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Recent advances in the interfacial engineering

Cite this: Nanoscale, 2024, 16, 7716
of MOF-based mixed matrix membranes for gas
separation
Shuwen Yu,a,b Conger Li,b,c Shuke Zhao,b Milton Chai, b
Jingwei Hou *b and
Rijia Lin *b
Published on 06 March 2024. Downloaded on 11/10/2024 [Link] AM.

The membrane process stands as a promising and transformative technology for efficient gas separation
due to its high energy efficiency, operational simplicity, low environmental impact, and easy up-and-
down scaling. Metal–organic framework (MOF)–polymer mixed matrix membranes (MMMs) combine
MOFs’ superior gas-separation performance with polymers’ processing versatility, offering the opportunity
to address the limitations of pure polymer or inorganic membranes for large-scale integration. However,
the incompatibility between the rigid MOFs and flexible polymer chains poses a challenge in MOF MMM
fabrication, which can cause issues such as MOF agglomeration, sedimentation, and interfacial defects,
substantially weakening membrane separation efficiency and mechanical properties, particularly gas sep-
aration. This review focuses on engineering MMMs’ interfaces, detailing recent strategies for reducing
Received 8th January 2024, interfacial defects, improving MOF dispersion, and enhancing MOF loading. Advanced characterisation
Accepted 6th March 2024
techniques for understanding membrane properties, specifically the MOF–polymer interface, are outlined.
DOI: 10.1039/d4nr00096j Lastly, it explores the remaining challenges in MMM research and outlines potential future research
[Link]/nanoscale directions.

a
School of Chemistry and Chemical Engineering, Suzhou University, Suzhou, 234000,
1 Introduction
China
b
School of Chemical Engineering, The University of Queensland, St Lucia, QLD,
Membrane separation is an energy-efficient technology with a
4072, Australia. E-mail: r.lin1@[Link], [Link]@[Link] low carbon footprint, which can be widely adopted in indus-
c
School of Physical Science and Technology, Shanghai Tech University, Shanghai, trial separations.1–3 Polymer membranes stand out as domi-
201210, China nant due to their exceptional processability, widespread avail-
ability, and satisfactory mechanical properties, making them
well-suited for a variety of gas separation applications.3
Dr Rijia Lin received his PhD However, most conventional polymer membranes face an
degree in 2016 from the inherent trade-off between the mass transport rates and separ-
University of Queensland. He is ation efficiency, on top of operational stability against challen-
currently an Australian Research ging conditions.1
Council (ARC) Discovery Early Nanoporous materials, such as zeolites and MOFs, have
Career Research (DECRA) Fellow been considered as potential membrane materials to offer sim-
at the School of Chemical ultaneously high gas permeability and selectivity due to their
Engineering, the University of well-defined pore structures. MOFs have been widely studied
Queensland. He was a recipient as membrane materials due to their large surface area, rich
of the 2021 Early Career chemical functionality, and tunable pore size and porosity.4
Researcher Award from the Continuous MOF crystalline membranes showed impressive
Australian Institute of Nuclear performance in advanced gas purification, demonstrating
Rijia Lin Science and Engineering. His potential for precise sieving and breaking the permeation-
main research interests include selectivity trade-off.5–10 Nevertheless, the large-area fabrication
the design and synthesis of metal–organic framework composites of defect-free and selective MOF crystalline membranes
and porous glass materials, focusing on membrane gas separation remains challenging because controlling the intercrystalline
and catalysis. defects and grain boundary is difficult.

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In order to overcome the limitations associated with pure interfacial structure and interactions. Consequently, the most
polymer or MOF crystalline membranes, MOF-based MMMs recent design strategies for addressing the interfacial compat-
have emerged as promising membrane configurations with ibility and MOF dispersion issues are summarised. The last
MOFs as dispersed fillers within the continuous polymer part offers a concise perspective for the future advancement of
matrix.11 Utilising a polymer matrix offers excellent processa- MMMs and inspires researchers with more strategies to facili-
bility and mechanical stability complemented by nanoporous tate the implementation of membranes in practical
MOF fillers featuring a tunable pore system for efficient gas applications.
transport and molecular sieving, ultimately culminating in a
substantial enhancement of membrane separation
performance.12,13 Therefore, the selection of the MOF–polymer
pair is critical, as it determines the compatibility between the 2 Challenging fabrication of MOF-
two phases and significantly influences the performance of
based MMMs
membrane separation. However, the effective incorporation of
MOF fillers into polymer matrices and achieving an ideal inter- While the combination of MOFs and polymers in MMMs
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facial morphology remain difficult because of the intrinsic holds great promise for advanced membrane applications,
differences between the MOF and polymer phases. The fabrica- addressing the challenges of MOF agglomeration, interfacial
tion of MOF MMMs is often accompanied by the formation of compatibility, and mechanical properties in MMMs is crucial
interfacial defects and agglomeration of MOF fillers, especially for unlocking the full potential of MOFs. This section summar-
at high filler loadings (>30 vol%), resulting in deterioration in ises and compares the preparation methods of MMMs from
membrane selectivity and mechanical properties.14,15 two perspectives: symmetric MMMs and thin-film nano-
Recent advancements in the fabrication of MOF-based composite (TFN) membranes with an ultrathin MMM layer.
MMMs incorporate meticulous interfacial engineering, pre- A common way to prepare symmetric MMMs is through the
senting prospects for scalable MMM production while main- solution blending method, which involves the preparation of
taining exceptional separation capabilities. While there have polymer–MOF suspensions, membrane casting, and solvent
been several excellent reviews on MOF-based MMMs published removal.14 Some examples of commonly used polymer
previously, this review will cover a gap by also exploring a rela- matrices are PIM-1,19,20 6FDA-polyimide,15,18 Matrimid,21 and
tively newer group of MOFs exhibiting glass transition behav- Pebax.22 To mitigate the agglomeration of MOF fillers, MOF
iour known as MOF glass.3,13,16,17 This review will place a particles were typically dispersed in a solvent prior to the
strong emphasis on the engineering of MOF and polymer addition of the polymer. Alternatively, MOFs were dispersed in
interfaces given its importance in improving the gas separ- a solvent and the polymer was dissolved in another solvent
ation performance (Fig. 1).18 First, a concise discussion of the separately followed by adding the MOF suspension to the
major technical issues encountered in membrane fabrication polymer solution.11,16 The after-mixed polymer–MOF suspen-
will be provided, followed by advanced characterisation tech- sion was spread onto a level surface through casting or spin
niques to gain an in-depth understanding of the membrane coating, followed by solvent evaporation at a specific tempera-

Fig. 1 Schematic diagram of the interfacial engineering of MOF-based MMMs (the schematic illustration of the matrix design is reproduced with
permission from ref. 18 and copyright 2023 by AAAS Publishing).

