English

Fabrication of Polymer-Supported Metal Organic Framework Membrane and Its Gas Separation Performance

• Fu Jingru ^1, ,
• Ben Teng ^1, ,
• Qiu Shilun ^{2, ,}

• 1.

  College of Chemistry, Jilin University, Changchun 130012, P. R. China

• 2.

  State Key Laboratory of Inorganic Synthesis and Preparation Chemistry, Jilin University, Changchun 130012, P. R. China

Corresponding author: Email: sqiu@jlu.edu.cn; Tel.: +86-431-85168589

• Received Date: 29 January 2019
  Accepted Date: 26 February 2019
  Revised Date: 25 February 2019
  Available Online: 15 January 2020
• Fund Project:

  The project was supported by the National Natural Science Foundation of China (21390394, 21471065, 21871103) and the Science and Technology Department of Jilin Province Foundation, China (20180414009GH)

Abstract: The fabrication of compact, continuous, and large-scale metal organic framework (MOF) membranes with high permeability and H₂/CO₂ selectivity remains challenging because of the wake interaction between the MOF membrane and the substrate. In addition, substrates with smooth and plain surfaces and suitable pore size are required to prepare high-quality MOF membranes because it is difficult to obtain dense and continuous MOF membranes on a substrate with large pores and rough surfaces. To overcome these challenges, numerous MOF membrane growth methods have emerged, including in situ (direct) growth, secondary (seeded) growth, and layer-by-layer growth methods as well as electrostatic spinning and the chemical modification of the substrate. Among these methods, usage of substrates suitable for surface-functionalization is a promising technique. Herein, Al₂O₃ was selected as the substrate and was coated with PIM-1 (one polymer of intrinsic microporosity), followed by carboxylation of PIM-1 to furnish a large number of carboxyl groups on the surface. In situ growth of the MOF membrane using the interactions between the carboxyl group and the metal yielded two types of compact, continuous, and large-scale polymer-supported MOF membranes (PIM-1-COOH/ZIF-8 and PIM-1-COOH/HKUST-1). Furthermore, the fabricated polymer-supported MOF membrane structures were investigated by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). Gas separation experiments were performed to explore the gas permeability and selectivity of the prepared MOF membranes. The XRD characterization confirmed the pure phase and high crystallinity of the MOF membranes. The SEM images showed that the MOF membranes were compact and continuous with a tight combination between the MOF crystal membrane and the substrate. Gas separation measurements showed that both MOF membranes exhibited high H₂ permeability and selectivity for H₂/CO₂. For the PIM-1-COOH/ZIF-8 and PIM-1-COOH/HKUST-1 membranes, the 1 : 1 binary mixtures gas separation factors of H₂/CO₂ calculated as the gas molar ratios in the permeate and retentate side 7.32 and 9.69, respectively, at room temperature and atmospheric pressure. The H₂/CO₂ mixture separation factors of the two MOF membranes exceeded the corresponding Knudsen constants (4.7), with H₂ permeances higher than 3.16 × 10^-6 and 1.14 × 10^-6 mol·m^-2·s^-1·Pa^-1, respectively. The ideal separation factors of H₂/CO₂ of both MOF membranes calculated as the ratio of single gas permeances were 7.70 and 12.04, respectively, with the respective H₂ permeances of up to 3.73 × 10^-6 and 3.86 × 10^-6 mol·m^-2·s^-1·Pa^-1. Because of their outstanding characteristics, these novel MOF membranes can be widely used in the fields of H₂ purification and separation.

