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Metalorganic frameworks (MOFs) have received much attention because of their attractive properties.
They show great potential applications in many fields. An emerging trend in MOF research is hybridization
with flexible materials, which is the subject of this review. Polymers possess a variety of unique attributes,
such as softness, thermal and chemical stability, and optoelectrical properties that can be integrated with
Received 20th January 2017 MOFs to make hybrids with sophisticated architectures. Hybridization of MOFs and polymers is producing
DOI: 10.1039/c7cs00041c new and versatile materials that exhibit peculiar properties hard to realize with the individual components.
This review article focuses on the methodology for hybridization of MOFs and polymers, as well as the
rsc.li/chem-soc-rev intriguing functions of hybrid materials.
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Susumu Kitagawa chemical and physical properties If polymerizable monomers can be accommodated in the pores
of porous coordination polymers/ as guests, these monomers can be subsequently polymerized in
metal organic frameworks. the porous materials.15 In many cases, monomers are small
Bo Wang obtained his BS, MS and Takashi Uemura received his PhD
PhD from Peking University in at Department of Polymer Chemi-
2004, University of Michigan in stry, Kyoto University in 2002.
2006 and University of California He then joined as an assistant
Los Angeles in 2008, respectively. professor in Department of Syn-
He has been a professor in the thetic Chemistry and Biological
School of Chemistry and Chemical Chemistry in Kyoto University, and
Engineering, Beijing Institute has been an associate professor
of Technology since 2011. His since 2010. He has been also a
research interests focus on metal research director for a CREST
organic frameworks, membranes/ program of Japan Science and
films and other functional porous Technology Agency (JST) since
Bo Wang composites for gas separation, Takashi Uemura 2013. His research interest is pre-
purification and toxicant capture paration of synergistic nanohybrids
and sensing. between coordination compounds and polymeric materials, in
particular, polymer chemistry in confined nanospaces.
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Fig. 2 Schematic illustration of a variety of methods for the hybridization of MOFs and polymers. (a) Polymerization within nanochannels of MOFs.
(b) Polymerization of ligands. (c) Introduction of polymer chains into nanochannels of MOFs. (d) Polymer containing ligand monomers. (e and f) Post-synthetic
polymer-tethered ligands (grafting on and grafting from). (g) MOF-based mixed matrix membrane (MMM).
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undergo this transformation. DVTP. (b) Monomers used in hostguest cross-polymerizations. (c) Cross-
As demonstrated by Sada and colleagues, the ligands of linkable MOF [Cu(DVTP)x(bdc)1x(ted)0.5]n (1x; shown in light blue) prepared
MOFs can also be cross-linked in the pores of MOFs to create in a solid-solution fashion. (d) The host 1x accommodates vinyl monomers
in its nanocavities. (e) Heat treatment triggers radical cross-polymerization
polymer networks.61 The cyclodextrin MOF (CD-MOF) was chosen
in the presence of AIBN initiator, yielding 1x*polymer nanocomposites.
because of the abundant hydroxyl groups of the ligand g-CD. (f) Selective decomposition of the PCP matrix generates highly ordered
Cubic crystals of CD-MOF with dierent sizes were prepared, and cross-linked polymers. Reprinted from ref. 39 with permission from Macmillan
reacted with the cross-linker ethylene glycol diglycidyl ether in Publishers Ltd: Nat. Chem., copyright 2013.
ethanol at 65 1C. Unlike the CD-MOF, which could be dissolved
easily in water, the resultant cross-linked CD-MOF (CL-CD-MOF)
with the same underlying structure and improved thermal and copolymerized in the channels of the engineered MOF
stability was insoluble in water. The CL-CD-MOF was further while cross-linking with the DVTPA on the framework, generating
immersed in H2Oethanol to break the coordination bonds and highly ordered PSt chains covalently bonded to each other. Because
remove the residual metal ions and cross-linkers, providing of the hostguest cross-polymerization, the polymers obtained after
cubic gel particles (CGPs) with volume expansion. The cross- removing the MOF matrix present diffraction peaks in their X-ray
linking reactions took place in the pores of MOFs, leading to powder diffraction (XRPD) patterns. Polymers prepared in this way
the formation of polymer networks, and the MOF crystals were possess higher glass transition temperatures (Tg) and enhanced
sacrificed as templates to give CGPs with similar shapes. stability when exposed to solvents and high temperatures. Taking
Other reactions have also been applied to cross-link the advantage of the well-defined channels of MOFs and the cross-
linkers in the voids of MOFs. For example, Sada et al. employed linking reactions between the host ligands and the organic mono-
the in situ click reaction to obtain polymer networks without mers is a facile and promising way to prepare MOFpolymer
aecting the structures of MOFs.62 The linkers, modified with hybrids and polymers with controllable chain packing.
