Advanced membrane separation based on two-dimensional porous nanosheets

doi:10.1007/s11705-024-2479-0

Front. Chem. Sci. Eng.

2024, Vol. 18

Issue (11) : 128 https://doi.org/10.1007/s11705-024-2479-0

Advanced membrane separation based on two-dimensional porous nanosheets

Yanli Zhang, Shurui Han, Fengkai Wang, Hui Ye(

), Qingping Xin(

), Xiaoli Ding, Lizhi Zhao, Ligang Lin, Hong Li, Yuzhong Zhang(

)

State Key Laboratory of Separation Membranes and Membrane Processes, School of Materials Science and Engineering, Tiangong University, Tianjin 300387, China

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Abstract

Two-dimensional porous nanosheets such as metal-organic frameworks, covalent organic frameworks, fluorides of light lanthanide, and perforated graphene oxide are a class of nanomaterials with sheet-like morphologies and defined pore structures. Due to their porous structure and large lateral sizes, these materials exhibit excellent molecular transport properties in separation processes. This review focuses on the pore formation strategies for two-dimensional porous nanosheets and applications of these nanosheets and their constructed membranes in gas separation processes and separation processes applicable to water treatment and the humidity control of gas permeation. A brief discussion of challenges and future developments of separation applications with two-dimensional porous nanosheets and their constructed membranes is included in this review.

Keywords two-dimensional porous nanosheets membranes gas separation water treatment humidity control

Corresponding Author(s): Hui Ye,Qingping Xin,Yuzhong Zhang

About author:

^#These authors contributed equally to this work.

Just Accepted Date: 24 May 2024 Issue Date: 13 August 2024

Cite this article:

Yuzhong Zhang,Hong Li,Ligang Lin, et al. Advanced membrane separation based on two-dimensional porous nanosheets[J]. Front. Chem. Sci. Eng., 2024, 18(11): 128.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2479-0
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I11/128

Scheme1 The method to synthesize the 2D porous MOF.

Fig.1 (a) Schematic of the fabrication process of IPM-1 nanosheet, atomic force microscope (AFM) and pore-size distribution of IPM-1. Reprinted with permission from Ref. [29], copyright 2022, Chinese Chemical Society. (b) AFM images and X-ray diffraction (XRD) patterns of FICN-12-MONs and FICN-12. Reprinted with permission from Ref. [30], copyright 2023, American Chemical Society. (c) Schematic of the fabrication process of Co-NH₂ MOF nanosheet; scanning electron microscope (SEM), energy dispersive spectrometer mapping, selected area electron diffraction (SAED) and AFM images of Co-NH₂. Reprinted with permission from Ref. [31], copyright 2024, Wiley-Blackwell.

Fig.2 (a) Surfactant-assisted solvothermal synthesis of CuBDC·DMF. Reprinted with permission from Ref. [32], copyright 2020, Elsevier. (b) Illustration of the preparation of ZIF-8. Reprinted with permission from Ref. [33], copyright 2023, Elsevier. (c) Illustration of 4 mol·L^–1 window of ZIF-8, SEM and AFM images of ZIF-8. Reprinted with permission from Ref. [34], copyright 2024, Elsevier.

Fig.3 (a) Illustration of Cu-TCPP synthesis via the interfacial method and AFM image of Cu-TCPP. Reprinted with permission from Ref. [35], copyright 2024, Elsevier. (b) Surface and cross-section SEM images of particles obtained at different concentrations. Reprinted with permission from Ref. [36], copyright 2013, Wiley-VCH Verlag GmbH. (c) Illustration of the assembly process of Ni₃(HITP)₂ and its transmission electron microscope (TEM) images. Reprinted with permission from Ref. [37], copyright 2024, Springer.

Scheme2 The method to synthesize the 2D porous COFs.

Fig.4 (a) SEM and TEM images of DhaTph and DhaTph CONs. Reprinted with permission from Ref. [38], copyright 2022, Royal Society of Chemistry. (b) Morphostructural characterization images of Tp-AD-50, Tp-Pa-50, and Tp-BD-50. Reprinted with permission from Ref. [39], copyright 2020, Elsevier. (c) Schematic illustration of the exfoliation procedure and AFM images. Reprinted with permission from Ref. [40], copyright 2024, Royal Society of Chemistry.

