Polyhedron 145 (2018) 1–15

Contents lists available at ScienceDirect

Polyhedron
journal homepage: www.elsevier.com/locate/poly

Review

Shape engineering of metal–organic frameworks

Bardiya Valizadeh, Tu N. Nguyen, Kyriakos C. Stylianou ⇑
Laboratory of Molecular Simulation, Institut des sciences et ingénierie chimiques (ISIC), Ecole polytechnique fédérale de Lausanne (EPFL Valais), Rue de l’Industrie 17, 1951
Sion, Switzerland

a r t i c l e i n f o a b s t r a c t

Article history: Metal–organic frameworks (MOFs) are a class of porous materials prepared by the self-assembly of metal
Received 8 November 2017 ions or clusters with organic ligands to form reticular structures. Studies of MOFs started by chemists
Accepted 2 January 2018 who looked for materials with new porous structures and topologies. The unique characteristics of
Available online 9 January 2018
MOFs such as high surface areas, low densities, and structural tunability were soon realized and MOF
materials have become the platform for applications in many scientific areas, ranging from gas separation
Keywords: to catalysis, magnetism, conductivity, sensing, drug delivery, electronics and others. Recently, the field
Metal–organic framework
has been directed towards large-scale synthesis of MOFs and their industrial applications. In terms of
Granule
Pellet
synthesis, MOFs are normally isolated as crystalline powders that are not industrially favorable due to
Thin film their limitations in processing. Shaping MOFs into different forms while preserving or improving their
Gel properties offers several advantages as they can be easily processed, handled, and stored. Controlling
the shape of MOFs in a systematic way can represent a major step forward to bringing them to the mar-
ket, testing them at industrial scales and realizing their true potential. In this review, we firstly discuss
the methods used to shape MOFs into granules, pellets, thin films, foams, gels, paper sheets and hollow
structures, and then overview the importance of shaping towards potential industrial applications.
Ó 2018 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Shaping of MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Granules. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. Pellets. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3. Thin films. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.4. Foams and gels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.5. Paper sheet, hollow structures and other shapes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3. Shaped MOFs in action . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1. Capture, storage, and separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.2. Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.3. Sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.4. Biomedicine and drug delivery. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.5. Electronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4. Conclusions and future outlook. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

⇑ Corresponding author.
E-mail address: kyriakos.stylianou@epfl.ch (K.C. Stylianou).