the clickable azide function group, were used to synthesize As demonstrated above, ligands of MOFs can participate in
MOFs with metal ions including Zn2+, Cu2+, and Zr4+, and the polymerization reactions in two ways: (i) polymerization with
resultant MOFs were then reacted with multifunctional acetylene each other within the framework; or (ii) reaction with newly
compounds accompanied by Cu+ to aord cross-linked MOFs added monomers. One important precondition for these reac-
with polymers in the pores. Once the composites were soaked in tions is the stability of the structure during the process. For the
acid, the decomposition of the host MOFs liberated polymer gels first method, the polymerizable linkers must be included in the
with a similar shape. Similarly, Woll and colleagues converted MOFs, and their positions directly influence the polymerization
highly ordered surface-mounted MOFs (SURMOFs) prepared via process. Therefore, MOFs with regulated spatial arrangement
liquid-phase epitaxy (LPE) to polymer gel coatings through cross- of the ligands are only able to undergo polymerization between
linking the linkers containing azido groups with alkyne.63 The adjacent ligands. The second method is regarded to be more
surface-grafted gels (SURGELs) obtained had homogeneous universal, and the key factors are the polymerizable functional
thickness and showed remarkable stability. The post-synthetic groups and suitable channels for the occurrence of polymeriza-
click reactions between the ligands within the MOF and the tion. By designing and tailoring the sites of functional groups
added cross-linkers proved to be a universal way to form polymer and the structure of the channels in MOFs, high-dimensional
gels. Although the macroscopic shape of the polymers obtained polymers with controlled structures can be synthesized, provid-
could be controlled, the regularity of the polymer chains remains ing unprecedented polymer materials with various fascinating
dicult to achieve. properties.
Uemura et al. utilized cross-linking between the host MOF
and the polymer chains produced in its channels for the first 2.3. Utilization of polymer-tethered ligands (pre-synthetic or
time, achieving precise control of the alignment of a vinyl poly- post-synthetic methods)
mer (Fig. 5).39 [Cu2(bdc)2(ted)]n was employed as an underlying To alter the properties such as stability, dispersity, and flexibility
structural motif, where the bdc in the host was partially sub- of MOFs, a promising method is to modify these crystalline solids
stituted with a polymerizable 2,5-divinyl-terephthalic acid (DVTPA) with polymers. Preparation of MOF tethering polymers can be
ligand. The ratio of the two ligands could be adjusted, which is achieved during the formation of MOF crystals by using pre-
a crucial factor in cross-polymerization. St monomer was added prepared polymeric linkers (pre-synthetic method) or attaching
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polymer chains onto the functional ligand sites of MOF crystals With the grafting to method, polymers with special prop-
(post-synthetic method). These MOF/polymer hybrid materials erties can be directly bonded to the functional groups on MOFs
inherit porosity and crystallinity from the MOF together with giving hybrid materials. Kokado and Sada et al. reported the
flexibility, processability and many other interesting properties, covalent attachment of the thermosensitive polymer poly(N-iso-
such as response to external stimulus from the polymers. propylacrylamide) (PNIPAM) onto the surface of MOFs allowing for
In the pre-synthetic method, polymers containing ligand controlled guest release.69 [(Zr6O4(OH)4(bdc-NH2)6)]n (UiO-66-NH2)
monomers were used to synthesize MOF derivatives. Recently, was selected for its stability under harsh conditions and its
Cohens group has pursued a series of studies in this respect to amino functional groups for further modification reactions. The
give MOF/polymer hybrid materials, polyMOFs. The initial study grafting reaction was achieved by immersing the MOF particles
used cross-linked NH2-bdc with dierent linker lengths to synthe- in PNIPAM-NHS-chloroform and subsequent heating at 60 1C.
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size cross-linked isoreticular MOF (IRMOF) analogues using the According to that study, the polymer undergoes a surface-
solvothermal method.64 Based on this, rationally designed oligo- selective modification because its molecules are larger than the
meric ligands that contain three H2bdc units linked together pore size of UiO-66-NH2. The MOF-tethering PNIPAM loaded with
were applied to construct IRMOF derivatives.65 Their successful guest molecules exhibits temperature controlled release behavior,
preparation demonstrates that the topology of IRMOFs can which is derived from the coilglobule transition of the thermo-
endure some variations in ligands. Polymer ligands with repeat- responsive polymer at different temperatures. Grafting polymer
ing H2bdc units were also attempted to produce crystalline chains to MOFs is a straightforward way to tune the properties of
MOFs.66 As shown in Fig. 6, 1-D polymer chains with H2bdc the inorganic crystalline materials; however, the modification
moieties in the backbone were prepared and then converted to degree (grafting density) may vary because of the different con-
crystalline IRMOF analogues by annealing with Zn2+. The formations and sizes of polymers.
polyMOFs obtained possess the features of polymers (flexibility To achieve precise modification of the external surfaces of
and hydrophilicity) and MOFs (crystallinity and porosity), which MOFs, Lachelt and Wuttke et al. made use of unsaturated func-
demonstrates that the inclusion of polymer chains within the tional groups of linkers for the covalent attachment of polymers.70
framework is a good way to tailor the properties. The concept of Since the linkers with unsaturated sites exist only on the outer
polyMOFs was further applied to MOFs with pillared-layer struc- surfaces of particles in most cases, the modification reactions
tures by combining the polymer ligand with the pillar ligand.67 are limited to the surfaces. A stable MOF [Fe3F(H2O)2O(btc)2]n
Analogues of the MOF [Zn2(BME-bdc)2(bpy)]n (BME-bdc = 2,5- (MIL-100(Fe)) with free aromatic carboxylic acid groups was
bis(2-methoxyethoxy)-1,4-benzenedicarboxylate) were obtained by selectively functionalized with polyethylene glycol (PEG) 5000
changing the BME-bdc to a polymer ligand containing H2bdc and Stp10-C by a carbodiimide mediated reaction under mild
moieties with methylene spacers. Note that the incorporation of conditions. MOF particles with surface polymer coatings reveal
polymer chains enhanced the stability and hydrophobicity of the enhanced colloidal stability and possibilities for biomedical
MOFs. However, the polymer chains of the ligands also influence applications.
