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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

Received 20th January 2017
DOI: 10.1039/c7cs00041c
rsc.li/chem-soc-rev
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
MOFs to make hybrids with sophisticated architectures. Hybridization of MOFs and polymers is producing
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
intriguing functions of hybrid materials.

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

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

This journal is The Royal Society of Chemistry 2017 Chem. Soc. Rev.

Review Article
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-
posite materials integrating MOF crystals with polymer films.
This approach can also endow MOFs with improved functions,
such as gas adsorption selectivity, hydrolytic stability, and bio-
compatibility, expanding their practical applications.
Controlled integration of polymers and MOFs is leading
to the creation of advanced functional composites exhibiting
intriguing properties that are superior to those of the individual
Susumu Kitagawa received his
PhD from Kyoto University in
1979. He was promoted to a full
professor at Tokyo Metropolitan
University in 1992, and he moved
to Kyoto University as a professor
of Inorganic Chemistry in 1998.
Presently, he is also Director of
the Institute for Integrated Cell-
Material Sciences (WPI-iCeMS)
at Kyoto University. His current
research interests include the
Susumu Kitagawa chemical and physical properties
of porous coordination polymers/
metal organic frameworks.
Bo Wang obtained his BS, MS and
PhD from Peking University in
2004, University of Michigan in
2006 and University of California
Los Angeles in 2008, respectively.
He has been a professor in the
School of Chemistry and Chemical
Engineering, Beijing Institute
of Technology since 2011. His
research interests focus on metal
organic frameworks, membranes/
films and other functional porous
Bo Wang composites for gas separation,
purification and toxicant capture
and sensing.
Chem. Soc. Rev.
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Fig. 1 The number of papers published per year on MOF/polymer hybrids.
The numbers were determined based on a Scopus search using keywords
metalorganic frameworks, porous coordination polymers, and polymers.
components.13,14 To highlight the significance of this field, we
have analyzed the publication trend for the period 20052016.
As shown in Fig. 1, the number of papers published per year
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
obtaining the desired functional materials. In this review, we
describe the recent developments in MOF/polymer hybridization
procedures as well as the functions of hybrid materials.
2. Synthetic approaches for hybrids of
MOFs and polymers
In this section, we describe a variety of synthesis procedures for
the hybridization of polymers and MOFs, as shown in Fig. 2.
2.1. Polymerization within nanochannels of MOFs
If polymerizable monomers can be accommodated in the pores
as guests, these monomers can be subsequently polymerized in
the porous materials.15 In many cases, monomers are small
Takashi Uemura received his PhD
at Department of Polymer Chemi-
stry, Kyoto University in 2002.
He then joined as an assistant
professor in Department of Syn-
thetic Chemistry and Biological
Chemistry in Kyoto University, and
has been an associate professor
since 2010. He has been also a
research director for a CREST
program of Japan Science and
Technology Agency (JST) since
Takashi Uemura 2013. His research interest is pre-
paration of synergistic nanohybrids
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
are polymerizations in the microporous channels of zeolites and
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
on the kinetics and selectivity of polymerization.21,22 However,
polymerization in previous crystalline porous materials suffered
from intrinsic issues of their narrow, discontinuous, and/or fragile
cavities for allowing the polymerization of large monomers
(46 ). MOFs with their designable framework structures are
of particular interest; the size, shape, dimensions, and surface
functionalities of the nanochannels can be systematically tuned
by the precise choice of metal ions and bridging organic ligands.
These sophisticated features are attractive enough to motivate
researchers to utilize MOF nanochannels as unique nanosized
polymerization fields. Here, we highlight radical, ionic, and
oxidative polymerizations in MOFs to incorporate polymers into
the nanochannels.
Radical polymerization has been widely used for polymer
synthesis. It is applicable to a wide variety of monomers. In
2005, in their pioneering work, Uemura et al. performed radical
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Fig. 3 Schematic illustration of the polymerization of St in the nanochannels
of [Zn2(bdc)2(ted)]n. Adapted from ref. 23 with permission from the Royal
Society of Chemistry.
polymerization of styrene (St) in one-dimensional nanochannels
of [Zn2(bdc)2(ted)]n (bdc = 1,4-benzenedicarboxylate, ted = tri-
ethylenediamine) to accommodate a polymer inside the pores
(Fig. 3).23 In this system, St was fully introduced into the nano-
channels by immersion of [Zn2(bdc)2(ted)]n in St, and then excess
monomer outside the host crystal was evacuated under reduced
pressure, providing a hostmonomer adduct. Polymerization
of the monomer accommodated in the nanochannels was per-
formed by heating the adduct with a radical initiator to afford a
polystyrene (PSt)MOF composite. To date, a large variety of vinyl
polymers have been prepared inside the nanochannels of MOFs,
including PSt,2327 poly(methyl methacrylate) (PMMA),28 poly(vinyl
acetate),28 polyacrylonitrile (PAN),29 poly(N-vinylcarbazole)
(PVCz),30,31 poly(vinylbenzyl trimethylammonium hydroxide),32
poly(p-divinylbenzene),33 and poly(4-styrene sulfonate) (PSS).34
Control of molecular weight by radical polymerization is very
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
contrasts with the results obtained from conventional polymeri-
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,
basicity, and redox activity, can be tailored by precise choice
of functional organic ligands and metal ions.43 Thus, MOFs
bearing active sites in their nanochannels have been envisioned
as eective catalysts in polymer synthesis. Anionic polymerization
of substituted acetylene has been performed in the 1-D nano-
channels of [Cu2(pzdc)2(pyrazine)]n (pzdc = 2,3-pyrazinedi-
carboxylate), with basic carboxylate oxygen atoms as catalytic
interaction sites.44 It should be noted that polyacetylene
extracted from the nanochannels indicated the dominance of
its highly conjugated trans form because of the restriction of
the molecular conformation in the confined space.
Oxidative polymerization has been widely utilized for the
synthesis of a variety of p-conjugated polymers that have attracted
the attention of the scientific and technical community for their
various applications. It is essential to develop a method for
oxidatively polymerizing monomers in MOFs for the preparation
of functional nanohybrids from coordination and p-conjugated
polymers. The nanospaces of MOFs can be used as templates to
control p-conjugated polymer arrangements for improved and
anisotropic functions. Oxidative polymerization is classified
into two categories: chemical- and electrooxidative polymeri-
zation. Redox-active metal sites can act as an oxidant for the
preparation of p-conjugated polymers.45 A chemical-oxidative
polymerization of pyrrole was performed within a layered MOF
[(Ni(dmen2))2(FeIII(CN)6)]PhBSO3 (dmen = 1,1-dimethylethylene-
diamine; PhBSO3 = p-phenylbenzenesulfonate), where the Fe3+
ions were reduced to Fe2+ ions, accompanied by the polymeriza-
tion of the monomers to polypyrrole (Fig. 4).46 It has been also
demonstrated that accessible Cu2+ sites on the pore surface of
[Cu3(btc)2]n (HKUST-1; btc = 1,3,5-benzenetricarboxylate) could
catalyze the oxidative polymerization of pyrrole.47 Oxidative
reagents can also allow us to polymerize monomers with high
oxidation potentials.4853 In this regard, polythiophene has been
prepared using iodine as an oxidative reagent in the 1-D channels
of [La(BTB)]n, resulting in the formation of unprecedented assem-
bly structures mediated by the host framework.48 Fedin et al.
reported the synthesis of polyaniline in [Cr3(bdc)3OF(H2O)2]n
(MIL-101(Cr)) using (NH4)2S2O8 to increase the materials
adsorption selectivity towards CO2 over N2.49 A report on the
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Fig. 4 Schematic illustration of oxidative polymerization of pyrrole in
[Ni(dmen)2]2[FeIII(CN)6](PhBSO3). Adapted with permission from ref. 46.
Copyright 2008, Wiley-VCH.
electropolymerization of aniline inside HKUST-1 was recently
published by Qius group.54 Electropolymerization enables con-
trol of polymerization reactions by varying the electrochemical
parameters such as applied current density or potential. Because
of the mild conditions of electropolymerization, this approach
can be expected to expand the scope of functional MOFs and
p-conjugated polymers for nanohybridization.
2.2. Polymerizations of ligands
The polymerization of organic ligands within MOF structures
may produce hybrid materials with special chemical, mechanical,
electrical, and optical properties. There are numerous choices for
the linkers and metal ions that can be employed to construct
MOFs with diverse topologies. The MOFs obtained can be further
modified with functional groups by post-synthetic modification
(PSM)5557 and linker exchange58 to adjust the surface features
and pore sizes. Because of the tunable characteristic of MOFs,
polymerizable ligands can be placed in specific positions to
polymerize with each other and form polymer chains within the
framework.59,60 Alternatively, the ligands may form polymers by
reacting with a cross-linker in the pores of MOFs.
Lee, Vittal, and coworkers reported the photopolymerization
of adjacent photoactive ligands within a MOF to obtain a metal
organic organopolymeric hybrid network.59 In the structure of
[Zn(bpeb)(bdc)]n (bpeb = 1,4-bis[2-(40 -pyridyl)ethenyl] benzene),
the bpeb ligands aligned in a slip-stack manner with adjacent
CQC distances of 3.68 . This is a key factor for the following
[2+2] cycloaddition reaction under UV light. In this way, the
pristine MOF with a six-fold interpenetrated net transformed
into a new network [Zn(poly-bppcb)(bdc)]n (poly-bppcb = 1,3-
(4,4 0 -bipyridyl)-2-phenylcyclobutane polymer) with a single net
while preserving the tetrahedral geometry around the Zn2+. The
resulting cyclobutane rings could be cleaved after heating and
the pristine structure could be obtained again, proving that the
transformation between the two structures is fully reversible.
Later, the same group utilized a similar approach to form a
syndiotactic polymer ligand in another MOF with a pillared-
layer structure.60 The MOF [Zn2(bpeb)(obc)2]n (obc = 4,4 0 -oxybis-
(benzoic acetate)) shows different photoreactivities with different
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
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undergo this transformation.
As demonstrated by Sada and colleagues, the ligands of
MOFs can also be cross-linked in the pores of MOFs to create
polymer networks.61 The cyclodextrin MOF (CD-MOF) was chosen
because of the abundant hydroxyl groups of the ligand g-CD.