https://doi.org/10.1016/j.poly.2018.01.004
0277-5387/Ó 2018 Elsevier Ltd. All rights reserved.
2 B. Valizadeh et al. / Polyhedron 145 (2018) 1–15
1. Introduction
Metal–organic frameworks (MOFs) are a class of crystalline
microporous materials that were introduced in the 1990s [1],
which comprise metal ions or clusters linked by organic ligands
via coordination bonds forming 1-, 2- or 3-dimensional networks.
Different from other porous solids such as zeolites, silica, or acti-
vated carbon, MOFs are unique due to their structural tunability,
e.g., by changing the metal site and/or the organic ligand, different
structures with a variety of properties are possible to be synthe-
sized [2,3]. During the last two decades, an extensive amount of
research has been conducted on the synthesis and characterization
of MOF materials with different methods in order to achieve
diverse structures and functionalities. A variety of MOFs with dif-
ferent structures and topologies have been reported since then
[4–12]. In recent years, scientists have slowly shifted their focus
toward application-oriented studies rather than just the synthesis
of new structures of MOFs.
The low density and high porosity of MOFs make these materi-
als excellent candidates for gas capture, storage and separation
[13–18]. Recently, MOFs have been employed for a wide variety
of other applications in areas such as catalysis [19–23], sensing
[11,24–33], nonlinear optics [34], ferroelectricity [35], magnetism
[36,37], electrical conductivity [38–41], and drug delivery [42–
45]. In parallel with the efforts of finding new laboratory-scale
applications for MOFs, investigating the possibility of synthesizing
and using MOFs for applications at an industrial scale has also been
of great interest. Several MOF-based companies have been founded
to launch large-scale production of these materials [46] and a few
MOFs such as HKUST-1, ZIF-8, MOF-5, MIL-101 and MOF-177 are
now commercially available [47]. In industrial applications, the
shapes and sizes of the targeted MOF materials become of great
importance due to their impact on the performance of the material
in the application processes [43,48,24,49]. Thus, engineering of
these materials at the macroscopic scale is as important as tuning
the chemical functionalities of MOFs in order to achieve high effi-
ciency materials in practice.
Conventional methods of MOF synthesis normally result in MOF
crystalline powders with crystallite sizes ranging from nanometers
to hundreds of microns [50]. Typically, the polycrystalline powder
material is not industrially favorable due to the difficulties in pro-
cessing such as pressure drop for fluid flow through a packed bed,
dustiness, clogging, abrasion, mass loss, and challenges in transfer
and handling [51]. Shaping MOFs into the more application-ori-
ented forms such as granules, pellets, or films has recently
attracted considerable attention [46]. Several synthetic method-
ologies have been developed to agglomerate MOF crystallites
directly at the stage of synthesis [52]; however, in many cases,
shaping of MOFs involves their conjugation with existing shaped
substrates; leading to the production of advanced materials having
desired properties and applications. For example, monoliths of
MOFs can be formed by a direct powder-packing synthesis or by
impregnating the MOF powder into the pore of a porous silica
monolith. Despite the importance of the subject, to the best of
our knowledge, there are a few references in the literature in which
a short overview on the shaping of MOFs is provided [46,53].
Hence, there is a gap for a systematic and detailed review on the
MOF shaping techniques. To fill this gap, we will overview the
strategies used to shape MOFs into processable forms and discuss
the applicability of the shaped MOFs in various areas. Thus, the
review is split into two parts; the first part is devoted to the meth-
ods of forming MOFs into a variety of shapes, whilst the second
part focuses on the impact of shaping on the physical and chemical
