Remarkable enhancement of gas selectivity on organosilica hybrid membranes using urea-modulated metal-organic framework nanoparticles

Abstract

Metal-organic framework/organosilica hybrid membranes on tubular ceramic substrates have shown great potential for the implementation of membrane technology in practical gas separation projects due to their higher permeance compared to commercial polymers. However, the selectivities of the reported membranes are moderate. Here, we have incorporated urea-modulated metal-organic frameworks into organosilica membranes to greatly enhance its separation performance. The urea-modulated metal-organic frameworks exhibit less-defined edges of crystallographic facets and high defect density. They can be well-dispersed in the organosilica layer, which substantially suppresses the interfacial defects between metal-organic frameworks and organosilica, which is beneficial for improving the selectivity of membranes for gas separation. The results have shown that the enhanced ideal selectivity of H₂/CH₄ was 165 and that of CO₂/CH₄ was 43, with H₂ permeance of about 1.25 × 10⁻⁶ mol·m⁻²·s⁻¹·Pa⁻¹ and CO₂ permeance of 3.27 × 10⁻⁷ mol·m⁻²·s⁻¹·Pa⁻¹ at 0.2 MPa and 25 °C. In conclusion, the high level of hybrid membranes can be used to separate H₂ (or CO₂) from the binary gas mixture H₂/CH₄ (or CO₂/CH₄), which is important for gas separation in practical applications. Moreover, the simple and feasible modulation of metal-organic framework is a promising strategy to tune different metal-organic frameworks for membranes according to the actual demands.

Key words： ZIF-8 nanocrystals; urea; organosilica; hybrid membrane; enhanced separation performance

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

We acknowledge the financial supports of this work from “Pioneer” and “Leading Goose” R&D Program of Zhejiang Province (Grant No. 2022C01029), National Natural Science Foundation of China (Grant No. 21978309), Natural Science Foundation of Zhejiang Province (Grant No. LY21E020008), Youth Innovation Promotion Association, Chinese Acadenry of Sciences (Grant No. 2020300), Ningbo Natural Science Foundation (Grant No. 2023J354), and Ningbo S&T Innovation 2025 Major Special Program (Grant No. 2020Z036).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2383-7 and is accessible for authorized users.

References

1 Zhang S , Shen L , Deng H , Liu Q , You X , Yuan J , Jiang Z , Zhang S . Ultrathin membranes for separations: a new era driven by advanced nanotechnology. Advanced Materials, 2022, 34(21): 2108457

2 Sholl D S , Lively R P . Seven chemical separations to change the world. Nature, 2016, 532(7600): 435–437

3 GohP SIsmailA F. Chapter 9—Challenges, future directions, and conclusion. In: Goh P S, Ismail A F, eds. Nanocomposite Membranes for Gas Separation. Elsevier, 2020, 273–290

4 Jia Y , Liu P , Liu Y , Zhang D , Ning Y , Xu C , Zhang Y . In-situ interfacial crosslinking of NH₂-MIL-53 and polyimide in MOF-incorporated mixed matrix membranes for efficient H₂ purification. Fuel, 2023, 339: 126938

5 Hou Q , Wu Y , Zhou S , Wei Y , Caro J , Wang H . Ultra-tuning of the aperture size in stiffened ZIF-8_Cm frameworks with mixed-linker strategy for enhanced CO₂/CH₄ separation. Angewandte Chemie International Edition, 2019, 58(1): 327–331

6 Choi E , Choi J I , Kim Y J , Kim Y J , Eum K , Choi Y , Kwon O , Kim M , Choi W , Ji H . . Graphene nanoribbon hybridization of zeolitic imidazolate framework membranes for intrinsic molecular separation. Angewandte Chemie International Edition, 2022, 61(49): e202214269

7 AsadASameotoDSadrzadehM. Chapter 1—Overview of membrane technology. In: Sadrzadeh M, Mohammadi T, eds. Nanocomposite Membranes for Water and Gas Separation. Elsevier, 2020, 1–28

8 Su N C , Sun D T , Beavers C M , Britt D K , Queen W L , Urban J J . Enhanced permeation arising from dual transport pathways in hybrid polymer-MOF membranes. Energy & Environmental Science, 2016, 9(3): 922–931

9 Bachman J E , Smith Z P , Li T , Xu T , Long J R . Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal-organic framework nanocrystals. Nature Materials, 2016, 15(8): 845–849

10 Guo Y , Ying Y , Mao Y , Peng X , Chen B . Polystyrene sulfonate threaded through a metal-organic framework membrane for fast and selective lithium-ion separation. Angewandte Chemie International Edition, 2016, 55(48): 15120–15124

11 Li C , Qi A , Ling Y , Tao Y , Zhang Y B , Li T . Establishing gas transport highways in MOF-based mixed matrix membranes. Science Advances, 2023, 9(13): eadf5087