the process of formation of MOFs, often resulting in amorphous To control the modification degree and the thickness of
products. the polymer coating eectively, a post-synthetic polymerization
A more general way to access MOF tethering polymers is to (PSP) method, which resembles the grafting from reaction,
attach polymers to the synthesized MOF particles. In general, can be adopted to functionalize the MOF particles with poly-
two major methods have been applied to modify MOFs with mers. The precondition for the occurrence of the PSP is that the
polymer shells post-synthetically. The first involves covalently MOFs contain polymerizable groups or functional groups to
attaching the polymer chains to the functional groups on MOFs, which active sites can be attached. Then the MOF particles with
which is similar to the grafting to process in graft copolymeri- active sites can be polymerized with organic monomers or oligo-
zation.68 Another approach, called the post-synthetic poly- mers to oer composites possessing the advantages of both MOFs
merization (PSP) strategy, utilizes the copolymerization and polymers.
between organic monomers or oligomers and polymerizable From the authors group, Wang et al. developed the concept
functional groups on MOFs, which resembles grafting from of photoinduced post-synthetic polymerization (PSP) for the
reactions.68 polymer modification of MOFs via covalent bonds and enhanced
processability of such crystalline materials for the first time.71
The preparation procedures are shown in Fig. 7. Nanosized
crystals of UiO-66-NH2 were first modified with methacrylamide
groups, and their further copolymerization with organic mono-
mer butyl methacrylate (BMA) or MMA was induced by UV light.
The MOFmonomer suspension was dripped into a mold, and
the membrane afforded after radiation could be easily peeled
off and showed flexibility. In this way, the MOF nanoparticles
Fig. 6 The strategy described herein to convert a 1-D (linear), nonporous,
were covalently linked by the polymers. Photo-induced PSP is
mostly amorphous polymer into a 3-D, porous, crystalline polyMOF hybrid a facile and universal approach for fabricating MOFpolymer
material. Adapted with permission from ref. 66. Copyright 2015 Wiley-VCH. hybrid composites and membranes. Such PSP-derived composites
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MOF nanosheets embedded in polymers tend to present a always possess defects, and further surface modification is
uniform occupation and to improve the membrane performance necessary to cover those voids. Vankelecom et al. prepared a
because of their special nanostructure and large exposed surface series of asymmetric PI membranes containing HKUST-1, ZIF-8,
area.129,130 In contrast, large MOF particles are prone to form and [Al(OH)(bdc)]n (MIL-53(Al)), and then coated the membranes
sediments in the course of casting, which lead to inhomogeneous with permeable polydimethylsiloxane (PDMS) layers on the sur-
and brittle membranes.141 face by spin coating to seal the undesirable defects. In some cases,
Agglomerates are often formed during the drying of MOF the phase inversion method has also been utilized to prepare a
particles; once this happens, it is dicult to redisperse them. porous polymer that serves as the support for MMMs.151 Dip
Therefore, direct incorporation of the synthesized wet-state MOF coating is also a good way to fabricate asymmetric membranes.152
without drying would be a good choice.104,110,142,143 Sivaniah Diestel and colleagues prepared a-alumina-supported ZIF-8
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et al. applied the solution-mixing strategy in the fabrication of polymethylphenylsiloxane (PMPS) membranes by dipping the
ZIF-8Matrimids 5218 membranes, and the resultant mem- substrate in the solution and withdrawing at a constant rate.153
branes showed good particle dispersion, even at a high loading HFMs, with their high packing density, large area per volume,
of MOFs.142 tolerance to pressure and low cost, are the most desired mem-
Other methods have been developed to facilitate particle brane geometry for real applications.154 HFMs are usually prepared
dispersion throughout the polymer matrices. Employing MOF by dry jetwet quench spinning (also called phase inversion
composites as fillers has proved to be an eective way to enhance spinning), which is similar in principle to the method for asym-
the dispersion of the MOF.144,145 Zhu et al. prepared a composite metric MMMs. Fabrication of pure polymer HFMs has been
filler by growing ZIF-8 in situ on the surface of carbon nanotubes well explored; however, the addition of MOF particles may
(CNTs). ZIF-8 showed good dispersion in the membrane with the require addressing of further issues.109,155157 Liu et al. reported
help of the CNTs.144 In addition, surface modification of MOFs the first MOF-based mixed-matrix HFMs consisting of HKUST-1
with long-chain organic compounds may oer another way to and PI.156 The MOF particles were first mixed with poly(amic
achieve even dispersion. Queen and colleagues modified the acid) (PAA) to form a homogeneous dispersion solution for
hydrophilic UiO-66-NH2 with oleic acid through post-synthetic spinning, and then the solution was coextruded with water as
ligand exchange, and the modified MOFs showed good disper- the bore fluid into a water-ice coagulation bath and collected by
sion in a hydrophobic cyclic olefin copolymer.146 a setup in which the phase inversion happened and hollow
In most cases, poor interactions between the MOF filler and fibers were formed. The fibers were then immersed in water to
the polymer, as well as the aggregation of MOFs, are closely exchange fully with the solvent and washed with methanol and
related and should be considered together. Enhancing the hexane, followed by heating to complete the imidation process
compatibility between the two phases also improves the dis- of PAA to form PI. The spinning temperature was set at 3045 1C
persability of the particles. The photoinduced PSP strategy is a to achieve suitable viscosity.
