 10.1016/j.cclet.2023.108779
16. [16]
  Xuying Yu , Jiarong Mi , Yulan Han , Cai Sun , Mingsheng Wang , Guocong Guo . A stable radiochromic semiconductive viologen-based metal–organic framework for dual-mode direct X-ray detection. Chinese Chemical Letters, 2024, 35(9): 109233-. doi: 10.1016/j.cclet.2023.109233
17. [17]
  Sixiao Liu , Tianyi Wang , Lei Zhang , Chengyin Wang , Huan Pang . Cerium-based metal-organic framework-modified natural mineral vermiculite for photocatalytic nitrogen fixation under visible-light irradiation. Chinese Chemical Letters, 2025, 36(3): 110058-. doi: 10.1016/j.cclet.2024.110058
18. [18]
  Ning Zhang , Mengjie Qin , Jiawen Zhu , Xuejing Lou , Xiao Tian , Wende Ma , Youmei Wang , Minghua Lu , Zongwei Cai . Thickness-controllable synthesis of metal-organic framework based hollow nanoflowers with magnetic core via liquid phase epitaxy for phosphopeptides enrichment. Chinese Chemical Letters, 2025, 36(4): 110177-. doi: 10.1016/j.cclet.2024.110177
19. [19]
  Ziyi Zhu , Yang Cao , Jun Zhang . CO2-switched porous metal-organic framework magnets. Chinese Journal of Structural Chemistry, 2024, 43(2): 100241-100241. doi: 10.1016/j.cjsc.2024.100241
20. [20]
  Manoj Kumar Sarangi , L․D Patel , Goutam Rath , Sitansu Sekhar Nanda , Dong Kee Yi . Metal organic framework modulated nanozymes tailored with their biomedical approaches. Chinese Chemical Letters, 2024, 35(11): 109381-. doi: 10.1016/j.cclet.2023.109381

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(3)
HTML views(1)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142