Cubic crystals of CD-MOF with dierent sizes were prepared, and
reacted with the cross-linker ethylene glycol diglycidyl ether in
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
stability was insoluble in water. The CL-CD-MOF was further
immersed in H2Oethanol to break the coordination bonds and
remove the residual metal ions and cross-linkers, providing
cubic gel particles (CGPs) with volume expansion. The cross-
linking reactions took place in the pores of MOFs, leading to
the formation of polymer networks, and the MOF crystals were
sacrificed as templates to give CGPs with similar shapes.
Other reactions have also been applied to cross-link the
linkers in the voids of MOFs. For example, Sada et al. employed
the in situ click reaction to obtain polymer networks without
aecting the structures of MOFs.62 The linkers, modified with
the clickable azide function group, were used to synthesize
MOFs with metal ions including Zn2+, Cu2+, and Zr4+, and the
resultant MOFs were then reacted with multifunctional acetylene
compounds accompanied by Cu+ to aord cross-linked MOFs
with polymers in the pores. Once the composites were soaked in
acid, the decomposition of the host MOFs liberated polymer gels
with a similar shape. Similarly, Woll and colleagues converted
highly ordered surface-mounted MOFs (SURMOFs) prepared via
liquid-phase epitaxy (LPE) to polymer gel coatings through cross-
linking the linkers containing azido groups with alkyne.63 The
surface-grafted gels (SURGELs) obtained had homogeneous
thickness and showed remarkable stability. The post-synthetic
click reactions between the ligands within the MOF and the
added cross-linkers proved to be a universal way to form polymer
gels. Although the macroscopic shape of the polymers obtained
could be controlled, the regularity of the polymer chains remains
dicult to achieve.
Uemura et al. utilized cross-linking between the host MOF
and the polymer chains produced in its channels for the first
time, achieving precise control of the alignment of a vinyl poly-
mer (Fig. 5).39 [Cu2(bdc)2(ted)]n was employed as an underlying
structural motif, where the bdc in the host was partially sub-
stituted with a polymerizable 2,5-divinyl-terephthalic acid (DVTPA)
ligand. The ratio of the two ligands could be adjusted, which is
a crucial factor in cross-polymerization. St monomer was added
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Fig. 5 Schematic of hostguest cross-polymerization. (a) Structure of
DVTP. (b) Monomers used in hostguest cross-polymerizations. (c) Cross-
linkable MOF [Cu(DVTP)x(bdc)1x(ted)0.5]n (1x; shown in light blue) prepared
in a solid-solution fashion. (d) The host 1x accommodates vinyl monomers
in its nanocavities. (e) Heat treatment triggers radical cross-polymerization
in the presence of AIBN initiator, yielding 1x*polymer nanocomposites.
(f) Selective decomposition of the PCP matrix generates highly ordered
cross-linked polymers. Reprinted from ref. 39 with permission from Macmillan
Publishers Ltd: Nat. Chem., copyright 2013.
and copolymerized in the channels of the engineered MOF
while cross-linking with the DVTPA on the framework, generating
highly ordered PSt chains covalently bonded to each other. Because
of the hostguest cross-polymerization, the polymers obtained after
removing the MOF matrix present diffraction peaks in their X-ray
powder diffraction (XRPD) patterns. Polymers prepared in this way
possess higher glass transition temperatures (Tg) and enhanced
stability when exposed to solvents and high temperatures. Taking
advantage of the well-defined channels of MOFs and the cross-
linking reactions between the host ligands and the organic mono-
mers is a facile and promising way to prepare MOFpolymer
hybrids and polymers with controllable chain packing.
As demonstrated above, ligands of MOFs can participate in
polymerization reactions in two ways: (i) polymerization with
each other within the framework; or (ii) reaction with newly
added monomers. One important precondition for these reac-
tions is the stability of the structure during the process. For the
first method, the polymerizable linkers must be included in the
MOFs, and their positions directly influence the polymerization
process. Therefore, MOFs with regulated spatial arrangement
of the ligands are only able to undergo polymerization between
adjacent ligands. The second method is regarded to be more
universal, and the key factors are the polymerizable functional
groups and suitable channels for the occurrence of polymeriza-
tion. By designing and tailoring the sites of functional groups
and the structure of the channels in MOFs, high-dimensional
polymers with controlled structures can be synthesized, provid-
ing unprecedented polymer materials with various fascinating
properties.
2.3. Utilization of polymer-tethered ligands (pre-synthetic or
post-synthetic methods)
To alter the properties such as stability, dispersity, and flexibility
of MOFs, a promising method is to modify these crystalline solids
with polymers. Preparation of MOF tethering polymers can be
achieved during the formation of MOF crystals by using pre-
prepared polymeric linkers (pre-synthetic method) or attaching
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polymer chains onto the functional ligand sites of MOF crystals
(post-synthetic method). These MOF/polymer hybrid materials
inherit porosity and crystallinity from the MOF together with
flexibility, processability and many other interesting properties,
such as response to external stimulus from the polymers.
In the pre-synthetic method, polymers containing ligand
monomers were used to synthesize MOF derivatives. Recently,
Cohens group has pursued a series of studies in this respect to
give MOF/polymer hybrid materials, polyMOFs. The initial study
used cross-linked NH2-bdc with dierent linker lengths to synthe-
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size cross-linked isoreticular MOF (IRMOF) analogues using the
solvothermal method.64 Based on this, rationally designed oligo-
meric ligands that contain three H2bdc units linked together
were applied to construct IRMOF derivatives.65 Their successful
preparation demonstrates that the topology of IRMOFs can
endure some variations in ligands. Polymer ligands with repeat-
ing H2bdc units were also attempted to produce crystalline
MOFs.66 As shown in Fig. 6, 1-D polymer chains with H2bdc
moieties in the backbone were prepared and then converted to
crystalline IRMOF analogues by annealing with Zn2+. The
polyMOFs obtained possess the features of polymers (flexibility
and hydrophilicity) and MOFs (crystallinity and porosity), which
demonstrates that the inclusion of polymer chains within the
framework is a good way to tailor the properties. The concept of
polyMOFs was further applied to MOFs with pillared-layer struc-
tures by combining the polymer ligand with the pillar ligand.67
Analogues of the MOF [Zn2(BME-bdc)2(bpy)]n (BME-bdc = 2,5-
bis(2-methoxyethoxy)-1,4-benzenedicarboxylate) were obtained by
changing the BME-bdc to a polymer ligand containing H2bdc
moieties with methylene spacers. Note that the incorporation of
polymer chains enhanced the stability and hydrophobicity of the
MOFs. However, the polymer chains of the ligands also influence
the process of formation of MOFs, often resulting in amorphous
products.
A more general way to access MOF tethering polymers is to
attach polymers to the synthesized MOF particles. In general,
two major methods have been applied to modify MOFs with
polymer shells post-synthetically. The first involves covalently
attaching the polymer chains to the functional groups on MOFs,
which is similar to the grafting to process in graft copolymeri-
zation.68 Another approach, called the post-synthetic poly-
merization (PSP) strategy, utilizes the copolymerization
between organic monomers or oligomers and polymerizable
functional groups on MOFs, which resembles grafting from
reactions.68
Fig. 6 The strategy described herein to convert a 1-D (linear), nonporous,
mostly amorphous polymer into a 3-D, porous, crystalline polyMOF hybrid
material. Adapted with permission from ref. 66. Copyright 2015 Wiley-VCH.
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With the grafting to method, polymers with special prop-
erties can be directly bonded to the functional groups on MOFs
giving hybrid materials. Kokado and Sada et al. reported the
covalent attachment of the thermosensitive polymer poly(N-iso-
propylacrylamide) (PNIPAM) onto the surface of MOFs allowing for
controlled guest release.69 [(Zr6O4(OH)4(bdc-NH2)6)]n (UiO-66-NH2)
was selected for its stability under harsh conditions and its
amino functional groups for further modification reactions. The
grafting reaction was achieved by immersing the MOF particles
in PNIPAM-NHS-chloroform and subsequent heating at 60 1C.
According to that study, the polymer undergoes a surface-
selective modification because its molecules are larger than the
pore size of UiO-66-NH2. The MOF-tethering PNIPAM loaded with
guest molecules exhibits temperature controlled release behavior,
which is derived from the coilglobule transition of the thermo-
responsive polymer at different temperatures. Grafting polymer
chains to MOFs is a straightforward way to tune the properties of
the inorganic crystalline materials; however, the modification
degree (grafting density) may vary because of the different con-
formations and sizes of polymers.
To achieve precise modification of the external surfaces of
MOFs, Lachelt and Wuttke et al. made use of unsaturated func-
tional groups of linkers for the covalent attachment of polymers.70
Since the linkers with unsaturated sites exist only on the outer
surfaces of particles in most cases, the modification reactions
are limited to the surfaces. A stable MOF [Fe3F(H2O)2O(btc)2]n
(MIL-100(Fe)) with free aromatic carboxylic acid groups was
selectively functionalized with polyethylene glycol (PEG) 5000
and Stp10-C by a carbodiimide mediated reaction under mild
conditions. MOF particles with surface polymer coatings reveal
enhanced colloidal stability and possibilities for biomedical
applications.
To control the modification degree and the thickness of
the polymer coating eectively, a post-synthetic polymerization
(PSP) method, which resembles the grafting from reaction,
can be adopted to functionalize the MOF particles with poly-
mers. The precondition for the occurrence of the PSP is that the
MOFs contain polymerizable groups or functional groups to
which active sites can be attached. Then the MOF particles with
active sites can be polymerized with organic monomers or oligo-
mers to oer composites possessing the advantages of both MOFs
and polymers.
From the authors group, Wang et al. developed the concept
of photoinduced post-synthetic polymerization (PSP) for the
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
were covalently linked by the polymers. Photo-induced PSP is
a facile and universal approach for fabricating MOFpolymer
hybrid composites and membranes. Such PSP-derived composites
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Fig. 7 Preparation of a PSP-derived membrane by photoinduced post-
synthetic polymerization. Adapted with permission from ref. 71. Copyright
2015 Wiley-VCH.
shed light on the fabrication of new MOF hybrid materials for
practical applications. Utilizing the PSP strategy, Dong and
colleagues prepared UiO-66-NH2polyurea hybrid membranes
with different MOF loadings.72 The amino-functionalized MOF was
cross-linked with an isocyanate-terminated polyurethane oligomer,
giving free-standing membranes without obvious defects. The
hybrid membranes showed potential for dye removal.
