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Hybridization of MOFs and polymers


Takashi Kitao, a Yuanyuan Zhang, b Susumu Kitagawa,ac Bo Wang *b and
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Cite this: DOI: 10.1039/c7cs00041c


Takashi Uemura *ad

Metalorganic frameworks (MOFs) have received much attention because of their attractive properties.
They show great potential applications in many fields. An emerging trend in MOF research is hybridization
with flexible materials, which is the subject of this review. Polymers possess a variety of unique attributes,
such as softness, thermal and chemical stability, and optoelectrical properties that can be integrated with
Received 20th January 2017 MOFs to make hybrids with sophisticated architectures. Hybridization of MOFs and polymers is producing
DOI: 10.1039/c7cs00041c new and versatile materials that exhibit peculiar properties hard to realize with the individual components.
This review article focuses on the methodology for hybridization of MOFs and polymers, as well as the
rsc.li/chem-soc-rev intriguing functions of hybrid materials.

1. Introduction porous materials.13 MOFs have been recognized as an excel-


lent platform for hostguest chemistry; their wide applications
Recently, metalorganic frameworks (MOFs), or porous coordi- include gas storage, separation, drug delivery, and sensing.47
nation polymers (PCPs), which are composed of metal ions One of the most striking features of MOFs lies in their tunable
and bridging organic ligands, have emerged as a new class of nanospaces, which can provide ideal accommodation for a variety
of guest species.810
Much eort has been devoted to developing nanohybridiza-
a
Department of Synthetic Chemistry and Biological Chemistry, tion of MOFs and polymers. In most cases, polymer chains are
Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku,
randomly entangled in the bulk state. Therefore, properties
Kyoto 615-8510, Japan. E-mail: uemura@sbchem.kyoto-u.ac.jp
b
Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials,
that can be exploited usually result from the averaged behaviors
Key Laboratory of Cluster Science, Ministry of Education, School of Chemistry, of disordered multiple chains. From the viewpoint of polymer
Beijing Institute of Technology, 5 South Zhongguancun Street, Beijing 100081, encapsulation systems, the regulated and tunable nanochannels
P. R. China. E-mail: bowang@bit.edu.cn of MOFs are of key importance for achieving unique polymer
c
Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University,
assemblies in which the number of polymer chains, the environ-
Yoshida, Sakyo-ku, Kyoto 606-8501, Japan
d
CREST, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi,
ment of the polymers, and the chain orientations are precisely
Saitama 332-0012, Japan controlled.11 This approach can allow for not only controlling
These authors contributed equally to this work. the polymer properties but also eliciting potentially useful yet

Takashi Kitao is currently pursuing Yuanyuan Zhang received her BS


his PhD studies at Kyoto University. degree in chemistry at Tianjin
He has been a JSPS Fellow since Normal University in 2013. Then
2016. His research interests include she joined Prof. Bo Wangs group
the controlled assemblies of conju- as a doctoral student in Beijing
gated polymers using coordination Institute of Technology. Her current
nanospaces. research interest focuses on
metalorganic framework-based
membranes for gas separation
and sensing.

Takashi Kitao Yuanyuan Zhang

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unexplored properties. In addition, the encapsulation of func-


tional polymers in MOFs can lead to the emergence of hostguest
synergies and provide unprecedented functions that are hard to
realize from individual components.
In addition to polymer encapsulation systems, surface modi-
fication of MOF crystals with polymers is a fascinating MOF/
polymer hybridization approach. Films or membranes of MOFs
are of potential interest for a wide variety of applications, such as
gas separation, pervaporation, and solvent-resistant nanofiltration.12
However, MOFs are not as malleable as soft materials because of
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their crystalline nature, which stands as a critical obstacle to


their manipulation and processability. To circumvent this issue,
considerable eort has been applied to the fabrication of com- Fig. 1 The number of papers published per year on MOF/polymer hybrids.
The numbers were determined based on a Scopus search using keywords
posite materials integrating MOF crystals with polymer films.
metalorganic frameworks, porous coordination polymers, and polymers.
This approach can also endow MOFs with improved functions,
such as gas adsorption selectivity, hydrolytic stability, and bio-
compatibility, expanding their practical applications. components.13,14 To highlight the significance of this field, we
Controlled integration of polymers and MOFs is leading have analyzed the publication trend for the period 20052016.
to the creation of advanced functional composites exhibiting As shown in Fig. 1, the number of papers published per year
intriguing properties that are superior to those of the individual regarding the hybridization of polymers and MOFs has increased
continuously. Since the variety of MOFs and polymers affords
an essentially infinite number of possible combinations, it is
necessary to choose hybridization methods appropriately towards
Susumu Kitagawa received his obtaining the desired functional materials. In this review, we
PhD from Kyoto University in describe the recent developments in MOF/polymer hybridization
1979. He was promoted to a full procedures as well as the functions of hybrid materials.
professor at Tokyo Metropolitan
University in 1992, and he moved
to Kyoto University as a professor 2. Synthetic approaches for hybrids of
of Inorganic Chemistry in 1998. MOFs and polymers
Presently, he is also Director of
the Institute for Integrated Cell- In this section, we describe a variety of synthesis procedures for
Material Sciences (WPI-iCeMS) the hybridization of polymers and MOFs, as shown in Fig. 2.
at Kyoto University. His current
research interests include the 2.1. Polymerization within nanochannels of MOFs

Susumu Kitagawa chemical and physical properties If polymerizable monomers can be accommodated in the pores
of porous coordination polymers/ as guests, these monomers can be subsequently polymerized in
metal organic frameworks. the porous materials.15 In many cases, monomers are small

Bo Wang obtained his BS, MS and Takashi Uemura received his PhD
PhD from Peking University in at Department of Polymer Chemi-
2004, University of Michigan in stry, Kyoto University in 2002.
2006 and University of California He then joined as an assistant
Los Angeles in 2008, respectively. professor in Department of Syn-
He has been a professor in the thetic Chemistry and Biological
School of Chemistry and Chemical Chemistry in Kyoto University, and
Engineering, Beijing Institute has been an associate professor
of Technology since 2011. His since 2010. He has been also a
research interests focus on metal research director for a CREST
organic frameworks, membranes/ program of Japan Science and
films and other functional porous Technology Agency (JST) since
Bo Wang composites for gas separation, Takashi Uemura 2013. His research interest is pre-
purification and toxicant capture paration of synergistic nanohybrids
and sensing. between coordination compounds and polymeric materials, in
particular, polymer chemistry in confined nanospaces.

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Fig. 2 Schematic illustration of a variety of methods for the hybridization of MOFs and polymers. (a) Polymerization within nanochannels of MOFs.
(b) Polymerization of ligands. (c) Introduction of polymer chains into nanochannels of MOFs. (d) Polymer containing ligand monomers. (e and f) Post-synthetic
polymer-tethered ligands (grafting on and grafting from). (g) MOF-based mixed matrix membrane (MMM).

molecules that can be introduced into the pores easily; thus,


in situ polymerization is well known as a simple and convenient
method for the hybridization of polymers and porous materials.
Furthermore, polymerization in confined spaces can allow the
synthesis of structure-controlled polymers, which is of key
importance for tuning and enhancing the functions of hybrid
materials. Hence, polymerization in porous materials has been
extensively developed over the past few decades. Typical examples Fig. 3 Schematic illustration of the polymerization of St in the nanochannels
are polymerizations in the microporous channels of zeolites and of [Zn2(bdc)2(ted)]n. Adapted from ref. 23 with permission from the Royal
Society of Chemistry.
organic hosts.1620 For example, g-ray-assisted polymerization
of conjugated diene monomers was carried out in organic hosts,
which showed specific size and shape effects of the nanochannels polymerization of styrene (St) in one-dimensional nanochannels
on the kinetics and selectivity of polymerization.21,22 However, of [Zn2(bdc)2(ted)]n (bdc = 1,4-benzenedicarboxylate, ted = tri-
polymerization in previous crystalline porous materials suffered ethylenediamine) to accommodate a polymer inside the pores
from intrinsic issues of their narrow, discontinuous, and/or fragile (Fig. 3).23 In this system, St was fully introduced into the nano-
cavities for allowing the polymerization of large monomers channels by immersion of [Zn2(bdc)2(ted)]n in St, and then excess
(46 ). MOFs with their designable framework structures are monomer outside the host crystal was evacuated under reduced
of particular interest; the size, shape, dimensions, and surface pressure, providing a hostmonomer adduct. Polymerization
functionalities of the nanochannels can be systematically tuned of the monomer accommodated in the nanochannels was per-
by the precise choice of metal ions and bridging organic ligands. formed by heating the adduct with a radical initiator to afford a
These sophisticated features are attractive enough to motivate polystyrene (PSt)MOF composite. To date, a large variety of vinyl
researchers to utilize MOF nanochannels as unique nanosized polymers have been prepared inside the nanochannels of MOFs,
polymerization fields. Here, we highlight radical, ionic, and including PSt,2327 poly(methyl methacrylate) (PMMA),28 poly(vinyl
oxidative polymerizations in MOFs to incorporate polymers into acetate),28 polyacrylonitrile (PAN),29 poly(N-vinylcarbazole)
the nanochannels. (PVCz),30,31 poly(vinylbenzyl trimethylammonium hydroxide),32
Radical polymerization has been widely used for polymer poly(p-divinylbenzene),33 and poly(4-styrene sulfonate) (PSS).34
synthesis. It is applicable to a wide variety of monomers. In Control of molecular weight by radical polymerization is very
2005, in their pioneering work, Uemura et al. performed radical difficult because of the high reactivity of the growing radical species.

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Compared with the bulk and solution polymerizations, the


isolated PSt in [Zn2(bdc)2(ted)]n showed a much narrower mole-
cular weight distribution, as the propagating radical in this system
is free from side reactions because of its effective protection in the
nanochannel.28 In subsequent studies, efforts in radical polymer-
ization were further directed to controlling the tacticity,28,35,36
reaction site,33,37,38 assembly structure,25,29,39 and copolymer
sequence40,41 of the resulting polymers.
Ionic polymerization is classified into cationic and anionic
polymerizations based on the nature of the ions in the initiation
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process. Cationic ring-opening polymerization of 1,6-anhydro-


