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RESEARCH
RESEARCH: Review
Composites of metalorganic
frameworks: Preparation and application
in adsorption
Imteaz Ahmed and Sung Hwa Jhung*
Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Daegu 702-701, Republic of Korea
Metalorganic frameworks (MOFs) are one of the most discussed materials of the last decade. Their
extraordinary porosity and functionality from metals and organic linkers make them one of the most
promising materials for a vast array of applications. The easy tunability of their pore size and shape from
the micro- to meso-scale, by changing the connectivity of the inorganic moiety and the nature of the
organic linkers, makes these materials special. Moreover, by combining with other suitable materials,
the properties of MOFs can be improved further for enhanced functionality/stability, ease of preparation
and selectivity of operation. In this review, various methods and paths for the preparation of composites
are discussed, especially for those which have been successfully applied to gas and liquid phase
adsorptions. In the second part of this paper, several applications in adsorptive processes are discussed.
Introduction
Remarkable progress on porous materials has been achieved
because of developments in mesoporous materials [1,2] and
metalorganic frameworks (MOFs) [35], which are one of the
most important and rapidly growing groups of porous materials.
MOF materials are composed of metal ions (or clusters) and
coordinating linkers which impart high porosity to the MOF
structures. The particular interest in MOF materials is due to the
easy tunability of their pore size and shape from a microporous to a
mesoporous scale, by changing the connectivity of the inorganic
moiety and the nature of the organic linkers. Recently, MOF
materials have been used in many applications including gas
adsorption/storage, separation, catalysis, adsorption of organic
molecules, drug delivery, luminescence, electrode materials, carriers for nanomaterials, magnetism, polymerization, imaging,
membranes and so on [311]. Their potential increases every year
due to the easy modification of MOFs, which make them a
prominent group of materials in a vast number of published
reports.
As mentioned, MOFs show very promising physical and chemical properties for various applications; moreover, their properties can be further improved by several means. Some of these
are grafting active groups [12], changing organic linkers [13],
*Corresponding author. Jhung, S.H. (sung@knu.ac.kr)
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1369-7021/06/$ - see front matter 2014 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.mattod.2014.03.002
Discussion
Preparation of MOF composites
Several methods and approaches have been applied for the synthesis of MOF composites. In general, there are two basic types of
MOF composites according to the formation of the composite [39].
In MOF composites, MOFs can be in both the discontinuous phase
and the continuous phase. However, the first type of composites
(discontinuous MOFs) is not commonly used for application in
adsorption and are prepared mainly for purposes such as composites that require different sizes/shapes and that demand easy
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FIGURE 1
Schematic comparison of the coordination between GO carbon layers and MOF units for different types of MOF networks (MOFs are MOF-5, HKUST-1 and
MIL-100). Adapted from Ref. [44].
field has recently started and there are vast opportunities for
utilizing this encapsulation method for MOFs.
If the solubility of composing materials is not an issue for
applications, the composing procedure may be carried out using
postsynthesis methods. Simple loading, or impregnation, is one
widely applied method of this type. Jhungs group loaded soluble
salts and polyoxometalates (POM) and used them for liquid phase
adsorptions [52,53]. One of the best examples of these materials is
the loaded metal oxides or insolubilized materials inside the pores,
achieved through chemical means (e.g. changing the oxidation
state, and so on). This method has been used for the preparation of
MOFs composed of metal oxide (e.g. Cu2O) [54]. There have also
been reports on the insolubilization of composing materials in
which precipitates were formed from the solution by changing the
oxidation state of the soluble salts [55,56]. Lu et al. [57] reported a
controlled encapsulation strategy that enables surfactant-capped
nanostructured objects of various sizes, shapes and compositions
to be enshrouded by a zeolitic imidazolate framework (ZIF-8). This
strategy worked for the incorporation of several types of functional
nanoparticles into the MOF pores. The incorporated nanoparticles
are well dispersed and fully confined within the ZIF-8 crystals.