promising method to solve both issues.71 MOFs modified with Koros and colleagues prepared MOF-based dual layer HFMs
polymerizable functional groups are expected to disperse well that consist of one layer of polymer as the support and another
in a monomer with a similar structure, and further copolymer- layer with ZIF-8 particles as the selective skin.155 The core solu-
ization between the MOF and polymer ensures their intimate tion was prepared by mixing Ultems 1000 (in tetrahydrofuran
contact. As discussed in Section 2.3, MOFs decorated with poly- (THF)) and LiNO3 acting as a pore-forming agent (in N-methyl-
mers become more dispersable, which makes them promising 2-pyrrolidione (NMP)). The sheath solution was prepared using
fillers for MMMs. The attached polymers on the MOF surface also a priming procedure by combining a ZIF-8NMPTHF sus-
improve the interface compatibility. pension and an Ultems 1000LiNO3NMP solution. The core
As for the asymmetric MMMs, a low mass transfer resistance and sheath solution together with the bore fluid solution
and high flux are expected because of their thin selective layer (10 wt% water in NMP) were then coextruded through a compo-
supported on porous substrates, which are of practical value for site spinneret into a quench bath. The fibers obtained were then
gas separation. According to their geometry, asymmetric mem- immersed in water, ethanol and hexane separately before drying
branes can be classified into flat-sheet and hollow-fiber mem- in an oven. Later, Koros and colleagues carried out a systematic
branes (HFMs). investigation of the preparation parameters of MOF-based
Several approaches have been developed for the preparation mixed-matrix HFMs with high MOF loadings.157 They further
of asymmetric flat-sheet membranes, including phase inver- treated these fibers with a PDMS and/or polyaramid coating to
sion, dip coating, solution casting, and spin coating. The phase seal the cracks on the surfaces. The dual-layer HFMs are more
inversion method (also called drywet phase inversion) is the attractive and promising because they only need porous particles
most commonly applied method.147150 In a typical procedure and selective polymers in the skin layer, thus decreasing the cost
for MOFPI membrane preparation, the polymerMOF solution for molecular sieves and the core polymers.
was first cast onto a substrate followed by a solvent evaporation Mixed-matrix HFMs can also be produced by coating a
process, and then immersed in water for solidification, followed polymerMOF layer onto polymer or ceramic hollow fibers.158,159
by solvent exchange in isopropanol. The membrane obtained On one hand, the coating layer can cover the defects on the
then is dried in an oven to remove the solvent completely. support and improve the overall selectivity; on the other hand,
However, the asymmetric membranes prepared in this way it can protect the support to some degree under harsh conditions.
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Ismail and coworkers first fabricated PSF hollow fibers by phase because of its photoconductivity.163 In the bulk state, partially
inversion spinning and subsequently coated them in a PDMS overlapped structures of neighboring carbazolyl groups led to a
HKUST-1 dispersion using a dip coating method.159 Considering relatively low hole mobility (107 cm2 V1 s1).164 However,
the numerous merits of asymmetric membranes, especially HFMs, confinement of PVCz in 1-D nanochannels of [La(BTB)]n dras-
more strategies should be developed to fabricate membranes with tically enhanced the hole transport properties.30 PVCz chains in
perfect structures on a large scale. [La(BTB)]n formed an extended linear structure with enhance-
ment of the pp stacking of carbazoles, which was confirmed by
fluorescence measurements and molecular dynamics simula-
3. Functions tions. This unusual structure led to an increase in the carrier
mobility, which was about five orders of magnitude higher than
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The variety of MOFs and polymers aords an essentially infinite that in the bulk.
number of possible combinations. Table 1 summarizes the As conjugated polymers play crucial roles in advanced nano-
combinations of MOFs and polymers along with the functions scale devices, understanding of nanoscale electronics is highly
explored for the resulting hybrid materials. desirable for future applications. Polysilanes exhibit intriguing
optoelectrical properties, such as high quantum yield of fluores-
3.1. Properties of polymer chains confined in MOFs cence and high mobility of charge carriers, which are attributed
Understanding the properties of a few polymer chain assemblies to the delocalization of s-electrons along the main chain.165
is important because of their potential applications for molecular- The accommodation of single polysilane chains in [Al(OH)(L)]n,
based devices.160 Confinement of polymer chains in porous where the ligand L corresponds to 2,6-naphthalenedicarboxylate
materials is a feasible method to control polymer assemblies and 4,4 0 -biphenyldicarboxylate, increased the values of carrier
because this approach can prevent the entanglement and con- mobility compared with that in the bulk state because of the
formational disorder of polymer chains in the bulk state.161 The elimination of slow interchain carrier hopping.81 The confor-
regulated and tailor-made pore characteristics of MOFs allow mation of the polysilane chains pivoted on the pore size, as
the achievement of precise molecular assemblies in the nano- evidenced by 29Si NMR, Raman spectroscopy measurements,
channels, permitting fundamental studies on inherent polymer and molecular dynamics simulations, allowing precise mani-
properties that, until now, have remained elusive. In this regard, the pulation of carrier transport properties even in the single-chain
Uemura and Kitagawa group has widely studied the various intrigu- manner. Recently, a report on the optoelectrical properties of
ing properties of polymers confined in nanochannels of MOFs. a few polymer chains confined in MOFs has been published.