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ture or pressure. The simplicity of this operation has made it the aqueous and organic phase monomers during the inter-
the most extensively used approach for preparing MMMs. facial polymerisation.
Interfacial issues between the MOF fillers and the polymer To optimise the dispersion of MOF nanofillers and MOF–
matrix are critical in creating desirable MMMs.23 The poor polymer interfacial compatibility, the utilisation of in situ syn-
interfacial interaction can lead to nonselective voids or cracks thesis for MOF fillers within TFN membranes represents an
between the two components and damage the performance of alternative strategy.14,35 Recent reports indicate that this
the membranes. Various methods have been explored to approach has achieved significant advancements in enhancing
improve interfacial compatibility, such as modifying MOFs interfacial compatibility and MOF loading, resulting in a sub-
with functional groups or polymer chains,24,25 and using MOF stantial improvement in separation performance for MOF-
nanosheets with high surface area to volume ratios,15 more based MMMs. In addition, some other techniques, including
specific examples are highlighted in Section 4. spin-coating,15,36 dip-coating,37,38 and solution casting,39 were
In addition, MOF loading in preparative MMMs is a crucial considered to prepare TFN membranes according to their
factor. A greater number of molecular sieving channels can be different advantages in lab-scale research and cost-effective
generated by higher MOF loading, but it is difficult to achieve processes. For example, Datta et al. prepared a [001]-oriented
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MMMs with uniformly dispersed MOF fillers due to their ultrathin membrane on a porous support with aligned MOF
agglomeration. To mitigate MOF agglomeration in MMMs, the AlFFIVE-1-Ni nanosheets by spin-coating.15 The dip-coating
modulation of MOF fillers is related to the MOF geometry and technique is suitable for preparing an ultrathin selective layer
modification. For example, the MOF geometry can be adjusted on the surface of hollow fibres.37 The solution casting method
by manipulating the synthesis conditions, including the reac- is ideal for the large-scale and continuous production of TFN
tion solvent,26 temperature, concentration, and modulators membranes. Qiao et al. successfully prepared ultrathin and
(e.g., acids, bases or surfactant).27,28 At the same time, the rollable MOF membranes on a polysulfone (PSf ) support with
amount of MOF loading can also affect the mechanical pro- a large area of 2400 cm2 through solution casting followed by
perties of the membranes. A higher MOF loading often MOF growth.40 These studies have shown promise in improv-
decreases the mechanical integrity provided by the polymer ing membrane performance by integrating MOF fillers into the
matrix, making it crucial to balance MOF loading and mem- ultrathin selective layer of TFN membranes.
brane properties. Ultimately, the interfacial issues, MOF In addition, MOF glass is a promising candidate for solving
loading, and mechanical integrity are closely related and challenges in MOF-based membranes, which can be prepared
decide the entire separation performance of the membranes. by melting and then quickly cooling certain MOF crystals.41
On the other hand, gas permeance is a pivotal membrane Recently, MOF glasses have attracted much attention in MOF
parameter that dictates its effectiveness for achieving separ- crystal–glass composite (CGC)42–45 and MOF glass–polymer
ation performance.29 It measures the rate at which gas mole- composite membranes,46,47 attributed to their high processa-
cules can pass through the membrane and is inversely related bility, structural tunability, and enhanced porosity. The fasci-
to the membrane’s thickness. In other words, the thinner the nating properties endow MOF glass with great superiority for
membrane, the faster the gas molecules can penetrate through eliminating intergrain boundary defects, like crystal lattice
it. Therefore, TFN membranes, which comprise an ultrathin mismatches and cracks.
selective layer of MMMs and a porous support with strong It is important that the efforts made in addressing the
mechanical properties, contribute significantly to enhance gas different challenges faced in MOF-based MMM fabrication are
permeance and overcome the restriction of the mechanical complemented by appropriate advanced characterisation tools.
integrity of MMMs.12,23,30,31 Recently, TFN membranes have The following section will discuss the most suitable character-
attracted considerable interest in membrane research owing to isation techniques that can be used to probe the interfacial
the incorporation of distinctive nanofillers and their pro- properties, defects, MOF loading and dispersion in MOF-
duction scalability. based MMMs.
TFN membranes can be prepared using the in situ inter-
facial polymerisation technique, which can foster chemical
bonding between the polymer and the filler, thereby improving 3 Advanced characterisation
interfacial compatibility.32 Nevertheless, the high concen- techniques
tration of MOF particles in solution poses a challenge due to
their poor dispersibility, which easily aggregates on the Appropriate advanced characterisation techniques are critical
support surface during the interfacial polymerisation in tackling the challenges faced by MMMs by providing a
process.33,34 Addressing the challenges associated with thorough understanding of the MOF and polymer properties
agglomerated MOFs in TFN membranes involves surface and interactions in the interface region. Advanced characteris-
engineering of MOFs to enhance the dispersity and careful ation techniques offer excellent opportunities to comprehend
control of production processes to prevent sedimentation and the interfacial morphologies and interfacial properties of
agglomeration. Furthermore, achieving optimal loading of MMMs. This section provides a detailed introduction to the
MOF fillers into ultrathin selective layers also poses a chal- existing techniques for evaluating the MOF–polymer compat-
lenge, primarily attributed to the brief reaction time between ibility and determining MOF particle size and distribution

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within the polymer matrix, quantifying the volume fraction of provided by TEM (Fig. 2a–c).48,49 Moreover, it enables the
interfacial defects, probing MOF–MOF and MOF–polymer examination of the MOF–polymer interfacial, as shown by the
interfacial interactions, and monitoring the thicknesses and varying degrees of interfacial tears along the direction of the
adsorption properties of thin films. knife cut. These tears occur due to differential shear stress
levels experienced during the cutting process, making the
3.1 Electron microscopy mechanical interplay within the composite material more visu-
Scanning electron microscopy (SEM), transmission electron ally discernible.18
microscopy (TEM) and tomographic-focused ion beam scan- Tomographic FIB-SEM can quantitatively provide 3D infor-
ning electron microscopy (FIB-SEM) are critical and extensively mation on the membrane interfacial structure, demonstrating
employed techniques for characterising membrane interfacial the distribution and volume fraction of various phases within
morphologies, in particular for filler distribution and inter- MMMs, including fillers, matrices and interfacial voids/
facial defects. defects.27,50 In this process, a trench is created on the upper
Scanning electron microscopy (SEM) is a traditional tech- surface of the membrane by applying a FIB, followed by cap-
nique applied to qualitatively investigate the dispersion of turing a series of SEM images of the cross-sections at sequen-
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MOFs and their interfacial issues with the polymer through tial intervals during FIB milling. The alignment and stacking
the morphology of the cross-section of MMMs. In order to of these images allow for the segmentation of individual
obtain SEM samples featuring an exposed membrane cross- phases (fillers, matrices and interfacial voids) in the mem-
section, the membranes are often soaked in liquid nitrogen to brane through image thresholding, offering three-dimensional
induce a brittle fracture. SEM allows for direct visualisation of surface-render views and phase distributions of the membrane
the MOF distribution and interfacial morphology within the and providing the volume fraction of interfacial defects.
MMMs at a high magnification and resolution. It is important Rodenas et al. used tomographic FIB-SEM to investigate the
to note that the efficacy of this process highly depends on the internal structure of MMMs with different forms of MOF
polymer’s properties, which can influence how quickly and fillers, such as bulk-type nanoparticles or nanosheets (Fig. 2d–
uniformly the polymer cools and contracts, which can, in turn, g).27 The study results indicate that CuBDC nanosheets were
affect the fracture behaviour and the quality of cross-section more uniformly dispersed in the polymer than other forms of
images. As a result, it may fail to accurately represent the orig- Cu-BDC when the same amount of a filler was used in the
inal structure and properties of the MMMs. On the other MMMs. Chi et al. introduced branched HKUST-1 nanoparticles
hand, cutting the membrane into ultrathin slices, typically into polyimides to form a uniform branched MOF network
ranging from 50 to 150 nm, using an ultramicrotome for TEM within the matrix.51 Tomographic FIB-SEM was applied to
analysis is another effective technique. This method facilitates confirm the connectivity of branched HKUST-1 in the matrix,
the observation of particle dispersion due to the stark contrast showing the highly interconnected nanostructures.

Fig. 2 (a) Scheme of cutting ultrathin slices by using ultramicrotome. Reproduced with authorisation from ref. 48 and copyright 2018 by American
Chemical Society. (b and c) TEM images of an ultrathin slice (100 nm) of MMMs with incompatible interfaces and compatible interfaces (the scale
bar is 1 mm). Reproduced with authorisation from ref. 49 and copyright 2021 by Wiley-VCH GmbH. (d) SEM image of MOF-based MMMs with a
trench-formed surface using a FIB. (e) Orthogonal cross-sectional views derived from the 3D-converted FIB-SEM tomogram of the composite
material consisting of a MOF and a polymer. Segmented FIB-SEM tomograms of MMMs including MOF fillers with the geometry of bulk type (f ) and
nanosheets (g). Reproduced with authorisation from ref. 27 and copyright 2015 by Springer Nature.

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3.2 Positron annihilation lifetime spectroscopy (PALS) intensities were reduced according to the extended EXAFS
PALS can detect pore size information, free volumes, and profile (Fig. 4a). Besides, significant changes were found in the
depth profiles in thin films by using positrons as the probe.52 peaks of Cu–Cu and Cu–C when comparing MOF nanosheets
The technique involves measuring the time between positron and crystals. These changes can be ascribed to the irregular
implantation and annihilation by detecting the emitted coordination between the organic ligands and the metal ions
gamma rays (Fig. 3a), and the pore radius can be derived by in the MOF nanosheets (Fig. 4b and c). Ao et al. analysed the
fitting either a continuous range of lifetimes or a set of dis- local structure of Zn in MOF CGC membranes using XAS
crete lifetimes (Fig. 3b). Compared with other routine physi- (Fig. 4d–f ).45 The resulting XANES and EXAFS R-plot showed
sorption methods, PALS can offer significant flexibility in that all MOF CGC membranes had the same coordination
terms of the material form and sample quantity. Zhu et al. numbers and distances, suggesting no new formation of
detected the free volume size and distribution in ZIF-8/PIM-1 coordination sites.
MMMs using PALS (Fig. 3c).36 Increased pore radii were
observed in MMMs compared to those of pristine PIM-1 owing 3.4 Small-angle X-ray scattering (SAXS)
to the porous structure of the MOF (ZIF-8) and loose chain SAXS offers multiple characteristics at the nanometre scale,
Published on 06 March 2024. Downloaded on 11/10/2024 [Link] AM.