b-D-glucose in [La(BTB)]n (BTB = 1,3,5-benzentrisbenzoate) with
1-D regular nanochannels gave a quasilinear polyglucose, which Fig. 4 Schematic illustration of oxidative polymerization of pyrrole in
[Ni(dmen)2]2[FeIII(CN)6](PhBSO3). Adapted with permission from ref. 46.
contrasts with the results obtained from conventional polymeri-
Copyright 2008, Wiley-VCH.
zations in bulk and solution.42 In this system, 1-benzyltetrahydro-
thiophenium bromide was the cationic initiator for polymerization.
The versatile pore features of MOFs, such as Lewis acidity, electropolymerization of aniline inside HKUST-1 was recently
basicity, and redox activity, can be tailored by precise choice published by Qius group.54 Electropolymerization enables con-
of functional organic ligands and metal ions.43 Thus, MOFs trol of polymerization reactions by varying the electrochemical
bearing active sites in their nanochannels have been envisioned parameters such as applied current density or potential. Because
as eective catalysts in polymer synthesis. Anionic polymerization of the mild conditions of electropolymerization, this approach
of substituted acetylene has been performed in the 1-D nano- can be expected to expand the scope of functional MOFs and
channels of [Cu2(pzdc)2(pyrazine)]n (pzdc = 2,3-pyrazinedi- p-conjugated polymers for nanohybridization.
carboxylate), with basic carboxylate oxygen atoms as catalytic
interaction sites.44 It should be noted that polyacetylene 2.2. Polymerizations of ligands
extracted from the nanochannels indicated the dominance of The polymerization of organic ligands within MOF structures
its highly conjugated trans form because of the restriction of may produce hybrid materials with special chemical, mechanical,
the molecular conformation in the confined space. electrical, and optical properties. There are numerous choices for
Oxidative polymerization has been widely utilized for the the linkers and metal ions that can be employed to construct
synthesis of a variety of p-conjugated polymers that have attracted MOFs with diverse topologies. The MOFs obtained can be further
the attention of the scientific and technical community for their modified with functional groups by post-synthetic modification
various applications. It is essential to develop a method for (PSM)5557 and linker exchange58 to adjust the surface features
oxidatively polymerizing monomers in MOFs for the preparation and pore sizes. Because of the tunable characteristic of MOFs,
of functional nanohybrids from coordination and p-conjugated polymerizable ligands can be placed in specific positions to
polymers. The nanospaces of MOFs can be used as templates to polymerize with each other and form polymer chains within the
control p-conjugated polymer arrangements for improved and framework.59,60 Alternatively, the ligands may form polymers by
anisotropic functions. Oxidative polymerization is classified reacting with a cross-linker in the pores of MOFs.
into two categories: chemical- and electrooxidative polymeri- Lee, Vittal, and coworkers reported the photopolymerization
zation. Redox-active metal sites can act as an oxidant for the of adjacent photoactive ligands within a MOF to obtain a metal
preparation of p-conjugated polymers.45 A chemical-oxidative organic organopolymeric hybrid network.59 In the structure of
polymerization of pyrrole was performed within a layered MOF [Zn(bpeb)(bdc)]n (bpeb = 1,4-bis[2-(40 -pyridyl)ethenyl] benzene),
[(Ni(dmen2))2(FeIII(CN)6)]PhBSO3 (dmen = 1,1-dimethylethylene- the bpeb ligands aligned in a slip-stack manner with adjacent
diamine; PhBSO3 = p-phenylbenzenesulfonate), where the Fe3+ CQC distances of 3.68 . This is a key factor for the following
ions were reduced to Fe2+ ions, accompanied by the polymeriza- [2+2] cycloaddition reaction under UV light. In this way, the
tion of the monomers to polypyrrole (Fig. 4).46 It has been also pristine MOF with a six-fold interpenetrated net transformed
demonstrated that accessible Cu2+ sites on the pore surface of into a new network [Zn(poly-bppcb)(bdc)]n (poly-bppcb = 1,3-
[Cu3(btc)2]n (HKUST-1; btc = 1,3,5-benzenetricarboxylate) could (4,4 0 -bipyridyl)-2-phenylcyclobutane polymer) with a single net
catalyze the oxidative polymerization of pyrrole.47 Oxidative while preserving the tetrahedral geometry around the Zn2+. The
reagents can also allow us to polymerize monomers with high resulting cyclobutane rings could be cleaved after heating and
oxidation potentials.4853 In this regard, polythiophene has been the pristine structure could be obtained again, proving that the
prepared using iodine as an oxidative reagent in the 1-D channels transformation between the two structures is fully reversible.
of [La(BTB)]n, resulting in the formation of unprecedented assem- Later, the same group utilized a similar approach to form a
bly structures mediated by the host framework.48 Fedin et al. syndiotactic polymer ligand in another MOF with a pillared-
reported the synthesis of polyaniline in [Cr3(bdc)3OF(H2O)2]n layer structure.60 The MOF [Zn2(bpeb)(obc)2]n (obc = 4,4 0 -oxybis-
(MIL-101(Cr)) using (NH4)2S2O8 to increase the materials (benzoic acetate)) shows different photoreactivities with different
adsorption selectivity towards CO2 over N2.49 A report on the guest solvents. When the guest (DMF or methanol) in the channel

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was replaced by water, the position of the bpeb ligand was


spatially arranged, meeting the criteria for photopolymerization.
Through the cycloaddition reaction, a new MOF comprising both a
2-D coordination polymer and an organic polymer ligand was
developed, and the organic polymer formed could be depolymerized
upon heating. The merits of this strategy lie in forming a polymer
with a desired structure in the MOF and creating hybrid materials
with different features. However, the challenge here is to design a
framework with photoactive ligands aligned in suitable positions,
and the MOF structure should be stable and flexible enough to Fig. 5 Schematic of hostguest cross-polymerization. (a) Structure of
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undergo this transformation. DVTP. (b) Monomers used in hostguest cross-polymerizations. (c) Cross-
As demonstrated by Sada and colleagues, the ligands of linkable MOF [Cu(DVTP)x(bdc)1x(ted)0.5]n (1x; shown in light blue) prepared
MOFs can also be cross-linked in the pores of MOFs to create in a solid-solution fashion. (d) The host 1x accommodates vinyl monomers
in its nanocavities. (e) Heat treatment triggers radical cross-polymerization
polymer networks.61 The cyclodextrin MOF (CD-MOF) was chosen
in the presence of AIBN initiator, yielding 1x*polymer nanocomposites.
because of the abundant hydroxyl groups of the ligand g-CD. (f) Selective decomposition of the PCP matrix generates highly ordered
Cubic crystals of CD-MOF with dierent sizes were prepared, and cross-linked polymers. Reprinted from ref. 39 with permission from Macmillan
reacted with the cross-linker ethylene glycol diglycidyl ether in Publishers Ltd: Nat. Chem., copyright 2013.
ethanol at 65 1C. Unlike the CD-MOF, which could be dissolved
easily in water, the resultant cross-linked CD-MOF (CL-CD-MOF)
with the same underlying structure and improved thermal and copolymerized in the channels of the engineered MOF
stability was insoluble in water. The CL-CD-MOF was further while cross-linking with the DVTPA on the framework, generating
immersed in H2Oethanol to break the coordination bonds and highly ordered PSt chains covalently bonded to each other. Because
remove the residual metal ions and cross-linkers, providing of the hostguest cross-polymerization, the polymers obtained after
cubic gel particles (CGPs) with volume expansion. The cross- removing the MOF matrix present diffraction peaks in their X-ray
linking reactions took place in the pores of MOFs, leading to powder diffraction (XRPD) patterns. Polymers prepared in this way
the formation of polymer networks, and the MOF crystals were possess higher glass transition temperatures (Tg) and enhanced
sacrificed as templates to give CGPs with similar shapes. stability when exposed to solvents and high temperatures. Taking
Other reactions have also been applied to cross-link the advantage of the well-defined channels of MOFs and the cross-
linkers in the voids of MOFs. For example, Sada et al. employed linking reactions between the host ligands and the organic mono-
the in situ click reaction to obtain polymer networks without mers is a facile and promising way to prepare MOFpolymer
aecting the structures of MOFs.62 The linkers, modified with hybrids and polymers with controllable chain packing.
the clickable azide function group, were used to synthesize As demonstrated above, ligands of MOFs can participate in
MOFs with metal ions including Zn2+, Cu2+, and Zr4+, and the polymerization reactions in two ways: (i) polymerization with
resultant MOFs were then reacted with multifunctional acetylene each other within the framework; or (ii) reaction with newly
compounds accompanied by Cu+ to aord cross-linked MOFs added monomers. One important precondition for these reac-
with polymers in the pores. Once the composites were soaked in tions is the stability of the structure during the process. For the
acid, the decomposition of the host MOFs liberated polymer gels first method, the polymerizable linkers must be included in the
with a similar shape. Similarly, Woll and colleagues converted MOFs, and their positions directly influence the polymerization
highly ordered surface-mounted MOFs (SURMOFs) prepared via process. Therefore, MOFs with regulated spatial arrangement
liquid-phase epitaxy (LPE) to polymer gel coatings through cross- of the ligands are only able to undergo polymerization between
linking the linkers containing azido groups with alkyne.63 The adjacent ligands. The second method is regarded to be more
surface-grafted gels (SURGELs) obtained had homogeneous universal, and the key factors are the polymerizable functional
thickness and showed remarkable stability. The post-synthetic groups and suitable channels for the occurrence of polymeriza-
click reactions between the ligands within the MOF and the tion. By designing and tailoring the sites of functional groups
added cross-linkers proved to be a universal way to form polymer and the structure of the channels in MOFs, high-dimensional
gels. Although the macroscopic shape of the polymers obtained polymers with controlled structures can be synthesized, provid-
could be controlled, the regularity of the polymer chains remains ing unprecedented polymer materials with various fascinating
dicult to achieve. properties.
Uemura et al. utilized cross-linking between the host MOF
and the polymer chains produced in its channels for the first 2.3. Utilization of polymer-tethered ligands (pre-synthetic or
time, achieving precise control of the alignment of a vinyl poly- post-synthetic methods)
mer (Fig. 5).39 [Cu2(bdc)2(ted)]n was employed as an underlying To alter the properties such as stability, dispersity, and flexibility
structural motif, where the bdc in the host was partially sub- of MOFs, a promising method is to modify these crystalline solids
stituted with a polymerizable 2,5-divinyl-terephthalic acid (DVTPA) with polymers. Preparation of MOF tethering polymers can be
ligand. The ratio of the two ligands could be adjusted, which is achieved during the formation of MOF crystals by using pre-
a crucial factor in cross-polymerization. St monomer was added prepared polymeric linkers (pre-synthetic method) or attaching

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polymer chains onto the functional ligand sites of MOF crystals With the grafting to method, polymers with special prop-
(post-synthetic method). These MOF/polymer hybrid materials erties can be directly bonded to the functional groups on MOFs
inherit porosity and crystallinity from the MOF together with giving hybrid materials. Kokado and Sada et al. reported the
flexibility, processability and many other interesting properties, covalent attachment of the thermosensitive polymer poly(N-iso-
such as response to external stimulus from the polymers. propylacrylamide) (PNIPAM) onto the surface of MOFs allowing for
In the pre-synthetic method, polymers containing ligand controlled guest release.69 [(Zr6O4(OH)4(bdc-NH2)6)]n (UiO-66-NH2)
monomers were used to synthesize MOF derivatives. Recently, was selected for its stability under harsh conditions and its
Cohens group has pursued a series of studies in this respect to amino functional groups for further modification reactions. The
give MOF/polymer hybrid materials, polyMOFs. The initial study grafting reaction was achieved by immersing the MOF particles
used cross-linked NH2-bdc with dierent linker lengths to synthe- in PNIPAM-NHS-chloroform and subsequent heating at 60 1C.
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size cross-linked isoreticular MOF (IRMOF) analogues using the According to that study, the polymer undergoes a surface-
solvothermal method.64 Based on this, rationally designed oligo- selective modification because its molecules are larger than the
meric ligands that contain three H2bdc units linked together pore size of UiO-66-NH2. The MOF-tethering PNIPAM loaded with
were applied to construct IRMOF derivatives.65 Their successful guest molecules exhibits temperature controlled release behavior,
preparation demonstrates that the topology of IRMOFs can which is derived from the coilglobule transition of the thermo-
endure some variations in ligands. Polymer ligands with repeat- responsive polymer at different temperatures. Grafting polymer
ing H2bdc units were also attempted to produce crystalline chains to MOFs is a straightforward way to tune the properties of
MOFs.66 As shown in Fig. 6, 1-D polymer chains with H2bdc the inorganic crystalline materials; however, the modification
moieties in the backbone were prepared and then converted to degree (grafting density) may vary because of the different con-
crystalline IRMOF analogues by annealing with Zn2+. The formations and sizes of polymers.
polyMOFs obtained possess the features of polymers (flexibility To achieve precise modification of the external surfaces of
and hydrophilicity) and MOFs (crystallinity and porosity), which MOFs, Lachelt and Wuttke et al. made use of unsaturated func-
demonstrates that the inclusion of polymer chains within the tional groups of linkers for the covalent attachment of polymers.70
framework is a good way to tailor the properties. The concept of Since the linkers with unsaturated sites exist only on the outer
polyMOFs was further applied to MOFs with pillared-layer struc- surfaces of particles in most cases, the modification reactions
tures by combining the polymer ligand with the pillar ligand.67 are limited to the surfaces. A stable MOF [Fe3F(H2O)2O(btc)2]n
Analogues of the MOF [Zn2(BME-bdc)2(bpy)]n (BME-bdc = 2,5- (MIL-100(Fe)) with free aromatic carboxylic acid groups was
bis(2-methoxyethoxy)-1,4-benzenedicarboxylate) were obtained by selectively functionalized with polyethylene glycol (PEG) 5000
changing the BME-bdc to a polymer ligand containing H2bdc and Stp10-C by a carbodiimide mediated reaction under mild
moieties with methylene spacers. Note that the incorporation of conditions. MOF particles with surface polymer coatings reveal
polymer chains enhanced the stability and hydrophobicity of the enhanced colloidal stability and possibilities for biomedical
MOFs. However, the polymer chains of the ligands also influence applications.
the process of formation of MOFs, often resulting in amorphous To control the modification degree and the thickness of
products. the polymer coating eectively, a post-synthetic polymerization
A more general way to access MOF tethering polymers is to (PSP) method, which resembles the grafting from reaction,
attach polymers to the synthesized MOF particles. In general, can be adopted to functionalize the MOF particles with poly-
two major methods have been applied to modify MOFs with mers. The precondition for the occurrence of the PSP is that the
polymer shells post-synthetically. The first involves covalently MOFs contain polymerizable groups or functional groups to
attaching the polymer chains to the functional groups on MOFs, which active sites can be attached. Then the MOF particles with
which is similar to the grafting to process in graft copolymeri- active sites can be polymerized with organic monomers or oligo-
zation.68 Another approach, called the post-synthetic poly- mers to oer composites possessing the advantages of both MOFs
merization (PSP) strategy, utilizes the copolymerization and polymers.
between organic monomers or oligomers and polymerizable From the authors group, Wang et al. developed the concept
functional groups on MOFs, which resembles grafting from of photoinduced post-synthetic polymerization (PSP) for the
reactions.68 polymer modification of MOFs via covalent bonds and enhanced
processability of such crystalline materials for the first time.71
The preparation procedures are shown in Fig. 7. Nanosized
crystals of UiO-66-NH2 were first modified with methacrylamide
groups, and their further copolymerization with organic mono-
mer butyl methacrylate (BMA) or MMA was induced by UV light.
The MOFmonomer suspension was dripped into a mold, and
the membrane afforded after radiation could be easily peeled
off and showed flexibility. In this way, the MOF nanoparticles
Fig. 6 The strategy described herein to convert a 1-D (linear), nonporous,
were covalently linked by the polymers. Photo-induced PSP is
mostly amorphous polymer into a 3-D, porous, crystalline polyMOF hybrid a facile and universal approach for fabricating MOFpolymer
material. Adapted with permission from ref. 66. Copyright 2015 Wiley-VCH. hybrid composites and membranes. Such PSP-derived composites