Fig.5 (a) Schematic process of porous COF synthesis via the template technique. Reprinted with permission from Ref. [41], copyright 2022, Elsevier. (b) Three-step fabrication procedure of porous COF membranes. Reprinted with permission from Ref. [42], copyright 2021, Wiley-VCH Verlag.

Fig.6 (a) Preparation of COFs via different methods and their pore size distributions. Reprinted with permission from Ref. [43], copyright 2024, Elsevier. (b) Illustration of 2D COF preparation at air-water interfaces via different methods. Reprinted with permission from Ref. [44], copyright 2021, American Chemical Society. (c) Illustration of COF at air-water interface and AMF images. Reprinted with permission from Ref. [45], copyright 2021, Wiley-Blackwell.

Fig.7 (a) Illustration of sNaCl@TpBD and released TpBD CONs. Reprinted with permission from Ref. [46], copyright 2020, Royal Society of Chemistry. (b) Illustration of COF growth at the liquid-solid interface. Reprinted with permission from Ref. [47], copyright 2023, Wiley-VCH Verlag.

Fig.8 (a) The structure of 2D porous inorganic F-Ln nanosheets. (b) microstructural analysis of F-Ln: a single disk-like TEM image, the corresponding SADE image, and the fast Fourier transform pattern. (c) SEM and AFM image of F-Ln. Reprinted with permission from Ref. [48], copyright 2019, American Chemical Society.

Fig.9 Exfoliation method for g-C₃N₄. (a) Ultrasonic exfoliation. Reprinted with permission from Ref. [54], copyright 2012, American Chemical Society. (b) Strong acid exfoliation. Reprinted with permission from Ref. [55], copyright 2013, Royal Society of Chemistry. (c) Thermal exfoliation. Reprinted with permission from Ref. [56], copyright 2015, Elsevier.

Fig.10 (a) Illustration of the preparation of NS-POPs and their SEM and TEM images. Reprinted with permission from Ref. [57], copyright 2024, Elsevier. (b) SEM and TEM images and pore size distribution of SnO₂ synthesized at different pH. Reprinted with permission from Ref. [58], copyright 2024, Royal Society of Chemistry. (c) Illustration of the preparation of CoP and its SEM images. Reprinted with permission from Ref. [59], copyright 2024, Elsevier.

Fig.11 (a) Illustration of the preparation of SAFe-NMPC and its SEM TEM images. Reprinted with permission from Ref. [60], copyright 2024, Royal Society of Chemistry. (b) Illustration of the preparation of Epi-MWW and its TEM images. Reprinted with permission from Ref. [61], copyright 2024, American Chemical Society. (c) Illustration of the preparation of PAM and its TEM images. Reprinted with permission from Ref. [62], copyright 2024, Science China Press.

Fig.12 (a) Illustration of a graphene monolayer suspended over a pore with a diameter of 5 μm. Reprinted with permission from Ref. [64], copyright 2015, Springer Nature. (b) TEM images of the fabrication procedure of porous MXene nanosheets. Reprinted with permission from Ref. [65], copyright 2021, Elsevier. (c) Illustration of ion transmission by chemical-etched nanoaperture and 2D slit pathways in layered MXene membranes. Reprinted with permission from Ref. [66], copyright 2022, American Chemical Society. (d) Schematic of the membrane fabrication procedure by combining slot die-coating and hot pressing processes. Reprinted with permission from Ref. [67], copyright 2023, Elsevier.

Fig.13 (a) SEM, TEM, and AFM images and pore size distribution of rGO. Reprinted with permission from Ref. [68], copyright 2015, Elsevier. (b) Illustration of nanoporous GO preparation by ion beam irradiation. Reprinted with permission from Ref. [69], copyright 2020, Elsevier. (c) Illustration of the fabrication procedure of porous GO. Reprinted with permission from Ref. [70], copyright 2023, Elsevier. (d) Illustration of rPGO synthesis, and its TEM images and AFM images. PDA, polydopamine. Reprinted with permission from Ref. [71], copyright 2023, Elsevier.