Mahdavi et al. investigated the preparation of MOF plus
sulfonated polymer hybrid nanoparticles by surface-initiated
radical polymerization.73 Amino groups in MIL-101(Al)-NH2 reacted
with 4,40 -azobis(4-cyanovaleric acid) endowing the MOF particles
with initiator sites (forming macro-initiators). The following graft
polymerization of 2-acrylamido-2-methyl-1-propane sulfonic acid
(AMPS) occurs from the active sites on the MOF; therefore, the
grafted polymer chains are formed around the external surface
of the particles. The same method also works for silica particles
to give super-acidic hybrid particles. By changing the active sites
attached to MOFs, the same group proved that the method was
suitable for the redox polymerization of AMPS from the MOF
surface.74
The aggregation problem and poor dispersity of MOF particles
hinder their further applications in liquid systems. Modification
with polymers can tailor the properties of MOFs to some extent.
Webley and colleagues showed that the grafting of a hydrophilic
PEG polymer would benefit the dispersity of MOF particles in
water.75 UiO-66-NH2 was first anchored with a multifunction-
alized initiator by reacting with bromoisobutyryl bromide (BiBB),
followed by an atom-transfer radical polymerization (ATRP) of the
macromonomer poly(ethylene glycol) methyl ether methacrylate
(PEGMA) initials from the MOF substrate. The PEG-grafted MOFs
obtained from this procedure showed excellent dispersity in
aqueous solution. This can be explained by the isolation of the
MOF particles and the elimination of interactions after polymer
attachment. The dispersity can be tuned by varying pH for MOFs
with short polymer chains. Using a similar method, Zhu et al.
realized the reversible dispersability/collectability in MOF
polymer hybrid materials by immobilizing the thermally
switchable copolymers.76 MIL-101(Al)-NH2 modified with BIBB
underwent surface-initiated ATRP of 2-(2-methoxyethoxy)ethyl
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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
immobilization as well as the attachment of polymer chains.77
IRMOF-3@MOF-5 was first synthesized, and then 2-bromoiso-
butyric anhydride was reacted with the amine groups in the
IRMOF-3 shell. The polymer@MOF@MOF was obtained by ATRP
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
and polymerization.
The tethered polymer chains can also act as bridges to link
MOFs onto certain substrates. As shown by Li and colleagues,
MIL-101(Cr) was covalently attached to nylon fabrics by poly-
merization with 2-hydroxyethyl acrylate (HEA) induced by g-ray
irradiation.78 Due to the existence of vast benzene rings in MIL-101,
free radicals can be produced on its surface when exposed to g-ray
irradiation. The same process also occurs on the surface of the
nylon substrate. In this situation, the generated radicals can initiate
the polymerization of HEA, and the formed PHEA chains firmly
link MOF particles to the substrates.
2.4. Introduction of polymer chains into nanochannels of
MOFs
The synthesis of polymers inside or outside MOFs has been
widely investigated for the preparation of polymerMOF com-
posites. However, with the in situ polymerization method, precisely
controlling the molecular weight and loading amounts of poly-
mers, which are important factors in determining the polymer
chain assembly structures and their functions, remains challeng-
ing. Polymer incorporation into MOFs is a simple yet powerful
method to overcome these limitations. In addition, one of the
significant advantages of this method is its ability to introduce
polymers that pose a synthesis problem inside MOFs. To intro-
duce polymers into MOFs, several approaches have been studied,
including melt processing, solution-mediated incorporation, and
growth of MOFs in the presence of polymers.
Uemura and Kitagawa et al. demonstrated that MOFs can
adsorb polymer chains in their channels to form MOFpolymer
composites via polymer melt processing. In this method, PEG
(MW = 3000),79 linear alkanes,80 and polymethylpropylsilane
(Mn = 3600)81 have been incorporated into MOFs by heating
polymers and MOFs above the melting temperature of the
polymers. However, melt processing cannot be used with poly-
mers with high molecular weights because of their low diffu-
sivity into the pores.
The solution-mediated approach enables us to incorporate
polymers with high molecular weights into the nanopores of
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
enough to allow the incorporation of MP-11 molecules and their
accommodation in the mesopores. Subsequent eorts have also
been made to introduce other enzymes including the heme
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
for Cyt c and Mb, respectively).85,86 They proposed a tentative
mechanism for Cyt c encapsulation into the Tb-meso MOF,
which involves a significant conformational change of Cyt c
molecules during translocation into the MOF interior through
the relatively small nanopores.
Another approach to encapsulating polymer chains in MOFs
is the growth of MOFs in the presence of polymers via self-
assembly. Takamizawa et al. reported the synthesis of inclusion
complexes between [Mo2(fumarate)2]n and PEG of various mole-
cular weights ranging from 2007500.87 The amount of PEG
included increased with an increase in the molecular weight of
PEG. In contrast to the other methods, this approach has high
versatility because there are fewer limitations on the molecular
size of the polymers. Two strategies have been reported for the
synthesis of composite materials. The first employs a copreci-
pitation method in which biomolecules stabilized by capping
agents (i.e., polyvinylpyrrolidone) are added to a solution con-
taining MOF precursors.88 The second approach, termed bio-
mimetic mineralization, is performed in the absence of
capping agents.89 A wide range of giant biopolymers, such as
trypsin, horse-radish peroxidase (HRP), and insulin, have been
successfully encapsulated into [Zn(MeIM)2]n (ZIF-8; MeIM =
2-methylimidazole) through a biomimetic mineralization
strategy.89 The proteins and MeIM were first dissolved in water
and then combined with a solution of zinc acetate, resulting in
the formation of ZIF-8-coated proteins. Proteins rapidly induce
the formation of MOF coatings by concentrating the framework
building blocks and facilitating crystallization around the pro-
teins. In contrast to the coprecipitation method, SEM images
showed that the crystal morphology changed, depending on the
biomolecules (Fig. 8). The authors demonstrated that other
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Fig. 8 Scanning electron microscopy images showing ZIF-8 crystals obtained
using: (a) trypsin, (b) HRP, (c) insulin, and (d) quinone-dependent glucose
dehydrogenase. Scale bars, 1 mm. Reprinted by permission from Macmillan
Publishers Ltd: Nat. Commun., ref. 89, copyright 2015.
MOFs (i.e., HKUST-1) could also be synthesized, highlighting the
generality of this biomimetic mineralization method. In addition,
this technique extended the bioactive temperature range of
enzymes in comparison with the free enzymes and the enzymes
encapsulated via the coprecipitation method, demonstrating that
biomimetic mineralization can allow the practical use of enzymes
for various industrial applications.90
The accommodation of polymer chains within MOF particles
has been demonstrated using common techniques, such as XRPD,
particle size distribution, gas adsorption, Raman spectroscopy,
DSC, SEM, confocal microscopy, and NMR.79 Multinuclear 2-D
NMR is one of the most powerful methods to provide direct
evidence of the encapsulation of polymer chains in pores. When
polymer chains are incorporated into pores and are in close proxi-
mity to the host materials at the molecular level, cross-correlations
are observed because of heteronuclear magnetization transfer
between polymer chains and hosts.24,39,79,81
2.5. MOF-based mixed-matrix membranes (MMMs)
For practical applications such as gas separation, catalysis, and
sensing, powder-form MOFs must be processed into certain
shapes. Since such crystalline materials always lack flexibility
and processability, the combination with polymers can be a good
choice. Numerous MOF membranes have been prepared accom-
panied by polymers that act as a continuous phase or support.
Mixed-matrix membranes (MMMs), composed of porous inorganic
fillers dispersed in a polymer matrix, are promising materials
given their combination of advantages from both compo-
nents.91,92 Among the various inorganic fillers, MOFs stand
out because of their good compatibility with polymers and high
degree of designability. The pioneering work was conducted
by Musselman and coworkers, who incorporated a copper(II)
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Fig. 9 Schematic illustration of the dierent types of MOF-based MMMs.
biphenyl dicarboxylate-triethylenediamine MOF into a poly(3-
acetoxyethylthiophene) (PEAT) matrix.93 Since that study, remark-
able MOF-based MMMs have been prepared and applied in
various applications, such as gas separation, pervaporation, nano-
filtration, and solid electrolytes.13,94100
Based on the morphology of the membranes, MOF-based
MMMs are characterized as symmetric dense membranes and
asymmetric membranes (Fig. 9). Symmetric membranes pos-
sess a uniform structure with MOF particles dispersed in the
polymer, while asymmetric membranes consist of a thin and
selective MOFpolymer layer supported on a nonselective porous
substrate.
A common fabrication method for symmetric MOF-based
MMMs is the solution casting approach. In this process, one
crucial issue is the particle dispersion in the casting solution.
Usually, MOF particles are first dispersed in the solvent by
stirring or sonication, and then mixed with the polymer solution
to form the final casting solution. A priming technique is often
applied to obtain a well-dispersed solution.101,102 In this step, a
small portion of the polymer is first mixed with the MOF
suspension to form a layer of polymer on the surface of the
MOF particles to prevent aggregation. The step is repeated until
all the required polymers have been added. Sucient stirring or
sonication is required before casting to avoid agglomeration and
remove air bubbles. Then the MOFpolymer dispersion is cast
onto a flat substrate, usually with a casting knife, and left for
evaporation of the solvent. When the solvents used for casting
are volatile, the evaporation rate in the initial process should be
controlled by partial coverage or by applying low heating
temperature to avoid forming defects. Heating under vacuum
removes all of the residual solvents. It is believed that post-
treatment under high temperatures would improve the membrane
performance, especially for gas permeability, as the solvent in the
pores of MOFs can be eliminated.103,104
Membranes with uniform and defect-free structures are
desirable, especially for separation applications. Two main issues
that may influence membrane performance are poor compati-
bility between the MOF fillers and polymer matrices (leading to
interface defects) and particle agglomeration and sedimenta-
tion (resulting in nonselective voids and brittle membranes).