Radical polymerization of St was performed in the nano- Unsubstituted polythiophene (PTh) was prepared in the 1-D
channels of [Zn2(bdc)2(ted)]n to study the behavior of single PSt nanochannels of [La(BTB)]n, where the number of polymer chains
chains with a linearly extended conformation.24 Molecular was controlled.81 Regardless of the number of chains in the
simulation and 2H NMR spectroscopy indicated that these nanochannels, the PTh chains exist in a planar fashion because
single PSt chains aorded unprecedented molecular dynamics of the association of the polymer chain with the pore walls. The
in the 1-D nanochannels: homogeneous rotation of phenyl rings accommodation of PTh chains in [La(BTB)]n resulted in a blue
with a very low activation energy. This behavior can be ascribed shift of the emission wavelength; moreover, as the loading
to both the linear extension of the single-chain conformation in amount of polymers in the MOF decreased, the magnitude of
the nanochannels and the exclusion of the multiple interactions the blue shift increased. In addition, the carrier transport proper-
observed in the bulk polymer. ties of PTh were also drastically changed by varying the number
Incorporation of PEG into 1-D nanochannels of [Cu2(L)2(ted)]n of polymer chains through the formation of the pp stacked
revealed a thermal transition of only a few chain assemblies structure. Strong interchain interactions render PTh nonmelting
(Fig. 10).79 In this system, the pore size and surface functionality and insoluble; hence, control of the assembly structure, which
of [Cu2(L)2(ted)]n were easily tailored by changing the ligand L, so has a profound effect on its optoelectrical properties, has never
that the thickness of the chain bundles, as well as the environ- been achieved. The results obtained highlight that encapsulation
ment of the polymer chains, could be precisely controlled. Taking of polymer chains is a key strategy for controlling the low-
advantage of MOFs, the transition behavior of the PEG bundles dimensional assembly structures to elicit potentially useful yet
could be systematically controlled for the first time. Note that the unexplored properties.
transition temperature of confined PEG decreased as the mole-
cular weight of PEG increased, which contrasts strongly with the 3.2. Functions of hostguest nanocomposites
conventional bulk system. The mobile nature of PEG chains While a great deal of research eort has been aimed at prepar-
in MOFs was exploited in the area of lithium conductivity. ing new MOF structures for various applications, hybridization
Incorporation of Li ions into MOFPEG composites led to of MOFs with a variety of functional guests has been proposed
liquid-like high mobility of Li ions with an activation energy, to combine the merits and mitigate the shortcomings of both
Ea, of 0.18 eV.162 components.14 Polymers possess many unique attributes, includ-
The spatial control of polymer chain arrangements is a key ing thermal and chemical stability, fluorescence, and conductivity,
strategy for improving their functions, such as fluorescence which are desirable to integrate with MOFs to make composites
and conductivity. PVCz has attracted a great deal of attention with sophisticated architectures.
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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
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)
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dierent acceptors with dierent sizes. Uemura et al. reported a Good accessibility of the reactive sites by the reactants is
new luminescent sensor system utilizing coupled transforma- also essential for the eciency of solid catalysts. Hybridization
tions of a flexible MOF and a fluorescent reporter oligomer, of polymers with catalytic activity and MOFs with high surface
distyrylbenzene (DSB).169 The [Zn2(bdc)2(ted)]nDSB composite areas is an eective strategy for fabricating noble heterogeneous
selectively adsorbed CO2 over other atmospheric gases, such as catalysts. Bromberg et al. reported the synthesis of cross-linked
N2, O2, and Ar, with concomitant structural change of the frame- poly(N-bromomaleimide) in MIL-101(Cr), resulting in a hybrid
work. This structural change induced conformational variations composite with a large surface area (SBET = 1600 m2 g1), in con-
of the accommodated DSB, which caused a critical change in DSB trast to cross-linked poly(N-bromomaleimide) prepared by solution
fluorescence. Hostguest coupled transformations thus convert polymerization (SBET = 20 m2 g1).171 Because of their high
gas adsorption events into detectable output signals. The variety accessibility, the active bromine groups in the polymer network
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of polymers and MOFs affords an essentially infinite number of allowed high activity of the composites in heterogeneous catalysis
possible combinations, which should expand the versatility and for fructose dehydration into 5-hydroxymethylfurfural.
possibility of sensing materials. Enzymes are known to be the most sophisticated materials in
Ion exchange is an important process in a diverse range of terms of catalysts because of their remarkable abilities, such as high
applications, such as water purification and precious metal anities towards substrate and high catalytic eciency based on
recovery.170 Conventional ion exchange resins consist of cross- their high stereo-, chemo-, and regioselectivities.83 However, even
linked polymers with a low surface area, which decreases the with these advantages, the practical use of enzymes is limited by
contact eciency between the ion-exchange sites and guest their low operational stability, dicult recovery, and lack of reusabi-
species. Chans group demonstrated that the open porous lity under operational conditions. Enzyme immobilization in porous
structure of MOFs allowed the encapsulated ion-exchange poly- materials is one of the most eective approaches to surmounting
mer to contact the solvent and exchange ions eciently.32 Vinyl these problems, making them industrially and commercially