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methacrylate and oligo(ethylene glycol)methacrylate. Because


of the attachment of thermoresponsive copolymers, the MOF
particles can reversibly switch their dispersion and collection
state by heating and cooling.
In the above situations, the initiator sites might be immo-
bilized in the pores of MOFs, and thus the subsequent polymeri-
zation probably proceeds in the cavities, which will decrease
the surface area of the resulting porous materials. To solve this
problem, Matzger and coworkers introduced a MOF@MOF core
shell system where the MOF shell was used for the initiator
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immobilization as well as the attachment of polymer chains.77


IRMOF-3@MOF-5 was first synthesized, and then 2-bromoiso-
Fig. 7 Preparation of a PSP-derived membrane by photoinduced post- butyric anhydride was reacted with the amine groups in the
synthetic polymerization. Adapted with permission from ref. 71. Copyright IRMOF-3 shell. The polymer@MOF@MOF was obtained by ATRP
2015 Wiley-VCH. with an organic monomer MMA. The special structure ensures
that polymerization occurs on the outer shell; therefore, the high
surface area is maintained during the process of functionalization
shed light on the fabrication of new MOF hybrid materials for and polymerization.
practical applications. Utilizing the PSP strategy, Dong and The tethered polymer chains can also act as bridges to link
colleagues prepared UiO-66-NH2polyurea hybrid membranes MOFs onto certain substrates. As shown by Li and colleagues,
with different MOF loadings.72 The amino-functionalized MOF was MIL-101(Cr) was covalently attached to nylon fabrics by poly-
cross-linked with an isocyanate-terminated polyurethane oligomer, merization with 2-hydroxyethyl acrylate (HEA) induced by g-ray
giving free-standing membranes without obvious defects. The irradiation.78 Due to the existence of vast benzene rings in MIL-101,
hybrid membranes showed potential for dye removal. free radicals can be produced on its surface when exposed to g-ray
Mahdavi et al. investigated the preparation of MOF plus irradiation. The same process also occurs on the surface of the
sulfonated polymer hybrid nanoparticles by surface-initiated nylon substrate. In this situation, the generated radicals can initiate
radical polymerization.73 Amino groups in MIL-101(Al)-NH2 reacted the polymerization of HEA, and the formed PHEA chains firmly
with 4,40 -azobis(4-cyanovaleric acid) endowing the MOF particles link MOF particles to the substrates.
with initiator sites (forming macro-initiators). The following graft
polymerization of 2-acrylamido-2-methyl-1-propane sulfonic acid 2.4. Introduction of polymer chains into nanochannels of
(AMPS) occurs from the active sites on the MOF; therefore, the MOFs
grafted polymer chains are formed around the external surface The synthesis of polymers inside or outside MOFs has been
of the particles. The same method also works for silica particles widely investigated for the preparation of polymerMOF com-
to give super-acidic hybrid particles. By changing the active sites posites. However, with the in situ polymerization method, precisely
attached to MOFs, the same group proved that the method was controlling the molecular weight and loading amounts of poly-
suitable for the redox polymerization of AMPS from the MOF mers, which are important factors in determining the polymer
surface.74 chain assembly structures and their functions, remains challeng-
The aggregation problem and poor dispersity of MOF particles ing. Polymer incorporation into MOFs is a simple yet powerful
hinder their further applications in liquid systems. Modification method to overcome these limitations. In addition, one of the
with polymers can tailor the properties of MOFs to some extent. significant advantages of this method is its ability to introduce
Webley and colleagues showed that the grafting of a hydrophilic polymers that pose a synthesis problem inside MOFs. To intro-
PEG polymer would benefit the dispersity of MOF particles in duce polymers into MOFs, several approaches have been studied,
water.75 UiO-66-NH2 was first anchored with a multifunction- including melt processing, solution-mediated incorporation, and
alized initiator by reacting with bromoisobutyryl bromide (BiBB), growth of MOFs in the presence of polymers.
followed by an atom-transfer radical polymerization (ATRP) of the Uemura and Kitagawa et al. demonstrated that MOFs can
macromonomer poly(ethylene glycol) methyl ether methacrylate adsorb polymer chains in their channels to form MOFpolymer
(PEGMA) initials from the MOF substrate. The PEG-grafted MOFs composites via polymer melt processing. In this method, PEG
obtained from this procedure showed excellent dispersity in (MW = 3000),79 linear alkanes,80 and polymethylpropylsilane
aqueous solution. This can be explained by the isolation of the (Mn = 3600)81 have been incorporated into MOFs by heating
MOF particles and the elimination of interactions after polymer polymers and MOFs above the melting temperature of the
attachment. The dispersity can be tuned by varying pH for MOFs polymers. However, melt processing cannot be used with poly-
with short polymer chains. Using a similar method, Zhu et al. mers with high molecular weights because of their low diffu-
realized the reversible dispersability/collectability in MOF sivity into the pores.
polymer hybrid materials by immobilizing the thermally The solution-mediated approach enables us to incorporate
switchable copolymers.76 MIL-101(Al)-NH2 modified with BIBB polymers with high molecular weights into the nanopores of
underwent surface-initiated ATRP of 2-(2-methoxyethoxy)ethyl MOFs. The MOF/polymer composites are formed by immersion

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of MOFs in a solution containing the desirable polymer. In


many cases, the polymer intercalation is accelerated by heat
treatment. Matzger et al. introduced poly(3-hexylthiophene)
(P3HT) with a high molecular weight (Mn = 21 700) into the
mesoporous channels of [Zn4O(bdc)(BTB)4/3]n, resulting in the
uniaxial alignment of the P3HT chains.82 MOFs can adsorb even
biomolecules with a large molecular size through judicious
choice of solvents and temperature. Enzymes are biomolecules
that are well known to be natures catalysts with high reactivity
and selectivity. Immobilization of enzymes into porous materials
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can enhance their stability as well as facilitate separation and


recovery for reuse while maintaining activity and selectivity.83
Encapsulation of microperoxidase-11 (MP-11) in [Tb16(TATB)16]n
(Tb-mesoMOF, TATB = triazine-1,3,5-tribenzoate) was reported
by Mas group.84 Immersing the Tb-mesoMOF in MP-11 solution
for 50 h at 37 1C led to a saturated loading of 19.1 mmol g1.
In this MOF, two nanocages 3.9 and 4.7 nm in diameter are
connected through hexagonal and pentagonal windows with
diameters of 1.7 and 1.5 nm, respectively, which are large
Fig. 8 Scanning electron microscopy images showing ZIF-8 crystals obtained
enough to allow the incorporation of MP-11 molecules and their using: (a) trypsin, (b) HRP, (c) insulin, and (d) quinone-dependent glucose
accommodation in the mesopores. Subsequent eorts have also dehydrogenase. Scale bars, 1 mm. Reprinted by permission from Macmillan
been made to introduce other enzymes including the heme Publishers Ltd: Nat. Commun., ref. 89, copyright 2015.
protein cytochrome c (Cyt c) and myoglobin (Mb) into the
Tb-meso MOF, despite the larger molecular dimensions of
the proteins (2.6  3.2  3.3 nm3 and 2.1  3.5  4.4 nm3 MOFs (i.e., HKUST-1) could also be synthesized, highlighting the
for Cyt c and Mb, respectively).85,86 They proposed a tentative generality of this biomimetic mineralization method. In addition,
mechanism for Cyt c encapsulation into the Tb-meso MOF, this technique extended the bioactive temperature range of
which involves a significant conformational change of Cyt c enzymes in comparison with the free enzymes and the enzymes
molecules during translocation into the MOF interior through encapsulated via the coprecipitation method, demonstrating that
the relatively small nanopores. biomimetic mineralization can allow the practical use of enzymes
Another approach to encapsulating polymer chains in MOFs for various industrial applications.90
is the growth of MOFs in the presence of polymers via self- The accommodation of polymer chains within MOF particles
assembly. Takamizawa et al. reported the synthesis of inclusion has been demonstrated using common techniques, such as XRPD,
complexes between [Mo2(fumarate)2]n and PEG of various mole- particle size distribution, gas adsorption, Raman spectroscopy,
cular weights ranging from 2007500.87 The amount of PEG DSC, SEM, confocal microscopy, and NMR.79 Multinuclear 2-D
included increased with an increase in the molecular weight of NMR is one of the most powerful methods to provide direct
PEG. In contrast to the other methods, this approach has high evidence of the encapsulation of polymer chains in pores. When
versatility because there are fewer limitations on the molecular polymer chains are incorporated into pores and are in close proxi-
size of the polymers. Two strategies have been reported for the mity to the host materials at the molecular level, cross-correlations
synthesis of composite materials. The first employs a copreci- are observed because of heteronuclear magnetization transfer
pitation method in which biomolecules stabilized by capping between polymer chains and hosts.24,39,79,81
agents (i.e., polyvinylpyrrolidone) are added to a solution con-
taining MOF precursors.88 The second approach, termed bio- 2.5. MOF-based mixed-matrix membranes (MMMs)
mimetic mineralization, is performed in the absence of For practical applications such as gas separation, catalysis, and
capping agents.89 A wide range of giant biopolymers, such as sensing, powder-form MOFs must be processed into certain
trypsin, horse-radish peroxidase (HRP), and insulin, have been shapes. Since such crystalline materials always lack flexibility
successfully encapsulated into [Zn(MeIM)2]n (ZIF-8; MeIM = and processability, the combination with polymers can be a good
2-methylimidazole) through a biomimetic mineralization choice. Numerous MOF membranes have been prepared accom-
strategy.89 The proteins and MeIM were first dissolved in water panied by polymers that act as a continuous phase or support.
and then combined with a solution of zinc acetate, resulting in Mixed-matrix membranes (MMMs), composed of porous inorganic
the formation of ZIF-8-coated proteins. Proteins rapidly induce fillers dispersed in a polymer matrix, are promising materials
the formation of MOF coatings by concentrating the framework given their combination of advantages from both compo-
building blocks and facilitating crystallization around the pro- nents.91,92 Among the various inorganic fillers, MOFs stand
teins. In contrast to the coprecipitation method, SEM images out because of their good compatibility with polymers and high
showed that the crystal morphology changed, depending on the degree of designability. The pioneering work was conducted
biomolecules (Fig. 8). The authors demonstrated that other by Musselman and coworkers, who incorporated a copper(II)