They used polyvinylpyrrolidone (PVP) as a surfactant, and the
procedure is shown in Fig. 5. Canioni et al. [58] synthesized
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FIGURE 2
Composite formation by encapsulation with different strategies: (a) bottle around ship approach in which the porous host materials are produced around
the encapsulated materials; (b) ship in a bottle in which guest moieties are prepared in the presence of porous host and; and (c) the composite prepared
by any of the two methods. Adapted from Ref. [19].
bifunctional nanoscale building block that can undergo face-toface assembly. They demonstrated that benzoic acid-functionalized graphene (BFG) can act as a structure-directing agent (SDA) in
influencing the crystal growth of an MOF. Moreover, BFG can also
be imparted into the MOF structure as a linker (Fig. 6). New
electrical properties were also imparted into the MOF by intercalation with graphene oxide while the original MOF is insulating.
Bajpe et al. showed that a POM/HKUST-1 composite can remarkably improve the kinetics of the synthesis. The interaction
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FIGURE 3
(a) Components of the crystal structures of NENU-n (n = 16): (a) a cube of five truncated-octahedral cages sharing square faces; (b) the pore A
accommodating the Keggin polyanion, Cu2+ cluster (blue polyhedra), Keggin polyanion (polyhedral in yellow circle), C (gray), and O (red); (c) (1) a Keggin
type of POM; (2) three-connected node and hexagonal face (blue) defined by a BTC ligand linked to six adjacent Cu2+ ions; (3) secondary building unit (SBU)
and square face (green) defined by four Cu2+ ions; and (4) cube of eight sodalite-like truncated octahedral cages sharing square faces. Reproduced with
permission from Refs. [48,49]. Copyright 2009 and 2011 American Chemical Society, respectively.
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FIGURE 4
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FIGURE 5
Scheme of the controlled encapsulation of nanoparticles in ZIF-8 crystals. Through surface modification with surfactant PVP, nanoparticles of various sizes,
shapes and compositions can be encapsulated in a well-dispersed fashion in ZIF-8 crystals, themselves formed by assembling zinc ions with imidazolate
ligands. Reproduced with permission from Ref. [57]. Copyright 2012 Nature Publishing Group.
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FIGURE 6
Schematic of proposed bonding between (a) MOF and graphene and (b) MOF and BFG. Reproduced with permission from Ref. [23]. Copyright 2010
American Chemical Society.
Composing material
Application
Mechanism
Experiment conditions
Result a
Ref.
MOF-5
Multiwalled carbon
nanotube (MWCNT)
H2 storage through
adsorption
[16]
MOF-5
Adsorption of NH3
HKUST-1
Adsorption of NH3
HKUST-1
Graphite oxide
MIL-101
H2 storage through
adsorption
MOF-5
H2 storage through
adsorption
IRMOF-10
Multiwalled carbon
nanotube (MWCNT)
loaded with Pt
Li coated fullerene
H2 storage application
HKUST-1
Polyoxometalate (POM)
H2 adsorption
MIL-101
Multiwalled carbon
nano-tube (MWCNT)
MIL-101
Polyethyleneimine (PEI)
[24]
[25]
[45]
TABLE 1
[70]
[77]
[79]
[80]
[81]
[82]
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FIGURE 8
upon loading, the Cu2+ sites readily turn to Cu+ sites by reacting
with the V3+ of MIL-47 and hence a p-complexation site is automatically created through the loading. By contrast, other analogous MOFs [85] having a similar structure, such as MIL-53(Al) and
MIL-53(Cr), do not show a reduction ability to form Cu+ because of
the lack of reducibility of Al3+ and Cr3+, respectively [56]. In
another study the same group reported on BT adsorption using
Cu2O/MIL-100(Fe), presenting improved performance [54]. Very
recently, they showed that ionic liquid/MOFs are effective in
removing SCCs compared to pristine MOFs [86]. Ahmed et al.
showed the improved adsorption of quinoline (QUI), one of the
typical NCCs, over POM-loaded MIL-101 [53]. It was found that a
1% loading of POM could improve the adsorption of QUI up to
20%. They showed that the adsorption of a neutral NCC, indole,
could not be improved by the loading of POM, although basic QUI
adsorption was nicely improved through an acid-base interaction.
