Citation: Yongqin Zhu, Zhenyu Ji, Yunzhe Zhou, Mingyan Wu. Immobilization of multiple hydrogen-bond acceptor sites in a stable cage-based framework for efficient C₂F₆ purification[J]. Chinese Chemical Letters, ;2026, 37(9): 111478. doi: 10.1016/j.cclet.2025.111478 shu

Immobilization of multiple hydrogen-bond acceptor sites in a stable cage-based framework for efficient C₂F₆ purification

Yongqin Zhu ^{a, b, 1} ,
Zhenyu Ji ^{a, b, 1} ,
Yunzhe Zhou ^{a, c} ,
Mingyan Wu ^{a, c, *,}

a.
State Key Lab of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
b.
College of Chemistry, Fuzhou University, Fuzhou 350108, China
c.
University of Chinese Academy of Sciences, Beijing 100049, China

wumy@fjirsm.ac.cn

Received Date: 21 May 2025
Revised Date: 12 June 2025
Accepted Date: 17 June 2025
Available Online: 18 June 2025

Figures(5)

The efficient removal of CF₃CH₂F and CF₃CHF₂ to obtain high-purity C₂F₆ is of critical importance for electronics industry but remains a big challenge. Currently, few adsorbents have been developed for one-step purification of C₂F₆ from multicomponent perfluorocarbons and hydrofluorocarbons mixtures. Herein, we report a metal-organic framework (FJI-W20) with multiple immobilized hydrogen-bond acceptors including F, O, N atoms which can form hydrogen bonds interactions with the H atoms of CF₃CH₂F and CF₃CHF₂, prompting it high selectivities for CF₃CH₂F/C₂F₆ and CF₃CHF₂/C₂F₆. More importantly, the special cage-like structure in turn ensures the high adsorption capacities of CF₃CH₂F and CF₃CHF₂. Adsorption experiments show that FJI-W20 can absorb 132.9 cm³/g of CF₃CH₂F and 110.1 cm³/g of CF₃CHF₂ but only adsorb 57.9 cm³/g of C₂F₆ at 298 K and 1 bar, delivering the selectivities as high as 17.6 and 12.3 for CF₃CH₂F/C₂F₆ (5/95, v/v) and CF₃CHF₂/C₂F₆ (5/95, v/v). Practical breakthrough experiments indicate that FJI-W20 can purify C₂F₆ from CF₃CH₂F/CF₃CHF₂/C₂F₆ (5/5/90, v/v/v) in one step at different gas flow rates as well as various temperatures and 20.6 mol/kg of high-purity (≥99.99%) C₂F₆ can be directly obtained under ambient conditions.
- Electronic specialty gases,
- Cage-based framework,
- C₂F₆ purification,
- Gas separation,
- Metal-organic framework
1. [1]
  A.J. Sicard, R.T. Baker, Chem. Rev. 120 (2020) 9164–9303. doi: 10.1021/acs.chemrev.9b00719
2. [2]
  Z. Zhang, B. Tan, P. Wang, X. Cui, H. Xing, AlChE J. 66 (2020) e16236. doi: 10.1002/aic.16236
3. [3]
  W.T. Tsai, H.P. Chen, W.Y. Hsien, J. Loss Prev. Process Ind. 15 (2002) 65–75. doi: 10.1016/S0950-4230(01)00067-5
4. [4]
  J.R. Clark, J. Chem. Educ. 83 (2006) 857. doi: 10.1021/ed083p857
5. [5]
  M.B. Chang, J.S. Chang, Ind. Eng. Chem. Res. 45 (2006) 4101–4109. doi: 10.1021/ie051227b
6. [6]
  X. Zhang, Y.L. Zhao, X.Y. Li, et al., J. Am. Chem. Soc. 146 (2024) 19303–19309. doi: 10.1021/jacs.4c05075
7. [7]
  H.Y. Ruan, X.Q. Wu, C.L. Liao, et al., Angew. Chem. Int. Ed. 64 (2025) e202419302. doi: 10.1002/anie.202419302
8. [8]
  J. He, H. Meng, X. Wang, Y. Xu, L. Feng, Sens. Actuator. B: Chem. 418 (2024) 136335. doi: 10.1016/j.snb.2024.136335
9. [9]
