Citation: Huiying LIN, Xiang ZHAO, Banghao WEI, Bufeng WANG, Zhiyong LU, Junfeng BAI. Perfluroalkane functionalization on MOF-808 for acetylene purification[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(10): 2103-2114. doi: 10.11862/CJIC.20250110 shu

Perfluroalkane functionalization on MOF-808 for acetylene purification

Huiying LIN ^{1, #} ,
Xiang ZHAO ^{1, #} ,
Banghao WEI ¹ ,
Bufeng WANG ¹ ,
Zhiyong LU ^{1, 2,,} ,
Junfeng BAI ^1,,

1.
College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 210009, China
2.
College of Mechanics and Materials, Hohai University, Nanjing 210098, China

Corresponding author: Zhiyong LU, zhiyong.lu@njtech.edu.cn Junfeng BAI, bjunfeng@njtech.edu.cn
Received Date: 1 April 2025
Revised Date: 22 July 2025

Figures(8)

Perfluoroalkyl acids of different chain lengths, including trifluoroacetic acid, heptafluorobutyric acid, and nonafluoropentanoic acid, were used as second ligands to replace the formic acid on the Zr₆ clusters in MOF-808. This led to the formation of a series of MOF-808-R materials (R=F₃, F₇, F₉, corresponding to trifluoroacetic acid, heptafluorobutyric acid, and nonafluoropentanoic acid) with multiple ligands, and we investigated the impact of the second ligand modification on pore size and pore environment. The loading amount of the second ligand was determined using NMR and other methods. We conducted adsorption tests for acetylene and carbon dioxide at different temperatures on both MOF-808 and MOF-808-R to explore the effects of the ligand diversification on acetylene separation performance. It was found that MOF-808-F₇ exhibited the best performance in acetylene-carbon dioxide separation.
- MOF-808,
- fluorocarboxylate-modified,
- C₂H₂/CO₂ separation
1. [1]
  MOREAU F, SILVA I D, AL SMAIL N H, EASUN T L, SAVAGE M, GODFREY H G W, PARKER S F, MANUEL P, YANG S, SCHRÖDER M. Unravelling exceptional acetylene and carbon dioxide adsorption within a tetra-amide functionalized metal-organic framework[J]. Nat. Commun., 2017, 8(1): 14085 doi: 10.1038/ncomms14085
2. [2]
  JIE C K, MADDEN D G, SOUMYA M, TONY P, FORREST K A, AMRIT K, BRIAN S, JIE K, YU Z Q, ZAWOROTKO M J. Synergistic sorbent separation for one-step ethylene purification from a four-component mixture[J]. Science, 2019, 366(6462): 241-246 doi: 10.1126/science.aax8666
3. [3]
  CHEN T W, ZHANG Q, WANG J F, WANG T. Simulation of industrial-scale gas quenching process for partial oxidation of nature gas to acetylene[J]. Chem. Eng. J., 2017, 329: 238-249 doi: 10.1016/j.cej.2017.04.016
4. [4]
  AMGHIZAR I, VANDEWALLE L A, VAN GEEM K M, MARIN G B. New trends in olefin production[J]. Engineering, 2017, 3(2): 171-178 doi: 10.1016/J.ENG.2017.02.006
5. [5]
  CAI L Z, YU X Y, WANG M S, YUAN D Q, CHEN W F, WU M Y, GUO G C. In situ stimulus response study on the acetylene/ethylene purification process in MOFs[J]. Angew. Chem.-Int. Edit., 2024, 64(5): e202417072
6. [6]