12 Wang C , Sun Y , Li L , Krishna R , Ji T , Chen S , Yan J , Liu Y . Titanium-oxo cluster assisted fabrication of a defect-rich Ti-MOF membrane showing versatile gas-separation performance. Angewandte Chemie International Edition, 2022, 61(26): e202203663

13 Duan Y , Li L , Shen Z , Cheng J , He K . Engineering metal-organic-framework (MOF)-based membranes for gas and liquid separation. Membranes, 2023, 13(5): 480

14 Carta M , Malpass-Evans R , Croad M , Rogan Y , Jansen J C , Bernardo P , Bazzarelli F , McKeown N B . An efficient polymer molecular sieve for membrane gas separations. Science, 2013, 339(6117): 303–307

15 Seong J G , Zhuang Y , Kim S , Do Y S , Lee W H , Guiver M D , Lee Y M . Effect of methanol treatment on gas sorption and transport behavior of intrinsically microporous polyimide membranes incorporating Troger’s base. Journal of Membrane Science, 2015, 480: 104–114

16 Qian Q , Wu A X , Chi W S , Asinger P A , Lin S , Hypsher A , Smith Z P . Mixed-matrix membranes formed from imide-functionalized UiO-66-NH₂ for improved interfacial compatibility. ACS Applied Materials & Interfaces, 2019, 11(34): 31257–31269

17 Qureshi H F , Nijmeijer A , Winnubst L . Influence of sol-gel process parameters on the micro-structure and performance of hybrid silica membranes. Journal of Membrane Science, 2013, 446: 19–25

18 Yu L , Kanezashi M , Nagasawa H , Guo M , Moriyama N , Ito K , Tsuru T . Tailoring ultramicroporosity to maximize CO₂ transport within pyrimidine-bridged organosilica membranes. ACS Applied Materials & Interfaces, 2019, 11(7): 7164–7173

19 Mirza E Ş , Topuz B . Nanoscale tailoring on thin bimetallic organo-oxide membranes for H₂/CO₂ separation. Separation and Purification Technology, 2022, 280: 119801

20 Kong C , Du H , Chen L , Chen B . Nanoscale MOF/organosilica membranes on tubular ceramic substrates for highly selective gas separation. Energy & Environmental Science, 2017, 10(8): 1812–1819

21 Ge L , Zhou W , Rudolph V , Zhu Z . Mixed matrix membranes incorporated with size-reduced Cu-BTC for improved gas separation. Journal of Materials Chemistry A, 2013, 1(21): 6350–6358

22 He S , Zhu B , Jiang X , Han G , Li S , Lau C H , Wu Y , Zhang Y , Shao L . Symbiosis-inspired de novo synthesis of ultrahigh MOF growth mixed matrix membranes for sustainable carbon capture. Proceedings of the National Academy of Sciences of the United States of America, 2022, 119(1): e2114964119

23 Chen K , Ni L , Zhang H , Li L , Guo X , Qi J , Zhou Y , Zhu Z , Sun X , Li J . Phenolic resin regulated interface of ZIF-8 based mixed matrix membrane for enhanced gas separation. Journal of Membrane Science, 2023, 666: 121117

24 Jiang X , He S , Han G , Long J , Li S , Lau C H , Zhang S , Shao L . Aqueous one-step modulation for synthesizing monodispersed ZIF-8 nanocrystals for mixed-matrix membrane. ACS Applied Materials & Interfaces, 2021, 13(9): 11296–11305

25 Zhao Y , Zhou C , Kong C , Chen L . Ultrathin reduced graphene oxide/organosilica hybrid membrane for gas separation. JACS Au, 2021, 1(3): 328–335

26 Wang Y , Xu Y , Ma H , Xu R , Liu H , Li D , Tian Z . Synthesis of ZIF-8 in a deep eutectic solvent using cooling-induced crystallisation. Microporous and Mesoporous Materials, 2014, 195: 50–59

27 Wu H , Chua Y S , Krungleviciute V , Tyagi M , Chen P , Yildirim T , Zhou W . Unusual and highly tunable missing-linker defects in zirconium metal-organic framework UiO-66 and their important effects on gas adsorption. Journal of the American Chemical Society, 2013, 135(28): 10525–10532

28 Zornoza B , Martinez-Joaristi A , Serra-Crespo P , Tellez C , Coronas J , Gascon J , Kapteijn F . Functionalized flexible MOFs as fillers in mixed matrix membranes for highly selective separation of CO₂ from CH₄ at elevated pressures. Chemical Communications, 2011, 47(33): 9522–9524

29 Robeson L M . The upper bound revisited. Journal of Membrane Science, 2008, 320(1–2): 390–400

30 Swaidan R , Ghanem B , Pinnau I . Fine-tuned intrinsically ultramicroporous polymers redefine the permeability/selectivity upper bounds of membrane-based air and hydrogen separations. ACS Macro Letters, 2015, 4(9): 947–951