properties of MOFs and their performance in industrial processes,
and the potential applications for each shape.
2. Shaping of MOFs
In general, MOFs can be shaped into different forms either in-
situ (direct way) or by a post-synthetic process (indirect way). In
the former case, as the MOF crystalline powder is formed, the crys-
tallites are directly arranged into the desired shape such as thin
films or hollow superstructures. In the latter case, shaping is a sec-
ondary process performed on the pre-formed crystalline powders.
The choice of a shaping method depends on the specific applica-
tion, which imposes the preferred shape of the object (e.g., thin
film for membranes, micronic spherical particles for fluidized
beds), and on the stability and functionality of the MOF structure.
Nevertheless, the most important challenge is that the shaped
MOFs should maintain the intrinsic features of the original MOF
powders. Their crystallinity, porosity and functionality should
remain intact, and at the same time the shaped MOFs should pos-
sess sufficient mechanical and chemical stability as well as resis-
tance to abrasion and attrition in order to fulfill requirements
adequate for a given process.
The desired shape of a material for industrial applications is
governed by process parameters such as heat and mass transfer
properties, gas diffusion kinetics, pressure drop, and volumetric
efficiency. To date, MOFs have been shaped into granules, pellets,
thin films, foams, fluids, paper sheets, and hollow superstructures
(Fig. 1). The intrinsic MOF properties are also crucial in choosing
the shaping method; for instance, due to the mechanical fragility
of MOFs [54], they may partially lose their crystallinity or even
amorphize under pressure, which limits the application of high
pressure while shaping. In this section, we overview the fabrication
methods that have been used to engineer MOF powders into differ-
ent shapes.
2.1. Granules
Granulation is the process of agglomeration of powder materi-
als without changing their chemical identity. The resultant
agglomerates, granules, have been widely used in chemical, phar-
maceutical, and food industries to process, store, and transfer pow-
der materials. As a facile and conventional method, granulation has
also been employed to produce shaped materials for adsorption
and separation applications, including shaped MOF powders. Gran-
ulation processes can be categorized in two types: wet and dry. In
the wet granulation, a volatile solvent is usually used to bind the
powder particles into granules, and then is removed by drying,
however, if cohesion forces are not sufficient to hold the granular
form after drying, a binder can be added. The three general steps
of wet granulation include (i) wetting and nucleation, (ii) consoli-
dation and coalescence, and (iii) attrition and breakage (Fig. 2). The
dry granulation is used when the material is sensitive to solvents
or heat. In this case, the granules are formed only by applying high
pressure, e.g., shaping by compression.
The objective of granulation of MOFs is to form a dense and
compact medium with minimum compensation of the surface area
of the MOF crystallites. The properties of the formed granules are
strongly dependent on the properties of the source MOF powder,
the surface tension and viscosity of the binder, and the interactions
between them, hence the choice of the binder is crucial. Different
binders such as poly(vinyl alcohol) [64], graphite [56], cellulose
ester [65], and silica [66] have been used in shaping of MOFs.
The addition of binder can improve the mechanical stability of
the granular particles; however, the contribution of the targeted
MOFs to the overall mass of particles is reduced, and decrease of
their accessible surface area, mainly due to the coverage of the bin-
der on the surface of the crystals, has been reported [55,66]. The
MOF granulation is often performed with an extruder [67], a high
 B. Valizadeh et al. / Polyhedron 145 (2018) 1–15 3