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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
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
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
bond between the MOF and the polymer matrix. A more general
method is to modify the MOF particles with functional groups or
polymers to tailor the surface properties and thus improve their
adhesion to the polymers.118121 As illustrated by Wu and collea-
gues, MIL-101(Cr) decorated with polyethylenimine (PEI) showed
increased interactions when mixed with sulfonated poly(ether
ether ketone).121
The size and morphology of the MOF particles are also crucial
parameters when fabricating membranes.122 Nanoparticles are
often preferred because they can provide larger interfacial areas
at the MOFpolymer boundary, thereby allowing closer integra-
tion.123128 In Nairs study, size-reduced [Zn(ICA)2]n (ZIF-90; ICA =
2-imidazolatecarboxyaldehyde) was incorporated into PI, giving
membranes with excellent gas separation performance.123 MOF
nanosheets are another attractive candidate for the MMM
filler.129,130 Therefore, developing methods to tune the morphol-
ogy and size of MOF particles will also boost the advancement of
MOF-based membranes.
Some novel methods have been designed to produce hybrid
membranes with defect-free interfaces. Quemener et al. developed
a particle fusion approach that involves the growth of ZIF-8 in a
Matrimids 5218 particle suspension followed by slowly fusing the
MOFpolymer composite to fabricated membranes without com-
patibility problems.131 One-pot synthesis of MMMs was studied by
Coronas et al.; the key step is to find a common solvent for the
preparation of both the MOFs and casting solution, which ensures
strong interactions in the final composite membranes.132 Later,
crystallization of MOFs in the polymer solution or even monomer
solution in the continuous phase was successfully realized by
Dong.133 The in situ construction of MOFs within the polymer
(monomer) system leads to membranes without defects at the
interfaces. Furthermore, as demonstrated by He et al., ionic liquid
(IL) can act as a cross-linking agent to strengthen the inter-
actions between the two phases.134
Another diculty that must be overcome is the agglomera-
tion of MOF particles, especially for nanoparticles, which will
degrade the membrane performance and mechanical properties. As
mentioned above, the most commonly used method is priming
the MOF particles with a layer of polymer before mixing to
prevent aggregation in the casting solution.135140 In addition,
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MOF nanosheets embedded in polymers tend to present a
uniform occupation and to improve the membrane performance
because of their special nanostructure and large exposed surface
area.129,130 In contrast, large MOF particles are prone to form
sediments in the course of casting, which lead to inhomogeneous
and brittle membranes.141
Agglomerates are often formed during the drying of MOF
particles; once this happens, it is dicult to redisperse them.
Therefore, direct incorporation of the synthesized wet-state MOF
without drying would be a good choice.104,110,142,143 Sivaniah
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et al. applied the solution-mixing strategy in the fabrication of
ZIF-8Matrimids 5218 membranes, and the resultant mem-
branes showed good particle dispersion, even at a high loading
of MOFs.142
Other methods have been developed to facilitate particle
dispersion throughout the polymer matrices. Employing MOF
composites as fillers has proved to be an eective way to enhance
the dispersion of the MOF.144,145 Zhu et al. prepared a composite
filler by growing ZIF-8 in situ on the surface of carbon nanotubes
(CNTs). ZIF-8 showed good dispersion in the membrane with the
help of the CNTs.144 In addition, surface modification of MOFs
with long-chain organic compounds may oer another way to
achieve even dispersion. Queen and colleagues modified the
hydrophilic UiO-66-NH2 with oleic acid through post-synthetic
ligand exchange, and the modified MOFs showed good disper-
sion in a hydrophobic cyclic olefin copolymer.146
In most cases, poor interactions between the MOF filler and
the polymer, as well as the aggregation of MOFs, are closely
related and should be considered together. Enhancing the
compatibility between the two phases also improves the dis-
persability of the particles. The photoinduced PSP strategy is a
promising method to solve both issues.71 MOFs modified with
polymerizable functional groups are expected to disperse well
in a monomer with a similar structure, and further copolymer-
ization between the MOF and polymer ensures their intimate
contact. As discussed in Section 2.3, MOFs decorated with poly-
mers become more dispersable, which makes them promising
fillers for MMMs. The attached polymers on the MOF surface also
improve the interface compatibility.
As for the asymmetric MMMs, a low mass transfer resistance
and high flux are expected because of their thin selective layer
supported on porous substrates, which are of practical value for
gas separation. According to their geometry, asymmetric mem-
branes can be classified into flat-sheet and hollow-fiber mem-
branes (HFMs).
Several approaches have been developed for the preparation
of asymmetric flat-sheet membranes, including phase inver-
sion, dip coating, solution casting, and spin coating. The phase
inversion method (also called drywet phase inversion) is the
most commonly applied method.147150 In a typical procedure
for MOFPI membrane preparation, the polymerMOF solution
was first cast onto a substrate followed by a solvent evaporation
process, and then immersed in water for solidification, followed
by solvent exchange in isopropanol. The membrane obtained
then is dried in an oven to remove the solvent completely.
However, the asymmetric membranes prepared in this way
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always possess defects, and further surface modification is
necessary to cover those voids. Vankelecom et al. prepared a
series of asymmetric PI membranes containing HKUST-1, ZIF-8,
and [Al(OH)(bdc)]n (MIL-53(Al)), and then coated the membranes
with permeable polydimethylsiloxane (PDMS) layers on the sur-
face by spin coating to seal the undesirable defects. In some cases,
the phase inversion method has also been utilized to prepare a
porous polymer that serves as the support for MMMs.151 Dip
coating is also a good way to fabricate asymmetric membranes.152
Diestel and colleagues prepared a-alumina-supported ZIF-8
polymethylphenylsiloxane (PMPS) membranes by dipping the
substrate in the solution and withdrawing at a constant rate.153
HFMs, with their high packing density, large area per volume,
tolerance to pressure and low cost, are the most desired mem-
brane geometry for real applications.154 HFMs are usually prepared
by dry jetwet quench spinning (also called phase inversion
spinning), which is similar in principle to the method for asym-
metric MMMs. Fabrication of pure polymer HFMs has been
well explored; however, the addition of MOF particles may
require addressing of further issues.109,155157 Liu et al. reported
the first MOF-based mixed-matrix HFMs consisting of HKUST-1
and PI.156 The MOF particles were first mixed with poly(amic
acid) (PAA) to form a homogeneous dispersion solution for
spinning, and then the solution was coextruded with water as
the bore fluid into a water-ice coagulation bath and collected by
a setup in which the phase inversion happened and hollow
fibers were formed. The fibers were then immersed in water to
exchange fully with the solvent and washed with methanol and
hexane, followed by heating to complete the imidation process
of PAA to form PI. The spinning temperature was set at 3045 1C
to achieve suitable viscosity.
Koros and colleagues prepared MOF-based dual layer HFMs
that consist of one layer of polymer as the support and another
layer with ZIF-8 particles as the selective skin.155 The core solu-
tion was prepared by mixing Ultems 1000 (in tetrahydrofuran
(THF)) and LiNO3 acting as a pore-forming agent (in N-methyl-
2-pyrrolidione (NMP)). The sheath solution was prepared using
a priming procedure by combining a ZIF-8NMPTHF sus-
pension and an Ultems 1000LiNO3NMP solution. The core
and sheath solution together with the bore fluid solution
(10 wt% water in NMP) were then coextruded through a compo-
site spinneret into a quench bath. The fibers obtained were then
immersed in water, ethanol and hexane separately before drying
in an oven. Later, Koros and colleagues carried out a systematic
investigation of the preparation parameters of MOF-based
mixed-matrix HFMs with high MOF loadings.157 They further
treated these fibers with a PDMS and/or polyaramid coating to
seal the cracks on the surfaces. The dual-layer HFMs are more
attractive and promising because they only need porous particles
and selective polymers in the skin layer, thus decreasing the cost
for molecular sieves and the core polymers.
Mixed-matrix HFMs can also be produced by coating a
polymerMOF layer onto polymer or ceramic hollow fibers.158,159
On one hand, the coating layer can cover the defects on the
support and improve the overall selectivity; on the other hand,
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
inversion spinning and subsequently coated them in a PDMS
HKUST-1 dispersion using a dip coating method.159 Considering
the numerous merits of asymmetric membranes, especially HFMs,
more strategies should be developed to fabricate membranes with
perfect structures on a large scale.
3. Functions
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The variety of MOFs and polymers aords an essentially infinite
number of possible combinations. Table 1 summarizes the
combinations of MOFs and polymers along with the functions
explored for the resulting hybrid materials.
3.1. Properties of polymer chains confined in MOFs
Understanding the properties of a few polymer chain assemblies
is important because of their potential applications for molecular-
based devices.160 Confinement of polymer chains in porous
materials is a feasible method to control polymer assemblies
because this approach can prevent the entanglement and con-
formational disorder of polymer chains in the bulk state.161 The
regulated and tailor-made pore characteristics of MOFs allow
the achievement of precise molecular assemblies in the nano-
channels, permitting fundamental studies on inherent polymer
properties that, until now, have remained elusive. In this regard, the
Uemura and Kitagawa group has widely studied the various intrigu-
ing properties of polymers confined in nanochannels of MOFs.
Radical polymerization of St was performed in the nano-
channels of [Zn2(bdc)2(ted)]n to study the behavior of single PSt
chains with a linearly extended conformation.24 Molecular
simulation and 2H NMR spectroscopy indicated that these
single PSt chains aorded unprecedented molecular dynamics
in the 1-D nanochannels: homogeneous rotation of phenyl rings
with a very low activation energy. This behavior can be ascribed
to both the linear extension of the single-chain conformation in
the nanochannels and the exclusion of the multiple interactions
observed in the bulk polymer.
Incorporation of PEG into 1-D nanochannels of [Cu2(L)2(ted)]n
revealed a thermal transition of only a few chain assemblies
(Fig. 10).79 In this system, the pore size and surface functionality
of [Cu2(L)2(ted)]n were easily tailored by changing the ligand L, so
that the thickness of the chain bundles, as well as the environ-
ment of the polymer chains, could be precisely controlled. Taking
advantage of MOFs, the transition behavior of the PEG bundles
could be systematically controlled for the first time. Note that the
transition temperature of confined PEG decreased as the mole-
cular weight of PEG increased, which contrasts strongly with the
conventional bulk system. The mobile nature of PEG chains
in MOFs was exploited in the area of lithium conductivity.