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To address these problems, researchers have devised various


preparation strategies.
Numerous polymers have been used with MOFs to fabricate
MMMs, including polyimide (PI), polysulfone (PSF), polybenz-
imidazole (PBI) and PMMA. One important thing to consider is
the property matching between these two phases. For example,
ZIFs are expected to possess better compatibility with PBI because
of their similar components.105110 Good adhesion can be achieved
by forming noncovalent interactions and covalent bonds between
fillers and polymers. MOFs with amino and hydroxyl groups are
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preferred because they can form hydrogen bonds with many


polymers, such as PSF, PMMA, and PI.111116 Employing in situ
polymerization, Zhu et al. chose a MOF with a ligand that is also a
Fig. 9 Schematic illustration of the dierent types of MOF-based MMMs. moiety in the polymer, and thus the MOFs can interact with the
resulting polymers very effectively.117 The membranes obtained
show defect-free structures at the boundary because of the covalent
biphenyl dicarboxylate-triethylenediamine MOF into a poly(3- bond between the MOF and the polymer matrix. A more general
acetoxyethylthiophene) (PEAT) matrix.93 Since that study, remark- method is to modify the MOF particles with functional groups or
able MOF-based MMMs have been prepared and applied in polymers to tailor the surface properties and thus improve their
various applications, such as gas separation, pervaporation, nano- adhesion to the polymers.118121 As illustrated by Wu and collea-
filtration, and solid electrolytes.13,94100 gues, MIL-101(Cr) decorated with polyethylenimine (PEI) showed
Based on the morphology of the membranes, MOF-based increased interactions when mixed with sulfonated poly(ether
MMMs are characterized as symmetric dense membranes and ether ketone).121
asymmetric membranes (Fig. 9). Symmetric membranes pos- The size and morphology of the MOF particles are also crucial
sess a uniform structure with MOF particles dispersed in the parameters when fabricating membranes.122 Nanoparticles are
polymer, while asymmetric membranes consist of a thin and often preferred because they can provide larger interfacial areas
selective MOFpolymer layer supported on a nonselective porous at the MOFpolymer boundary, thereby allowing closer integra-
substrate. tion.123128 In Nairs study, size-reduced [Zn(ICA)2]n (ZIF-90; ICA =
A common fabrication method for symmetric MOF-based 2-imidazolatecarboxyaldehyde) was incorporated into PI, giving
MMMs is the solution casting approach. In this process, one membranes with excellent gas separation performance.123 MOF
crucial issue is the particle dispersion in the casting solution. nanosheets are another attractive candidate for the MMM
Usually, MOF particles are first dispersed in the solvent by filler.129,130 Therefore, developing methods to tune the morphol-
stirring or sonication, and then mixed with the polymer solution ogy and size of MOF particles will also boost the advancement of
to form the final casting solution. A priming technique is often MOF-based membranes.
applied to obtain a well-dispersed solution.101,102 In this step, a Some novel methods have been designed to produce hybrid
small portion of the polymer is first mixed with the MOF membranes with defect-free interfaces. Quemener et al. developed
suspension to form a layer of polymer on the surface of the a particle fusion approach that involves the growth of ZIF-8 in a
MOF particles to prevent aggregation. The step is repeated until Matrimids 5218 particle suspension followed by slowly fusing the
all the required polymers have been added. Sucient stirring or MOFpolymer composite to fabricated membranes without com-
sonication is required before casting to avoid agglomeration and patibility problems.131 One-pot synthesis of MMMs was studied by
remove air bubbles. Then the MOFpolymer dispersion is cast Coronas et al.; the key step is to find a common solvent for the
onto a flat substrate, usually with a casting knife, and left for preparation of both the MOFs and casting solution, which ensures
evaporation of the solvent. When the solvents used for casting strong interactions in the final composite membranes.132 Later,
are volatile, the evaporation rate in the initial process should be crystallization of MOFs in the polymer solution or even monomer
controlled by partial coverage or by applying low heating solution in the continuous phase was successfully realized by
temperature to avoid forming defects. Heating under vacuum Dong.133 The in situ construction of MOFs within the polymer
removes all of the residual solvents. It is believed that post- (monomer) system leads to membranes without defects at the
treatment under high temperatures would improve the membrane interfaces. Furthermore, as demonstrated by He et al., ionic liquid
performance, especially for gas permeability, as the solvent in the (IL) can act as a cross-linking agent to strengthen the inter-
pores of MOFs can be eliminated.103,104 actions between the two phases.134
Membranes with uniform and defect-free structures are Another diculty that must be overcome is the agglomera-
desirable, especially for separation applications. Two main issues tion of MOF particles, especially for nanoparticles, which will
that may influence membrane performance are poor compati- degrade the membrane performance and mechanical properties. As
bility between the MOF fillers and polymer matrices (leading to mentioned above, the most commonly used method is priming
interface defects) and particle agglomeration and sedimenta- the MOF particles with a layer of polymer before mixing to
tion (resulting in nonselective voids and brittle membranes). prevent aggregation in the casting solution.135140 In addition,

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MOF nanosheets embedded in polymers tend to present a always possess defects, and further surface modification is
uniform occupation and to improve the membrane performance necessary to cover those voids. Vankelecom et al. prepared a
because of their special nanostructure and large exposed surface series of asymmetric PI membranes containing HKUST-1, ZIF-8,
area.129,130 In contrast, large MOF particles are prone to form and [Al(OH)(bdc)]n (MIL-53(Al)), and then coated the membranes
sediments in the course of casting, which lead to inhomogeneous with permeable polydimethylsiloxane (PDMS) layers on the sur-
and brittle membranes.141 face by spin coating to seal the undesirable defects. In some cases,
Agglomerates are often formed during the drying of MOF the phase inversion method has also been utilized to prepare a
particles; once this happens, it is dicult to redisperse them. porous polymer that serves as the support for MMMs.151 Dip
Therefore, direct incorporation of the synthesized wet-state MOF coating is also a good way to fabricate asymmetric membranes.152
without drying would be a good choice.104,110,142,143 Sivaniah Diestel and colleagues prepared a-alumina-supported ZIF-8
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et al. applied the solution-mixing strategy in the fabrication of polymethylphenylsiloxane (PMPS) membranes by dipping the
ZIF-8Matrimids 5218 membranes, and the resultant mem- substrate in the solution and withdrawing at a constant rate.153
branes showed good particle dispersion, even at a high loading HFMs, with their high packing density, large area per volume,
of MOFs.142 tolerance to pressure and low cost, are the most desired mem-
Other methods have been developed to facilitate particle brane geometry for real applications.154 HFMs are usually prepared
dispersion throughout the polymer matrices. Employing MOF by dry jetwet quench spinning (also called phase inversion
composites as fillers has proved to be an eective way to enhance spinning), which is similar in principle to the method for asym-
the dispersion of the MOF.144,145 Zhu et al. prepared a composite metric MMMs. Fabrication of pure polymer HFMs has been
filler by growing ZIF-8 in situ on the surface of carbon nanotubes well explored; however, the addition of MOF particles may
(CNTs). ZIF-8 showed good dispersion in the membrane with the require addressing of further issues.109,155157 Liu et al. reported
help of the CNTs.144 In addition, surface modification of MOFs the first MOF-based mixed-matrix HFMs consisting of HKUST-1
with long-chain organic compounds may oer another way to and PI.156 The MOF particles were first mixed with poly(amic
achieve even dispersion. Queen and colleagues modified the acid) (PAA) to form a homogeneous dispersion solution for
hydrophilic UiO-66-NH2 with oleic acid through post-synthetic spinning, and then the solution was coextruded with water as
ligand exchange, and the modified MOFs showed good disper- the bore fluid into a water-ice coagulation bath and collected by
sion in a hydrophobic cyclic olefin copolymer.146 a setup in which the phase inversion happened and hollow
In most cases, poor interactions between the MOF filler and fibers were formed. The fibers were then immersed in water to
the polymer, as well as the aggregation of MOFs, are closely exchange fully with the solvent and washed with methanol and
related and should be considered together. Enhancing the hexane, followed by heating to complete the imidation process
compatibility between the two phases also improves the dis- of PAA to form PI. The spinning temperature was set at 3045 1C
persability of the particles. The photoinduced PSP strategy is a to achieve suitable viscosity.
promising method to solve both issues.71 MOFs modified with Koros and colleagues prepared MOF-based dual layer HFMs
polymerizable functional groups are expected to disperse well that consist of one layer of polymer as the support and another
in a monomer with a similar structure, and further copolymer- layer with ZIF-8 particles as the selective skin.155 The core solu-
ization between the MOF and polymer ensures their intimate tion was prepared by mixing Ultems 1000 (in tetrahydrofuran
contact. As discussed in Section 2.3, MOFs decorated with poly- (THF)) and LiNO3 acting as a pore-forming agent (in N-methyl-
mers become more dispersable, which makes them promising 2-pyrrolidione (NMP)). The sheath solution was prepared using
fillers for MMMs. The attached polymers on the MOF surface also a priming procedure by combining a ZIF-8NMPTHF sus-
improve the interface compatibility. pension and an Ultems 1000LiNO3NMP solution. The core
As for the asymmetric MMMs, a low mass transfer resistance and sheath solution together with the bore fluid solution
and high flux are expected because of their thin selective layer (10 wt% water in NMP) were then coextruded through a compo-
supported on porous substrates, which are of practical value for site spinneret into a quench bath. The fibers obtained were then
gas separation. According to their geometry, asymmetric mem- immersed in water, ethanol and hexane separately before drying
branes can be classified into flat-sheet and hollow-fiber mem- in an oven. Later, Koros and colleagues carried out a systematic
branes (HFMs). investigation of the preparation parameters of MOF-based
Several approaches have been developed for the preparation mixed-matrix HFMs with high MOF loadings.157 They further
of asymmetric flat-sheet membranes, including phase inver- treated these fibers with a PDMS and/or polyaramid coating to
sion, dip coating, solution casting, and spin coating. The phase seal the cracks on the surfaces. The dual-layer HFMs are more
inversion method (also called drywet phase inversion) is the attractive and promising because they only need porous particles
most commonly applied method.147150 In a typical procedure and selective polymers in the skin layer, thus decreasing the cost
for MOFPI membrane preparation, the polymerMOF solution for molecular sieves and the core polymers.
was first cast onto a substrate followed by a solvent evaporation Mixed-matrix HFMs can also be produced by coating a
process, and then immersed in water for solidification, followed polymerMOF layer onto polymer or ceramic hollow fibers.158,159
by solvent exchange in isopropanol. The membrane obtained On one hand, the coating layer can cover the defects on the
then is dried in an oven to remove the solvent completely. support and improve the overall selectivity; on the other hand,
However, the asymmetric membranes prepared in this way it can protect the support to some degree under harsh conditions.

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Ismail and coworkers first fabricated PSF hollow fibers by phase because of its photoconductivity.163 In the bulk state, partially
inversion spinning and subsequently coated them in a PDMS overlapped structures of neighboring carbazolyl groups led to a
HKUST-1 dispersion using a dip coating method.159 Considering relatively low hole mobility (107 cm2 V1 s1).164 However,
the numerous merits of asymmetric membranes, especially HFMs, confinement of PVCz in 1-D nanochannels of [La(BTB)]n dras-
more strategies should be developed to fabricate membranes with tically enhanced the hole transport properties.30 PVCz chains in
perfect structures on a large scale. [La(BTB)]n formed an extended linear structure with enhance-
ment of the pp stacking of carbazoles, which was confirmed by
fluorescence measurements and molecular dynamics simula-
3. Functions tions. This unusual structure led to an increase in the carrier
mobility, which was about five orders of magnitude higher than
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The variety of MOFs and polymers aords an essentially infinite that in the bulk.
number of possible combinations. Table 1 summarizes the As conjugated polymers play crucial roles in advanced nano-
combinations of MOFs and polymers along with the functions scale devices, understanding of nanoscale electronics is highly
explored for the resulting hybrid materials. desirable for future applications. Polysilanes exhibit intriguing
optoelectrical properties, such as high quantum yield of fluores-
3.1. Properties of polymer chains confined in MOFs cence and high mobility of charge carriers, which are attributed
Understanding the properties of a few polymer chain assemblies to the delocalization of s-electrons along the main chain.165
is important because of their potential applications for molecular- The accommodation of single polysilane chains in [Al(OH)(L)]n,
based devices.160 Confinement of polymer chains in porous where the ligand L corresponds to 2,6-naphthalenedicarboxylate
materials is a feasible method to control polymer assemblies and 4,4 0 -biphenyldicarboxylate, increased the values of carrier
because this approach can prevent the entanglement and con- mobility compared with that in the bulk state because of the
formational disorder of polymer chains in the bulk state.161 The elimination of slow interchain carrier hopping.81 The confor-
regulated and tailor-made pore characteristics of MOFs allow mation of the polysilane chains pivoted on the pore size, as
the achievement of precise molecular assemblies in the nano- evidenced by 29Si NMR, Raman spectroscopy measurements,
channels, permitting fundamental studies on inherent polymer and molecular dynamics simulations, allowing precise mani-
properties that, until now, have remained elusive. In this regard, the pulation of carrier transport properties even in the single-chain
Uemura and Kitagawa group has widely studied the various intrigu- manner. Recently, a report on the optoelectrical properties of
ing properties of polymers confined in nanochannels of MOFs. a few polymer chains confined in MOFs has been published.
Radical polymerization of St was performed in the nano- Unsubstituted polythiophene (PTh) was prepared in the 1-D
channels of [Zn2(bdc)2(ted)]n to study the behavior of single PSt nanochannels of [La(BTB)]n, where the number of polymer chains
chains with a linearly extended conformation.24 Molecular was controlled.81 Regardless of the number of chains in the
simulation and 2H NMR spectroscopy indicated that these nanochannels, the PTh chains exist in a planar fashion because
single PSt chains aorded unprecedented molecular dynamics of the association of the polymer chain with the pore walls. The
in the 1-D nanochannels: homogeneous rotation of phenyl rings accommodation of PTh chains in [La(BTB)]n resulted in a blue
with a very low activation energy. This behavior can be ascribed shift of the emission wavelength; moreover, as the loading
to both the linear extension of the single-chain conformation in amount of polymers in the MOF decreased, the magnitude of
the nanochannels and the exclusion of the multiple interactions the blue shift increased. In addition, the carrier transport proper-
observed in the bulk polymer. ties of PTh were also drastically changed by varying the number
Incorporation of PEG into 1-D nanochannels of [Cu2(L)2(ted)]n of polymer chains through the formation of the pp stacked
revealed a thermal transition of only a few chain assemblies structure. Strong interchain interactions render PTh nonmelting
(Fig. 10).79 In this system, the pore size and surface functionality and insoluble; hence, control of the assembly structure, which
of [Cu2(L)2(ted)]n were easily tailored by changing the ligand L, so has a profound effect on its optoelectrical properties, has never
that the thickness of the chain bundles, as well as the environ- been achieved. The results obtained highlight that encapsulation
ment of the polymer chains, could be precisely controlled. Taking of polymer chains is a key strategy for controlling the low-
advantage of MOFs, the transition behavior of the PEG bundles dimensional assembly structures to elicit potentially useful yet
could be systematically controlled for the first time. Note that the unexplored properties.
transition temperature of confined PEG decreased as the mole-
cular weight of PEG increased, which contrasts strongly with the 3.2. Functions of hostguest nanocomposites
conventional bulk system. The mobile nature of PEG chains While a great deal of research eort has been aimed at prepar-
in MOFs was exploited in the area of lithium conductivity. ing new MOF structures for various applications, hybridization
Incorporation of Li ions into MOFPEG composites led to of MOFs with a variety of functional guests has been proposed
liquid-like high mobility of Li ions with an activation energy, to combine the merits and mitigate the shortcomings of both
Ea, of 0.18 eV.162 components.14 Polymers possess many unique attributes, includ-
The spatial control of polymer chain arrangements is a key ing thermal and chemical stability, fluorescence, and conductivity,
strategy for improving their functions, such as fluorescence which are desirable to integrate with MOFs to make composites
and conductivity. PVCz has attracted a great deal of attention with sophisticated architectures.