benzyl chloride monomers were impregnated into ZIF-8 and viable.172 MOFs are envisioned as the most appropriate candidate
polymerized in situ, aording poly(vinyl benzyl chloride) (PVBC) for this purpose because of their ultrahigh porosity, tunable pore
and the ZIF-8 composite. Subsequent amination and ion exchange shape, and adjustable surface functionality. Mas group introduced
of PVBC yielded poly(vinyl benzyl trimethylammonium hydroxide) MP-11 into Tb-mesoMOF at a loading of 19.1 mmol g1.84 The
(PVBTAH) in ZIF-8. With its high surface area and facile accessi- hybrid material demonstrated superior catalytic activity and recycl-
bility, the extraction rate of gold cyanide anions by PVBTAH and ability, even in an organic solvent (methanol), surpassing the free
the ZIF-8 composite was much higher than that of a conven- MP-11 counterpart. The same group also encapsulated a series of
tional ion-exchange resin (Fig. 12). In 25 s, 490% of the gold other enzymes into mesoporous MOFs, and investigated the cata-
cyanide anion was extracted, in contrast to 7% extraction by lysis and mechanisms of those biocatalysts.85,86 More recently, it has
Amberlysts-A26. Recently, preparation of a cation exchange been demonstrated that trapping single enzyme molecules in each
polymer in a MOF was reported by the same group.34 Sodium predesigned cage of MOFs can eliminate enzyme aggregation and
poly(4-styrenesulfonate) (NaPSS) was synthesized in MIL-101(Cr) maintain high catalytic eciency. Feng et al. synthesized a chemi-
using a one-step in situ polymerization process. In addition to cally stable MOF (PCN-333) with ultra-large cavities (5.5 nm), which
fast cation exchange and high ion adsorption capacity, the provided single-molecule traps for enzyme encapsulation.173 In this
NaPSS and MIL-101(Cr) composite exhibited high selectivity with work, three heme-proteins (horseradish peroxidase, Cyt c, and
co-ion rejection, which is a critical performance indicator of a MP-11) were encapsulated in PCN-333. A saturated loading of each
good ion exchange material. enzyme in PCN-333 was rapidly achieved, indicating a strong
interaction between the cage and the enzyme. In fact, almost no
leaching from these accommodated enzymes occurred during the
catalytic reactions, while high apparent leaching was observed in the
mesoporous silica material SBA-15. It should be noted that horse-
radish peroxidase (size: 4.0 4.4 6.8 nm3) and Cyt c (size: 2.6
3.2 3.3 nm3) with sizes comparable to the mesocages exhibited
better catalytic activity than the free enzymes under harsh condi-
tions. This result indicates that single-molecule traps are an eective
strategy to eliminate enzyme aggregation and leaching and achieve
remarkable catalytic performance. Very recently, Farha and
coworkers reported that MOFs excel at stabilizing enzymes at
high temperature and in a dry form, whereas the free enzyme
denatures rapidly under these conditions, expanding the appli-
cations of enzymes in industry.174
Fig. 12 Au(CN2) concentration after immersing equal masses of PVBTAH B 3.3. Polymer modification of the surface of MOFs
ZIF-8 and Amberlyst-A26 in KAu(CN)2 solution. Inset: enlarged profiles for the
first 120 s. Adapted with permission from ref. 32. Copyright 2014 American As described in Section 2.3, polymer coatings on MOFs are an
Chemical Society. eective approach for the improvement of properties such as
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MMMs in these fields. The separation behavior of the membranes (202 GPU with selectivity of 7.7) or high selectivity (12.3 with H2
in a single gas and mixed gases may be different, and the results permeance of 64.5 GPU) at 180 1C. To further test the practic-
of the latter are more meaningful; therefore, here we mainly focus ability of such MMMs in actual applications, they modified the
on tests of membranes in mixed gas systems. fabrication method and measured the separation capabilities
Hydrogen is a green and eective energy source and is con- at 230 1C in the presence of CO and water vapor. Mixed-gas
sidered a good substitute for fossil fuels. Currently, a common measurements demonstrate that the impurities in the feed gas
way to produce hydrogen is steam reforming of hydrocarbon do not significantly weaken the separation of ZIF-8PBI mem-
fuels followed by a gas-shift reaction. In this process, CO2 is the branes at high temperatures.
main by-product that must be separated to ensure the quality of Coronas et al. fabricated ZIF-8/PBI membranes and tuned
the produced hydrogen and to reduce emissions of this green- parameters including the sizes of ZIF-8 (50, 70, and 150 nm),
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house gas. Since the steam reforming reaction is strongly endo- ZIF-8 loadings (10 and 20 wt%) and states of ZIF-8 (wet and
thermic, the process is conducted under high temperatures. dry).187 A European interlaboratory Round Robin test was employed
Moreover, the products incorporate large amounts of water vapor to confirm the reproducibility of the membrane permeation
and some impurities (CO and CH4) besides H2 and CO2.185 tests. The MMMs were tested for the separation of H2 and CO2
Therefore, hydrothermally stable membranes with good separa- at 150 1C with feeding pressures from 3 to 6 bar, and both
tion performance under high temperature and pressure are permeability and selectivity values declined with the increasing of
desirable for hydrogen purification. The same separation is the feeding pressures. At 20% filler loading, MMMs with ZIF-8 of
also required for precombustion CO2 capture in which the shift 150 nm exhibit the best performance (an improvement of six
products of coal gasification dier from those of steam reforming times in H2 permeability and nearly twice in selectivity), and this
in the partial pressures of the gases. may be due to the lower degree of aggregation in the case of larger
Because of its high thermal stability and compatibility with particle size. Furthermore, MMMs containing dry fillers present
ZIFs, PBI is often used to prepare MMMs. Chung and colleagues better separation properties than those with wet fillers.