Incorporation of Li ions into MOFPEG composites led to
liquid-like high mobility of Li ions with an activation energy,
Ea, of 0.18 eV.162
The spatial control of polymer chain arrangements is a key
strategy for improving their functions, such as fluorescence
and conductivity. PVCz has attracted a great deal of attention
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because of its photoconductivity.163 In the bulk state, partially
overlapped structures of neighboring carbazolyl groups led to a
relatively low hole mobility (107 cm2 V1 s1).164 However,
confinement of PVCz in 1-D nanochannels of [La(BTB)]n dras-
tically enhanced the hole transport properties.30 PVCz chains in
[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-
tions. This unusual structure led to an increase in the carrier
mobility, which was about five orders of magnitude higher than
that in the bulk.
As conjugated polymers play crucial roles in advanced nano-
scale devices, understanding of nanoscale electronics is highly
desirable for future applications. Polysilanes exhibit intriguing
optoelectrical properties, such as high quantum yield of fluores-
cence and high mobility of charge carriers, which are attributed
to the delocalization of s-electrons along the main chain.165
The accommodation of single polysilane chains in [Al(OH)(L)]n,
where the ligand L corresponds to 2,6-naphthalenedicarboxylate
and 4,4 0 -biphenyldicarboxylate, increased the values of carrier
mobility compared with that in the bulk state because of the
elimination of slow interchain carrier hopping.81 The confor-
mation of the polysilane chains pivoted on the pore size, as
evidenced by 29Si NMR, Raman spectroscopy measurements,
and molecular dynamics simulations, allowing precise mani-
pulation of carrier transport properties even in the single-chain
manner. Recently, a report on the optoelectrical properties of
a few polymer chains confined in MOFs has been published.
Unsubstituted polythiophene (PTh) was prepared in the 1-D
nanochannels of [La(BTB)]n, where the number of polymer chains
was controlled.81 Regardless of the number of chains in the
nanochannels, the PTh chains exist in a planar fashion because
of the association of the polymer chain with the pore walls. The
accommodation of PTh chains in [La(BTB)]n resulted in a blue
shift of the emission wavelength; moreover, as the loading
amount of polymers in the MOF decreased, the magnitude of
the blue shift increased. In addition, the carrier transport proper-
ties of PTh were also drastically changed by varying the number
of polymer chains through the formation of the pp stacked
structure. Strong interchain interactions render PTh nonmelting
and insoluble; hence, control of the assembly structure, which
has a profound effect on its optoelectrical properties, has never
been achieved. The results obtained highlight that encapsulation
of polymer chains is a key strategy for controlling the low-
dimensional assembly structures to elicit potentially useful yet
unexplored properties.
3.2. Functions of hostguest nanocomposites
While a great deal of research eort has been aimed at prepar-
ing new MOF structures for various applications, hybridization
of MOFs with a variety of functional guests has been proposed
to combine the merits and mitigate the shortcomings of both
components.14 Polymers possess many unique attributes, includ-
ing thermal and chemical stability, fluorescence, and conductivity,
which are desirable to integrate with MOFs to make composites
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
HKUST-1 Polyimide
ZIF-8 Poly(1,4-phenylene ether-ether-sulfone)
ZIF-8 Poly(methylphenylsiloxane)
ZIF-8 Sodium poly(4-styrenesulfonate)
UiO-66 Poly(vinylidene fluoride)
ZIF-8 Polyamide
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Fig. 10 (a) Molecular dynamics structure of PEG-confined [Cu2(bdc)2(ted)]n.
(b) DSC profiles of neat PEG, [Cu2(bdc)2ted]n, and PEG in [Cu2(bdc)2(ted)]n.
Mw of PEG = 600. Reprinted from ref. 79 with permission from Macmillan
Publishers Ltd: Nat. Commun., copyright 2010.
Recent research has shown that the gas adsorption ability of
MOFs can be tuned by the encapsulation of polymers in the
frameworks. 1,2-Diethynylbenzene as the monomer was infil-
trated into MOF-5 and then heated to aord polynaphthylene
(PN) in the channels.166 The accommodation of PN in MOF-5
drastically enhanced CO2 adsorption from 38 to 78 cm3 g1 and
CO2N2 selectivity from 9 to 212 at 273 K and 1 bar. The N2
adsorption isotherm of the composites indicated that by increasing
the loading amount of PN, pores with widths of 1.2 nm gradually
diminished, while those with widths of 0.6 nm emerged, suggesting
that the polymer chains divided the MOF pores into confined
compartments because of their linear conformation (Fig. 11).
The enhancement of CO2 adsorption ability was attributed to
the confined pore size effect as well as the greater amount of
exposed aromatic surface. It is also noteworthy that the hydro-
phobic PN in MOF-5 improved the stability of the composites
toward moisture, demonstrating that this strategy is beneficial
for industrial applications.
There are requirements for sensitive and selective detection
of gas and vapor phase analytes for a range of applications,
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Properties Ref.
C2H4C2H6 separation, removal of 204 and 210
polystyrene from acetone
C2H4C2H6 separation 205
Isobutanol dehydration 209
Removal of methyl blue from water 211
Separation of Coomassie blue R-250 and 212
methyl orange
Removal of NaCl from water 214
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
polymers is a simple and eective method for obtaining con-
ductive and porous materials that have potential as excellent
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
conductivity. Thus, PEDOT can be utilized for the chemiresistive
detection of NO2, which has a toxic eect on the respiratory
system at concentrations of 1 ppm or less. However, an NO2
sensor using bulk PEDOT obtained by solution polymerization
presented a very low sensitivity (10 ppm) because of low accessi-
bility for NO2 molecules (SBET = 2 m2 g1). To overcome this
problem, oxidative polymerization of 3,4-ethylenedioxythiophene
was performed in a 3-D MOF, MIL-101(Cr), to give a hybrid
material with high electrical conductivity (1.1  103 S cm1)
while maintaining high porosity (SBET = 803 m2 g1).51 Because of
the high accessibility for the gas analytes, this hybrid material
showed high sensitivity (200 ppb) for NO2 gas.
Luminescence sensors provide a sensing output that is visible to
the naked eye, allowing on-site, instantaneous decision-making.168
Zhao et al. reported a luminescence sensor based on a charge
transfer process between the donor polymer threaded in a MOF
and the acceptor analytes.31 PVCz and the MIL-101(Cr) compo-
site could very quickly detect 1,3,5-trinitrobenzene, a highly
explosive substance, with a detection limit as low as 1 ppm.
In addition, the remaining pores could provide selectivity for
Chem. Soc. Rev.

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dierent acceptors with dierent sizes. Uemura et al. reported a
new luminescent sensor system utilizing coupled transforma-
tions of a flexible MOF and a fluorescent reporter oligomer,
distyrylbenzene (DSB).169 The [Zn2(bdc)2(ted)]nDSB composite
selectively adsorbed CO2 over other atmospheric gases, such as
N2, O2, and Ar, with concomitant structural change of the frame-
work. This structural change induced conformational variations
of the accommodated DSB, which caused a critical change in DSB
fluorescence. Hostguest coupled transformations thus convert
gas adsorption events into detectable output signals. The variety
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of polymers and MOFs affords an essentially infinite number of
possible combinations, which should expand the versatility and
possibility of sensing materials.
Ion exchange is an important process in a diverse range of
applications, such as water purification and precious metal
recovery.170 Conventional ion exchange resins consist of cross-
linked polymers with a low surface area, which decreases the
contact eciency between the ion-exchange sites and guest
species. Chans group demonstrated that the open porous
structure of MOFs allowed the encapsulated ion-exchange poly-
mer to contact the solvent and exchange ions eciently.32 Vinyl
benzyl chloride monomers were impregnated into ZIF-8 and
polymerized in situ, aording poly(vinyl benzyl chloride) (PVBC)
and the ZIF-8 composite. Subsequent amination and ion exchange
of PVBC yielded poly(vinyl benzyl trimethylammonium hydroxide)
(PVBTAH) in ZIF-8. With its high surface area and facile accessi-
bility, the extraction rate of gold cyanide anions by PVBTAH and
the ZIF-8 composite was much higher than that of a conven-
tional ion-exchange resin (Fig. 12). In 25 s, 490% of the gold
cyanide anion was extracted, in contrast to 7% extraction by
Amberlysts-A26. Recently, preparation of a cation exchange
polymer in a MOF was reported by the same group.34 Sodium
poly(4-styrenesulfonate) (NaPSS) was synthesized in MIL-101(Cr)
using a one-step in situ polymerization process. In addition to
fast cation exchange and high ion adsorption capacity, the
NaPSS and MIL-101(Cr) composite exhibited high selectivity with
co-ion rejection, which is a critical performance indicator of a
good ion exchange material.
Fig. 12 Au(CN2) concentration after immersing equal masses of PVBTAH B
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
Chemical Society.
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Good accessibility of the reactive sites by the reactants is
also essential for the eciency of solid catalysts. Hybridization
of polymers with catalytic activity and MOFs with high surface
areas is an eective strategy for fabricating noble heterogeneous
catalysts. Bromberg et al. reported the synthesis of cross-linked
poly(N-bromomaleimide) in MIL-101(Cr), resulting in a hybrid
composite with a large surface area (SBET = 1600 m2 g1), in con-
trast to cross-linked poly(N-bromomaleimide) prepared by solution
polymerization (SBET = 20 m2 g1).171 Because of their high
accessibility, the active bromine groups in the polymer network
allowed high activity of the composites in heterogeneous catalysis
for fructose dehydration into 5-hydroxymethylfurfural.