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Table 1 Summary of the reported MOF and polymer hybrids

MOF Polymer Properties Ref.


Polymer chains confined in MOFs
[La(BTB)]n (BTB = 1,3,5- Poly(N-vinylcarbazole) Charge carrier transporting 30
benzentrisbenzoate)
[La(BTB)]n Polythiophene Fluorescence, charge carrier transporting 48
[Cu2(bdc)2(ted)]n (bdc = Poly(ethylene glycol) Thermal transition, Li ion conductivity 79, 80
benzenedicarboxylate; ted = and 162
triethylenediamine)
[Al(OH)2,6-naphthalenedicarboxylate]n Polysilane Enhancement of photostability, charge 81
carrier transporting
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Hostguest nanocomposites
MOF-5 Polystyrene Enhancement of CO2 adsorption and 26
moisture stability
MIL-101(Cr) Poly(N-vinylcarbazole) Fluorescence sensing for 1,3,5- 31
trinitrobenzene
ZIF-8 Poly(vinyl benzyl trimethylammonium Removal of gold cyanide anion 32
hydroxide)
MIL-101(Cr) Sodium poly(4-styrenesulfonate) Removal of cobalt cation 34
MIL-101(Cr) Polyaniline Enhancement of CO2 adsorption 49
MIL-101(Cr) Poly(3,4-ethylenedioxythiophene) Chemiresistive detection of NO2 51
[Zn4O(bdc)(BTB)4/3]n Polythiophene Fluorescence anisotropy 82
[Tb16(TATB)16]n (TATB = Micoperoxidase-11 Oxidation of 3,5-di-t-butyl-catechol 84
triazine-1,3,5-tribenzoate)
ZIF-8 Cytochrome c Fluorescence sensing for organic peroxides 88
ZIF-8 DQ-ovalbumin Enhancement of thermal stability 89
MOF-5 Polynaphthylene Enhancement of CO2 adsorption and 166
moisture stability
MIL-101(Cr) Poly(N-bromomaleimide) Dehydration of fructose 171
PCN-333 Horseradish peroxidase Oxidation of o-phenylenediamine 173
PCN-128y Organophosphorous acid anhydrolase Hydrolysis of o-pinacolyl methyl 174
fluorophosphonate

Polymer modification of the surface of MOFs


MOF-5 Polyether containing benzenedicarboxylic Enhancement of CO2 adsorption and 66 and 67
acid moisture stability
UiO-66 Poly(N-isopropylacrylamide) Controlled release of guest molecules 69
MIL-100(Fe) Poly(ethylene glycol) Colloidal stability in water 70
UiO-66 Poly(methyl methacrylate) Separation of chromium ions from water 71
UiO-66 Polyurea Separation of eosin Y and methylene blue 72
MIL-53(Al) Poly(2-acrylamido-2-methyl-1- Proton conductivity 74
propanesulfonic acid)
UiO-66 Poly(ethylene glycol) Colloidal stability in water 75
HKUST-1 Poly(dimethylsiloxane) Enhancement of moisture stability 178
HKUST-1 Poly(vinylidene fluoride) Enhancement of moisture stability 179
MIL-100(Fe) Heparin Enhancement of biocompatibility 182
UiO-66 DNA Enhancement of biocompatibility 183

MMMs
ZIF-90 Polybenzimidazole H2CO2 separation 106
ZIF-8 Polybenzimidazole H2CO2 separation 109 and 187
ZIF-7 Polybenzimidazole H2CO2 separation 110
HKUST-1 Poly(dimethylsiloxane) Removal of Rose Bengal from isopropanol 119
NH2-MIL-53(Al) Matrimids 5218 CO2CH4 separation 122 and 198
ZIF-90 6FDADAM (FDA = 4,4 0 -(hexafluoroisopro- CO2CH4 separation 123
pylidene)diphthalic anhydride; DAM =
2,4,6-trimethyl-1,3-phenylenediamine)
Cubdc Polyimide CO2CH4 separation 130
ZIF-8 Poly(vinyl alcohol) Ethanol dehydration 143
MIL-101(Cr) Polyamide Removal of styrene oligomer from THF and 151 and 213
MeOH, Removal of NaCl from water
Ionic liquid@ZIF-8 Polysulfone CO2CH4 separation 152
ZIF-8 Ultems 1000 CO2N2 separation 155
ZIF-8 6FDADAM C3H6C3H8 separation 157
MIL-88 Matrimids 5128 H2CH4 separation 189
ZIF-8 PEBAX-2533 CO2N2 separation 192
Polydopamine@ZIF-8 PEBAX-4033 CO2N2 separation 193
UiO-66 PEBAX MH 1657 CO2N2 separation 194
ZIF-8 Poly(vinylamine) CO2N2 separation 195
MOF-74 6FDADAM C2H4C2H6 separation 203

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Table 1 (continued)

MOF Polymer Properties Ref.


HKUST-1 Polyimide C2H4C2H6 separation, removal of 204 and 210
polystyrene from acetone
ZIF-8 Poly(1,4-phenylene ether-ether-sulfone) C2H4C2H6 separation 205
ZIF-8 Poly(methylphenylsiloxane) Isobutanol dehydration 209
ZIF-8 Sodium poly(4-styrenesulfonate) Removal of methyl blue from water 211
UiO-66 Poly(vinylidene fluoride) Separation of Coomassie blue R-250 and 212
methyl orange
ZIF-8 Polyamide Removal of NaCl from water 214
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Fig. 11 (a) Pore size distribution of a PN and MOF-5 composite (denoted


as PNx@MOF-5, where x is the wt% PN loading) based on quenched solid-
state density functional theory. (b) CO2 sorption isotherms of PN@MOF-5
and MOF-5 at 273, 283, and 298 K. Adapted with permission from ref. 166.
Copyright 2016 American Chemical Society.

including industrial process management and environmental


monitoring. To endow MOFs with conducting properties, specific
metal ions or ligands are required;167 hence, the vast majority
of MOFs are insulators. Hybridization of MOFs with conducting
Fig. 10 (a) Molecular dynamics structure of PEG-confined [Cu2(bdc)2(ted)]n. polymers is a simple and eective method for obtaining con-
(b) DSC profiles of neat PEG, [Cu2(bdc)2ted]n, and PEG in [Cu2(bdc)2(ted)]n.
ductive and porous materials that have potential as excellent
Mw of PEG = 600. Reprinted from ref. 79 with permission from Macmillan
Publishers Ltd: Nat. Commun., copyright 2010. electrically resistive sensors. Poly(3,4-ethylenedioxythiophene)
(PEDOT) is a p-type semiconductor; its Fermi level can be modified
by oxidizing analytes, resulting in measurable changes of its
Recent research has shown that the gas adsorption ability of conductivity. Thus, PEDOT can be utilized for the chemiresistive
MOFs can be tuned by the encapsulation of polymers in the detection of NO2, which has a toxic eect on the respiratory
frameworks. 1,2-Diethynylbenzene as the monomer was infil- system at concentrations of 1 ppm or less. However, an NO2
trated into MOF-5 and then heated to aord polynaphthylene sensor using bulk PEDOT obtained by solution polymerization
(PN) in the channels.166 The accommodation of PN in MOF-5 presented a very low sensitivity (10 ppm) because of low accessi-
drastically enhanced CO2 adsorption from 38 to 78 cm3 g1 and bility for NO2 molecules (SBET = 2 m2 g1). To overcome this
CO2N2 selectivity from 9 to 212 at 273 K and 1 bar. The N2 problem, oxidative polymerization of 3,4-ethylenedioxythiophene
adsorption isotherm of the composites indicated that by increasing was performed in a 3-D MOF, MIL-101(Cr), to give a hybrid
the loading amount of PN, pores with widths of 1.2 nm gradually material with high electrical conductivity (1.1  103 S cm1)
diminished, while those with widths of 0.6 nm emerged, suggesting while maintaining high porosity (SBET = 803 m2 g1).51 Because of
that the polymer chains divided the MOF pores into confined the high accessibility for the gas analytes, this hybrid material
compartments because of their linear conformation (Fig. 11). showed high sensitivity (200 ppb) for NO2 gas.
The enhancement of CO2 adsorption ability was attributed to Luminescence sensors provide a sensing output that is visible to
the confined pore size effect as well as the greater amount of the naked eye, allowing on-site, instantaneous decision-making.168
exposed aromatic surface. It is also noteworthy that the hydro- Zhao et al. reported a luminescence sensor based on a charge
phobic PN in MOF-5 improved the stability of the composites transfer process between the donor polymer threaded in a MOF
toward moisture, demonstrating that this strategy is beneficial and the acceptor analytes.31 PVCz and the MIL-101(Cr) compo-
for industrial applications. site could very quickly detect 1,3,5-trinitrobenzene, a highly
There are requirements for sensitive and selective detection explosive substance, with a detection limit as low as 1 ppm.
of gas and vapor phase analytes for a range of applications, In addition, the remaining pores could provide selectivity for