  J. Zhu, J. Hu, H. Xiao, et al., Sep. Purif. Technol. 331 (2024) 125614. doi: 10.1016/j.seppur.2023.125614
10. [10]
  G. Xu, T. Ke, R. Fan, et al., Adv. Sci. 12 (2025) 2411083. doi: 10.1002/advs.202411083
11. [11]
  Y. Zhu, Y. Zhou, Z. Ji, W. Zhang, M. Wu, Sep. Purif. Technol. 353 (2025) 128373. doi: 10.1016/j.seppur.2024.128373
12. [12]
  Y.L. Zhao, X. Zhang, M.Z. Li, J.R. Li, Chem. Soc. Rev. 53 (2024) 2056–2098. doi: 10.1039/d3cs00285c
13. [13]
  H. Wang, W.P. Lustig, J. Li, Chem. Soc. Rev. 47 (2018) 4729–4756. doi: 10.1039/c7cs00885f
14. [14]
  D.K.J.A. Wanigarathna, J. Gao, B. Liu, Mater. Adv. 1 (2020) 310–320. doi: 10.1039/d0ma00083c
15. [15]
  W. Xia, Z. Zhou, L. Sheng, et al., Sci. Bull. 70 (2024) 232–240.
16. [16]
  M. Wu, Z. Ji, Y. Zhou, et al., Angew. Chem. Int. Ed. 63 (2024) e202319674. doi: 10.1002/anie.202319674
17. [17]
  Z. Ji, Q. Li, Y. Zhou, et al., Angew. Chem. Int. Ed. 63 (2024) e202411175. doi: 10.1002/anie.202411175
18. [18]
  Z. Ji, Y. Zhou, Y. Zhu, et al., ACS Mater. Lett. 7 (2025) 837–844. doi: 10.1021/acsmaterialslett.4c02383
19. [19]
  Y. Zhou, C. Chen, R. Krishna, et al., Angew. Chem. Int. Ed. 62 (2023) e202305041. doi: 10.1002/anie.202305041
20. [20]
  Z. Di, C. Liu, J. Pang, et al., Angew. Chem. Int. Ed. 61 (2022) e202210343. doi: 10.1002/anie.202210343
21. [21]
  X. Huang, F. Chen, H. Sun, et al., J. Am. Chem. Soc. 146 (2024) 617–626. doi: 10.1021/jacs.3c10495
22. [22]
  Y. Wang, Z.J. Jiang, D.R. Wang, W. Lu, D. Li, J. Am. Chem. Soc. 146 (2024) 6955–6961. doi: 10.1021/jacs.3c14610
23. [23]
  M. Liu, X.W. Gu, C. Lin, et al., J. Mater. Chem. A 13 (2024) 1034–1041.
24. [24]
  Y. He, R. Krishna, B. Chen, Energy Environ. Sci. 5 (2012) 9107–9120. doi: 10.1039/c2ee22858k
25. [25]
  M.Y. Gao, A.A. Bezrukov, B.Q. Song, et al., J. Am. Chem. Soc. 145 (2023) 11837–11845. doi: 10.1021/jacs.3c03505
26. [26]
  T. Ke, Q. Wang, J. Shen, et al., Angew. Chem. Int. Ed. 59 (2020) 12725–12730. doi: 10.1002/anie.202003421
27. [27]
  C. Chen, H. Guan, H. Li, et al., Angew. Chem. Int. Ed. 61 (2022) e202201646. doi: 10.1002/anie.202201646
28. [28]
  F. Xie, L. Chen, E.M.C. Morales, et al., Nat. Commun. 15 (2024) 2240. doi: 10.1038/s41467-024-46556-6
29. [29]
  R.C. Zhao, L.H. Xie, X.M. Liu, et al., J. Am. Chem. Soc. 147 (2024) 2467–2475.
30. [30]
  Y. Han, Y. Chen, Y. Ma, et al., Chem. 9 (2023) 3532–3543. doi: 10.1016/j.chempr.2023.07.016
31. [31]
  W. Xia, Y. Yang, L. Sheng, et al., Sci. Adv. 10 (2024) eadj6473. doi: 10.1126/sciadv.adj6473
32. [32]
  A.R. Ravishankara, S. Solomon, A.A. Turnipseed, R.F. Warren, Science 259 (1993) 194–199. doi: 10.1126/science.259.5092.194
33. [33]
  S. Wang, L. Zhou, H. Qin, et al., Molecules 29 (2024) 1721. doi: 10.3390/molecules29081721
34. [34]
  R.K. Motkuri, H.V.R. Annapureddy, M. Vijaykumar, et al., Nat. Commun. 5 (2014) 4368. doi: 10.1038/ncomms5368
35. [35]
  T.-H. Chen, I. Popov, W. Kaveevivitchai, et al., Angew. Chem. Int. Ed. 54 (2015) 13902–13906. doi: 10.1002/anie.201505149
36. [36]
  J.W. Huang, J.J. Peng, X. Wei, et al., AICHE J. 69 (2023) e18027. doi: 10.1002/aic.18027
37. [37]