Enzymes are known to be the most sophisticated materials in
terms of catalysts because of their remarkable abilities, such as high
anities towards substrate and high catalytic eciency based on
their high stereo-, chemo-, and regioselectivities.83 However, even
with these advantages, the practical use of enzymes is limited by
their low operational stability, dicult recovery, and lack of reusabi-
lity under operational conditions. Enzyme immobilization in porous
materials is one of the most eective approaches to surmounting
these problems, making them industrially and commercially
viable.172 MOFs are envisioned as the most appropriate candidate
for this purpose because of their ultrahigh porosity, tunable pore
shape, and adjustable surface functionality. Mas group introduced
MP-11 into Tb-mesoMOF at a loading of 19.1 mmol g1.84 The
hybrid material demonstrated superior catalytic activity and recycl-
ability, even in an organic solvent (methanol), surpassing the free
MP-11 counterpart. The same group also encapsulated a series of
other enzymes into mesoporous MOFs, and investigated the cata-
lysis and mechanisms of those biocatalysts.85,86 More recently, it has
been demonstrated that trapping single enzyme molecules in each
predesigned cage of MOFs can eliminate enzyme aggregation and
maintain high catalytic eciency. Feng et al. synthesized a chemi-
cally stable MOF (PCN-333) with ultra-large cavities (5.5 nm), which
provided single-molecule traps for enzyme encapsulation.173 In this
work, three heme-proteins (horseradish peroxidase, Cyt c, and
MP-11) were encapsulated in PCN-333. A saturated loading of each
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
3.3. Polymer modification of the surface of MOFs
As described in Section 2.3, polymer coatings on MOFs are an
eective approach for the improvement of properties such as
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Chem Soc Rev
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
The SBET values for pristine and coated HKUST-1 were 1547 and
1544 m2 g1, respectively, suggesting that the PDMS layer does
not affect the accessibility of the pores. Compared with pristine
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.
Recent reports demonstrate that MOFs are of potential
interest in biomedical applications, such as drug carrier systems
and contrast agents for medical imaging.180,181 The surface
functions of MOF particles change the type of interactions taking
place between the MOFs and their surroundings, thereby strongly
aecting their colloidal stability, biocompatibility, recognition
capabilities, and biodistribution. Surface modification of MOFs
with well-defined polymers can provide precise control over
surface functionalities. For example, PEG surface coating is
widely used to confer stealth properties on nanoparticles in
biological applications. PEG with functional groups has been
shown to react directly with MOF particles, which prevented
their aggregation.180 However, the surface modification leads to
a decrease in the porous character because of the inclusion of
PEG chains within the pores. To circumvent this problem, the
surface agent should present a rigid section larger than the size
of the accessible windows of MOFs. Hence, Bellido et al.
modified the external surface of MIL-100(Fe) with heparin,
a polysaccharide with large molecular dimensions (heparin
unit E8.2  8.9 ; window size of MIL-101(Fe) E 8.6 ).182 This
coating improved the colloidal stability of the MOF, while the
intrinsic porosity and chemical stability remained unchanged. In
addition, the heparin coating endowed the MOF with improved
biological properties, such as the capacity to evade the immune
system and the production of oxygen species. Morris et al.
synthesized MOFnucleic acid nanoparticle conjugates via an
alkyne click reaction between dibenzylcyclooctyne-functionalized
DNA and azide-functionalized UiO-66-N3 (Fig. 13).183 The small
pore size of UiO-66-N3 meant that the particles were only
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Fig. 13 (a) DNA functionalization of UiO-66-N3 nanoparticles, using DNA
functionalized with dibenzylcyclooctyne (DBCO). (b) Nanoparticle uptake
per cell. (c) Cell viability assay data showing no significant cell toxicity for the
MOF nanoparticleDNA hybrids. Adapted with permission from ref. 183.
Copyright 2014 American Chemical Society.
modified on their surfaces. The DNA created a steric and electrostatic
barrier that stabilized the particles in high-dielectric media, which
increased cellular uptake efficiency for MOFDNA nanoparticles
compared with that of unfunctionalized MOF nanoparticles. The
MOFDNA hybrid showed no significant cytotoxicity to HeLa human
cervical cancer cells after 24 h of incubation. Because of the high
designability of synthetic polymers, MOF particles can be endowed
with multiple functions. Gd MOF nanoparticles were prepared for
theragnostics and their surface was modified by the covalent attach-
ment of multifunctional polymer chains with both optical imaging
capabilities and conjugate additional agents via the succinimide
groups.184 The succinimide was utilized to graft a therapeutic agent
and target ligands. A polymer-modified Gd MOF was shown to be
biocompatible and to have cancer cell targeting, bimodal imaging,
and disease treatment capabilities.
3.4. Applications of MMMs
Membrane-based separation has gained increased attention
because of its low cost, ease of operation, and high energy
eciency compared with traditional methods such as adsorp-
tion or cryogenic distillation. The combination of the molecular
sieving feature of MOFs and processability and mechanical
stability of polymers makes MMMs promising candidates for
various industrial separation processes. Numerous MOFs have
been incorporated into glassy or rubbery polymers to give MMMs
with significantly improved performance in applications including
gas separation, pervaporation, and nanofiltration.94100
3.4.1. Gas separation. Hydrogen purification, carbon dioxide
capture, and olefinparaffin separation are all important processes
in industry, and we now review recent progress in MOF-based
Chem. Soc. Rev.

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MMMs in these fields. The separation behavior of the membranes
in a single gas and mixed gases may be different, and the results
of the latter are more meaningful; therefore, here we mainly focus
on tests of membranes in mixed gas systems.
Hydrogen is a green and eective energy source and is con-
sidered a good substitute for fossil fuels. Currently, a common
way to produce hydrogen is steam reforming of hydrocarbon
fuels followed by a gas-shift reaction. In this process, CO2 is the
main by-product that must be separated to ensure the quality of
the produced hydrogen and to reduce emissions of this green-
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house gas. Since the steam reforming reaction is strongly endo-
thermic, the process is conducted under high temperatures.
Moreover, the products incorporate large amounts of water vapor
and some impurities (CO and CH4) besides H2 and CO2.185
Therefore, hydrothermally stable membranes with good separa-
tion performance under high temperature and pressure are
desirable for hydrogen purification. The same separation is
also required for precombustion CO2 capture in which the shift
products of coal gasification dier from those of steam reforming
in the partial pressures of the gases.
Because of its high thermal stability and compatibility with
ZIFs, PBI is often used to prepare MMMs. Chung and colleagues
mixed [Zn(bIM)2]n (ZIF-7, bIM = benzimidazole) nanoparticles
with PBI at the high loading of 50 wt% and the flexible
membranes obtained exhibit good dispersability and enhanced
H2CO2 separation performance compared with pure PBI or
ZIF-7 membranes.110 In the mixed-gas tests, the hybrid membrane
showed an H2 permeability of 13.3 Barrer and a H2CO2 separa-
tion factor of 7.2 at 35 1C (Fig. 14). The result at the high
temperature of 180 1C is above the Robeson upper bound186
proving that the ZIF-7PBI membranes are promising for indus-
trialization. Given the practicability of HFMs in large-scale gas
separation, the same group conducted research on fabricating
ZIF-8PBI dual-layer HFMs for H2 purification.109 The prepared
fibers are free of defects and agglomeration with excellent sepa-
ration performance at high temperatures. Tuning the loading of
ZIF-8 in the polymer can contribute to either high H2 permeance
Fig. 14 H2/CO2 separation performance of pure PBI and ZIF-7/PBI nano-
composite membranes compared with the Robeson upper bound (open
symbols: pure gas separation performance; closed symbols: mixed gas
separation performance). Reproduced from ref. 110 with permission from
The Royal Society of Chemistry.
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(202 GPU with selectivity of 7.7) or high selectivity (12.3 with H2
permeance of 64.5 GPU) at 180 1C. To further test the practic-
ability of such MMMs in actual applications, they modified the
fabrication method and measured the separation capabilities
at 230 1C in the presence of CO and water vapor. Mixed-gas
measurements demonstrate that the impurities in the feed gas
do not significantly weaken the separation of ZIF-8PBI mem-
branes at high temperatures.
Coronas et al. fabricated ZIF-8/PBI membranes and tuned
parameters including the sizes of ZIF-8 (50, 70, and 150 nm),
ZIF-8 loadings (10 and 20 wt%) and states of ZIF-8 (wet and
dry).187 A European interlaboratory Round Robin test was employed
to confirm the reproducibility of the membrane permeation
tests. The MMMs were tested for the separation of H2 and CO2
at 150 1C with feeding pressures from 3 to 6 bar, and both
permeability and selectivity values declined with the increasing of
the feeding pressures. At 20% filler loading, MMMs with ZIF-8 of
150 nm exhibit the best performance (an improvement of six
times in H2 permeability and nearly twice in selectivity), and this
may be due to the lower degree of aggregation in the case of larger
particle size. Furthermore, MMMs containing dry fillers present
better separation properties than those with wet fillers.
Nanoparticles of other ZIFs including ZIF-90, [Zn(bIM)2]n
ZIF-11, and MOF nanosheets have also been prepared and
blended with PBI to fabricate composite membranes for H2CO2
separation.106,129,188
Steam methane reforming (SMR) is the most common way
to produce hydrogen and the products often contain a small
amount of methane that should be removed. Huang and Zhong
et al. synthesized a biocompatible MOF [Fe3O(bdc)3]n (MIL-88)
and embedded the particles into Matrimids 5218 to fabricate
MMMs for H2CH4 separation.189 The composite membranes
offer improvements in both H2 permeability and selectivity in
equimolar mixture tests compared with pure polymer membranes.
A high separation factor of 96 was observed in the MMMs with
10 wt% filler loading.
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
layer, the fibers were post-treated with a coating of PDMS. In
single-gas tests, the composite fibers showed an 85% increase in
CO2 permeance and a 20% increase in selectivity compared with
pure polymer fibers. When a mixed gas (20% CO2 in N2) was used
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Chem Soc Rev
as the feed gas, the ZIF-8Ultems 1000 fibers showed a high
selectivity of 32 and H2 permeance of 26 GPU at 25 1C.
Polyether block polyamide (PEBA) contains soft polyether
segments and rigid polyamide (PA) segments. It shows promising
capability for CO2 separation because of its high anity for CO2
together with good mechanical stability.191 Hagg and colleagues
investigated the CO2N2 separation properties of ZIF-8PEBAX-
2533 in both dry and humid situations.192 Because of the aggre-
gation and sedimentation of the ZIF-8 particles, the hybrid
membrane (i.e., a polymer-based phase and a filler-based phase)
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has a special dual-layer morphology. A mixture of 10% CO2 and
90% N2 was used as the feed gas for the mixed-gas measurement.