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dierent acceptors with dierent sizes. Uemura et al. reported a Good accessibility of the reactive sites by the reactants is
new luminescent sensor system utilizing coupled transforma- also essential for the eciency of solid catalysts. Hybridization
tions of a flexible MOF and a fluorescent reporter oligomer, of polymers with catalytic activity and MOFs with high surface
distyrylbenzene (DSB).169 The [Zn2(bdc)2(ted)]nDSB composite areas is an eective strategy for fabricating noble heterogeneous
selectively adsorbed CO2 over other atmospheric gases, such as catalysts. Bromberg et al. reported the synthesis of cross-linked
N2, O2, and Ar, with concomitant structural change of the frame- poly(N-bromomaleimide) in MIL-101(Cr), resulting in a hybrid
work. This structural change induced conformational variations composite with a large surface area (SBET = 1600 m2 g1), in con-
of the accommodated DSB, which caused a critical change in DSB trast to cross-linked poly(N-bromomaleimide) prepared by solution
fluorescence. Hostguest coupled transformations thus convert polymerization (SBET = 20 m2 g1).171 Because of their high
gas adsorption events into detectable output signals. The variety accessibility, the active bromine groups in the polymer network
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of polymers and MOFs affords an essentially infinite number of allowed high activity of the composites in heterogeneous catalysis
possible combinations, which should expand the versatility and for fructose dehydration into 5-hydroxymethylfurfural.
possibility of sensing materials. Enzymes are known to be the most sophisticated materials in
Ion exchange is an important process in a diverse range of terms of catalysts because of their remarkable abilities, such as high
applications, such as water purification and precious metal anities towards substrate and high catalytic eciency based on
recovery.170 Conventional ion exchange resins consist of cross- their high stereo-, chemo-, and regioselectivities.83 However, even
linked polymers with a low surface area, which decreases the with these advantages, the practical use of enzymes is limited by
contact eciency between the ion-exchange sites and guest their low operational stability, dicult recovery, and lack of reusabi-
species. Chans group demonstrated that the open porous lity under operational conditions. Enzyme immobilization in porous
structure of MOFs allowed the encapsulated ion-exchange poly- materials is one of the most eective approaches to surmounting
mer to contact the solvent and exchange ions eciently.32 Vinyl these problems, making them industrially and commercially
benzyl chloride monomers were impregnated into ZIF-8 and viable.172 MOFs are envisioned as the most appropriate candidate
polymerized in situ, aording poly(vinyl benzyl chloride) (PVBC) for this purpose because of their ultrahigh porosity, tunable pore
and the ZIF-8 composite. Subsequent amination and ion exchange shape, and adjustable surface functionality. Mas group introduced
of PVBC yielded poly(vinyl benzyl trimethylammonium hydroxide) MP-11 into Tb-mesoMOF at a loading of 19.1 mmol g1.84 The
(PVBTAH) in ZIF-8. With its high surface area and facile accessi- hybrid material demonstrated superior catalytic activity and recycl-
bility, the extraction rate of gold cyanide anions by PVBTAH and ability, even in an organic solvent (methanol), surpassing the free
the ZIF-8 composite was much higher than that of a conven- MP-11 counterpart. The same group also encapsulated a series of
tional ion-exchange resin (Fig. 12). In 25 s, 490% of the gold other enzymes into mesoporous MOFs, and investigated the cata-
cyanide anion was extracted, in contrast to 7% extraction by lysis and mechanisms of those biocatalysts.85,86 More recently, it has
Amberlysts-A26. Recently, preparation of a cation exchange been demonstrated that trapping single enzyme molecules in each
polymer in a MOF was reported by the same group.34 Sodium predesigned cage of MOFs can eliminate enzyme aggregation and
poly(4-styrenesulfonate) (NaPSS) was synthesized in MIL-101(Cr) maintain high catalytic eciency. Feng et al. synthesized a chemi-
using a one-step in situ polymerization process. In addition to cally stable MOF (PCN-333) with ultra-large cavities (5.5 nm), which
fast cation exchange and high ion adsorption capacity, the provided single-molecule traps for enzyme encapsulation.173 In this
NaPSS and MIL-101(Cr) composite exhibited high selectivity with work, three heme-proteins (horseradish peroxidase, Cyt c, and
co-ion rejection, which is a critical performance indicator of a MP-11) were encapsulated in PCN-333. A saturated loading of each
good ion exchange material. enzyme in PCN-333 was rapidly achieved, indicating a strong
interaction between the cage and the enzyme. In fact, almost no
leaching from these accommodated enzymes occurred during the
catalytic reactions, while high apparent leaching was observed in the
mesoporous silica material SBA-15. It should be noted that horse-
radish peroxidase (size: 4.0  4.4  6.8 nm3) and Cyt c (size: 2.6 
3.2  3.3 nm3) with sizes comparable to the mesocages exhibited
better catalytic activity than the free enzymes under harsh condi-
tions. This result indicates that single-molecule traps are an eective
strategy to eliminate enzyme aggregation and leaching and achieve
remarkable catalytic performance. Very recently, Farha and
coworkers reported that MOFs excel at stabilizing enzymes at
high temperature and in a dry form, whereas the free enzyme
denatures rapidly under these conditions, expanding the appli-
cations of enzymes in industry.174

Fig. 12 Au(CN2) concentration after immersing equal masses of PVBTAH B 3.3. Polymer modification of the surface of MOFs
ZIF-8 and Amberlyst-A26 in KAu(CN)2 solution. Inset: enlarged profiles for the
first 120 s. Adapted with permission from ref. 32. Copyright 2014 American As described in Section 2.3, polymer coatings on MOFs are an
Chemical Society. eective approach for the improvement of properties such as

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dispersability75 and flexibility.71 In this section, we focus on the


eect of polymer modification on the stability and biocompati-
bility of MOFs.
Although their large surface areas equip MOFs for myriad
applications, including gas adsorption and catalysis, stability
has been recognized as a major barrier that limits their practical
application. Most MOFs with weak metalligand coordination
bonds are very sensitive to moisture. The approaches that have
been reported to enhance their water resistance include incorpora-
tion of hydrophobic ligands into the framework,175 encapsulation
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of hydrophobic guest molecules in the pores,176 and functionaliza-


tion of the surface via ligand modification.177 Although they
enhance the water resistance of MOFs, these approaches suffer
from various limitations, such as reduced porosity and tedious
procedures. Coating the MOF crystals with hydrophobic polymers
is a simple yet versatile approach for improving their water
resistance while retaining their intrinsic properties (i.e., porosity,
pore texture, and crystalline structure).178,179 HKUST-1 showed
enhanced water resistance in terms of porosity and catalytic
properties after coating the MOF surface with a thin hydropho-
bic PDMS layer via the thermal vapor deposition technique.178 Fig. 13 (a) DNA functionalization of UiO-66-N3 nanoparticles, using DNA
The SBET values for pristine and coated HKUST-1 were 1547 and functionalized with dibenzylcyclooctyne (DBCO). (b) Nanoparticle uptake
1544 m2 g1, respectively, suggesting that the PDMS layer does per cell. (c) Cell viability assay data showing no significant cell toxicity for the
not affect the accessibility of the pores. Compared with pristine MOF nanoparticleDNA hybrids. Adapted with permission from ref. 183.
Copyright 2014 American Chemical Society.
HKUST-1, the porosity and SBET of coated HKUST-1 are comple-
tely retained after water treatment, which is consistent with SEM
and XRPD results. modified on their surfaces. The DNA created a steric and electrostatic
Recent reports demonstrate that MOFs are of potential barrier that stabilized the particles in high-dielectric media, which
interest in biomedical applications, such as drug carrier systems increased cellular uptake efficiency for MOFDNA nanoparticles
and contrast agents for medical imaging.180,181 The surface compared with that of unfunctionalized MOF nanoparticles. The
functions of MOF particles change the type of interactions taking MOFDNA hybrid showed no significant cytotoxicity to HeLa human
place between the MOFs and their surroundings, thereby strongly cervical cancer cells after 24 h of incubation. Because of the high
aecting their colloidal stability, biocompatibility, recognition designability of synthetic polymers, MOF particles can be endowed
capabilities, and biodistribution. Surface modification of MOFs with multiple functions. Gd MOF nanoparticles were prepared for
with well-defined polymers can provide precise control over theragnostics and their surface was modified by the covalent attach-
surface functionalities. For example, PEG surface coating is ment of multifunctional polymer chains with both optical imaging
widely used to confer stealth properties on nanoparticles in capabilities and conjugate additional agents via the succinimide
biological applications. PEG with functional groups has been groups.184 The succinimide was utilized to graft a therapeutic agent
shown to react directly with MOF particles, which prevented and target ligands. A polymer-modified Gd MOF was shown to be
their aggregation.180 However, the surface modification leads to biocompatible and to have cancer cell targeting, bimodal imaging,
a decrease in the porous character because of the inclusion of and disease treatment capabilities.
PEG chains within the pores. To circumvent this problem, the
surface agent should present a rigid section larger than the size 3.4. Applications of MMMs
of the accessible windows of MOFs. Hence, Bellido et al. Membrane-based separation has gained increased attention
modified the external surface of MIL-100(Fe) with heparin, because of its low cost, ease of operation, and high energy
a polysaccharide with large molecular dimensions (heparin eciency compared with traditional methods such as adsorp-
unit E8.2  8.9 ; window size of MIL-101(Fe) E 8.6 ).182 This tion or cryogenic distillation. The combination of the molecular
coating improved the colloidal stability of the MOF, while the sieving feature of MOFs and processability and mechanical
intrinsic porosity and chemical stability remained unchanged. In stability of polymers makes MMMs promising candidates for
addition, the heparin coating endowed the MOF with improved various industrial separation processes. Numerous MOFs have
biological properties, such as the capacity to evade the immune been incorporated into glassy or rubbery polymers to give MMMs
system and the production of oxygen species. Morris et al. with significantly improved performance in applications including
synthesized MOFnucleic acid nanoparticle conjugates via an gas separation, pervaporation, and nanofiltration.94100
alkyne click reaction between dibenzylcyclooctyne-functionalized 3.4.1. Gas separation. Hydrogen purification, carbon dioxide
DNA and azide-functionalized UiO-66-N3 (Fig. 13).183 The small capture, and olefinparaffin separation are all important processes
pore size of UiO-66-N3 meant that the particles were only in industry, and we now review recent progress in MOF-based

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MMMs in these fields. The separation behavior of the membranes (202 GPU with selectivity of 7.7) or high selectivity (12.3 with H2
in a single gas and mixed gases may be different, and the results permeance of 64.5 GPU) at 180 1C. To further test the practic-
of the latter are more meaningful; therefore, here we mainly focus ability of such MMMs in actual applications, they modified the
on tests of membranes in mixed gas systems. fabrication method and measured the separation capabilities
Hydrogen is a green and eective energy source and is con- at 230 1C in the presence of CO and water vapor. Mixed-gas
sidered a good substitute for fossil fuels. Currently, a common measurements demonstrate that the impurities in the feed gas
way to produce hydrogen is steam reforming of hydrocarbon do not significantly weaken the separation of ZIF-8PBI mem-
fuels followed by a gas-shift reaction. In this process, CO2 is the branes at high temperatures.
main by-product that must be separated to ensure the quality of Coronas et al. fabricated ZIF-8/PBI membranes and tuned
the produced hydrogen and to reduce emissions of this green- parameters including the sizes of ZIF-8 (50, 70, and 150 nm),
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house gas. Since the steam reforming reaction is strongly endo- ZIF-8 loadings (10 and 20 wt%) and states of ZIF-8 (wet and
thermic, the process is conducted under high temperatures. dry).187 A European interlaboratory Round Robin test was employed
Moreover, the products incorporate large amounts of water vapor to confirm the reproducibility of the membrane permeation
and some impurities (CO and CH4) besides H2 and CO2.185 tests. The MMMs were tested for the separation of H2 and CO2
Therefore, hydrothermally stable membranes with good separa- at 150 1C with feeding pressures from 3 to 6 bar, and both
tion performance under high temperature and pressure are permeability and selectivity values declined with the increasing of
desirable for hydrogen purification. The same separation is the feeding pressures. At 20% filler loading, MMMs with ZIF-8 of
also required for precombustion CO2 capture in which the shift 150 nm exhibit the best performance (an improvement of six
products of coal gasification dier from those of steam reforming times in H2 permeability and nearly twice in selectivity), and this
in the partial pressures of the gases. may be due to the lower degree of aggregation in the case of larger
Because of its high thermal stability and compatibility with particle size. Furthermore, MMMs containing dry fillers present
ZIFs, PBI is often used to prepare MMMs. Chung and colleagues better separation properties than those with wet fillers.
mixed [Zn(bIM)2]n (ZIF-7, bIM = benzimidazole) nanoparticles Nanoparticles of other ZIFs including ZIF-90, [Zn(bIM)2]n
with PBI at the high loading of 50 wt% and the flexible ZIF-11, and MOF nanosheets have also been prepared and
membranes obtained exhibit good dispersability and enhanced blended with PBI to fabricate composite membranes for H2CO2
H2CO2 separation performance compared with pure PBI or separation.106,129,188
ZIF-7 membranes.110 In the mixed-gas tests, the hybrid membrane Steam methane reforming (SMR) is the most common way
showed an H2 permeability of 13.3 Barrer and a H2CO2 separa- to produce hydrogen and the products often contain a small
tion factor of 7.2 at 35 1C (Fig. 14). The result at the high amount of methane that should be removed. Huang and Zhong
temperature of 180 1C is above the Robeson upper bound186 et al. synthesized a biocompatible MOF [Fe3O(bdc)3]n (MIL-88)
proving that the ZIF-7PBI membranes are promising for indus- and embedded the particles into Matrimids 5218 to fabricate
trialization. Given the practicability of HFMs in large-scale gas MMMs for H2CH4 separation.189 The composite membranes
separation, the same group conducted research on fabricating offer improvements in both H2 permeability and selectivity in
ZIF-8PBI dual-layer HFMs for H2 purification.109 The prepared equimolar mixture tests compared with pure polymer membranes.
fibers are free of defects and agglomeration with excellent sepa- A high separation factor of 96 was observed in the MMMs with
ration performance at high temperatures. Tuning the loading of 10 wt% filler loading.
ZIF-8 in the polymer can contribute to either high H2 permeance Emission of CO2 into the atmosphere is a major cause for
global warming and climate change. Post-combustion CO2 cap-
ture refers to the capture of CO2 from flue gases generated mainly
by power plants, which is a key route to reducing the anthro-
pogenic release of CO2.4,190 Flue gas contains N2, CO2, H2O, O2,
and a small percentage of pollutants such as SOX, NOX, and
particulate matter.4 A main challenge in this field is the relatively
low CO2 partial pressure in the exhaust, which requires mem-
branes to be highly selective for CO2. By adding MOF fillers that
have high porosity and good interactions with CO2 into poly-
mers, researchers have made progress in the separation of CO2
from N2.97
Sholl, Koros, and coworkers prepared ZIF-8Ultems 1000
asymmetric HFMs with a MOF loading of 13 wt% in the outer
selective layer using the dry jetwet quench method to investigate
their CO2N2 separation.155 To seal the defects in the selective
Fig. 14 H2/CO2 separation performance of pure PBI and ZIF-7/PBI nano-
layer, the fibers were post-treated with a coating of PDMS. In
composite membranes compared with the Robeson upper bound (open
symbols: pure gas separation performance; closed symbols: mixed gas
single-gas tests, the composite fibers showed an 85% increase in
separation performance). Reproduced from ref. 110 with permission from CO2 permeance and a 20% increase in selectivity compared with
The Royal Society of Chemistry. pure polymer fibers. When a mixed gas (20% CO2 in N2) was used