  QAZVINI O T, BABARAO R, TELFER S G. Multipurpose metal-organic framework for the adsorption of acetylene: Ethylene purification and carbon dioxide removal[J]. Chem. Mater., 2019, 31(13): 4919-4926 doi: 10.1021/acs.chemmater.9b01691
7. [7]
  YANG J C, TONG M M, HAN G P, CHANG M, YAN T A, YING Y P, YANG Q Y, LIU D H. Solubility-boosted molecular sieving-based separation for purification of acetylene in core-shell IL@MOF composites[J]. Adv. Funct. Mater., 2023, 33(15): 2213743 doi: 10.1002/adfm.202213743
8. [8]
  WANG J W, MU X B, FAN S C, XIAO Y, FAN G J, PAN D C, YUAN W, ZHAI Q G. Maximizing electrostatic interaction in ultramicroporous metal-organic frameworks for the one-step purification of acetylene from ternary mixture[J]. Inorg. Chem., 2024, 63(7): 3436-3443 doi: 10.1021/acs.inorgchem.3c04156
9. [9]
  YAGHI O M, O′KEEFFE M, OCKWIG N W, CHAE H K, EDDAOUDI M, KIM J. Reticular synthesis and the design of new materials[J]. Nature, 2003, 423(6941): 705-714 doi: 10.1038/nature01650
10. [10]
  LI H P, WANG J W, DOU Z D, WU L Z, WANG Y, LIANG Y C, ZHAI Q G. Flexible-rigid aluminum-organic frameworks with ultra-fine pore-environment regulation for benchmark acetylene storage and purification[J]. Chem. Eng. J., 2024, 492: 152125 doi: 10.1016/j.cej.2024.152125
11. [11]
  LI L B, LIN R B, KRISHNA R, LI H, XIANG S C, WU H, LI J P, ZHOU W, CHEN B L. Ethane/ethylene separation in a metal-organic framework with iron-peroxo sites[J]. Science, 2018, 362(6413): 443-446 doi: 10.1126/science.aat0586
12. [12]
  HU T L, WANG H L, LI B, KRISHNA R, WU H, ZHOU W, ZHAO Y F, HAN Y, WANG X, ZHU W D, YAO Z Z, XIANG S C, CHEN B L. Microporous metal-organic framework with dual functionalities for highly efficient removal of acetylene from ethylene/acetylene mixtures[J]. Nat. Commun., 2015, 6(1): 7328 doi: 10.1038/ncomms8328
13. [13]
  SHEN J, HE X, KE T, KRISHNA R, VAN BATEN J M, CHEN R, BAO Z B, XING H B, DINCǍ M, ZHANG Z G, YANG Q W, REN Q L. Simultaneous interlayer and intralayer space control in two-dimensional metal-organic frameworks for acetylene/ethylene separation[J]. Nat. Commun., 2020, 11(1): 6259 doi: 10.1038/s41467-020-20101-7
14. [14]
  LU Z Y, DUAN J X, TAN H, DU L T, ZHAO X, WANG R, KATO S, YANG S L, HUPP J T. Isomer of NU-1000 with a blocking c-pore exhibits high water-vapor uptake capacity and greatly enhanced cycle stability[J]. J. Am. Chem. Soc., 2023, 145(7): 4150-4157 doi: 10.1021/jacs.2c12362
15. [15]
  SHI L, YANG Z N, SHA F R, CHEN Z J. Design, synthesis and applications of functional zirconium-based metal-organic frameworks[J]. Sci. China Chem., 2023, 66(12): 3383-3397 doi: 10.1007/s11426-023-1809-8
16. [16]
  TADDEI M. When defects turn into virtues: The curious case of zirconium-based metal-organic frameworks[J]. Coord. Chem. Rev., 2017, 343(15): 1-24
17. [17]
  LIU X Y, KIRLIKOVALI K O, CHEN Z J, MA K K, IDREES K B, CAO R, ZHANG X, ISLAMOGLU T, LIU Y L, FARHA O K. Small molecules, big effects: Tuning adsorption and catalytic properties of metal-organic frameworks[J]. Chem. Mater., 2021, 33(4): 1444-1454 doi: 10.1021/acs.chemmater.0c04675