Key words:
• Membrane
•  /  Polymer
•  /  Metal organic frameworks
•  /  Gas separation
•  /  Hydrogen purity

• 1. [1]

     Venna, S. R.; Carreon, M. A. J. Am. Chem. Soc. 2010, 132, 76. doi: 10.1021/ja909263x

  2. [2]

     Huang, A. S.; Chen, Y.; Liu, Q.; Wang, N.; Jiang, J.; Caro J. J. Membr. Sci. 2014, 454, 126. doi: 10.1016/j.memsci.2013.12.018

  3. [3]

     Zhao, Z. X.; Ma, X. L.; Kasik, A.; Li, Z.; Lin, Y. S. Ind. Eng. Chem. Res. 2013, 52, 1102. Doi: 10.1021/ie202777q

  4. [4]

     Bux, H.; Feldhoff, A.; Cravillon, J.; Wiebcke, M.; Li Y. S.; Caro J. Chem. Mater. 2011, 23, 2262. doi: 10.1021/cm200555s

  5. [5]

     Nian, P.; Li, Y. J.; Zhang, X.; Cao, Y.; Liu, H. O.; Zhang, X. F. ACS Appl. Mater. Interfaces 2018, 10, 4151. doi: 10.1021/acsami.7b17568

  6. [6]

     Wang, W. J.; Dong, X. L.; Nan, J. P.; Jin, W. Q.; Hu, Z. Q.; Chen, Y. F.; Jiang, J. W. Chem. Commun. 2012, 48, 7022. doi: 10.1039/c2cc32595k

  7. [7]

     Dong, X. L.; Lin, Y. S. Chem. Commun. 2013, 49, 1196. doi: 10.1039/C2CC38512K

  8. [8]

     Wang, C.; deKrafft, K. E.; Lin, W. B. J. Am. Chem. Soc. 2012, 134, 7211. doi: 10.1021/ja300539p

  9. [9]

     Maina, J. W.; Schutz, J. A.; Grundy, L.; Ligneris, E. D.; Yi, Z. F.; Kong, L. X.; Pozo-Gonzalo, C.; Ionescu, M.; Dumee, L. F. ACS Appl. Mater. Interfaces 2017, 9, 35010. doi: 10.1021/acsami.7b11150

  10. [10]

      Jain, I. P. J. Hydrog. Energy 2009, 34, 7368. doi: 10.1016/j.ijhydene.2009.05.093

  11. [11]

      Berry, G. D.; Pasternak, A. D.; Bambach, G. D.; Ray, Smith, J.; Schock, R. N. Energy 1996, 21, 289. doi: 10.1016/0360-5442(95)00104-2

  12. [12]

      Furukawa, H.; Cordova, K. E.; O'Keeffe, M.; Yaghi, O. M. Science 2013, 341, 1230444. doi: 10.1126/science.1230444

  13. [13]

      Liu, Y. Y.; Ng, Z. F.; Khan, K. A.; Jeong, H. K.; Ching, C. B.; Lai, Z. P. Microporous Mesoporous Mater. 2009, 118, 296. doi: 10.1016/j.micromeso.2008.08.054

  14. [14]

      Liu, Y. Y.; Hu, E. P.; Khan, E. A.; Lai, Z. P. J. Membr. Sci. 2010, 353, 36. doi: 10.1016/j.memsci.2010.02.023

  15. [15]

      Zhuang, J. L.; Terfort, A.; W ll, C. Coord. Coordination Chem. Rev. 2016, 307, 391. doi: 10.1016/j.ccr.2015.09.013

  16. [16]

      Makiura, R.; Motoyama, S.; Umemura, Y.; Yamanake, H.; Sakata, O.; Kitagawa, H. Nat. Mater. 2010, 9, 565. doi: 10.1038/nmat2769

  17. [17]

      Shekhah, O.; Wang, H.; Kowarik, S.; Schreiber, F.; Paulus, M.; Tolan, M.; Sternemann, C.; Evers, F.; Zacher, D.; Fischer, R. A.; et al. J. Am. Chem. Soc. 2007, 129, 15118. doi: 10.1021/ja076210u

  18. [18]

      Nijem, N.; Fürsich, K.; Kelly, S. T.; Swain, C.; Leone, S. R.; Gilles, M. K. Cryst. Growth Des. 2015, 15, 2948. doi: 10.1021/acs.cgd.5b00384

  19. [19]

      Ranjan, R.; Tsapatsis, M. Chem. Mater. 2009, 21, 4920. doi: 10.1021/cm902032y

  20. [20]

      Hu, Y. X.; Dong, X. L.; Nan, J. P.; Jin, W. Q.; Ren, X. M.; Xu, N. P.; Lee, Y. M. Chem. Commun. 2011, 47, 737. doi: 10.1039/c0cc03927f