packing after incorporating the MOF into PIM-1. This finding such as the particle size, shape, distribution, and porous struc-
was similar to that of the N2 isotherm test, which confirmed ture, which is an effective approach for analysing the nanopor-
that the chain rearrangement in PIM-1 is crucial to enhance ous structure and filler distribution in MMMs and then
the membrane’s ability for molecular sieving. Besides, Yang obtaining the impact of membrane structure on gas transport
et al. analysed the correlative pore size distributions of properties.55–59
ZIF-62 glass (agfZIF-62) and ZIF-62 glass foam (agfZIF-62) from Li et al. studied the effect of water in PSf (wet and dry) on
the PALS data, which proved the improved pore continuity and the penetrating PDMS layer by analysing the porous structure
porosity of agfZIF-62 compared to those of agZIF-62 (Fig. 3d).53 of the PDMS/PSf composite membrane using SAXS.58 The
strong scattering signal arises from the variations of electron
3.3 X-ray absorption spectroscopy (XAS) density in the membrane, encompassing a radius range of
XAS, comprised of X-ray absorption near-edge structure 1–100 nm (Fig. 5a). The pore volume fraction in the PDMS/PSf
(XANES) and extended X-ray absorption fine structure (EXAFS), (dry) (D-100) membrane is less than that in the PSf membrane,
can provide insights into the electronic structure and coordi- suggesting that the infiltrating PDMS occupied specific pores
nation environments of the metals in MOFs and MOF MMMs. in the PSf membrane that in the D-100 membrane with a
Liu et al. studied the coordination properties in MOF crystals radius of 10 to 30 nm (Fig. 5b). Kang et al. investigated the
and nanosheets using ex situ XAS.54 The result showed that the filler dispersion and structure alteration at the nanoscale for
Cu–O distance in the MOF nanosheets was similar to that in MMMs with different MOF (UiO-67 and MIL-140C) loadings
the MOF crystals in the main peak at 1.44 Å, but the peak by SAXS (Fig. 5c and d).60 The Kratky plot (q vs. q2I) of the
poly(glycidyl methacrylate-co-poly(oxyethylene methacrylate))
(PGO) copolymer showed a plateau at an elevated q value, sig-
nifying an extended or pliable structure. In contrast, the

Fig. 3 (a) Schematic diagram of PALS for porous materials and (b) pore
radius determined by employing an appropriate model based on the
ortho-positronium (o-Ps) lifetime. Reproduced with authorisation from Fig. 4 (a) EXAFS spectra of MOF crystals and nanosheets. Suggested
ref. 52 and copyright 2021 by Wiley-VCH GmbH. (c) PALS data of structures of (b) MOF crystals and (c) nanosheets deduced from the ana-
PIM-1 membranes with different MOF fillers. Reproduced with authoris- lysis of EXAFS. Reproduced with authorisation from ref. 54 and copyright
ation from ref. 36 and copyright 2023 by Springer Nature. (d) Pore size 2021 by The Royal Society of Chemistry. (d) Normalized XANES spectra
distributions of MOF glasses obtained by PALS. Reproduced with author- and (e) EXAFS R-plots of MOF CGC membranes. Reproduced with auth-
isation from ref. 53 and copyright 2023 by Springer Nature. orisation from ref. 45 and copyright 2023 by Wiley-VCH GmbH.

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Fig. 6 (a) QCM porosimetry. Reproduced with authorisation from ref.

52 and copyright 2021 by Wiley-VCH GmbH. (b) QCMD thickness–time
plots of the thin film composite membrane. Reproduced with authoris-
Published on 06 March 2024. Downloaded on 11/10/2024 [Link] AM.

ation from ref. 63 and copyright 2017 by Elsevier. Sorption isotherms of

(c) C3H6 and (d) C3H8 for 6FDA-DAM thin films with varying thicknesses
Fig. 5 (a and b) Pore volume distributions of PSf, PDMS/PSf (wet) determined by the QCM. Reproduced with authorisation from ref. 64
(W-100) and PDMS/PSf (dry) (D-100) membranes. Reproduced with and copyright 2022 by Elsevier.
authorisation from ref. 58 and copyright 2019 by Elsevier. (c and d) SAXS
patterns of MMMs containing UiO-67 or MIL-140C. Reproduced with
authorisation from ref. 60 and copyright 2022 by Elsevier.
3.6 Terahertz/far-infrared (THz/far-IR) spectroscopy
THz/far-IR spectroscopy technique has received attention in
Kratky plot of MMMs revealed a bell-shaped curve, suggesting
studying materials’ structural and dynamic properties, such as
a condensed structure. This observation implies that the PGO
MOF glass or MOF CGCs.65–67 Hou et al. were the first to use
copolymer matrix proficiently enveloped the evenly dispersed
THz/Far-IR to study MOF melting and halogenation within the
MOF particles. Moreover, it was observed that the diffraction
liquid MOF phase. They found Zn–F bond formation in fluori-
peak position ratio varied for PGO/UiO-67 MMMs, which
nated MOF glasses, resulting from the interaction between
suggested that the PGO matrix adeptly constrained the
uncoordinated Zn and F on the benzene ring during the phase
UiO-67 particles, causing a modification in the regular
transition formation process (Fig. 7a).65 Lin et al. applied THz/
arrangement of particles. Nevertheless, the SAXS profiles of
Far-IR to investigate the metal–N bonding environment in the
PGO/MIL-140C MMMs showed a unique peak, presumably
crystal and glass state of ZIF-62(Co) and bimetallic MOF
attributed to the substantial and irregular size of the
(ZIF-62(Co)-Fe) glass, respectively.66 Compared with ZIF-62(Co)
MIL-140C particles.
crystals and ZIF-62(Co) glass (agZIF-62(Co)) in Fig. 7b, the new
peaks of ZIF-62(Co)-Fe crystals and ZIF-62(Co)-Fe glass
3.5 Quartz crystal microbalance (QCM)
(agZIF-62(Co)-Fe) at 219 and 344 cm−1, attributed to the Fe–N
A QCM with dissipation is a precise and sensitive technique stretching vibration, conformed the formed Fe–N bonding in
for analysing the thicknesses and adsorption properties of the liquid MOF ZIF-62(Co)-Fe state (Fig. 7c). While THz/far-IR
thin films by monitoring the oscillation of a crystal spectroscopy has not been used to analyse membrane pro-
sensor.61,62 This characterisation method relies on thin piezo- perties, this technique can be translated into the study of the
electric quartz crystals that oscillate at a resonance frequency interfacial properties within the composites. For example, the
under the influence of an alternating voltage. The oscillation alterations of interfacial bonding within the mixture of
frequency shifts (Δν) in correlation with the increase in film (CsPbI3)0.25(agZIF-62)0.75 were obtained using THz/far-IR.68
mass caused by adsorption (Δm) (Fig. 6a).52 Song et al. uti- Therefore, based on these findings, THz/far-IR can also be
lised QCM measurements to determine the thickness of the effectively used to study the interfacial interactions between
ultrathin selective layer in a thin film composite (TFC) mem- the MOF and the polymer in MMMs.
brane by analysing the ratio of the deposited amount to their
density (Fig. 6b).63 To enhance the comprehension of the cor-
relation between the thickness and the C3H6/C3H8 separation 4 Design strategies of MMMs
performance of 6FDA-DAM TFC membranes, a QCM was also
used to investigate the gas sorption properties of these films Considering the known challenges in fabricating MOF-based
(Fig. 6c and d).64 The sorption isotherms obtained by the MMMs (Section 2) and a suite of advanced characterisation
QCM for 6FDA-DAM thin films are closely match with those techniques (Section 3) for these membranes, it is worth dis-
obtained by the dual-mode sorption model, which confirms cussing the various strategies that can be employed to design a
the precision and dependability of the QCM technique in high-performing MMM. To fabricate high-performance
assessing the gas sorption characteristics of membrane MMMs, the development of synthetic protocols is highly desir-
materials. able. Various synthetic strategies, including MOF adjustment,

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Fig. 8 (a) Photo images of pristine and functionalized ZIF-67 in mesity-

lene. (b) Single- and mixed-gas C3H6/C3H8 separation performances of
unmodified MMMs and modified MMMs with various MOF loadings.
Reproduced with authorisation from ref. 69 and copyright 2020 by
Published on 06 March 2024. Downloaded on 11/10/2024 [Link] AM.