18. [18]
  BELMABKHOUT Y, ZHANG Z Q, ADIL K, BHATT P M, CADIAU A, SOLOVYEVA V, XING H B, EDDAOUDI M. Hydrocarbon recovery using ultra-microporous fluorinated MOF platform with and without uncoordinated metal sites: I- structure properties relationships for C₂H₂/C₂H₄ and CO₂/C₂H₂ separation[J]. Chem. Eng. J., 2019, 359: 32-36 doi: 10.1016/j.cej.2018.11.113
19. [19]
  LI H Y, XUE Z Z, HAN S D, WANG G M, HE T. A microporous fluorinated MOF for efficient separation of C₂H₂ from C₂H₂/CO₂ and C₂H₂/C₂H₄ mixtures[J]. Sep. Purif. Technol., 2025, 357: 130094 doi: 10.1016/j.seppur.2024.130094
20. [20]
  YANG S Q, KRISHNA R, CHEN H W, LI L B, ZHOU L, AN Y F, ZHANG F Y, ZHANG Q, ZHANG Y H, LI W, HU T L, BU X H. Immobilization of the polar group into an ultramicroporous metal-organic framework enabling benchmark inverse selective CO₂/C₂H₂ separation with record C₂H₂ production[J]. J. Am. Chem. Soc., 2023, 145(25): 13901-13911 doi: 10.1021/jacs.3c03265
21. [21]
  MOROI Y, YANO H, SHIBATA O, YONEMITSU T. Determination of acidity constants of perfluoroalkanoic acids[J]. Bull. Chem. Soc. Jpn., 2002, 74(4): 667-672
22. [22]
  LU Z Y, DUAN J X, DU L T, LIU Q, SCHWEITZER N M, HUPP J T. Incorporation of free halide ions stabilizes metal-organic frameworks (MOFs) against pore collapse and renders large-pore Zr-MOFs functional for water harvesting[J]. J. Mater. Chem. A, 2022, 10(12): 6442-6447 doi: 10.1039/D1TA10217F
23. [23]
  LY H G T, FU G, KONDINSKI A, BUEKEN B, DE VOS D, PARAC-VOGT T N. Superactivity of MOF-808 toward peptide bond hydrolysis[J]. J. Am. Chem. Soc., 2018, 140(20): 6325-6335 doi: 10.1021/jacs.8b01902
24. [24]
  HU Z G, KUNDU T, WANG Y X, SUN Y, ZENG K Y, ZHAO D. Modulated hydrothermal synthesis of highly stable MOF-808(Hf) for methane storage[J]. ACS Sustain. Chem. Eng., 2020, 8(46): 17042-17053 doi: 10.1021/acssuschemeng.0c04486
25. [25]
  SHARMA A, LIM J, JEONG S, WON S, SEONG J, LEE S, KIM Y S, BAEK S B, LAH M S. Superprotonic conductivity of MOF-808 achieved by controlling the binding mode of grafted sulfamate[J]. Angew. Chem.-Int. Edit., 2021, 60(26): 14334-14338 doi: 10.1002/anie.202103191
26. [26]
  LU Z Y, LIU J, ZHANG X, LIAO Y J, WANG R, ZHANG K, LYU J F, FARHA O K, HUPP J T. Node-accessible zirconium MOFs[J]. J. Am. Chem. Soc., 2020, 142(50): 21110-21121 doi: 10.1021/jacs.0c09782
27. [27]
  ZHAO Z W, LEI R C, ZHANG Y Z, CAI T T, HAN B. Defect controlled MOF-808 for seawater uranium capture with high capacity and selectivity[J]. J. Mol. Liq., 2022, 367: 120514 doi: 10.1016/j.molliq.2022.120514
28. [28]
  SNYDER B E R, TURKIEWICZ A B, FURUKAWA H, PALEY M V, VELASQUEZ E O, DODS M N, LONG J R. A ligand insertion mechanism for cooperative NH₃ capture in metal-organic frameworks[J]. Nature, 2023, 613(7943): 287-291 doi: 10.1038/s41586-022-05409-2
29. [29]