  21. [21]

      Nan, J. P.; Dong, X. L.; Wang, W. J.; Jin, W. Q.; Xu, N. P. Langmuir 2011, 27, 4309. doi: 10.1021/la200103w

  22. [22]

      Guo, H. L.; Zhu, G. S.; Hewitt, I. J.; Qiu, S. L. J. Am. Chem. Soc. 2009, 131, 1646. doi: 10.1021/ja8074874

  23. [23]

      Zacher, D.; Baunemann, A.; Hermes, S.; Fischer, R. A. J. Mater. Chem. 2007, 17, 2785. doi: 10.1039/B703098C

  24. [24]

      Biemmi, E.; Scherb, C.; Bein, T. J. Am. Chem. Soc. 2007, 129, 8054. doi: 10.1021/ja0701208

  25. [25]

      Li, Y. S.; Liang, F. Y.; Bux, H.; Feldhoff, A.; Yang, W. S.; Caro, J. Angew. Chem. Int. Ed. 2010, 49, 548. doi: 10.1002/anie.200905645

  26. [26]

      Huang, A. S.; Bux, H.; Steinbach, F.; Caro, J. Angew. Chem. Int. Ed. 2010, 49, 4958. doi: 10.1002/anie.201001919

  27. [27]

      Huang, A. S.; Wang, N.; Kong, C. L.; Caro, J. Angew. Chem. Int. Ed. 2012, 51, 10551. doi: 10.1002/anie.201204621

  28. [28]

      Huang, A. S.; Chen, Y. F.; Wang, N.; Hu, Z. Q.; Jiang, J.; Caro, J. Chem. Commun. 2012, 48, 10981. doi: 10.1039/C2CC35691K

  29. [29]

      Ben, T.; Lu, C. J.; Pei, C. Y.; Xu, S. X.; Qiu, S. L. Chem. Eur. J. 2012, 18, 10250. doi: 10.1002/chem.201201574

  30. [30]

      Budd, P. M.; Elabas, E. S.; Ghanem, B. S.; Makhseed, S.; Mckeown, N. B.; Msayib, K. J.; Tattershall, C. E.; Wang, D. Adv. Mater. 2004, 16, 456. doi: 10.1002/adma.200306053

  31. [31]

      Zhao, H. Y.; Xie, Q.; Ding, X. L.; Chen, J. M.; Hua, M. M.; Tan, X. Y.; Zhang, Y. Z. J. Membr. Sci. 2016, 514, 305. doi: 10.1016/j.memsci.2016.05.013

  32. [32]

      Fu, J. R.; Das, D.; Xing, G. L.; Valtchev, V.; Qiu, S. L. J. Am. Chem. Soc. 2016, 138, 7673. doi: 10.1021/jacs.6b03348

  33. [33]

      McCarthy, M. C.; Varela-Guerrero, V.; Barnett, G. V.; Jeong, H. K. Langmuir 2010, 26, 14636. doi: 10.1021/la102409e

  34. [34]

      Pan, Y. C.; Lai Z. P. Chem. Commun. 2011, 47, 10275. doi: 10.1039/C1CC14051E

  35. [35]

      Nagaraju, D.; Bhagat, D. G.; Banerjee, R.; Kharul, U. K. J. Mater. Chem. A 2013, 1, 8828. doi: 10.1039/c3ta10438a

  36. [36]

      Guerrero, V. V.; Yoo, Y.; McCarthy, M. C.; Jeong, H. K. J. Mater. Chem. 2010, 20, 3938. doi: 10.1039/B924536G

  37. [37]

      Budd, P. M.; Msayib, K. J.; Tattershall, C. E.; Ghanem, B. S.; Reynolds, K. J.; McKeown, N. B.; Fritsch, D. J. Membr. Sci. 2005, 251, 263. doi: 10.1016/j.memsci.2005.01.009

  38. [38]

      Li, P.; Chung, T. S.; Paul, D. R. J. Membr. Sci. 2013, 432, 50. doi: 10.1016/j.memsci.2013.01.009

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