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as the feed gas, the ZIF-8Ultems 1000 fibers showed a high of such flexible polymers. By tuning the filler contents and
selectivity of 32 and H2 permeance of 26 GPU at 25 1C. preparation parameters, the hybrid membranes with 13.1 wt%
Polyether block polyamide (PEBA) contains soft polyether ZIF-8 loading prepared with 50 mm coating thickness possessed
segments and rigid polyamide (PA) segments. It shows promising uniform structures without interfacial voids. A high CO2 per-
capability for CO2 separation because of its high anity for CO2 meance of 297 GPU and selectivity of 83 were observed with the
together with good mechanical stability.191 Hagg and colleagues symmetric membranes in a binary-gas test (15 vol% CO2 and
investigated the CO2N2 separation properties of ZIF-8PEBAX- 85 vol% N2) with a feed pressure of 1.1 MPa.
2533 in both dry and humid situations.192 Because of the aggre- Natural gas is a vital and clean fossil fuel relative to oil and
gation and sedimentation of the ZIF-8 particles, the hybrid coal, and its major component is CH4. However, raw natural gas
membrane (i.e., a polymer-based phase and a filler-based phase) often contains impurities including CO2, H2S, and N2, which
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has a special dual-layer morphology. A mixture of 10% CO2 and decrease the calorific value and lead to pipe corrosion during
90% N2 was used as the feed gas for the mixed-gas measurement. delivery via pipeline. The removal of the major contaminant CO2
In the dry state, the membrane with 40 wt% ZIF-8 loading is crucial for further use of the fuel. Membrane-based separation
showed a high CO2 permeability of 1098 Barrer and a moderate is promising for natural gas sweetening because of its high energy
separation factor of 33 (a 50% drop compared with the pure eciency and low maintenance compared with the current
polymer); however, the permeability and selectivity are both amine absorption process.196 Despite their low cost and good
affected by humidity to some extent. To improve the adhesion processability, polymer membranes are often limited by a
between ZIF-8 fillers and the polymer matrix, Chen et al. coated trade-o between permeability and selectivity, and suer from
the surface of ZIF-8 with polydopamine (PDA) and then mixed plasticization eects under high pressure, leading to a loss of
these particles with PEBAX-4033.193 Given the many hydroxyl and selectivity.197 The addition of porous MOF crystals can be a
amino groups in PDA and their interactions with CO2, the coating good choice to overcome these problems. On one hand, the
layer can facilitate the permeation of CO2 (Fig. 15). The CO2 porosity of MOFs boosts permeability and the molecular sieving
permeability of PDA@ZIF-8PEBAX membranes with 15 wt% feature is expected to enhance the selectivity of the membranes.
ZIF-8 loading reached 267.74 Barrer with a CO2N2 selectivity of On the other hand, the added fillers reduce the chain mobility
62.65 in a single gas test in the humid state, which surpasses the and thereby improve the stability and plasticization resistance
Robeson upper bound. Other types of MOFs were also employed of the membranes, especially where bonds are formed between
to synthesize PEBAX-based MMMs. For example, nanoparticles MOFs and polymers.
of UiO-66 and UiO-66-NH2 were incorporated into PEBAX MH ZIF-90 with a pore window size of 0.35 nm is promising for
1657 and the derived UiO-66-NH2PEBA membranes with 10 wt% CO2CH4 separation through a size exclusion mechanism. Jones,
loading showed outstanding performance (CO2 permeability of Nair, and coworkers synthesized submicrometer-sized ZIF-90
130 Barrer and selectivity of 72) in the mixed gas test with a particles via nonsolvent-induced crystallization, and then mixed
relative humidity of 20%.194 them with three types of PI (Matrimid, Ultem and 6FDADAM)
To achieve better eects with fillers, Wang et al. fabricated (6FDA = 4,4 0 -(hexafluoroisopropylidene)diphthalic anhydride;
asymmetric membranes comprising a thin ZIF-8poly(vinylamine) DAM = 2,4,6-trimethyl-1,3-phenylenediamine) to prepare MMMs.123
(PVAm) coating on PSF substrates.195 On the one hand, the In mixed-gas tests, MMMs made from ZIF-90 of smaller size
selected flexible polymer may reduce the interfacial stress between (B0.81 mm) and 6FDADAM showed the best results, because
the polymer and fillers; on the other hand, the addition of ZIF-8 of their well-matched permeability. Specifically, upon ZIF-90
fillers can enhance free volume and thus improve the permeance incorporation (15 wt%) a high CO2 permeability of 720 Barrer
with a CO2CH4 selectivity of 37 was achieved, surpassing the
upper bound for polymer membranes defined in 1991. The high
permeability together with good selectivity makes these mem-
branes attractive for natural gas sweetening.
A breathing eect is a special phenomenon observed in some
MOFs involving structural changes upon adsorption of guests.
MIL-53 is a typical flexible MOF, and several groups have used
it or its functional counterparts as the dispersed phase in
MMMs.116,122,135,198200 Rodenas and Gascon et al. employed
NH2-MIL-53(Al) with Matrimids 5218 giving membranes with
good filler distribution and separation performance that derives
from the flexible framework and the abundant amino groups.198
The effects of preparation conditions on the configurations and
dispersion of MOFs in the MMMs and the corresponding separa-
tion performance were investigated. The authors showed that
Fig. 15 Schematic illustration of the synthesis of PDA@ZIF-8 and the CO2
higher solvent removal temperature (298 K) and thinner mem-
transport mechanism in PEBAX/PDA@ZIF-8 MMMs. Reproduced from ref. 193 branes led to a higher proportion of the narrow-pore configu-
with permission from The Royal Society of Chemistry. ration and enhanced separation properties. When an equimolar

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mixture of CO2 and CH4 was used as the feed gas, a CO2
permeability of B14.5 Barrer and a separation factor of 38
could be attained by MMMs with 25 wt% NH2-MIL-53 at 308 K
and 3 bar pressure difference. In this work, ion-beam scanning
electron microscopy (FIB-SEM) was applied to provide 3-D
and quantitative information about the membrane structures
including the filler distribution and boundary contact, showing
great potential for membrane structure characterization. Later,
the same group studied the effects of NH2-MIL-53 morphologies
(nanoparticles, nanorods, and microneedles) on the performance
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of the resultant membranes.122 The best performance was observed


in MMMs prepared from NH2-MIL-53 nanoparticles and
6FDADAM. The incorporation of 20 wt% MOF nanoparticles
resulted in a membrane with a CO2 permeability of 660 Barrer and Fig. 16 Illustration of the cavity-occupying concept for tailoring the mole-
cular sieving properties of ZIF-8 by incorporation of RTILs. The cut-o size
a CO2CH4 selectivity of 28. Researchers have realized the impor-
shifts from the aperture size of six-membered ring to the reduced eective
tance of the filler morphology for the ideal structure and separa- cage size by confinement of [bmim][Tf2N] in a ZIF-8s SOD cage. Adapted
tion capability of membranes. Another team also studied the with permission from ref. 152. Copyright 2015 Wiley-VCH.
effects of MOF nanosheets in a polyimide polymer, Matrimids
5218, for CO2CH4 separation.130 Free-standing nanosheets of
Cubdc were synthesized and used as the filler for PI membranes. incorporated a series of M2(dobdc) (M-MOF-74; M = Mg, Mn,
As demonstrated by FIB-SEM tomograms, the MOF nanosheets Fe, Co, Ni, Zn; dobdc = 2,5-dioxido-1,4-benzenedicarboxylate)
dispersed well across the polymer matrix leading to larger in 6FDADAM.203 These MOFs were chosen for their abundant
exposure areas and higher efficiency of molecular sieving. unsaturated metal sites that are supposed to be beneficial for
Consequently, the obtained nanosheet-CubdcPI membranes ethylene absorption and intimate interactions between MOFs
obtained exhibited higher selectivity over a wide pressure range and polymers. The membrane performances are shown in Fig. 17.
than the polymer membrane. Ni-MOF-74 and Co-MOF-74 with sizes below 20 nm show the best
In some cases, when the pore sizes of MOFs lie between the performance for ethyleneethane separation when embedded in
sizes of components to be separated, the flexible pore architec- 6FDADAM, lying above the polymer upper bound. In binary-gas
ture results in a loss of selectivity. Yang and coworkers proposed tests at the high pressure of 20.5 bar, Ni-MOF-746FDADAM
a strategy to tune the molecular sieving properties of MOFs by exhibited a selectivity of 4.1, which is close to the ideal selectivity
occupying the cages in ZIF-8 with the room temperature IL (4.6), illustrating the plasticization resistance caused by the MOF
1-butyl-3-methylimidazolium bis(trifluoromethyl-sulfonyl)imide fillers, which can be explained by the strong interactions between
([bmim][Tf2N]), which also has high anity for CO2.152 ILs@ZIF-8 the unsaturated metal sites and the polymer matrix. Nijmeijer
was employed as a filler to make PSF MMMs (6 vol% loading), and et al. incorporated HKUST-1, FeBTC and MIL-53(Al) into the PI
a distinct increase in CO2 permeability with high selectivities of P84 to make MMMs for ethylene/ethane separation.204 Compared
CO2CH4 and CO2N2 was achieved. Moreover, when tested under with pristine P84 membranes, membranes containing 20 wt%
pressures up to 20 bar, the selectivity of the ILs@ZIF-8PSF HKUST-1 present remarkable enhancements with selectivity
increased from 38 (6 bar) to 66 (20 bar) for CO2CH4 showing their improving from 4.1 to 7.1 and constant permeability. In another
resistance to plasticization and their potential for industrial separa- work, ZIF-8 particles were added in a poly(1,4-phenylene ether-
tion processes (Fig. 16). ether-sulfone) matrix, and the composite membranes were tested
Light olefins are the raw materials for many products and for the separation of C2H4/C2H6 resulting in an ideal selectivity of
chemicals, which makes them crucial in the chemical and 3 and C2H4 permeability of 3.15 Barrer.205
petroleum industries. For example, ethylene is the main HFMs are the most favored geometry for large-scale gas
ingredient of polyethylene, ethylene oxide, ethylbenzene, and separation because of their high packing eciency. For the
ethylene dichloride. In the petrochemical industry, olefins are first time, Koros et al. fabricated dual-layer ZIF-86FDADAM
produced by catalytic dehydrogenation following hydrocarbon HFMs with a high loading of 30 wt% for propylenepropane
cracking. The dehydrogenation process often leads to an equi- separation.157 By carefully tuning the parameters in the dry
molar mixture of olefins and parans that possess similar jetwet quench technique and the components in the coating
properties such as boiling point and molecular size, which layers, they obtained hybrid hollow fibers with 17 wt% loading
makes them dicult to separate.201 Cryogenic distillation, and PDMS coating that attained C3H6C3H8 selectivity of 17.7
the most common method utilized in industry, is cost and and C3H6 permeance of 2.2 GPU.
energy intensive; therefore, membrane-based separation might In general, the basic factors to be considered for large-scale
be an alternative approach because of its low cost and energy gas separation are the separation eciency (selectivity) and
consumption.202 productivity (permeability) of the membranes. In addition, their
To improve the separation performance and stability of stability in contact with complicated and aggressive feeds, together
polymer membranes under high pressure, Long and colleagues with the processing and operation costs, are vital for industrial