Springer Nature. (c) Illustrative diagram depicting the synthetic process

of TA-tailored HZIF-8. (d) Separation performance comparison of
different MMMs including MOFs and PIM-1. Reproduced with authoris-
ation from ref. 36 and copyright 2020 by Springer Nature.

faceted polyphenol-mediated approach to enhance gas trans-

port properties. In this process, polyphenol tannic acid (TA)
played a dual role as a surface modifier, augmenting func-
tional groups, and as an etching agent, creating channels to
Fig. 7 (a) Structure comparison of MOF crystals and glass by THz/far-IR
and the modes of ZnIm35-FbIm tetrahedra and aromatic rings utilized in facilitate high-speed gas transfer (Fig. 8c).36 The surface of the
DFT calculations. Reproduced with authorisation from ref. 65 and copy- functionalised ZIF-8 fillers had large numbers of phenolic
right 2020 by American Chemical Society. THz/Far-IR spectra of the hydroxyl groups, which enabled their multiple interactions,
vitrification for (b) ZIF-62(Co)-Fe and (c) ZIF-62(Co). Reproduced with such as π–π interactions and metal coordination, between the
authorisation from ref. 66 and copyright 2022 by Wiley-VCH GmbH.
MOF fillers and the polymer matrix. Thus, the adhesive charac-
ter of polyphenols can promote intricate interactions with the
polymer matrix and endow polyphenol-modified ZIF-8 with a
matrix design, the MOF–polymer interfacial reaction, and distinctive hollow structure, facilitating molecule transfer. The
in situ synthesis, have been employed to improve the filler– improved interfacial compatibility and creative hollow architec-
matrix compatibility, mitigate particle agglomeration, and ture inside the ZIF-8 nanocrystals provided synchronous
maximise MOF loading. In addition, the emerging MOF glass, enhancement in the separation performance of the resulting
produced by phase transition of MOF crystals via melt quench- MMMs. For instance, the CO2 permeability increased by up to
ing, holds great promise in enhancing the separation perform- 36%, and the CO2/N2 selectivity reached up to 28% (Fig. 8d).
ance of membranes by eliminating interface defects.44,45 Besides introducing functional ligands, ionic liquids can
also be used as binding agents to enhance the MOF–polymer
4.1 MOF adjustment adhesion in MMMs.70–72 For example, Gong et al. integrated
4.1.1 MOF functionalisation. In order to achieve desirable an amino-functionalised ionic liquid (IL) into ZIF-7-8 particles
MOF–polymer compatibility and good MOF dispersion in a to form ZIF-7-8-IL, the resulting MMMs showed enhanced
polymer matrix, the functionalisation of MOF particles has interfacial compatibility due to the formation of coordination
been extensively studied, which involves incorporated func- and hydrogen bonding.71 This coordination involved the ILs
tional groups, ionic liquid modification, MOF coating, correlating with the surface of Zn nodes, facilitating the
polymer coating, and multifunctional polyMOF systems. For uniform dispersion of MOF particles. The intentional design
example, ZIF-67 nanoparticles functionalised with of interface interactions using ILs is pivotal for enhancing
N-heterocyclic carbene ligands showed great colloidal stability interface compatibility and the separation performance of
in casting solutions, resulting in improved particle dispersion CO2/CH4, leading to a significant improvement in the pro-
and interaction with the polymer in MMMs (Fig. 8a).69 The perties of MMMs with 25% ZIF-7-8-IL loading, for example
resulting MMMs exhibited high selectivity and permeability CO2 permeability increased by 291.6%, surpassing the 2018
enhancement for C3H6/C3H8 separation. These membranes upper bound.
also showed good durability in the presence of steam, main- Modifying MOF surfaces with other MOFs or polymers to
taining their selectivity even after 30 days of continuous oper- construct a hierarchical core–shell structure provides a new
ation with a 50/50 C3H6/C3H8 mixture (Fig. 8b). Zhu et al. pro- platform for precisely tuning the surface properties of MOFs
duced MMMs including highly porous ZIF-8 through a multi- and presents a clear potential for improving MOF dispersibility

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and interfacial compatibility with the polymer. Wu et al. pro- polymers of intrinsic microporosity (PIM) by a one-step syn-
posed a dual-interfacial strategy, devising a MOF-801@MOF-74 thesis (Fig. 10a).25 The polymer ligand plays a dual role, which
core–shell structure in the development of MMMs for C2H4/ modulates the properties of polyMOF particles, imparting the
C2H6 separation (Fig. 9a and b).73 Within this core–shell con- framework with angstrom-scale porosity for effectively sieving
figuration, the MOF-74 shell, featuring high-density open molecules. In comparison with control MOFs constructed with
metal sites, played a crucial role in enhancing the filler– organic ligands, these polyMOFs demonstrated significant
polymer interfaces, leading to the development of a defect-free improvements, such as reduced particle size, enhanced ultra-
membrane. Simultaneously, the MOF-801 core exhibited a microporosity (3–4 Å), and improved colloidal stability. These
highly selective transport of C2H4. As a result of these synthetic unique characteristics make them well-suited for preparing
effects, the membrane composed of a MOF-801@MOF-74 polyMOF/PIM-1 MMMs with high gas separation performance.
core–shell structure exhibits a C2H4/C2H6 separation selectivity As expected, the resulting polyMOF/PIM-1 MMMs presented
of up to 5.91, a 76% increment compared to the pure polymer. high CO2 separation abilities, which were above the upper
Following the rule of “like dissolve like”, MOF@polymers as bound (Fig. 10b). Moreover, they also investigated the feasi-
fillers exhibit excellent dispersibility and enhanced interfacial bility of upscaling pU20/PIM-1 membranes, and a TFN mem-
Published on 06 March 2024. Downloaded on 11/10/2024 [Link] AM.

compatibility through polymer–polymer interactions. Wang brane with a pU20/PIM-1 layer was prepared by a scalable bar-
et al. functionalised UiO-66-NH2 particles by covalently graft- coating method. The resulting pU20/PIM-1 TFN membrane
ing polyimide (PI) brushes onto them through step-growth with a large area (20 × 20 cm2) showed a CO2/N2 separation
polymerisation (Fig. 9c).48 The grafted polymer brushes on performance that met the target required for CO2 capture.
MOF surfaces have the same molecular structure as the The study demonstrated the potential of the TFN membrane
polymer matrix, leading to a robust brush–brush interaction. with a pU20/PIM-1 layer in practical CO2/N2 separation pro-
With an escalation in MOF loading, the MMMs with PI-grafted cesses (Fig. 10c).25
structures exhibited a concurrent increase in CO2 permeability 4.1.2 MOF geometry. The geometry of MOFs, including the
and the ideal selectivity for CO2/CH4 and CO2/N2 pairs particle size and morphology, is a crucial factor in the design
(Fig. 9d). In contrast, the unmodified MOF-based MMMs and optimisation of MMMs. The MOF geometry can affect the
showed a sole improvement in permeability but a concurrent separation efficiency, mechanical properties, and other critical
loss in selectivity. This indicates that the introduction of PI parameters of the membranes. An optimal MMM should use
brushes enhanced the MOF–polymer interface and mitigated nano-sized MOF particles with high surface area-to-volume
defects within the MMMs. ratios and strong interactions with the polymer chain.
Besides, polymers can be introduced into MOF hosts
as guests, resulting in the formation of hybrid materials
commonly known as polymer–metal–organic frameworks
( polyMOFs).74–76 Lee et al. developed a versatile polyMOF
system that uses a microporous polymer ligand derived from

Fig. 9 (a) Illustration of the dual-interfacial engineering strategy. (b)

C2H4/C2H6 separation performance of MMMs with different core–shell
MOF loading. Reproduced with authorisation from ref. 73 and copyright Fig. 10 (a) Schematic of the MOF, polymer–MOF ( polyMOF), and PIM-
2020 by American Chemical Society. (c) Comparison of traditional based polyMOF system. (b) Optical patterns of pU20/PIM-1 MMMs and
MMMs and PI-grafted MMMs. (d) CO2/N2 separation performances of their separation performances compared with other membranes. (c)
modified MMMs and unmodified MMMs with various MOF loadings. Optical patterns of TFN membranes with a pU20/PIM-1 layer and separ-
Reproduced with authorisation from ref. 48 and copyright 2018 by ation performances compared with other membranes. Reproduced with
American Chemical Society. authorisation from ref. 25 and copyright 2023 by Springer Nature.