In the dry state, the membrane with 40 wt% ZIF-8 loading
showed a high CO2 permeability of 1098 Barrer and a moderate
separation factor of 33 (a 50% drop compared with the pure
polymer); however, the permeability and selectivity are both
affected by humidity to some extent. To improve the adhesion
between ZIF-8 fillers and the polymer matrix, Chen et al. coated
the surface of ZIF-8 with polydopamine (PDA) and then mixed
these particles with PEBAX-4033.193 Given the many hydroxyl and
amino groups in PDA and their interactions with CO2, the coating
layer can facilitate the permeation of CO2 (Fig. 15). The CO2
permeability of PDA@ZIF-8PEBAX membranes with 15 wt%
ZIF-8 loading reached 267.74 Barrer with a CO2N2 selectivity of
62.65 in a single gas test in the humid state, which surpasses the
Robeson upper bound. Other types of MOFs were also employed
to synthesize PEBAX-based MMMs. For example, nanoparticles
of UiO-66 and UiO-66-NH2 were incorporated into PEBAX MH
1657 and the derived UiO-66-NH2PEBA membranes with 10 wt%
loading showed outstanding performance (CO2 permeability of
130 Barrer and selectivity of 72) in the mixed gas test with a
relative humidity of 20%.194
To achieve better eects with fillers, Wang et al. fabricated
asymmetric membranes comprising a thin ZIF-8poly(vinylamine)
(PVAm) coating on PSF substrates.195 On the one hand, the
selected flexible polymer may reduce the interfacial stress between
the polymer and fillers; on the other hand, the addition of ZIF-8
fillers can enhance free volume and thus improve the permeance
Fig. 15 Schematic illustration of the synthesis of PDA@ZIF-8 and the CO2
transport mechanism in PEBAX/PDA@ZIF-8 MMMs. Reproduced from ref. 193
with permission from The Royal Society of Chemistry.
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of such flexible polymers. By tuning the filler contents and
preparation parameters, the hybrid membranes with 13.1 wt%
ZIF-8 loading prepared with 50 mm coating thickness possessed
uniform structures without interfacial voids. A high CO2 per-
meance of 297 GPU and selectivity of 83 were observed with the
symmetric membranes in a binary-gas test (15 vol% CO2 and
85 vol% N2) with a feed pressure of 1.1 MPa.
Natural gas is a vital and clean fossil fuel relative to oil and
coal, and its major component is CH4. However, raw natural gas
often contains impurities including CO2, H2S, and N2, which
decrease the calorific value and lead to pipe corrosion during
delivery via pipeline. The removal of the major contaminant CO2
is crucial for further use of the fuel. Membrane-based separation
is promising for natural gas sweetening because of its high energy
eciency and low maintenance compared with the current
amine absorption process.196 Despite their low cost and good
processability, polymer membranes are often limited by a
trade-o between permeability and selectivity, and suer from
plasticization eects under high pressure, leading to a loss of
selectivity.197 The addition of porous MOF crystals can be a
good choice to overcome these problems. On one hand, the
porosity of MOFs boosts permeability and the molecular sieving
feature is expected to enhance the selectivity of the membranes.
On the other hand, the added fillers reduce the chain mobility
and thereby improve the stability and plasticization resistance
of the membranes, especially where bonds are formed between
MOFs and polymers.
ZIF-90 with a pore window size of 0.35 nm is promising for
CO2CH4 separation through a size exclusion mechanism. Jones,
Nair, and coworkers synthesized submicrometer-sized ZIF-90
particles via nonsolvent-induced crystallization, and then mixed
them with three types of PI (Matrimid, Ultem and 6FDADAM)
(6FDA = 4,4 0 -(hexafluoroisopropylidene)diphthalic anhydride;
DAM = 2,4,6-trimethyl-1,3-phenylenediamine) to prepare MMMs.123
In mixed-gas tests, MMMs made from ZIF-90 of smaller size
(B0.81 mm) and 6FDADAM showed the best results, because
of their well-matched permeability. Specifically, upon ZIF-90
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
higher solvent removal temperature (298 K) and thinner mem-
branes led to a higher proportion of the narrow-pore configu-
ration and enhanced separation properties. When an equimolar
Chem. Soc. Rev.

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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
a CO2CH4 selectivity of 28. Researchers have realized the impor-
tance of the filler morphology for the ideal structure and separa-
tion capability of membranes. Another team also studied the
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.
As demonstrated by FIB-SEM tomograms, the MOF nanosheets
dispersed well across the polymer matrix leading to larger
exposure areas and higher efficiency of molecular sieving.
Consequently, the obtained nanosheet-CubdcPI membranes
obtained exhibited higher selectivity over a wide pressure range
than the polymer membrane.
In some cases, when the pore sizes of MOFs lie between the
sizes of components to be separated, the flexible pore architec-
ture results in a loss of selectivity. Yang and coworkers proposed
a strategy to tune the molecular sieving properties of MOFs by
occupying the cages in ZIF-8 with the room temperature IL
1-butyl-3-methylimidazolium bis(trifluoromethyl-sulfonyl)imide
([bmim][Tf2N]), which also has high anity for CO2.152 ILs@ZIF-8
was employed as a filler to make PSF MMMs (6 vol% loading), and
a distinct increase in CO2 permeability with high selectivities of
CO2CH4 and CO2N2 was achieved. Moreover, when tested under
pressures up to 20 bar, the selectivity of the ILs@ZIF-8PSF
increased from 38 (6 bar) to 66 (20 bar) for CO2CH4 showing their
resistance to plasticization and their potential for industrial separa-
tion processes (Fig. 16).
Light olefins are the raw materials for many products and
chemicals, which makes them crucial in the chemical and
petroleum industries. For example, ethylene is the main
ingredient of polyethylene, ethylene oxide, ethylbenzene, and
ethylene dichloride. In the petrochemical industry, olefins are
produced by catalytic dehydrogenation following hydrocarbon
cracking. The dehydrogenation process often leads to an equi-
molar mixture of olefins and parans that possess similar
properties such as boiling point and molecular size, which
makes them dicult to separate.201 Cryogenic distillation,
the most common method utilized in industry, is cost and
energy intensive; therefore, membrane-based separation might
be an alternative approach because of its low cost and energy
consumption.202
To improve the separation performance and stability of
polymer membranes under high pressure, Long and colleagues
Chem. Soc. Rev.
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Chem Soc Rev
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
shifts from the aperture size of six-membered ring to the reduced eective
cage size by confinement of [bmim][Tf2N] in a ZIF-8s SOD cage. Adapted
with permission from ref. 152. Copyright 2015 Wiley-VCH.
incorporated a series of M2(dobdc) (M-MOF-74; M = Mg, Mn,
Fe, Co, Ni, Zn; dobdc = 2,5-dioxido-1,4-benzenedicarboxylate)
in 6FDADAM.203 These MOFs were chosen for their abundant
unsaturated metal sites that are supposed to be beneficial for
ethylene absorption and intimate interactions between MOFs
and polymers. The membrane performances are shown in Fig. 17.
Ni-MOF-74 and Co-MOF-74 with sizes below 20 nm show the best
performance for ethyleneethane separation when embedded in
6FDADAM, lying above the polymer upper bound. In binary-gas
tests at the high pressure of 20.5 bar, Ni-MOF-746FDADAM
exhibited a selectivity of 4.1, which is close to the ideal selectivity
(4.6), illustrating the plasticization resistance caused by the MOF
fillers, which can be explained by the strong interactions between
the unsaturated metal sites and the polymer matrix. Nijmeijer
et al. incorporated HKUST-1, FeBTC and MIL-53(Al) into the PI
P84 to make MMMs for ethylene/ethane separation.204 Compared
with pristine P84 membranes, membranes containing 20 wt%
HKUST-1 present remarkable enhancements with selectivity
improving from 4.1 to 7.1 and constant permeability. In another
work, ZIF-8 particles were added in a poly(1,4-phenylene ether-
ether-sulfone) matrix, and the composite membranes were tested
for the separation of C2H4/C2H6 resulting in an ideal selectivity of
3 and C2H4 permeability of 3.15 Barrer.205
HFMs are the most favored geometry for large-scale gas
separation because of their high packing eciency. For the
first time, Koros et al. fabricated dual-layer ZIF-86FDADAM
HFMs with a high loading of 30 wt% for propylenepropane
separation.157 By carefully tuning the parameters in the dry
jetwet quench technique and the components in the coating
layers, they obtained hybrid hollow fibers with 17 wt% loading
and PDMS coating that attained C3H6C3H8 selectivity of 17.7
and C3H6 permeance of 2.2 GPU.
In general, the basic factors to be considered for large-scale
gas separation are the separation eciency (selectivity) and
productivity (permeability) of the membranes. In addition, their
stability in contact with complicated and aggressive feeds, together
with the processing and operation costs, are vital for industrial
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Fig. 17 Ethylene/ethane separation performance for M2(dobdc)/6FDA
DAM membranes. (a) Membrane performance at 2 bar feed pressure and
35 1C relative to the upper bound for polymers. Membrane loadings by
weight are 10% and 33% for Co2(dobdc), 6% and 25% for Ni2(dobdc), 23%
for Mg2(dobdc), and 13% for Mn2(dobdc). The uncertainty in selectivities
represents propagation of uncertainty in permeability based on two inde-
pendent membrane samples; each sample was measured twice to ensure no
plasticization or conditioning effects. Grey circles represent neat polymers
from the literature. (b) TEM images of 33% Co2(dobdc) and 23% Mg2(dobdc)
membrane cross-sections and corresponding illustrations of the proposed
gas transport mechanisms, where purple hexagons represent Co2(dobdc)
or Ni2(dobdc) nanocrystals and red hexagons represent Mg2(dobdc) or
Mn2(dobdc) nanocrystals. Reprinted by permission from Macmillan Publishers
Ltd: Nat. Mater., ref. 203, copyright 2016.
applications.206 MOF-based MMMs indeed oer significant
potential to overcome the drawbacks of the polymer membranes
that now occupy a vital position in this field by incorporating
fillers with sieving properties, good compatibility, and a high
degree of designability.