  CUI X L, CHEN K J, XING H B, YANG Q W, KRISHNA R, BAO Z B, WU H, ZHOU W, DONG X L, HAN Y, LI B, REN Q L, ZAWOROTKO M J, CHEN B L. Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene[J]. Science, 2016, 353(6295): 141-144 doi: 10.1126/science.aaf2458
30. [30]
  ZHANG X, LIN R B, WU H, HUANG Y H, YE Y X, DUAN J G, ZHOU W, LI J R, CHEN B L. Maximizing acetylene packing density for highly efficient C₂H₂/CO₂ separation through immobilization of amine sites within a prototype MOF[J]. Chem. Eng. J., 2022, 431(2): 134184
31. [31]
  KITAGAWA S, MATSUDA R. Chemistry of coordination space of porous coordination polymers[J]. Coord. Chem. Rev., 2007, 251(21/22/23/24): 2490-2509
32. [32]
  KAN L, LI G H, LIU Y L. Highly selective separation of C₃H₈ and C₂H₂ from CH₄ within two water-stable Zn₅ cluster-based metal-organic frameworks[J]. ACS Appl. Mater. Interfaces, 2020, 12(16): 18642-18649 doi: 10.1021/acsami.0c04538
33. [33]
  LIU X F, XU C Y, YANG X H, HE Y B, GUO Z Y, YAN D. An amine functionalized carbazolic porous organic framework for selective adsorption of CO₂ and C₂H₂ over CH₄[J]. Microporous Mesoporous Mat., 2019, 275: 95-101 doi: 10.1016/j.micromeso.2018.08.015
34. [34]
  ZHANG Y, DENG X Y, LI X R, LIU X, ZHANG P X, CHEN L H, YAN Z H, WANG J, DENG S G. A stable metal-organic framework with oxygen site for efficiently trapping acetylene from acetylene-containing mixtures[J]. Sep. Purif. Technol., 2023, 316: 123751 doi: 10.1016/j.seppur.2023.123751
35. [35]
  XIA Y P, WANG C X, YU M H, BU X H. A unique 3D microporous MOF constructed by cross-linking 1D coordination polymer chains for effectively selective separation of CO₂/CH₄ and C₂H₂/CH₄[J]. Chin. Chem. Lett., 2021, 32(3): 1153-1156 doi: 10.1016/j.cclet.2020.09.014
36. [36]
  CHEN K J, SCOTT H S, MADDEN D G, PHAM T, KUMAR A, BAJPAI A, LUSI M, FORREST K A, SPACE B, PERRY J J. Benchmark C₂H₂/CO₂ and CO₂/C₂H₂ separation by two closely related hybrid ultramicroporous materials[J]. Chem, 2016, 1(5): 753-765 doi: 10.1016/j.chempr.2016.10.009
37. [37]
  ZHENG Y L, YONG J Y, ZHU Z W, CHEN J Z, SONG Z Y, GAO J K. Spin crossover in metal-organic framework for improved separation of C₂H₂/CH₄ at room temperature[J]. J. Solid State Chem., 2021, 304: 122554 doi: 10.1016/j.jssc.2021.122554
38. [38]
  DUAN X, ZHANG Q, CAI J F, YANG Y, CUI Y J, HE Y B, WU C D, KRISHNA R, CHEN B L, QIAN G D. A new metal-organic framework with potential for adsorptive separation of methane from carbon dioxide, acetylene, ethylene, and ethane established by simulated breakthrough experiments[J]. J. Mater. Chem. A, 2014, 2(8): 2628-2633 doi: 10.1039/c3ta14454b
39. [39]
  XIE Y, SHI Y S, CEDEÑO MORALES E M, EL KARCH A, WANG B, ARMAN H, TAN K, CHEN B L. Optimal binding affinity for sieving separation of propylene from propane in an oxyfluoride anion-based metal-organic framework[J]. J. Am. Chem. Soc., 2023, 145(4): 2386-2394 doi: 10.1021/jacs.2c11365
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