Fig.14 (a) Preparation process of F-Ln nanosheets and SEM images of Pebax/F-Ln MMMs. Reprinted with permission from Ref. [75], copyright 2023, Elsevier. (b) Morphostructures of f-F-Ce at different scales and Pebax/f-F-Ce MMMs incorporating 4%, 8%, 12% and 16%. Reprinted with permission from Ref. [76], copyright 2020, American Chemical Society. (c) Illustration of PEI-F-Ce nanosheet; TEM image, SAED pattern, and high-intensity diffraction spot of PEI-F-Ce-2.5. Reprinted with permission from Ref. [77], copyright 2023, Elsevier.

Fig.15 (a) Illustration of UV etching on suspended graphene. Reprinted with permission from Ref. [79], copyright 2012, American Association for the Advancement of Science. (b) Isolation of smaller defects of the support hole diameter and flow resistance. Reprinted with permission from Ref. [80], copyright 2017, American Chemical Society.

Fig.16 (a) TEM images of graphene modified via gold deposition. Reprinted with permission from Ref. [81], copyright 2022, Wiley-Blackwell. (b) Schematic of PNG membrane fabrication. Reprinted with permission from Ref. [82], copyright 2024, American Chemical Society.

Fig.17 (a) Picture showing the spatial arrangement of CuBDC MOF nanosheets. Reprinted with permission from Ref. [83], copyright 2015, American Association for the Advancement of Science. (b) Schematic of the production of MMMs through the formation of H-bonds by finely designed MOF nanosheets. Reprinted with permission from Ref. [84], copyright 2022, Elsevier. (c) The structure of interfacial coordination interaction. Reprinted with permission from Ref. [85], copyright 2020, American Chemical Society. (d) Fabrication process and pore size distribution of a_gfZIF-62. Reprinted with permission from Ref. [86], copyright 2023, Springer Nature.

Fig.18 (a) SEM and TEM images of as-synthesized Zn₂(bim)₄ crystals and MSNs; pore size distribution of Zn₂(bim)₄ nanosheet. Reprinted with permission from Ref. [88], copyright 2014, American Association for the Advancement of Science. (b) Schematic of the exfoliation and Zn₂(Bim)₃ assembly procedure. Reprinted with permission from Ref. [89], copyright 2017, John Wiley and Sons Ltd. (c) Schematic representation of bimetallic (Zn/Co)₂(bim)₄ nanosheet membranes prepared by transforming a layer of Zn/Co-HDS through the vapor phase transformation method. Reprinted with permission from Ref. [90], copyright 2022, Elsevier. (d) Schematic cross-sections of pure Zn₂(bim)₄ nanosheet membrane and N-Zn₂(bim)₄ nanosheet membrane. Reprinted with permission from Ref. [91], copyright 2023, John Wiley and Sons Ltd.

Fig.19 (a) Illustration of COF preparation and its stacking models. Reprinted with permission from Ref. [92], copyright 2016, Wiley-VCH Verlag. (b) Pore size distribution and cross-sectional SEM images of nanosheets and PDA@TD-COF/PIM-1 MMMs. Reprinted with permission from Ref. [93], copyright 2023, Elsevier. (c) SEM and TEM images of TpPa-1 nanosheets and MMMs. Reprinted with permission from Ref. [94], copyright 2023, Elsevier.

Fig.20 (a) Schematic of the fabrication of COF-LZU1-ACOF-1 membranes via variable-temperature solvothermal method. Reprinted with permission from Ref. [95], copyright 2018, American Chemical Society. (b) Schematic of the staggered stacking of CON membranes. Reprinted with permission from Ref. [96], copyright 2020, American Chemical Society. (c) Illustration of TpPa-1, TpPa-2, and TpHz nanosheets. Reprinted with permission from Ref. [26], copyright 2021, John Wiley and Sons Ltd.