mixed [Zn(bIM)2]n (ZIF-7, bIM = benzimidazole) nanoparticles Nanoparticles of other ZIFs including ZIF-90, [Zn(bIM)2]n
with PBI at the high loading of 50 wt% and the flexible ZIF-11, and MOF nanosheets have also been prepared and
membranes obtained exhibit good dispersability and enhanced blended with PBI to fabricate composite membranes for H2CO2
H2CO2 separation performance compared with pure PBI or separation.106,129,188
ZIF-7 membranes.110 In the mixed-gas tests, the hybrid membrane Steam methane reforming (SMR) is the most common way
showed an H2 permeability of 13.3 Barrer and a H2CO2 separa- to produce hydrogen and the products often contain a small
tion factor of 7.2 at 35 1C (Fig. 14). The result at the high amount of methane that should be removed. Huang and Zhong
temperature of 180 1C is above the Robeson upper bound186 et al. synthesized a biocompatible MOF [Fe3O(bdc)3]n (MIL-88)
proving that the ZIF-7PBI membranes are promising for indus- and embedded the particles into Matrimids 5218 to fabricate
trialization. Given the practicability of HFMs in large-scale gas MMMs for H2CH4 separation.189 The composite membranes
separation, the same group conducted research on fabricating offer improvements in both H2 permeability and selectivity in
ZIF-8PBI dual-layer HFMs for H2 purification.109 The prepared equimolar mixture tests compared with pure polymer membranes.
fibers are free of defects and agglomeration with excellent sepa- A high separation factor of 96 was observed in the MMMs with
ration performance at high temperatures. Tuning the loading of 10 wt% filler loading.
ZIF-8 in the polymer can contribute to either high H2 permeance Emission of CO2 into the atmosphere is a major cause for
global warming and climate change. Post-combustion CO2 cap-
ture refers to the capture of CO2 from flue gases generated mainly
by power plants, which is a key route to reducing the anthro-
pogenic release of CO2.4,190 Flue gas contains N2, CO2, H2O, O2,
and a small percentage of pollutants such as SOX, NOX, and
particulate matter.4 A main challenge in this field is the relatively
low CO2 partial pressure in the exhaust, which requires mem-
branes to be highly selective for CO2. By adding MOF fillers that
have high porosity and good interactions with CO2 into poly-
mers, researchers have made progress in the separation of CO2
from N2.97
Sholl, Koros, and coworkers prepared ZIF-8Ultems 1000
asymmetric HFMs with a MOF loading of 13 wt% in the outer
selective layer using the dry jetwet quench method to investigate
their CO2N2 separation.155 To seal the defects in the selective
Fig. 14 H2/CO2 separation performance of pure PBI and ZIF-7/PBI nano-
layer, the fibers were post-treated with a coating of PDMS. In
composite membranes compared with the Robeson upper bound (open
symbols: pure gas separation performance; closed symbols: mixed gas
single-gas tests, the composite fibers showed an 85% increase in
separation performance). Reproduced from ref. 110 with permission from CO2 permeance and a 20% increase in selectivity compared with
The Royal Society of Chemistry. pure polymer fibers. When a mixed gas (20% CO2 in N2) was used
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as the feed gas, the ZIF-8Ultems 1000 fibers showed a high of such flexible polymers. By tuning the filler contents and
selectivity of 32 and H2 permeance of 26 GPU at 25 1C. preparation parameters, the hybrid membranes with 13.1 wt%
Polyether block polyamide (PEBA) contains soft polyether ZIF-8 loading prepared with 50 mm coating thickness possessed
segments and rigid polyamide (PA) segments. It shows promising uniform structures without interfacial voids. A high CO2 per-
capability for CO2 separation because of its high anity for CO2 meance of 297 GPU and selectivity of 83 were observed with the
together with good mechanical stability.191 Hagg and colleagues symmetric membranes in a binary-gas test (15 vol% CO2 and
investigated the CO2N2 separation properties of ZIF-8PEBAX- 85 vol% N2) with a feed pressure of 1.1 MPa.
2533 in both dry and humid situations.192 Because of the aggre- Natural gas is a vital and clean fossil fuel relative to oil and
gation and sedimentation of the ZIF-8 particles, the hybrid coal, and its major component is CH4. However, raw natural gas
membrane (i.e., a polymer-based phase and a filler-based phase) often contains impurities including CO2, H2S, and N2, which
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has a special dual-layer morphology. A mixture of 10% CO2 and decrease the calorific value and lead to pipe corrosion during
90% N2 was used as the feed gas for the mixed-gas measurement. delivery via pipeline. The removal of the major contaminant CO2
In the dry state, the membrane with 40 wt% ZIF-8 loading is crucial for further use of the fuel. Membrane-based separation
showed a high CO2 permeability of 1098 Barrer and a moderate is promising for natural gas sweetening because of its high energy
separation factor of 33 (a 50% drop compared with the pure eciency and low maintenance compared with the current
polymer); however, the permeability and selectivity are both amine absorption process.196 Despite their low cost and good
affected by humidity to some extent. To improve the adhesion processability, polymer membranes are often limited by a
between ZIF-8 fillers and the polymer matrix, Chen et al. coated trade-o between permeability and selectivity, and suer from
the surface of ZIF-8 with polydopamine (PDA) and then mixed plasticization eects under high pressure, leading to a loss of
these particles with PEBAX-4033.193 Given the many hydroxyl and selectivity.197 The addition of porous MOF crystals can be a
amino groups in PDA and their interactions with CO2, the coating good choice to overcome these problems. On one hand, the
layer can facilitate the permeation of CO2 (Fig. 15). The CO2 porosity of MOFs boosts permeability and the molecular sieving
permeability of PDA@ZIF-8PEBAX membranes with 15 wt% feature is expected to enhance the selectivity of the membranes.