  J. Zheng, D. Barpaga, O.Y. Gutierrez, et al., ACS Appl. Energ. Mater. 1 (2018) 5853–5858. doi: 10.1021/acsaem.8b01282
38. [38]
  Y. Wang, F. Zhang, Y. Yang, et al., J. Colloid Interface Sci. 687 (2025) 439–448. doi: 10.1016/j.jcis.2025.02.088
39. [39]
  W. Gong, Y. Geng, P. Gao, et al., J. Am. Chem. Soc. 146 (2024) 21806–21814. doi: 10.1021/jacs.4c06046
40. [40]
  M. Sadakiyo, T. Yamada, H. Kitagawa, J. Am. Chem. Soc. 133 (2011) 11050–11053. doi: 10.1021/ja203291n
41. [41]
  H. Wang, Y. Zhao, F. Zhang, et al., Sci. Adv. 7, (2021) eabg0396. doi: 10.1126/sciadv.abg0396
42. [42]
  X.H. Xiong, L. Song, W. Wang, et al., Adv. Sci. 11 (2024) 2308123. doi: 10.1002/advs.202308123
43. [43]
  R.T. Jerozal, J. Kim, C. Ma, et al., J. Am. Chem. Soc. 147 (2025) 7127–7136. doi: 10.1021/jacs.5c00393
44. [44]
  J. Zheng, D. Barpaga, B.A. Trump, et al., J. Am. Chem. Soc. 142 (2020) 3002–3012. doi: 10.1021/jacs.9b11963
45. [45]
  M. Zheng, W. Xue, T. Yan, et al., Angew. Chem. Int. Ed. 63 (2024) e202401770. doi: 10.1002/anie.202401770
46. [46]
  H. Li, C. Liu, C. Chen, et al., Angew. Chem. Int. Ed. 60 (2021) 7547–7552. doi: 10.1002/anie.202013988
47. [47]
  Z. Di, C. Liu, J. Pang, C. Chen, et al., Angew. Chem. Int. Ed. 60 (2021) 10828–10832. doi: 10.1002/anie.202101907
48. [48]
  Y. Zhang, Y. Han, B. Luan, et al., J. Am. Chem. Soc. 146 (2024) 17220–17229. doi: 10.1021/jacs.4c03442
49. [49]
  Y. Jiang, L. Wang, J. Hu, et al., Adv. Mater. 36 (2024) 2311140. doi: 10.1002/adma.202311140
50. [50]
  X.J. Xie, H. Zeng, Y.L. Huang, et al., Chem 11 (2025) 102339. doi: 10.1016/j.chempr.2024.10.006
51. [51]
  X.H. Xiong, Z.W. Wei, W. Wang, L.L. Meng, C.Y. Su, J. Am. Chem. Soc. 145 (2023) 14354–14364. doi: 10.1021/jacs.3c03309
52. [52]
  J. Cui, Z. Zhang, L. Yang, et al., Science 383 (2024) 179–183. doi: 10.1126/science.abn8418
53. [53]
  Y.J. Tian, C. Deng, L. Zhao, et al., Nat. Chem. 17 (2025) 141–147. doi: 10.1038/s41557-024-01672-0
54. [54]
  L. Hou, W.X. Zhang, J.P. Zhang, et al., Chem. Commun. 46 (2010) 6311–6313. doi: 10.1039/c0cc01106a
55. [55]
  A.L. Spek, J. Appl. Crystallogr. 36 (2003) 7–13. doi: 10.1107/S0021889802022112
56. [56]
  W. Fan, X. Wang, X. Zhang, et al., ACS Central Sci. 5 (2019) 1261–1268. doi: 10.1021/acscentsci.9b00423
57. [57]
  Y. Zhou, C. Chen, Z. Ji, et al., ACS Mater. Lett. 6 (2024) 1388–1395. doi: 10.1021/acsmaterialslett.4c00111
58. [58]
  Z.Y. Ji, Y. Fan, M. Wu, M. Hong, Chem. Commun. 57 (2021) 3785–3788. doi: 10.1039/d1cc00014d
59. [59]
  T. Steiner, W. Saenger, J. Am. Chem. Soc. 114 (1992) 10146–10154. doi: 10.1021/ja00052a009
60. [60]
  M.S. Thompson, T.J. Meyer, J. Am. Chem. Soc. 104 (1982) 5070–5076. doi: 10.1021/ja00383a013
61. [61]
  D.Z. Veljkovic, G.V. Janjic and S.D. Zaric, CrystEngComm 13 (2011) 5005–5010. doi: 10.1039/c1ce05065f
62. [62]
  G.R. Desiraju, Chem. Commun. (2005) 2995–3001. doi: 10.1039/b504372g
63. [63]
  N.A. Porter, B. Giese, D.P. Curran, Acc. Chem. Res. 24 (1991) 296–304. doi: 10.1021/ar00010a003
64. [64]
  W.T. Tsai, H.P. Chen, W.Y. Hsien, J. Loss Prev. Process Ind. 15 (2002) 65–75. doi: 10.1016/S0950-4230(01)00067-5