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Consequently, efforts have been focusing on decreasing the Eddaoudi et al. tailored cubic AlFFIVE-1-Ni crystals into 2D
optimal particle sizes of MOFs through modulated synthesis, nanosheets with maximally exposed (001) facets (Fig. 11a).
aiming to enhance the separation efficiency of MMMs.26,77,78 They found that the loading of MOF AlFFIVE-1-Ni nanosheets
For example, Bachman et al. demonstrated that the nanocrys- in MMMs could be up to 58.9 wt%.15 Their results confirmed
tals of Ni2(dobdc) and Co2(dobdc) MOFs, with particle sizes of the enhanced interfacial compatibility between the MOF
less than 20 nm, resulted in a more significant fraction nanosheets and the polymer matrix. Moreover, the orientation
of the polymer at their interface, thus reducing the occurrence of MOF nanosheets in MMMs provided parallel channels
of a molecular transport channel without selectivity.78 Japip toward the direction of gas diffusion. These advantages
et al. studied the effect of particle sizes on MMMs using ZIF-71 endowed the membrane with ultrahigh gas separation per-
as fillers between 30 and 600 nm. A comparative analysis of formance, which was far above the upper bounds for poly-
MMMs with different particle sizes revealed that the MMM meric membranes (Fig. 11b). Analogously, Kwon et al. reported
with ZIF-71 fillers of 200 nm exhibited superior separation the scalable synthesis of ZIF-8 nanoplates with a high aspect
performance.26 ratio by a direct template conversion method.29 As shown in
MOFs are usually designed with relatively straightforward Fig. 11c, ZIF-8 nanoplates were prepared through a process
Published on 06 March 2024. Downloaded on 11/10/2024 [Link] AM.

dimensionalities, including 1D, 2D, or 3D structures. In par- involving the synthesis of a high aspect ratio Zn template
ticular, the 1D configuration facilitates network percolation, known as Zn5(NO3)2(OH)8. The template was then subjected to
the 2D structure allows for the attainment of high aspect the introduction of 2-methylimidazole (2-MeIm) linkers, which
ratios, and the 3D arrangement ensures ease of processability. were dissolved in acetone to facilitate phase conversion. The
These distinct dimensionalities reflect the versatility of MOF shape of the nanoplates was maintained by controlling the
design, allowing for tailored structures that cater to specific injection rate of the reactants using syringe pumps. During the
applications while optimising membrane separation synthesis, alkaline ions were added to arrest the shape of
performance. Zn5(NO3)2(OH)8. When LiOH is used as the reactant, the
High-aspect-ratio 2D MOF nanosheets, such as CuBDC,27,79 Zn5(NO3)2(OH)8 nanosheet results in an 8 μm lateral length.
ZIF-7,80 Ni-MOF,22,81 NH2-MIL-5382 and AlFFIVE-1-Ni,15 are After being incorporated into a 6FDA-DAM polymer matrix
ideal for fabrication energy-efficient molecular sieve mem- through a straightforward bar-coating technique, the separ-
branes. Their large surface area can improve the interfacial ation performance of MMMs loaded with ZIF-8 nanoplates for
compatibility with the polymer. At the same time, their mole- C3H6/C3H8 far exceeded other reported MMMs (Fig. 11d).
cular sieving effect can empower them to function as highly Besides, the thermal stability and long-term stability of the
effective selective membranes. Rodenas et al. prepared 2D ZIF-8 nanoplate/6FDA-DAM MMMs indicated their enormous
CuBDC nanosheets using a bottom-up synthesis strategy and potential in practical situations.
the MMMs incorporated with CuBDC nanosheets exhibited Lee et al. revealed that branch-shaped ZIF-8 nanoparticles
excellent CO2 separation from the CO2/CH4 gas mixture.27 have a unique morphology that automatically interconnects,
which is beneficial for constructing the MOF percolation net-
works within the polymer matrix at only 20 wt% MOF loading.
Compared with the rhombic dodecahedral control ZIF-8, the
branched ZIF-8 exhibits a higher surface area-to-volume ratio
and allows a strong interaction between the fillers and the
polymer, effectively suppressing the mobility of polymer
chains. The resulting MMMs exhibited enhanced plasticisation
resistance.83
4.1.3 Defect engineering in MOFs. The deliberate introduc-
tion of defects, vacancies, or modifications in MOF structures
enables the customisation of various properties, such as an
optimal surface area, an adjustable pore size, and abundant
open metal sites.84 These characteristics of defective MOFs
provide a versatile platform for improving MOF–polymer inter-
facial adhesion and increasing selective sorption properties. The
relevant reports have demonstrated that the defective MOFs in
Fig. 11 (a) SEM images of MOF nanosheets and crystals and their dia-
MMMs, such as Ui-66,19,85–88 ZIF-8,89,90 ZIF-90,91 and Ni-MOF,22
grams in MMMs. (b) CO2/CH4 separation performances of MMMs with show great potential for enhancing gas separation performance.
different MOF nanosheet loadings and anticipated MOF nanosheet UiO-66 is widely recognised as a MOF with exceptional
membranes. Reproduced with authorisation from ref. 15 and copyright stability and the structure of this MOF has been extensively
2022 by AAAS Publishing. (c) Diagram depicting the synthesis of ZIF-8
tuned and characterised.92 Lee et al. studied the preparation of
nanoplates from Zn5(NO3)2(OH)8 nanosheets. (d) Performance compari-
son of MMMs with ZIF-8 nanoplates for C3H6/C3H8 separation.
defective UiO-66-based MMMs by a defect engineering strategy
Reproduced with authorisation from ref. 29 and copyright 2022 by AAAS and found that the highly defective UiO-66 nanoparticles, pre-
Publishing. pared using trifluoroacetic acid as a modulator, presented

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desirable open metal sites, pore size, pore volume and surface
area.85 These properties provide a rapid diffusion pathway and
selective adsorption sites for C3H6 due to the existence of Zr–
olefin complexation (Fig. 12a). The loading of defect-engin-
eered UiO-66 in the polymer matrix could reach 40 wt%,
leading to an increased C3H6 permeability of 365 Barrer
without sacrificing C3H6/C3H8 selectivity (Fig. 12b). Besides,
they also selected the poly (ethylene glycol) diacrylate (PEGDA) Fig. 13 Schematic representation of the synthesis process for alkyl
matrix with better gas adsorption capability to fabricate defect- amine-modulated ZIF-8 (AZIF8). Reproduced with authorisation from
engineered MOF/PEGDA MMMs, and this membrane showed ref. 89 and copyright 2021 by Wiley-VCH GmbH.
a boosted CO2 permeability of 470 Barrer and an unvaried
CO2/N2 selectivity of 41 (Fig. 12c and d).86 Moreover, the incor-
poration of defect-engineered UiO-66 particles into PIM-1 was 4.2 Matrix design
carried out to prepare MMMs and the CO2/N2 separation per- Polymers can undergo modifications involving the introduc-
Published on 06 March 2024. Downloaded on 11/10/2024 [Link] AM.

formance was improved due to the enhanced adhesion tion of functional groups to enhance compatibility with MOF
between the polymer and the defective MOF fillers.19,87 fillers, and the common functionalised polymers are PIM-1
As another renowned MOF material, defect-engineered and 6FDA-DAM.93,94 Kaliaguine et al. prepared NH2-MIL-53-
ZIF-8 fillers have also been investigated in MMMs to enhance based MMMs incorporated with hydroxyl groups into
the gas separation performance. An et al. synthesised defect- 6FDA-DAM to increase interfacial interactions.93 In a com-
engineered ZIF-8 nanoparticles using an alkyl amine modu- bined computational and experimental investigation, Carja
lator, which could coordinate with Zn2+ ions (Fig. 13).89 et al. explored the MOF–polymer interfacial interactions in
Compared with the routine ZIF-8 particles, defective ZIF-8 par- MMMs by the combination of UiO-66 and functional
ticles exhibited more rigid structures, narrower pore size distri- PIM-1 modified with various groups, including amidoxime
bution, and smaller openings, which can improve the mem- (AO), tetrazole (TZ), and N-((2-ethanolamino)ethyl)carboxa-
brane separation performance. The enhanced dispersibility is mide (EA) (Fig. 14a).94 These studies revealed that hydrogen
mainly attributed to grafting the outer surface with organic bonding between the MOF fillers and the functional groups in
alkyl amine molecules. The resulting AZIF8/6FDA-DAM MMMs the polymer chains (Fig. 14b) could improve the polymer–MOF
exhibited exceptional separation performance even as the adhesion and enhance the gas separation performance.
loading of defective ZIF-8 fillers reached 50%. Apart from Moreover, a metal-modified polymer was also considered to
ZIF-8, defective Ni-MOF nanosheets also showed uniform dis- engineer MOF–polymer interaction. Fan et al. reported Zn(II)-
persion and favourable interfacial compatibility in the Pebax modified 6FDA-BI/ZIF-8 MMMs with enhanced interfacial
matrix, which exhibited an improved separation performance,
in which the CO2 permeability and CO2/CH4 selectivity were
436 Barrer and 33, respectively.22

Fig. 12 Schematic illustration and separation performance comparison. Fig. 14 (a) Combination of UiO-66(Zr) fillers and PIM-1 functionalized
(a and b) Defect-engineered UiO-66/6FDA-DAM MMMs. Reproduced with AO, TZ and EA. Reproduced with authorisation from ref. 94 and
with authorisation from ref. 85 and copyright 2021 by Wiley-VCH copyright 2021 by American Chemical Society. (b) Metal-modified
GmbH. (c and d) Defect-engineered UiO-66/PEGDA MMMs. 6FDA-BI/ZIF-8 MMMs and separation performance comparison.
Reproduced with authorisation from ref. 86 and copyright 2021 by Reproduced with authorisation from ref. 95 and copyright 2022 by
Wiley-VCH GmbH. Elsevier.