3.4.2. Pervaporation. Pervaporation (PV), a separation
method for liquids, is used in many fields including dehydration
of solvents, exclusion of organic components from aqueous
phases, organic mixture separation, and membrane reactors.96
The mechanism of this process is based on solution-diusion
theory; specifically, that certain components should diuse
across the membrane and evaporate into the vapor phase on the
other side.207 Because of the dierent degrees of dissolution and
permeation rates of the components, the mixture can be separated
by the membranes. The most widely applied membranes in PV are
polymers; however, these tend to swell in this process, resulting in
a reduction of selectivity, and the incorporation of MOFs into
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Review Article
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
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,
which was confirmed by positron annihilation lifetime spectroscopy
analysis. In a mixture of ethanol and water (90/10 w/w), both the
separation factor and permeability of the membranes increased
with the ZIF-8 loading, and a high permeability of 2.07  106 Barrer
and selectivity of 4725 were attained at a loading of 39 wt%, which
is markedly better than the results obtained with pure PVA
membranes. The enhanced performance was due to the porosity
and molecular sieving of ZIF-8 fillers as well as their inhibition of
the swelling of the polymers.
Due to the characteristics of a flexible framework and super-
hydrophobic pore surface, ZIF-8 shows high adsorption selec-
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
PMPS membranes for the separation of isobutanol and water.
Specifically, the isobutanol permeance of the ZIF-8PMPS mem-
brane is 60007000 GPU with a separation factor in the range of
34.9 to 40.1.
3.4.3. Nanofiltration. Nanofiltration membranes usually
possess pore sizes in the range of 110 nm, and mostly are
made from polymers. They were originally used for molecular
separation in the aqueous phase, such as removal of polyvalent
cations and dyes from water. With the development of solvent-
stable membranes, nanofiltration can be more widely used in
organic solvents, extending their applications to such fields as
petrochemicals, food, and pharmaceuticals. The flux of the
membranes is a key factor in practical applications; therefore,
the addition of porous MOF fillers should contribute to higher
productivity. The tunable pore sizes of MOFs are also beneficial
for good selectivity. In some cases, the included MOF particles
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
polymerization on cross-linked PI supports for organic solvent
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
added. Among the four MOFs chosen (ZIF-8, MIL-53(Al),
NH2-MIL-53(Al), and MIL-101(Cr)), MIL-101(Cr) outperformed
the others because of its larger pore size, achieving high fluxes
of 3.9 and 11.1 L m2 h1 bar1 for PSMeOH and PSTHF,
which clearly illustrates that MOFs offer preferential flow paths
for the solvent molecules and prevent the passage of larger
impurities. Later, Livingston and coworkers reported the fabri-
cation of thin films of HKUST-1 on a PI P84 support membrane
by interfacial synthesis.210 The obtained hybrid membranes
with a thin layer of HKUST-1 beneath the surface were tested
for nanofiltration. Compared with membranes prepared by an
uncontrolled in situ growth method, thin film composite (TFC)
membranes show higher acetone permeance with similar PS
rejections, and this can be explained by the thinner selective
layer and lower resistance.
ZIF-8NaPSS membranes with uniform dispersion and a
crack-free interface between the two phases were prepared by
Li and coworkers by a coordination-driven, in situ, self-assembly
strategy.211 The ZIF-8 particles grew in the PSS polymer and the
Zn2+ ions were coordinated with the ligands and polymer
matrices as well as the PAN substrates. Importantly, the bonds
formed between the fillers and the continuous phase solved the
problems of agglomeration and incompatibility and also enhanced
the stability of the hybrid membranes. The separation performance
of the membranes was evaluated in the separation of methyl blue
from water, showing a high flux of 265 L m2 h1 MPa1 and
retention of 98.6% (Fig. 18).
As demonstrated by Cohen et al., MOFs in polyvinylidene
fluoride (PVDF) polymer membranes remained crystalline,
porous, and chemically accessible for further modification.212
They prepared free-standing MMMs with seven kinds of MOFs
at loadings up to 67%, and the addition of the fillers led to
improved stiness of the membranes. The porosity of the MOFs
within the polymers was confirmed by nitrogen adsorption
tests and the ability to separate the organic dyes from water.
The UiO-66PVDF membrane can not only remove Coomassie
dyes (B99% retention), but also achieve separation between
different dye molecules. For the first time, post-synthetic exchange
Chem. Soc. Rev.
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Chem Soc Rev
Fig. 18 Comparison of the dye-removal performance of the ZIF-8/PSS
membrane with that of previously reported membranes. Adapted with
permission from ref. 211. Copyright 2014 Wiley-VCH.
(PSE) and PSM were realized in MMMs, which provides possibi-
lities for in situ modification of MMMs and improved adhesion
between MOFs and polymers.
Similar to nanofiltration, reverse osmosis (RO) is also a
pressure driven process for the rejection of solutes and permea-
tion of the solvent, and the molecular weight cut-o for RO
membranes is below 100 g mol1. Most of the commercially
available RO membranes are composed of a TFC structure with
a thin selective layer of PA. To further improve the flux of the
membranes, porous materials including MOFs are embedded in
the PA layer giving TFN membranes. Pinnau et al. employed nano-
particles of ZIF-8 as fillers in the PA layer at a loading of 0.4% (w/v),
and in this case the water permeance is 3 times higher than the
pristine TFC membranes reaching 3.35  0.08 L m2 h1 bar1
while retaining the high NaCl rejection of 98.5  0.5%.213 In
another work, Gao and coworkers added hydrophilic MIL-101(Cr)
nanoparticles into a dense PA layer to provide direct water
channels achieving higher water permeance.214 The obtained
TFN membranes show a permeance of 2 L m2 h1 bar1 and
NaCl rejection of 99%. These results indicate that MOFs are
promising candidates for water purification.
As well as separation, MOF-based MMMs have also shown
their potential in applications including sensing,133 proton
conductivity,215217 and solid electrolytes.218221
4. Conclusion and outlook
This review article has described the methodologies for MOF
polymer hybridization, as well as the fascinating properties of
the hybrid materials. The integration of these two materials has
provided new aspects for both polymer and MOF chemistry.
Understanding of the specific properties based on low-dimensional
assemblies of polymers is central towards the development of
molecular-scale nanodevices. Rational design and preparation
of MOF hosts has permitted the precise control of polymer-
chain assembly structures, which has shed light on the unique
properties of polymers. Modification of MOFs with polymers
has improved their properties, such as gas adsorption, stability,
dispersability, and biocompatibility. In addition, this approach
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provides a simple but powerful way to fabricate MOF-based thin
films, which should stimulate the emergence of innovative
industrial applications in a diverse range of technologically
significant fields.
Tremendous advances have been made in MOFpolymer
hybrids; however, several challenges associated with hostguest
synergistic functions remain. One of the most appealing features
of MOFs that distinguishes them from conventional porous
materials is their structural flexibility, in which the framework
changes its structure upon exposure to external stimuli, such as
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heat, pressure, light, and magnetic fields.222 Cooperative struc-
tural transformations of flexible MOFs and functional polymers
could provide novel stimuli-responsive nanohybrid materials.
It is also clear that an important direction in this platform is
to pursue photoelectric synergy between MOFs and polymers.
Exploring photoinduced charge and energy transfer in donor
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
The spatial control of donoracceptor interfaces is an important
prerequisite because it is here that critical photophysical pro-
cesses take place.224 With a diversity of topologies and linkers,
MOFs represent a class of materials with electronic and conduct-
ing properties. Thus, hybridization of electroactive polymers
and MOFs could allow the creation of optimized systems with
periodic and well-defined networks of electron donor and
acceptor phases based on the original host structures.
MOF-based MMMs have shown their potential in separation
processes, especially in gas separation, because of the molecular
sieving feature of MOFs. Characteristics such as tunable pore
sizes, functional groups, open metal sites, and flexible structures
endow MMMs with attractive properties. Numerous strategies
have been developed to improve the dispersion of MOF particles,
and compatibility between the polymer matrix and the fillers
provides membranes with ideal configurations. Although rela-
tionships between the structure and performance of the MOF
MMMs are not quite clear, these two configuration parameters
seem to be essential according to most of the studies reported. As
illustrated by Rodenas and coworkers, FIB-SEM tomography is a
good way to study the filler distribution and quantify the interfacial
contact.198 But the real situations of the interfacial boundaries
between MOFs and polymers cannot be directly observed, making
it dicult to decide whether it is the pores of MOFs or the voids
between the two phases that mainly contribute to the sieving
performance of membranes. In addition, the size and morphol-
ogy of the fillers embedded also influence the performance
of membranes. For example, partial lamellar stacking of the
nanosheets in the polymer matrix is believed to be beneficial to
sieving eciency. However, it is dicult to characterize the
orientation of MOF nanosheets in the polymers that is critical
to achieve excellent separation performance. As for the mem-
branes containing MOF particles, current characterization tech-
niques cannot determine the pore distribution within the
membranes on the nanoscale that will be helpful for under-
standing the transport and sieving properties. With the develop-
ment of the characterization methods and the mathematics models,
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the relationships between the structure and performance will
become clear.
Despite the promising performance of the MOF MMMs, the
diculty of large-scale production of these membranes hinders
their further industrial application. The precursors of MOFs are
expensive and the reactions are mostly complicated. On the other
hand, continuous production of membranes is challenging. One
of the authors group proposed a scalable hot-pressing (HoP)
approach to fabricate MOF coatings.225 High temperature and
pressure are employed to assist the growth of various MOFs on
certain substrates without using any solvent. With the assis-
tance of a roll-to-roll machine, the HoP method may achieve
continuous production of MOF membranes in practical appli-
cations. With the rapid development of new and facile fabrica-
tion methods, MOF-based MMMs are bound to play a vital role
in practical separation processes.
Acknowledgements
T. U. acknowledges the financial support from JST-CREST and
JSPS KAKENHI Grant Number JP16H06517 (Coordination Asym-
metry). Y. Z. and B. W. acknowledge the financial support from
the 973 Program 2013CB834702 and the National Natural Science
Foundation of China (Grant No. 21625102, 21471018, 21404010,
21490570, 21674012).
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