Membranes	Gas permeability	Selectivity	Ref.
Pebax 1657/F-Nd-6%	$P C O 2$ 1265 Barrer	$α C O 2 / C H 4$ 35.7	[75]
Pebax 1657/f-F-Ce-8%	$P C O 2$ 1823 Barrer	$α C O 2 / C H 4$ 35	[76]
XLPEO/PEI-F-Ce-2%	$P C O 2$ 641 Barrer	$α C O 2 / N 2$ 70.1	[77]
GO membrane	$P O 2$ 29 Barrer	$α O 2 / N 2$ 6	[78]
Au-coated double-layer graphene	$P H 2$ 2.23 × 10⁵ GPU	$α H 2 / C O 2$ 31.3	[81]
6FDA-durene-DABA/CBMN MMMs	$P C O 2$ 400 Barrer	$α C O 2 / C H 4$ 23	[85]
Amino-functionalized Zn₂(bim)₄ nanosheet membranes	$P H 2$ 1417 GPU	$α H 2 / C O 2$ 1158	[91]
3% PDA@TD-COF	$P C O 2$ 9750.6 Barrer	$α C O 2 / N 2$ 26.4	[93]
TpPa-2 nanosheet membranes	$P C O 2$ 328 GPU	$α C O 2 / H 2$ 22	[26]

Tab.1 Gas separation performance of various membranes published in literature

Fig.21 (a) Schematic of the polyelectrolyte-mediated assembling technique for preparing an ultrathin COF membrane. Reprinted with permission from Ref. [97], copyright 2023, Wiley-VCH Verlag. (b) Schematic of AC₄tirmTpPaSO₃ preparation and TEM images of AC₄tirmTpPaSO₃ COF. Reprinted with permission from Ref. [98], copyright 2023, Wiley-VCH Verlag. (c) Schematic of ionic COFs preparation and TEM images of ionic COFs. Reprinted with permission from Ref. [99], copyright 2024, Elsevier. (d) Synthesis of ultrathin COF membranes of narrow aperture by multi-interfacial techniques. Reprinted with permission from Ref. [100], copyright 2022, Wiley-Blackwell.

Fig.22 (a) Illustration of COF-polymer membrane application; (b) evolution of the morphology and crystallinity of COF composite membranes. Reprinted with permission from Ref. [27], copyright 2019, Royal Society of Chemistry.

Fig.23 (a) Illustration of water vapor transport channels in MMMs. (b) Comparison of permeability and H₂O/N₂ selectivity of various materials. Reprinted with permission from Ref. [28], copyright 2022, Springer Nature.

Fig.24 (a) Illustration of GO coating routes and humidity dependence of water vapor permeability. Reprinted with permission from Ref. [103], copyright 2019, Elsevier. (b) Illustration of filtration and casting of GO layers. Reprinted with permission from Ref. [104], copyright 2023, Multidisciplinary Digital Publishing Institute.

Fig.25 (a) Illustration of calcination and reconstruction processes. (b) Illustration of the coating process and tortuous pathway. (c) Error bars indicate the standard deviation of two or more measurements. Reprinted with permission from Ref. [105], copyright 2019, Springer Nature.

Fig.26 (a) Fabrication process of (LDH/CMC)_n membranes. (b) XRD patterns and SEM image of LDH nanosheets. (c) Diagram of gas transport mechanism. (d) Water vapor selectivity and percentage of gas transmission of (LDH/CMC)_n membranes (n = 0–30). Reprinted with permission from Ref. [106], copyright 2018, American Chemical Society.

Tab.2 Humidity control of various membranes published in literature

Fig.27 (a) Fabrication process of UiO-66-NH₂ derived hollow fiber membranes and their water adsorption isotherms. Reprinted with permission from Ref. [107], copyright 2023, Elsevier. (b) Illustration of PFSA/MOF membrane fabrication and temperature curves of different membranes. Reprinted with permission from Ref. [108], copyright 2019, Elsevier.

Fig.28 (a) Schematic of graphene pore preparation and computer simulation results of water and salt passing through the membrane. Reprinted with permission from Ref. [109], copyright 2012, American Chemical Society. (b) Fabrication of the membrane. Reprinted with permission from Ref. [110], copyright 2014, American Association for the Advancement of Science. (c) Observation of pore formation processes and comparison of experimental and computational diffusion permeabilities. Reprinted with permission from Ref. [111], copyright 2014, American Chemical Society. (d) Water transport measurements and desalination experiments. Reprinted with permission from Ref. [64], copyright 2015, Springer Nature.