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interaction due to metal chelation with the nitrogen atom of MMMs.97 The PMMOF strategy involves four key steps:
imidazole groups (Fig. 14c).95 Notably, all the Zn2+ modified polymer hydrolysis, ion exchange, ligand treatment, and imi-
membranes presented increased H2/CH4 selectivity. dization. The in situ ZIF-8 fillers, with an average particle size
To harness the separation potential of MOFs in MMMs, it is of approximately 100 nm, displayed a robust affinity with the
essential to construct a continuous network of MOFs in the polyimide matrix, leading to enhanced interactions between
polymer matrix. Although it is possible to increase MOF the ZIF-8 fillers and the polymer. Moreover, the ZIF-8 loading
loading (at least 30 wt%) to achieve a percolation network, in MMMs could be up to 32.9% without any noticeable inter-
these membranes are too fragile to be of any practical value facial defects. In a subsequent study, they also reported the
unless percolation can be established at a low MOF loading. Li in situ growth of ZIF-7 nanoparticles to prepare 6FDA-DAM/
et al. developed a class of phase-separated (PS) MMMs.18 By ZIF-7 MMMs, resulting in notable enhancements with a
controlling the phase separation process between two immisci- 176% increase in H2 permeability and a 180% increase in H2/
ble polymers, the MOF particles can be automatically parti- CO2 selectivity.96 Recently, Li et al. utilised the “confined
tioned and squeezed into the preferred polymer domain at swelling coupled solvent-controlled crystallisation” method
over 50 vol% local packing density, leading to a percolated to tailor in situ ZIF-8 crystallisation in polyethylene oxide
Published on 06 March 2024. Downloaded on 11/10/2024 [Link] AM.

network with only 19 wt% MOF loading (Fig. 15a). The other (PEO) matrix, which formed defect-free channels for CO2
polymer phase is free of MOF particles which can serve as a transportation.98 Besides, the chelating interaction between
mechanical support to strengthen the membrane. Benefiting ZIF-8 and PEO improved CO2/N2 selectivity. Consequently,
from this unique co-continuous morphology, this PS-MMM the resulting ZIF-8/PEO membranes exhibited an impressive
UiO-66-NH2 exhibited 6.6 times CO2 permeability compared CO2 permeability of 2490 Barrer, accompanied by a high CO2/
with the pure polymer membrane without giving out its selecti- N2 selectivity of 37.
vity over N2 and CH4 (Fig. 15b). In addition, Chen et al.14 prepared an ultrathin and highly
loaded MMM with Cu(SiF6)( pyz)3 as a filler via a solid-solvent
4.3 In situ synthesis processing (SSP) strategy. Metal salts were uniformly immobi-
4.3.1 In situ growth of MOF fillers. The strategy of the lised within the polymer matrix, acting as a solid solvent,
in situ growth of MOF fillers in the polymer matrix has been which then undergoes in situ conversion to MOF crystals after
developed, which can simplify the fabrication process of ligand vapour treatment. The thickness of Cu(SiF6)
MMMs and offer numerous advantages in terms of dispersion, ( pyz)3@PEG MMM without observable defects could be as thin
compatibility, and potentially large-scale production. It should as 50 nm by facilely controlling the solution properties and
be noted that the success of this method depends on the com- coating parameters (Fig. 16a and b). More importantly, the
patibility of the MOF precursors with the polymer matrix and optimised Cu(SiF6)( pyz)3@PEG MMM with 80 vol% loading
the ability to control the MOF growth process. Researchers are showed outstanding separation performance, featuring an H2
refining these techniques to optimise the properties of MMMs permeance of 3640 GPU and a H2/CO2 selectivity of 76.1
for various applications, including gas separation. MOF fillers (Fig. 16c). Besides, they also found that Cu(SiF6)( pyz)3@PEG
in situ grown in MMMs, such as Cu(SiF6)( pyz)3,14 ZIF-7,96
ZIF-8,97–99 MOF Cd-6F 100 and UiO-66,101 have gained more
and more attention.
Park et al. developed a strategy called polymer modifi-
cation-enabled in situ MOF formation (PMMOF) to improve
the interaction between the fillers and the polymers in

Fig. 16 (a and b) Surface and cross-section SEM images of Cu(SiF6)

( pyz)3@PEG MMM. (c) Performance comparison of MMMs with different
Fig. 15 (a) TEM image of phase-separated MMMs with 19 wt% UiO-66- MOF loadings for H2/CO2 separation. (d) Performance comparison of Cu
NH2 loading. (b) CO2/N2 separation performance of phase-separated (SiF6)( pyz)3@PVA MMMs, and Ni(NbOF5)( pyz)3@PVA MMMs with other
and conventional MMMs with various MOF loadings. Reproduced with membranes for H2/CO2 separation. Reproduced with authorisation from
authorisation from ref. 18 and copyright 2023 by AAAS Publishing. ref. 14 and copyright 2023 by AAAS Publishing.

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MMM with 59.6 vol% loading presented high H2/CO2 separ- of 2740 GPU, coupled with a CO2/N2 selectivity of 104. This
ation performance, which exceeded the 100 °C upper bound of enhancement can be attributed to the addition of ZIF-8 provid-
conventional polymeric membranes and other advanced MOF- ing additional pathways for CO2 transport.103
based MMMs (Fig. 16d). The solid solvent ( polymer) facilitated In addition, ultraviolet (UV)-induced photopolymerisation
MOF filler dispersion, ensuring interfacial compatibility can also be applied to in situ synthesise a polymer matrix of
between the fillers and the polymer, maintaining the integrity MMMs for improved interfacial compatibility and MOF dis-
and flexibility of MMMs with high filler loading. persion. For example, ZIF-8 nanoparticles were dispersed in a
4.3.2 In situ polymerisation. In situ polymer synthesis was solution containing poly(ethylene glycol) diacrylate (PEGDA)
generally performed by interfacial polymerisation to fabricate and poly(ethylene glycol) methyl ether acrylate (PEGMEA)
TFN membranes with ultrathin MMMs.30,102 Recently, MOF monomers and then subjected to photopolymerisation. This
TFN membranes have gained popularity for molecular separ- resulted in the rapid formation of solid polymer networks
ation due to their adjustable interior architectures. Li et al. uti- within 30 seconds, preventing nanoparticle aggregation and
lised the swelling-controlled nanofiller positioning (SNP) tech- precipitation during the membrane formation process.104 In
nique to place ZIF-8 particles within the swollen PDMS inter- another study, Qiao et al. developed a bilayer modification
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mediate layer before interfacial polymerisation. The incorpor- strategy on MOFs to create efficient MOF-based MMMs for
ation of ZIF-8 nanoparticles into the resultant TFN membranes C3H6/C3H8 separation. The structure of MOFs can be improved
resulted in improved gas transport properties. The synthesised by grafting an octadecylphosphonic acid-lecithin-cholesterol
TFN membrane demonstrated an impressive CO2 permeance bilayer onto their surface. This enhances their sieving capacity

Table 1 Summary of the MOF–polymer interfacial reaction in MOF-based MMMs

Membrane performance

MOF Polymer General MMMs Covalently linked MMMs Ref.

PIM-1: PCO2 = 3027.7 Barrer, SCO2/N2 = 26.6; UiO-66-CN(20 wt%, 200 nm)/ 20
UiO-66-CN(20 wt%, 200 nm)/PIM-1: PCO2 = sPIM-1: PCO2 = 16 121.3 Barrer,
7070.9 Barrer, SCO2/N2 = 26.7; UiO-66- SCO2/N2 = 27.
NH2(20 wt%, 200 nm)/sPIM-1: PCO2 = 8619.5
Barrer, SCO2/N2 = 18.

PIM-1: PC3H6 = 689.1 Barrer, SC3H6/C3H8 = 5.7; ZIF-8-CN(10 wt%, 80 nm)@tPIM-1: 106
ZIF-8-CN(10 wt%, 80 nm)/PIM-1: PC3H6 = PC3H6 = 369.4 Barrer, SC3H6/C3H8 =
633.2 Barrer, SC3H6/C3H8 = 5.9; ZIF-8(10 wt%, 27.6.
80 nm)@tPIM-1: PC3H6 = 417.6 Barrer,
SC3H6/C3H8 = 15.6.