ZIF-8 loading reached 267.74 Barrer with a CO2N2 selectivity of On the other hand, the added fillers reduce the chain mobility
62.65 in a single gas test in the humid state, which surpasses the and thereby improve the stability and plasticization resistance
Robeson upper bound. Other types of MOFs were also employed of the membranes, especially where bonds are formed between
to synthesize PEBAX-based MMMs. For example, nanoparticles MOFs and polymers.
of UiO-66 and UiO-66-NH2 were incorporated into PEBAX MH ZIF-90 with a pore window size of 0.35 nm is promising for
1657 and the derived UiO-66-NH2PEBA membranes with 10 wt% CO2CH4 separation through a size exclusion mechanism. Jones,
loading showed outstanding performance (CO2 permeability of Nair, and coworkers synthesized submicrometer-sized ZIF-90
130 Barrer and selectivity of 72) in the mixed gas test with a particles via nonsolvent-induced crystallization, and then mixed
relative humidity of 20%.194 them with three types of PI (Matrimid, Ultem and 6FDADAM)
To achieve better eects with fillers, Wang et al. fabricated (6FDA = 4,4 0 -(hexafluoroisopropylidene)diphthalic anhydride;
asymmetric membranes comprising a thin ZIF-8poly(vinylamine) DAM = 2,4,6-trimethyl-1,3-phenylenediamine) to prepare MMMs.123
(PVAm) coating on PSF substrates.195 On the one hand, the In mixed-gas tests, MMMs made from ZIF-90 of smaller size
selected flexible polymer may reduce the interfacial stress between (B0.81 mm) and 6FDADAM showed the best results, because
the polymer and fillers; on the other hand, the addition of ZIF-8 of their well-matched permeability. Specifically, upon ZIF-90
fillers can enhance free volume and thus improve the permeance incorporation (15 wt%) a high CO2 permeability of 720 Barrer
with a CO2CH4 selectivity of 37 was achieved, surpassing the
upper bound for polymer membranes defined in 1991. The high
permeability together with good selectivity makes these mem-
branes attractive for natural gas sweetening.
A breathing eect is a special phenomenon observed in some
MOFs involving structural changes upon adsorption of guests.
MIL-53 is a typical flexible MOF, and several groups have used
it or its functional counterparts as the dispersed phase in
MMMs.116,122,135,198200 Rodenas and Gascon et al. employed
NH2-MIL-53(Al) with Matrimids 5218 giving membranes with
good filler distribution and separation performance that derives
from the flexible framework and the abundant amino groups.198
The effects of preparation conditions on the configurations and
dispersion of MOFs in the MMMs and the corresponding separa-
tion performance were investigated. The authors showed that
Fig. 15 Schematic illustration of the synthesis of PDA@ZIF-8 and the CO2
higher solvent removal temperature (298 K) and thinner mem-
transport mechanism in PEBAX/PDA@ZIF-8 MMMs. Reproduced from ref. 193 branes led to a higher proportion of the narrow-pore configu-
with permission from The Royal Society of Chemistry. ration and enhanced separation properties. When an equimolar
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mixture of CO2 and CH4 was used as the feed gas, a CO2
permeability of B14.5 Barrer and a separation factor of 38
could be attained by MMMs with 25 wt% NH2-MIL-53 at 308 K
and 3 bar pressure difference. In this work, ion-beam scanning
electron microscopy (FIB-SEM) was applied to provide 3-D
and quantitative information about the membrane structures
including the filler distribution and boundary contact, showing
great potential for membrane structure characterization. Later,
the same group studied the effects of NH2-MIL-53 morphologies
(nanoparticles, nanorods, and microneedles) on the performance
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provides a simple but powerful way to fabricate MOF-based thin the relationships between the structure and performance will
films, which should stimulate the emergence of innovative become clear.
industrial applications in a diverse range of technologically Despite the promising performance of the MOF MMMs, the
significant fields. diculty of large-scale production of these membranes hinders
Tremendous advances have been made in MOFpolymer their further industrial application. The precursors of MOFs are
hybrids; however, several challenges associated with hostguest expensive and the reactions are mostly complicated. On the other
synergistic functions remain. One of the most appealing features hand, continuous production of membranes is challenging. One
of MOFs that distinguishes them from conventional porous of the authors group proposed a scalable hot-pressing (HoP)
materials is their structural flexibility, in which the framework approach to fabricate MOF coatings.225 High temperature and
changes its structure upon exposure to external stimuli, such as pressure are employed to assist the growth of various MOFs on
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heat, pressure, light, and magnetic fields.222 Cooperative struc- certain substrates without using any solvent. With the assis-
tural transformations of flexible MOFs and functional polymers tance of a roll-to-roll machine, the HoP method may achieve
could provide novel stimuli-responsive nanohybrid materials. continuous production of MOF membranes in practical appli-
It is also clear that an important direction in this platform is cations. With the rapid development of new and facile fabrica-
to pursue photoelectric synergy between MOFs and polymers. tion methods, MOF-based MMMs are bound to play a vital role
Exploring photoinduced charge and energy transfer in donor in practical separation processes.
acceptor systems is an important field of research that is
essential for the fundamental knowledge necessary to develop
future applications, including photoenergy conversion devices.223 Acknowledgements
The spatial control of donoracceptor interfaces is an important
T. U. acknowledges the financial support from JST-CREST and
prerequisite because it is here that critical photophysical pro-
JSPS KAKENHI Grant Number JP16H06517 (Coordination Asym-
cesses take place.224 With a diversity of topologies and linkers,
metry). Y. Z. and B. W. acknowledge the financial support from
MOFs represent a class of materials with electronic and conduct-
the 973 Program 2013CB834702 and the National Natural Science
ing properties. Thus, hybridization of electroactive polymers
Foundation of China (Grant No. 21625102, 21471018, 21404010,
and MOFs could allow the creation of optimized systems with
21490570, 21674012).
periodic and well-defined networks of electron donor and
acceptor phases based on the original host structures.
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