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polymers is expected to enhance the selectivity and stability of the


pristine polymers.
The polymeric materials often employed in PV include hydro-
philic polymers such as poly(vinyl alcohol) (PVA), PAN, and
chitosan, and hydrophobic polymers such as PDMS, PEBA, and
PBI. The selection of polymers is determined by the separation
system.208 As for MOFs, stability in the solvents is the main
precondition, and stable MOFs, including MIL, ZIF, and UiO
series, have been widely investigated. Other parameters such as
pore size, functionalization, and hydrophilicityhydrophobicity
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should also be considered. Specifically, the pore size of the filler


should lie between the dimensions of the components to be
separated, and hydrophilic materials are preferred to remove
water from organic solvents. The review by Jia and Wu summar-
ized the state-of-the-art progress in MOF-based MMMs for PV, as
well as the features of the polymers and MOFs suitable for PV,
mass transportation processes, and specific applications, offering
suggestions for further study.96
Realizing the importance of the perfect membrane structure,
Tung and Wu et al. recently prepared ZIF-8PVA MMMs using
a drying-free, water-based process for ethanol dehydration.143
Nanoparticles of ZIF-8 were synthesized in water, which was
also the solvent of the polymer solution, and the direct combi-
nation without drying avoided the aggregation of the particles
forming membranes with good dispersion and defect-free interfaces,
Fig. 17 Ethylene/ethane separation performance for M2(dobdc)/6FDA which was confirmed by positron annihilation lifetime spectroscopy
DAM membranes. (a) Membrane performance at 2 bar feed pressure and analysis. In a mixture of ethanol and water (90/10 w/w), both the
35 1C relative to the upper bound for polymers. Membrane loadings by separation factor and permeability of the membranes increased
weight are 10% and 33% for Co2(dobdc), 6% and 25% for Ni2(dobdc), 23% with the ZIF-8 loading, and a high permeability of 2.07  106 Barrer
for Mg2(dobdc), and 13% for Mn2(dobdc). The uncertainty in selectivities
and selectivity of 4725 were attained at a loading of 39 wt%, which
represents propagation of uncertainty in permeability based on two inde-
pendent membrane samples; each sample was measured twice to ensure no is markedly better than the results obtained with pure PVA
plasticization or conditioning effects. Grey circles represent neat polymers membranes. The enhanced performance was due to the porosity
from the literature. (b) TEM images of 33% Co2(dobdc) and 23% Mg2(dobdc) and molecular sieving of ZIF-8 fillers as well as their inhibition of
membrane cross-sections and corresponding illustrations of the proposed the swelling of the polymers.
gas transport mechanisms, where purple hexagons represent Co2(dobdc)
Due to the characteristics of a flexible framework and super-
or Ni2(dobdc) nanocrystals and red hexagons represent Mg2(dobdc) or
Mn2(dobdc) nanocrystals. Reprinted by permission from Macmillan Publishers hydrophobic pore surface, ZIF-8 shows high adsorption selec-
Ltd: Nat. Mater., ref. 203, copyright 2016. tivity and capacity for isobutanol.209 When nanoparticles of
ZIF-8 were embedded in PMPS membranes, both isobutanol
permeability and selectivity were enhanced compared with pure
applications.206 MOF-based MMMs indeed oer significant PMPS membranes for the separation of isobutanol and water.
potential to overcome the drawbacks of the polymer membranes Specifically, the isobutanol permeance of the ZIF-8PMPS mem-
that now occupy a vital position in this field by incorporating brane is 60007000 GPU with a separation factor in the range of
fillers with sieving properties, good compatibility, and a high 34.9 to 40.1.
degree of designability. 3.4.3. Nanofiltration. Nanofiltration membranes usually
3.4.2. Pervaporation. Pervaporation (PV), a separation possess pore sizes in the range of 110 nm, and mostly are
method for liquids, is used in many fields including dehydration made from polymers. They were originally used for molecular
of solvents, exclusion of organic components from aqueous separation in the aqueous phase, such as removal of polyvalent
phases, organic mixture separation, and membrane reactors.96 cations and dyes from water. With the development of solvent-
The mechanism of this process is based on solution-diusion stable membranes, nanofiltration can be more widely used in
theory; specifically, that certain components should diuse organic solvents, extending their applications to such fields as
across the membrane and evaporate into the vapor phase on the petrochemicals, food, and pharmaceuticals. The flux of the
other side.207 Because of the dierent degrees of dissolution and membranes is a key factor in practical applications; therefore,
permeation rates of the components, the mixture can be separated the addition of porous MOF fillers should contribute to higher
by the membranes. The most widely applied membranes in PV are productivity. The tunable pore sizes of MOFs are also beneficial
polymers; however, these tend to swell in this process, resulting in for good selectivity. In some cases, the included MOF particles
a reduction of selectivity, and the incorporation of MOFs into can also help to mitigate the swelling of the polymers.

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For the first time, Vankelecom et al. incorporated MOF crystals


into polymers for solvent-resistant nanofiltration to remove Rose
Bengal (RB) from isopropanol.119 Four MOFs, HKUST-1, [VO(bdc)]n
(MIL-47), MIL-53(Al), and ZIF-8, were selected and silylated using
N-methyl-N-(trimethylsilyl)-trifluoroacetamide (MSTFA) to improve
their hydrophobicity before mixing with PDMS. The MOFPDMS
solutions were then coated on porous PI substrates as the selective
layers to form asymmetric membranes. These membranes all
showed exceptional improvements in retention (from 87% for
the MOF-free PDMS to 9298% for MMMs) while preserving the
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flux, which can be explained by size exclusion and the reduction in


swelling brought by MOF fillers.
MOFpolyamide thin film nanocomposite (TFN) membranes
were prepared by Coronas and Livingston et al. via interfacial Fig. 18 Comparison of the dye-removal performance of the ZIF-8/PSS
membrane with that of previously reported membranes. Adapted with
polymerization on cross-linked PI supports for organic solvent
permission from ref. 211. Copyright 2014 Wiley-VCH.
nanofiltration (styrene oligomers (PS)THF and PSMeOH).151
They observed that the flux of the organic solvents increased
without sacrificing the rejection when the MOF fillers were (PSE) and PSM were realized in MMMs, which provides possibi-
added. Among the four MOFs chosen (ZIF-8, MIL-53(Al), lities for in situ modification of MMMs and improved adhesion
NH2-MIL-53(Al), and MIL-101(Cr)), MIL-101(Cr) outperformed between MOFs and polymers.
the others because of its larger pore size, achieving high fluxes Similar to nanofiltration, reverse osmosis (RO) is also a
of 3.9 and 11.1 L m2 h1 bar1 for PSMeOH and PSTHF, pressure driven process for the rejection of solutes and permea-
which clearly illustrates that MOFs offer preferential flow paths tion of the solvent, and the molecular weight cut-o for RO
for the solvent molecules and prevent the passage of larger membranes is below 100 g mol1. Most of the commercially
impurities. Later, Livingston and coworkers reported the fabri- available RO membranes are composed of a TFC structure with
cation of thin films of HKUST-1 on a PI P84 support membrane a thin selective layer of PA. To further improve the flux of the
by interfacial synthesis.210 The obtained hybrid membranes membranes, porous materials including MOFs are embedded in
with a thin layer of HKUST-1 beneath the surface were tested the PA layer giving TFN membranes. Pinnau et al. employed nano-
for nanofiltration. Compared with membranes prepared by an particles of ZIF-8 as fillers in the PA layer at a loading of 0.4% (w/v),
uncontrolled in situ growth method, thin film composite (TFC) and in this case the water permeance is 3 times higher than the
membranes show higher acetone permeance with similar PS pristine TFC membranes reaching 3.35  0.08 L m2 h1 bar1
rejections, and this can be explained by the thinner selective while retaining the high NaCl rejection of 98.5  0.5%.213 In
layer and lower resistance. another work, Gao and coworkers added hydrophilic MIL-101(Cr)
ZIF-8NaPSS membranes with uniform dispersion and a nanoparticles into a dense PA layer to provide direct water
crack-free interface between the two phases were prepared by channels achieving higher water permeance.214 The obtained
Li and coworkers by a coordination-driven, in situ, self-assembly TFN membranes show a permeance of 2 L m2 h1 bar1 and
strategy.211 The ZIF-8 particles grew in the PSS polymer and the NaCl rejection of 99%. These results indicate that MOFs are
Zn2+ ions were coordinated with the ligands and polymer promising candidates for water purification.
matrices as well as the PAN substrates. Importantly, the bonds As well as separation, MOF-based MMMs have also shown
formed between the fillers and the continuous phase solved the their potential in applications including sensing,133 proton
problems of agglomeration and incompatibility and also enhanced conductivity,215217 and solid electrolytes.218221
the stability of the hybrid membranes. The separation performance
of the membranes was evaluated in the separation of methyl blue 4. Conclusion and outlook
from water, showing a high flux of 265 L m2 h1 MPa1 and
retention of 98.6% (Fig. 18). This review article has described the methodologies for MOF
As demonstrated by Cohen et al., MOFs in polyvinylidene polymer hybridization, as well as the fascinating properties of
fluoride (PVDF) polymer membranes remained crystalline, the hybrid materials. The integration of these two materials has
porous, and chemically accessible for further modification.212 provided new aspects for both polymer and MOF chemistry.
They prepared free-standing MMMs with seven kinds of MOFs Understanding of the specific properties based on low-dimensional
at loadings up to 67%, and the addition of the fillers led to assemblies of polymers is central towards the development of
improved stiness of the membranes. The porosity of the MOFs molecular-scale nanodevices. Rational design and preparation
within the polymers was confirmed by nitrogen adsorption of MOF hosts has permitted the precise control of polymer-
tests and the ability to separate the organic dyes from water. chain assembly structures, which has shed light on the unique
The UiO-66PVDF membrane can not only remove Coomassie properties of polymers. Modification of MOFs with polymers
dyes (B99% retention), but also achieve separation between has improved their properties, such as gas adsorption, stability,
different dye molecules. For the first time, post-synthetic exchange dispersability, and biocompatibility. In addition, this approach

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provides a simple but powerful way to fabricate MOF-based thin the relationships between the structure and performance will
films, which should stimulate the emergence of innovative become clear.
industrial applications in a diverse range of technologically Despite the promising performance of the MOF MMMs, the
significant fields. diculty of large-scale production of these membranes hinders
Tremendous advances have been made in MOFpolymer their further industrial application. The precursors of MOFs are
hybrids; however, several challenges associated with hostguest expensive and the reactions are mostly complicated. On the other
synergistic functions remain. One of the most appealing features hand, continuous production of membranes is challenging. One
of MOFs that distinguishes them from conventional porous of the authors group proposed a scalable hot-pressing (HoP)
materials is their structural flexibility, in which the framework approach to fabricate MOF coatings.225 High temperature and
changes its structure upon exposure to external stimuli, such as pressure are employed to assist the growth of various MOFs on
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heat, pressure, light, and magnetic fields.222 Cooperative struc- certain substrates without using any solvent. With the assis-
tural transformations of flexible MOFs and functional polymers tance of a roll-to-roll machine, the HoP method may achieve
could provide novel stimuli-responsive nanohybrid materials. continuous production of MOF membranes in practical appli-
It is also clear that an important direction in this platform is cations. With the rapid development of new and facile fabrica-
to pursue photoelectric synergy between MOFs and polymers. tion methods, MOF-based MMMs are bound to play a vital role
Exploring photoinduced charge and energy transfer in donor in practical separation processes.
acceptor systems is an important field of research that is
essential for the fundamental knowledge necessary to develop
future applications, including photoenergy conversion devices.223 Acknowledgements
The spatial control of donoracceptor interfaces is an important
T. U. acknowledges the financial support from JST-CREST and
prerequisite because it is here that critical photophysical pro-
JSPS KAKENHI Grant Number JP16H06517 (Coordination Asym-
cesses take place.224 With a diversity of topologies and linkers,
metry). Y. Z. and B. W. acknowledge the financial support from
MOFs represent a class of materials with electronic and conduct-
the 973 Program 2013CB834702 and the National Natural Science
ing properties. Thus, hybridization of electroactive polymers
Foundation of China (Grant No. 21625102, 21471018, 21404010,
and MOFs could allow the creation of optimized systems with
21490570, 21674012).
periodic and well-defined networks of electron donor and
acceptor phases based on the original host structures.
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