PIM-1: PCO2 = 6576 Barrer, SCO2/CH4 = 12.3, PIM-co-UiO-6672 h-NH2 (20 wt%, 107
SCO2/N2 = 18.7; UiO-66(20 wt%, 1 µm)/PIM-1: 1 µm): PCO2 = 12 498 Barrer,
PCO2 = 7100 Barrer, SCO2/CH4 = 11.6, SCO2/N2 = SCO2/CH4 = 31.9, SCO2/N2 = 54.2.
16.9.

Polyamide TFC membrane: PCO2 = 611 GPU, ZIF-8-NH2(1.0 wt%, 700 nm)/ 33
SCO2/N2 = 107; ZIF-8(1.0 wt%, 700 nm)/ Polyamide TFN membrane: PCO2 =
Polyamide TFN membrane: PCO2 = 926 GPU, 2004 GPU, SCO2/N2 = 220.
SCO2/N2 = 84.

Pure 6FDA-Durene-TAEA: PH2 = 228.7 Barrer, ZIF-90-NH2(45 wt%, 60–100 nm)/ 91

SH2/CO2 = 5.9. 6FDA-Durene-TAEA: PH2 = 487
Barrer, SH2/CO2 = 35.8.

Neat COOH-PI: PH2 = 538 Barrer, PCO2 = 368 UiO-66-NH2(20 wt%, 30 nm)/ 108
Barrer, SH2/CH4 = 23.1, SCO2/CH4 = 16. COOH-PI: PH2 = 1180 Barrer, PCO2 =
995 Barrer, SH2/CH4 = 27.2, SCO2/CH4 =
23.

Neat PIM-1: PCO2 = 6576 Barrer, SCO2/CH4 = MOF-74(20 wt%, 10–15 µm)/PIM-1: 109
12.3, SCO2/N2 = 18.7. PCO2 = 21 269 Barrer, SCO2/CH4 =
19.1, SCO2/N2 = 28.7.

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while preserving good interfacial compatibility. In addition, ZIF-8-CN fillers. Their permeation mechanism is schematically
the UV-induced photopolymerisation process promoted the illustrated in Fig. 17c. The resulting membranes present an
formation of holes in the cross-linked poly(ethylene oxide) excellent promise for the practical separation of C3H6 from
(XLPEO) polymer matrix. The resulting MMMs exhibit superior C3H8 in industry.
gas permeability and enhanced C3H6/C3H8 selectivity.105 Notably, the interfacial reaction approach can combine
with the in situ polymerisation strategy since polymer mono-
4.4 MOF–polymer interfacial reaction mers exhibit more crosslinking sites than existing polymers.
The interfacial reaction between the MOF fillers and the ZIF-8-NH2 was used to establish covalent bonds with polymer
polymer chains through forming new covalent bonds can chains during interfacial polymerisation (Fig. 17d).33 ZIF-8-
provide stronger interactions, facilitating the forming of NH2 not only provided a molecular sieve channel, but also dis-
defect-free membranes. To confirm the significant impact of rupted the segment packing in the polymer, creating more free
interfacial reactions, Table 1 lists relevant reports. All the volume and Langmuir gas sorption sites for molecular
selected literature investigates the effect of covalent bonds on diffusion. The resulting TFN membrane with ZIF-8-NH2
gas separation performance. These studies indicate that the demonstrated an exceptionally high CO2 permeance of 1572
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covalently linked MMMs exhibit improved permeability and GPU and a CO2/N2 selectivity of 230 (Fig. 17e and f ).
selectivity compared to the general MMMs. This is primarily
due to the improved anti-plasticisation of the polymer and 4.5 MOF phase transition
enhanced molecular sieves by highly porous MOFs, which is As a recently emerging material, MOF glasses can be melted
caused by optimal interfacial interaction between the MOFs into a processible liquid state from the crystalline phase at a
and the polymers. glass transition temperature, which presents significant poten-
Wang et al. detailed the creation of MOF-based MMMs tial to fabricate MOF-based MMMs using MOF glass as a con-
through a covalent-linking strategy to enhance interfacial com- tinuous phase.41,110 Due to the highly tunable interfacial
patibility.106 The modified ZIF-8 (ZIF-8-CN) could react with characteristics, recent research has shown that MOF glass can
PIM-1 upon thermal treatment. The establishment of robust combine with other functional materials, such as MIL-53,42
covalent bonds between the fillers and the polymer chains ZIF-67,43 and perovskites,68 Therefore, MOF glass becomes a
avoided interfacial gaps (Fig. 17a). The MMMs with ZIF-8-CN promising membrane, which can be conducive to eliminating
fillers exhibited an observable enhancement in separation per- intergrain boundary defects.44,111,112
formance with a high C3H6 permeability of 370 Barrer and tri- Jiang et al. reported a continuous MOF glass membrane
pling of the C3H6/C3H8 selectivity to 28, which surpassed the prepared through melt-quenching of ZIF-62 crystals for the
latest upper bound (Fig. 17b). The outstanding permeability first time. The resulting ZIF-62 glass membrane presented
and selectivity are attributed to the low gas-transport resis- effective molecular sieving abilities for CO2/N2, H2/CH4, and
tance in the PIM-1 matrix and the molecular sieve effect in CO2/CH4 mixtures.112 Wang et al. developed a series of free-

Fig. 17 (a) Schematic illustration of the covalent-linking strategy employed for enhancing interfacial compatibility in MMMs. (b) Performance com-
parison of the ZIF-8-CN@tPIM-1 membrane with other MMMs including ZIF-8. (c) Proposed separation mechanism of the ZIF-8-
CN@tPIM-1 membrane for C3H6 and C3H8 separation. Reproduced with authorisation from ref. 106 and copyright 2022 by Wiley-VCH GmbH. (d)
Diagram illustrating the formed covalent bonds and hydrogen bonds in the TFN membrane and its surface morphology.(e and f ) CO2/N2 separation
performance of TFN membranes with different ZIF-8 or ZIF-8-NH2 loadings. Reproduced with authorisation from ref. 33 and copyright 2017 by
Elsevier.

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standing MOF glass (M-P-dmbIm, M = Zn, Cd, Cu, and Mn)

membranes by hot pressing/casting, which showed high H2
separation performance from other gases (CO2, N2, and CH4)
and even exceeded the Robeson upper bound (Fig. 18a–c).111
Unfortunately, maintaining the continuity of pores and ultra-
micro porosity in MOF glass membranes is a significant chal-
lenge because of dead-end pores and inherent porosity
reduction after melt-quenching treatment. To address this
challenge, Qiao et al. reported self-supported ZIF-62 glass
foam membranes via a polymer-thermal-decomposition-
assisted melting strategy (Fig. 18d).53 The incorporated poly-
ethyleneimine (PEI) with a low molecular weight of only 300
could decompose to produce CO2, NH3 and H2O gases during Fig. 19 (a) Preparation process of ZIF-8/ZIF-62 CGC membranes. (b)
the thermal process, which induced high interconnected pores Mixed and (c) pure gas separation performance of ZIF-8/ZIF-62 CGC
membranes. Reproduced with authorisation from ref. 45 and copyright
Published on 06 March 2024. Downloaded on 11/10/2024 [Link] AM.

in ZIF-62 glass. Thus, the synthesised ZIF-62 glass foam mem-

2023 by Wiley-VCH GmbH.
branes, with a thickness of 200–330 µm and a diameter of
3.3 cm, showed extraordinary gas separation performance with
a CH4 permeance of 30 000–50 000 GPU and a CH4/N2 selecti- other reported membranes with similar CH4/N2 selectivity
vity of 4–6 (Fig. 18e). Notably, the CH4 permeance was approxi- (Fig. 18f ).
mately two orders of magnitude higher than that observed in Glass MOFs offer an alternative approach through in situ
melting. The MOF liquid state has metal nodes and organic
ligands, promoting bonding and minimising interfacial
defects between the MOFs and the polymers. We reported
6FDA-DAM/ZIF-62 glass MMMs prepared by melt quenching
and vitrification of ZIF-62 crystals in a 6FDA-DAM matrix.46
The results proved that the melting of ZIF-62 could fill the
cracks at the MOF–polymer interface. Moreover, the newly
formed Zn–O and Zn–F bonding between ZIF-62 glass and
6FDA-DAM enhanced the interfacial compatibility and
improved the rigidity of 6FDA-DAM, leading to increased CO2/
N2 selectivity.
Another significant strategy involves employing MOF glass
as a continuous phase to prepare MMMs for improving inter-
facial compatibility with incorporated fillers. ZIF-8 was
initially blended with ZIF-62 to form composite membranes
with porous alumina as the support and the C3H6/C3H8
selectivity increased from 2.5 of neat ZIF-62 to 17.44 Qiao
et al. synthesised a self-supported MMM using a combination
of ZIF-8 crystals and ZIF-62 glass (Fig. 19a).45 ZIF-62 crystals
could convert into glass while ZIF-8 maintained the crystal
state during the thermal process, which could diminish grain
boundary defects and improve separation selectivity. The
obtained ZIF-8/ZIF-62 composite membranes showed an
ultrahigh separation performance, due to the abundant pore
structure and the preferential adsorption for C2H6 (Fig. 19b
and c).