65. [65]
  Z. Zhang, S. Zhang, X. Liu, et al., J. Am. Chem. Soc. 146 (2024) 31213–31220. doi: 10.1021/jacs.4c11470
66. [66]
  T.H. Chen, I. Popov, W. Kaveevivitchai, et al., Nat. Commun. 5 (2014) 5131. doi: 10.1038/ncomms6131
67. [67]
  W. Zhang, Y. Li, Y. Wu, et al., Sep. Purif. Technol. 287 (2022) 120561. doi: 10.1016/j.seppur.2022.120561
1. [1]
  Zhenyu Ji , Yucheng Xiao , Yunzhe Zhou , Ting Zhao , Lingna Yang , Cheng Chen , Mingyan Wu , Maochun Hong . A stable Zr-MOF with trap-and-flow channels for efficient natural gas purification. Chinese Journal of Structural Chemistry, 2026, 45(4): 100862-100862. doi: 10.1016/j.cjsc.2025.100862
2. [2]
  Chengye Lou , Yu Hu , Yunjia Jiang , Lingyao Wang , Yuanbin Zhang . Borane cage hybrid supramolecular metal-organic frameworks (BSFs): Design, synthesis and gas separation performance. Chinese Journal of Structural Chemistry, 2026, 45(2): 100789-100789. doi: 10.1016/j.cjsc.2025.100789
3. [3]
  Jun-Xian Chen , Xian-Xian Xiao , Libo Li , Jinping Li , Rui-Biao Lin , Xiao-Ming Chen . Fine-tuning of Hofmann-type metal-organic frameworks for highly efficient separation of C4 olefins. Chinese Journal of Structural Chemistry, 2025, 44(12): 100744-100744. doi: 10.1016/j.cjsc.2025.100744
4. [4]
  Yongheng Ren , Yang Chen , Hongwei Chen , Lu Zhang , Jiangfeng Yang , Qi Shi , Lin-Bing Sun , Jinping Li , Libo Li . Electrostatically driven kinetic Inverse CO2/C2H2 separation in LTA-type zeolites. Chinese Journal of Structural Chemistry, 2024, 43(10): 100394-100394. doi: 10.1016/j.cjsc.2024.100394
5. [5]
  Le-Tian Zhang , Bin Xia , Nan Lu , Quan-Wen Li , Xia Zhang , Na Li , Xian-He Bu . A novel naphthalenediimide-based metal-organic framework for inkless erasable printing with ultra-long cycling performance. Chinese Chemical Letters, 2025, 36(12): 110534-. doi: 10.1016/j.cclet.2024.110534
6. [6]
  Hui Zhang , Haichao Wang , Jijie Zhang , Da-Shuai Zhang , Mei-Hui Yu , Ze Chang , Xian-He Bu . Enhanced methanol sensing performance of Pt@SnO₂-ZnO core-shell structure derived from Sn/Zn-ZIF-8 framework. Chinese Chemical Letters, 2026, 37(8): 111180-. doi: 10.1016/j.cclet.2025.111180
7. [7]
  Xiangshuai Li , Jian Zhao , Li Luo , Zhuohao Jiao , Ying Shi , Shengli Hou , Bin Zhao . Visual and portable detection of metronidazole realized by metal-organic framework flexible sensor and smartphone scanning. Chinese Chemical Letters, 2024, 35(10): 109407-. doi: 10.1016/j.cclet.2023.109407
8. [8]
  Xu Huang , Kai-Yin Wu , Chao Su , Lei Yang , Bei-Bei Xiao . Metal-organic framework Cu-BTC for overall water splitting: A density functional theory study. Chinese Chemical Letters, 2025, 36(4): 109720-. doi: 10.1016/j.cclet.2024.109720
9. [9]
  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
10. [10]
  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
11. [11]
  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
12. [12]