31 Cacho-Bailo F , Etxeberría-Benavides M , Karvan O , Téllez C , Coronas J . Sequential amine functionalization inducing structural transition in an aldehyde-containing zeolitic imidazolate framework: application to gas separation membranes. CrystEngComm, 2017, 19(11): 1545–1554

32 Chai S , Du H , Zhao Y , Lin Y , Kong C , Chen L . Fabrication of highly selective organosilica membrane for gas separation by mixing bis(triethoxysilyl)ethane with methyltriethoxysilane. Separation and Purification Technology, 2019, 222: 162–167

33 Fan Y , Li J , Wang S , Meng X , Jin Y , Yang N , Meng B , Li J , Liu S . Nickel(II) ion-intercalated MXene membranes for enhanced H₂/CO₂ separation. Frontiers of Chemical Science and Engineering, 2021, 15(4): 882–891

34 Ghalei B , Sakurai K , Kinoshita Y , Wakimoto K , Isfahani A P , Song Q , Doitomi K , Furukawa S , Hirao H , Kusuda H . . Enhanced selectivity in mixed matrix membranes for CO₂ capture through efficient dispersion of amine-functionalized MOF nanoparticles. Nature Energy, 2017, 2(7): 17086

35 Li J Y , Lin Y T , Wang D K , Tseng H H , Wey M Y . Effect of heat diffusivity for driving chain stitching of dual-type hybrid organosilica-derived membranes. Separation and Purification Technology, 2022, 290: 120848

36 Li Y , Ma C , Nian P , Liu H , Zhang X . Green synthesis of ZIF-8 tubular membranes from a recyclable 2-methylimidazole water-solvent solution by ZnO nanorods self-converted strategy for gas separation. Journal of Membrane Science, 2019, 581: 344–354

37 Ma X , Wan Z , Li Y , He X , Caro J , Huang A . Anisotropic gas separation in oriented ZIF-95 membranes prepared by vapor-assisted in-plane epitaxial growth. Angewandte Chemie International Edition, 2020, 59(47): 20858–20862

38 Mise Y , Ahn S J , Takagaki A , Kikuchi R , Oyama S T . Fabrication and evaluation of trimethylmethoxysilane (TMMOS)-derived membranes for gas separation. Membranes, 2019, 9(10): 123

39 Wang Y , Jin H , Ma Q , Mo K , Mao H , Feldhoff A , Cao X , Li Y , Pan F , Jiang Z . A MOF glass membrane for gas separation. Angewandte Chemie International Edition, 2020, 59(11): 4365–4369

40 Eljaddi T , Bouillon J , Roizard D , Lebrun L . Pebax-based composite membranes with high transport properties enhanced by ZIF-8 for CO₂ separation. Membranes, 2022, 12(9): 836

41 Guo A , Ban Y , Yang K , Zhou Y , Cao N , Zhao M , Yang W . Molecular sieving mixed matrix membranes embodying nano-fillers with extremely narrow pore-openings. Journal of Membrane Science, 2020, 601: 117880

42 Guo M , Kanezashi M , Nagasawa H , Yu L , Ohshita J , Tsuru T . Amino-decorated organosilica membranes for highly permeable CO₂ capture. Journal of Membrane Science, 2020, 611: 118328

43 Jia M , Zhang X F , Feng Y , Zhou Y , Yao J . In-situ growing ZIF-8 on cellulose nanofibers to form gas separation membrane for CO₂ separation. Journal of Membrane Science, 2020, 595: 117579

44 Jiang Y , Liu C , Caro J , Huang A . A new UiO-66-NH₂ based mixed-matrix membranes with high CO₂/CH₄ separation performance. Microporous and Mesoporous Materials, 2019, 274: 203–211

45 Krokidas P , Spera M B M , Boutsika L G , Bratsos I , Charalambopoulou G , Economou I G , Steriotis T . Nanoengineered ZIF fillers for mixed matrix membranes with enhanced CO₂/CH₄ selectivity. Separation and Purification Technology, 2023, 307: 122737

46 Liu B , Li D , Yao J , Sun H . Enhanced CO₂ selectivity of polyimide membranes through dispersion of polyethyleneimine decorated UiO-66 particles. Journal of Applied Polymer Science, 2020, 137(36): 49068

47 Liu B , Li Z , Li D , Sun H , Yao J . Polyzwitterion-grafted UiO-66-PEI incorporating polyimide membrane for high efficiency CO₂/CH₄ separation. Separation and Purification Technology, 2021, 267: 118617

48 Maleh M S , Raisi A . Preparation of high performance mixed matrix membranes by one-pot synthesis of ZIF-8 nanoparticles into Pebax-2533 for CO₂ separation. Chemical Engineering Research & Design, 2022, 186: 266–275