Fig. 18 (a and b) Photograph and SEM images of the MOF pellet and
the MOF glass membrane. (c) Separation performance comparison of 5 Conclusions and perspectives
MOF glass with other gas separation membranes. Reproduced with
authorisation from ref. 111 and copyright 2021 by Wiley-VCH GmbH. (d) MOF-based MMMs have emerged as potentially effective com-
Schematic illustration for forming MOF glass membranes by PEI pounds for enhancing membrane separation capabilities and
decomposition. (e) CH4/N2 permeance and selectivity of MOF glass
facilitating the industrial scale-up process. This is mainly
membranes with different thicknesses. (f ) Performance comparison of
MOF glass membranes with other high-performance membranes.
attributed to the outstanding sieving properties of MOFs,
Reproduced with authorisation from ref. 53 and copyright 2023 by which enable them to function as molecular sieves, leading to
Springer Nature. the separation performance. This review highlighted the

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Review Nanoscale

different designs and optimised strategies of preparing MMMs Therefore, the state-of-the-art reports about ultrathin MOF-
with MOF fillers for improving separation performance, and based MMMs will play a significant role in industrial separ-
their cutting-edge advances for separation have been over- ation with addressed issues.
viewed. Potential future directions for exploring new develop- On the other hand, the emerging MOF glasses open a new
ments and the practical applications of MOF-based mem- avenue for fabricating defect-free MOF-based MMMs with
branes are discussed. MOF glass as a matrix. Though only a few research studies
Further research on 2D MOF nanosheets should be con- investigated MOF CGC membranes (e.g., ZIF-8/ZIF-62),44,45 the
ducted to direct the development of 2D MOF-based MMMs. successful utilisation of MOF glass in gas separation mem-
Advanced composite materials using oriented 2D nanosheets branes has proven their enormous potential in the field of
have created MMMs with high separation performance membrane separation.53,112 For example, constructive MOF
because their high aspect ratio can improve the packing glass foam membranes provided abundantly unsaturated Zn2+
density.15 The application of 2D MOF-based MMMs is not only ions, which could induce preferential van der Waals inter-
for gas separation but also for nanofiltration113 and ion separ- actions with CH4 compared with N2, facilitating the selective
ation.114 It is important to note that although oriented 2D transport of CH4 molecules through the membrane. Besides,
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MOF nanosheets can endow MMMs with high separation per- the improved porosity and the existence of unsaturated metal
formance, only a few examples, such as AlFFIVE-1-Ni15 and centres in MOF glass make them suitable for gas separation
ZIF-95,115 have been reported. The development of 2D MOF- and applications in ion separation and chemical catalysis.41,117
based MMMs is hindered by various challenges faced by 2D Furthermore, we anticipate that additional modification tech-
MOF nanosheets. These challenges can be broadly divided niques for MMMs with MOF glass as a matrix will be reported
into three aspects. First, there needs to be more clarity on the and implemented in the industry in the near future.
conformational relationships of 2D MOF nanosheets, which Molecular modelling and simulation are crucial for under-
makes it challenging to synthesise high-quality nanosheets standing membrane materials, such as structural design, for-
using controlled synthesis strategies. Second, current exfolia- mation conditions, and separation mechanisms. Combining
tion techniques risk the structural integrity of MOF advanced molecular simulation with realistic structure model-
nanosheets, and their low monolayer yield hinders large-scale ling of MMMs can reveal relationships between the membrane
application. Third, the fragile structure and poor stability of components and the performance, leading to precise separ-
2D MOF nanosheets must be improved to make them practi- ations for various industries. Molecular simulations can be
cally applicable. Overcoming these challenges will open new used positively in developing screening studies to overcome
avenues for producing high-performance 2D MOF-based the limitations in membrane preparation and experimental
MMMs. characterisation. Recently, molecular simulations have pre-
Cutting-edge MOF-based MMMs featuring extremely thin, sented the potential to develop high-performance MMMs by
distinctive structures hold promise for achieving remarkable computational screening and deep-analysis fundamental
permeance and selectivity. However, manufacturing such thin methods. In the future, research efforts with advanced compu-
membranes remains challenging during the scale-up process, tational resources can analyse the relationship of molecule
particularly for MMMs with a thickness at the nanoscale. adsorption and transport with membrane characteristics,
There are two critical points to consider regarding ultrathin including structural modification, filler distribution, and inter-
membranes. First, thinner membranes lead to higher per- facial interactions.
meance, but this relationship becomes more complex at the Significant breakthroughs are required for more diverse
nanoscale. Designing membranes for specific applications and extensive applications of MMMs. Although there are cur-
requires understanding the interplay between the thickness, rently no industrial applications of MOF-based MMMs for
surface effects, and other factors. Second, the long-term dura- molecule separation, the improved interfacial compatibility
bility of most ultrathin MMMs is not well established. in MOF–polymer or MOF crystal–glass is expected to hasten
Research progress on ultrathin MOF-based MMMs has contin- their industrial implementation. Some reports have proved
ued over the past decade, accelerated by nanotechnology. For that MOF-based MMMs are expected to achieve large-scale
instance, the MOF-based MMMs prepared through the gravity- preparation. For example, Chen et al. scaled up the fabrica-
induced interface self-assembly method exhibited exceptional tion of flat-sheet MOF-based MMMs on a polyacrylonitrile
CO2/N2 separation performance due to the ultrathin and unob- substrate to an area of 720 cm2 using the SSP strategy.14 The
structed gas transport channels.116 This design concept and resulting stable separation performance highlighted the
approach can be applied to manufacture other MMMs using potential for large-scale applications. Qiao et al. achieved
various porous fillers or polymer matrices to achieve better MMM modules with a large area of ca. 2000 cm2 and 85 wt%
membrane performance. In addition, Chen et al. developed a ZIF-8 loading, which exhibited outstanding separation per-
promising SSP strategy for the fabrication of ultrathin MOF- formance.118 However, only a few MOF materials are suitable
based MMMs.14 This approach not only addresses persistent for large-scale MMM production. Therefore, more effort must
processability issues, but also offers the potential for exploring be made to meet practical application requirements by the
industrially applicable membrane configurations and contri- fundamental design rules and screening appropriate mem-
buting to the field of membrane separation technology. brane materials.

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Conflicts of interest 17 L. Hu, K. Clark, T. Alebrahim and H. Lin, J. Membr. Sci.,

2022, 644, 120140.
There are no conflicts to declare. 18 C. Li, A. Qi, Y. Ling, Y. Tao, Y.-B. Zhang and T. Li, Sci.
Adv., 2023, 9, eadf5087.
19 C. Geng, Y. Sun, Z. Zhang, Z. Qiao and C. Zhong, ACS
Acknowledgements Sustainable Chem. Eng., 2022, 10, 3643–3650.
20 G. Yu, X. Zou, L. Sun, B. Liu, Z. Wang, P. Zhang and
The authors acknowledge the funding support from the G. Zhu, Adv. Mater., 2019, 31, 1806853.
Australian Research Council (ARC) (DE230100173, 21 A. Akbari, J. Karimi-Sabet and S. M. Ghoreishi, Chem. Eng.
FT210100589, and DP230101901), the Excellent Youth Process., 2020, 148, 107804.
Research Project of Anhui province (2022AH030135 and 22 W. Zhu, L. Wang, H. Cao, R. Guo and C. Wang, J. Membr.
2022AH020083), the PhD Research Funding of Suzhou Sci., 2023, 669, 121305.
University (2021BSK041 and 2020BS019), the Natural Science 23 Z. Yang and D. Zhao, Science, 2023, 381, 1288–1289.
Foundation of Anhui province (2108085MB67) and the China 24 J. H. Jo, C. O. Lee, G. Y. Ryu, H. Jae, D. Roh and W. S. Chi,
Published on 06 March 2024. Downloaded on 11/10/2024 [Link] AM.

Scholarship Council (CSC). ACS Appl. Polym. Mater., 2022, 4, 6426–6439.

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