Fig.29 (a) Morphology and formation process of nanomesh. Reprinted with permission from Ref.[112], copyright 2010, American Chemical Society. (b) Schematic representation of the water permeability of GNM/SWCNT membrane and its salt separation properties. Reprinted with permission from Ref. [113], copyright 2019, American Association for the Advancement of Science. (c) Separation performance of GO, pGO, H/GO and H/pGO membranes and the paths of water across these membranes. Reprinted with permission from Ref. [114], copyright 2021, Elsevier.

Fig.30 (a) g-C₃N₄ nanosheet and its membrane separation performance. Reprinted with permission from Ref. [115], copyright 2017, John Wiley and Sons Ltd. (b) Simulation plots and radial distribution function of water in nanoporous g-C₃N₄ membrane in the presence of different cations. Reprinted with permission from Ref. [116], copyright 2018, Elsevier Ltd. (c) Images of g-C₃N₄ nanosheet and MB/g-C₃N₄ membrane and its separation performance. Reprinted with permission from Ref. [117], copyright 2019, John Wiley and Sons Ltd. (d) Schematic of 2D heterostructured nanofluidic channels and the desalination properties of the membrane. Reprinted with permission from Ref. [118], copyright 2021, American Chemical Society.

Fig.31 (a) Route to smaller pores in membrane and their separation performance. Reprinted with permission from Ref. [121], copyright 2020, Springer Nature. (b) Membrane construction process and ion transport properties. AAO, anodized aluminum oxide. Reprinted with permission from Ref. [122], copyright 2021, Wiley-Blackwell.

Fig.32 (a) Secondary growth of ACOF-1 composite membrane and its flux and rejection. Reprinted with permission from Ref. [123], copyright 2021, Elsevier. (b) Morphology and separation performance of TpPa-COF membrane. Reprinted with permission from Ref. [124], copyright 2021, American Association for the Advancement of Science.

Fig.33 (a) Porous MoS₂ nanosheets, nanodisks and their laminated membrane. Reprinted with permission from Ref. [125], copyright 2020, Springer Nature. (b) Nanofiltration performance of o-2DZTC membrane. Reprinted with permission from Ref. [126], copyright 2023, American Association for the Advancement of Science. (c) Schematic of F-Ce nanosheets membrane formation and its separation properties. Reprinted with permission from Ref. [127], copyright 2022, Elsevier.

Fig.34 (a) Schematic of the in situ growth of MIL-53-NH₂ MOFs, the measured flux of AAO and AAO/MIL-53-NH₂ membrane. Reprinted with permission from Ref. [128], copyright 2017, John Wiley and Sons Ltd. (b) Characterization of g-C₃N₄ sheets and g-C₃N₄ nanosheets and the separation performance of g-C₃N₄ nanosheets/SA/PVDF membrane for oil-in-water emulsions. Reprinted with permission from Ref. [129], copyright 2021, John Wiley and Sons Ltd.

Fig.35 (a) Characterization of g-C₃N₄ nanosheet, SEM image of the surface and cross-sectional SEM images of g-C₃N₄ membrane. Reprinted with permission from Ref. [131], copyright 2019, Elsevier. (b) Illustration of the preparation of g-C₃N₄ bulks and their liquid phase exfoliation and conversion efficiency of three different types of g-C₃N₄. Reprinted with permission from Ref. [131], copyright 2016, Royal Society of Chemistry.

Tab.3 Water treatment application of various membranes in literature

Fig.36 (a) Solvent permeation simulation system and the solvent flow through MoS₂ membrane. Reprinted with permission from Ref. [132], copyright 2022, Royal Society of Chemistry. (b) SEM and TEM images of Zr-BDC and Cu-BDC and the molecular weight cutoff of M_Zr-10 and M_Cu-10. Reprinted with permission from Ref. [133], copyright 2024, Elsevier. (c) Illustration of the fabrication of Cu-BDC/CNT composite membranes and their methanol permeance and chronic rejection. Reprinted with permission from Ref. [134], copyright 2024, Elsevier.

Fig.37 (a) Illustration of the fabrication of GO hybrid membrane and its rejection performance. Reprinted with permission from Ref. [135], copyright 2024, American Chemical Society. (b) Illustration of the preparation of CTF membrane, its separation performance for different dye molecules, and comparison with other membranes published in literature. Reprinted with permission from Ref. [136], copyright 2024, Elsevier.

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