  Jueqiong Wang , Liwei Cheng , Yang Yang , Dewen He , Yingtong Fan , Zhiwei Li , Junhao Lu , Yumin Wang , Jia Lei , Zhiyong Peng , Aiping Jin , Dan Zhou , Zhizai Li , Shuaihua Wang , Lixi Chen , Yaxing Wang , Yanlong Wang , Shuao Wang . Flexible two-dimensional uranium-organic framework with upgraded radiation resistant for X-ray imaging. Chinese Chemical Letters, 2026, 37(5): 111614-. doi: 10.1016/j.cclet.2025.111614
13. [13]
  Muzi Li , Xin Zhang , Xiang-Jing Kong , Qiancheng Chen , Xuefeng Bai , Tao He , Jian-Rong Li . Ion exchange for enhancing MOF adsorbents performance in humid C₂H₂/CO₂ separation. Chinese Chemical Letters, 2026, 37(3): 110709-. doi: 10.1016/j.cclet.2024.110709
14. [14]
  Ran Gao , Qian Zou , Qian-Qian Su , Xiu-Fang Ma , Ye-Hui Qin , Rui Liao , Song-Song Bao , Li-Min Zheng . Photoresponsive lanthanide-dianthracene framework: Introduction of photoactive anthracene pairs by controlling the synthesis temperature. Chinese Chemical Letters, 2025, 36(10): 110404-. doi: 10.1016/j.cclet.2024.110404
15. [15]
  Zhefei Hu , Jingwen Liao , Jiawen Zhou , Lulu Zhao , Yanjuan Liu , Yuefei Zhang , Wei Chen , Sheng Tang . A new green approach to synthesizing MIP-202@porous silica microspheres for positional isomer/enantiomer/hydrophilic separation. Chinese Chemical Letters, 2025, 36(1): 109985-. doi: 10.1016/j.cclet.2024.109985
16. [16]
  Yao-Yu Ma , Wen-Juan Shi , Gang-Ding Wang , Xin Liu , Lei Hou , Yao-Yu Wang . Enhancing ethane/ethylene separation performance through the amino-functionalization of ethane-selective MOF. Chinese Chemical Letters, 2025, 36(3): 109729-. doi: 10.1016/j.cclet.2024.109729
17. [17]
  Ruiyan CHEN , Yanping HE , Jian ZHANG . Synthesis and third-order nonlinear optical property of Ti₄L₆ cage-based metal-organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 2149-2156. doi: 10.11862/CJIC.20250177
18. [18]
  Hong-Yu Chu , Guang-Chi Liu , Fu-Xue Wang , Lian-Sheng Cui , Chong-Chen Wang . Microcystis aeruginosa removal over MOFs-based materials and the evaluation methods: State-of-the-art review. Chinese Chemical Letters, 2025, 36(10): 110745-. doi: 10.1016/j.cclet.2024.110745
19. [19]
  Siyuan Chen , Hongjun Lin , Zhiyu Zhao , Cheng Chen , Wei Yu , Boya Wang , Jing Ma , Leihong Zhao , Guanhua Jin , Liguo Shen . Self-cleaning MOFs (CoBDC-NH₂)/GO nanofluidic membranes via interfacial cooperative assembly for high-performance wastewater treatment. Chinese Chemical Letters, 2026, 37(6): 111982-. doi: 10.1016/j.cclet.2025.111982
20. [20]
  Huanhuan Zhang , Shisong Guo , Yanxiang Chen , Yan Bai , Shuyang Ye , Sha Zhang , Xinyi Chen , Peng Wang , Anqi Li , Long Li , Bingbing Chen , Hua-Yao Li , Huan Liu . MOF derived Pt-In₂O₃ hollow microtube for ultrasensitive ppb-level detection of p-xylene and aging characteristics analysis. Chinese Chemical Letters, 2026, 37(8): 111328-. doi: 10.1016/j.cclet.2025.111328

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(9)
HTML views(0)

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

Immobilization of multiple hydrogen-bond acceptor sites in a stable cage-based framework for efficient C2F6 purification

Metrics

通讯作者: 陈斌, bchen63@163.com

Immobilization of multiple hydrogen-bond acceptor sites in a stable cage-based framework for efficient C₂F₆ purification