Very recently, it was also reported that GO/MIL-101 was very
effective in removing NCCs partly because of the improved porosity of the adsorbent [87].
MOF composites have also been used for water purification,
similar to that performed with virgin MOFs [8891]. GO/HKUST1 composites were successfully applied in the removal of methylene blue (MB) with improved adsorptive performance. The study
showed a maximum adsorption capacity of 183 mg/g for MB
in water [92]. It was found that the efficiency of the adsorption
was high for a low concentration of MB in water for both
virgin HKUST-1 and GO/HKUST-1 composites with fast kinetics.
However, in the case of a high MB concentration, the efficiency
of HKUST-1 decreased below 50% of the original value, while
GO/HKUST-1 still removed the MB up to 80% within 30 min,
which indicates the much better adsorption ability of the
composite compared to the virgin MOF alone. Another report
shows the effective removal of several toxic chemicals (NH3, H2S,
and so on) from effluent water with Zr(OH)4/HKUST-1 composites [93].
Besides these applications, there are other adsorptive applications of MOF composites, such as separation with magnetic properties [94], drug delivery [95], static phase material for liquid
chromatography [96] and so on. In particular, drug delivery is
currently a widely studied topic in the field of MOFs [9799]. In
this case, the concern is more probably desorption rather than
adsorption. In many cases, the steady, slow and targeted release of
a drug in the body is essential for efficient therapeutics. MOF
composites have promising and prospective applications in this
field. Several studies on drug delivery have recently been reported
using MOF composites [95]. Ke et al. synthesized HKUST-1 with
incorporated Fe3O4 nanorods which could be potentially used for
drug delivery (Fig. 9(a)) [95]. This kind of material provides an
efficient platform for a new strategy of delivering an imaging
contrast agent and an anticancer drug by postsynthetic modifications of a highly porous nanoscale metalorganic framework
(NMOF). Another report on drug delivery was published by Taylor-Pashow et al. [100]: they demonstrated the synthesis of an
ironcarboxylate NMOF with a MIL-101 structure, and post-modification was performed by loading an organic fluorophore and an
anticancer drug via covalent modifications of the as-synthesized
nanoparticles for targeted drug delivery, magnetic resonance imaging and magnetic separation (Fig. 9(b)) [99].
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FIGURE 9
(a) Illustration of the synthesis and action of Fe3O4/HKUST-1 nanocomposites adapted from Ref. [95]; and (b) postsynthetic modifications of iron-carboxylate
nanoscale MOFs for imaging and drug delivery. Reproduced with permission from Ref. [100]. Copyright 2008 American Chemical Society.
Acknowledgements
This research was supported by Basic Science Research Program
through the National Research Foundation of Korea (NRF) grant
funded by the Korea government (MSIP) (grant number:
2013R1A2A2A01007176). Authors express their sincere thanks to
Dr. N.A. Khan and Dr. Z. Hasan for their helpful discussion.
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References
RESEARCH: Review
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
146
[51]
[52]
[53]
[54]
[55]
[56]
[57]
[58]
[59]
[60]
[61]
[62]
[63]
[64]
[65]
[66]
[67]
[68]
[69]
[70]
[71]
[72]
[73]
[74]
[75]
[76]
[77]
[78]
[79]
[80]
[81]
[82]
[83]
[84]
[85]
[86]
[87]
[88]
[89]
[90]
[91]
[92]
[93]
[94]
[95]
[96]
[97]
[98]
[99]
[100]