Fig. 1. Examples showing different shapes of MOFs (a) granule (b) pellet (c) thin film (d) gel (e) foam (f) paper sheet (g) monolith (h) hollow structure (scale bar 500 nm (inset
200 nm)). Reproduced with permission from Refs. [55–62].

Fig. 2. The three-step mechanism of wet granulation. Redrawn with permission from Ref. [63].

shear mixer [66], or a centrifugal granulator [55]. Although these 2.2. Pellets
methods allow for the formation of granules in a variety of sizes
and particle densities, the stability of MOFs under pressure, heat Forming pellets is the oldest, the most facile and efficient way of
and/or in solvents is usually a concern. shaping MOFs, and it follows the same principles as the granula-
4 B. Valizadeh et al. / Polyhedron 145 (2018) 1–15
tion, in which the particle agglomerates are formed by applying
pressure to the powder with or without adding the binder (wet
or dry). The difference between these methods relies on the shape
of the resultant agglomerates which, spherical for granules and
cylindrical for pellets, can play a crucial role in some industrial pro-
cesses. Using a binder such as an organic polymer can improve the
mechanical stability of the MOF pellets, whilst a graphite binder
can enhance their thermal conductivity [68]; however, this addi-
tion might also decrease the surface area of the MOF due to the
blockage of the pores. For example, Finsy et al. [69] were able to
improve the thermal (up to 300 °C) and physical stability of MIL-
53(Al) pellets in a packed column by adding poly(vinyl alcohol)
as the binder, while the accessible pore volume decreased by
32%. The binder-free (dry) pelletization process requires good con-
trol on the compression (the applied force, rate, and dwell time) to
prevent the loss of MOF crystallinity [64] (Fig. 3). Nevertheless, it
was shown that despite the decrease in the surface area, several
MOFs can still retain their performances toward catalysis or gas
adsorption [65,70]. Bazer-Bachi et al. [65] showed that while mod-
erate change in ZIF-8 structure might occur under compression,
the acid-base sites were not altered and the catalytic activity of
the pellets remained intact. Peterson et al. [70] investigated the
compression of HKUST-1 and UiO-66 at 1000 and 10,000 psi and
confirmed that neither material showed signs of structural degra-
dation during pressurization. Reduced porosity was observed for
HKUST-1, whilst the UiO-66 surface area remained consistent for
all compressed samples. Consequently, both MOFs displayed con-
sistent ammonia or octane uptake.
Mechanochemistry is an additional approach that is widely
used to shape MOF powders into pellets. This method allows sol-
vent-free synthesis (grinding the MOF precursors in the absence
of a solvent), which has a great potential for large-scale synthesis
of MOFs. In this regard, the extrusion method has been applied
for the synthesis of several MOFs such as HKUST-1, ZIF-8, and Al(-
fumarate)(OH) by applying pressure on precursor powders [71].
Pelletization of the MOF crystals into pellets of circular shape with
flat ends, desired diameter, and controlled thickness can be done
by mechanical or hydraulic pressing.
2.3. Thin films
The formation of MOF thin films on different substrates is per-
formed by the bottom-up approach employing methods such as
liquid-phase epitaxy (LPE), layer-by-layer (LBL), crystal growth
[72], seeding [73,74], Langmuir–Blodgett deposition [75], and elec-
trochemical deposition [76,77]. The LPE method involves the direct
growth of crystals on a substrate by reaction in the mother solution
– the substrate is submerged in a solution containing the precur-
sors, which is then heated as in the conventional synthesis proce-
dure [48]. The limitations of this method include the thermal
Fig. 3. Schematic view of the impact of compression on MOF structure.
sensitivity of the substrate, the affinity between the substrate sur-
face and MOF crystals, and the thermodynamics of MOF crystal
nucleation. A variety of substrates were subjected to MOF thin film
growth including metals, polymers, glass, silicon, and self-assem-
bled monolayers (SAMs) on noble metals. For those that are ther-
mally sensitive such as patterned substrates and integrated
devices, room-temperature synthesis can be employed to grow
thin film of MOFs. In this method, the nucleation and the growth
are separated steps. The supersaturated precursor solution is firstly
heated to initiate the nucleation and then cooled down to room
temperature. The substrate is then immersed in this solution at
room temperature to induce the growth of MOF thin films. Several
thin films of MOF-5 [78], HKUST-1 [79], Fe-MIL-88B [80] and CAU-
1 [81] have been synthesized by this method. MOFs can be grown
on substrates with a bare or a functionalized surface. In the former
case, the acidic/basic nature of the surface is crucial for the growth
of MOFs on the substrate [82,83]. For example, it was demon-
strated that HKUST-1 crystals can preferentially nucleate and
adhere to the basic Al2O3 while the acidic SiO2 substrate did not
support the growth of this MOF [82]. Functionalization of the sur-
face of substrates has been additionally applied to enhance the
interactions between the substrate and the MOF, and to facilitate
the crystal growth [84,85]. For example, when a gold substrate
(Au(111)) with a microcontact printing-patterned SAM of 16-mer-
captohexadecanoic acid and 1H,1H,2H,2H-perfluorododecane thiol
was immersed into a clear, supersaturated reaction mixture for the
synthesis of MOF-5, a thin film of MOF-5 was obtained and
anchored selectively at the carboxylate-terminated areas of the
SAM. Another example was the grafting of ZIF-90 onto the
amino-functionalized Al2O3 surface, which facilitated the imine
condensation with the aldehyde groups in the MOF [86]; in this
case the organic ligands play the mediate role between the surface
of the substrate and the MOF, and improve the binding of the crys-
tals to the surface [86,87]. Using substrates of the same metal as in
the MOF is another strategy to improve crystals binding and MOF
growth on the surface. Guo et al. [88] demonstrated the prepara-
tion of HKUST-1 thin films on a pre-oxidized Cu net (400 mesh).
By oxidizing the Cu net before the hydrothermal synthesis, homo-
geneous nucleation sites are formed for the continuous film
growth. Similarly, Ji et al. [89] prepared HKUST-1 and ZIF-8 thin
films on a Cu and a Zn substrate, respectively, where the substrates
act as the Cu2+ and Zn2+ metal source. Seeded growth, also known
as secondary growth, is a strategy in which the MOF thin films are
grown on the substrate surface utilizing pre-deposited MOF crys-
tals (homogenous), or in some cases other seed materials (heteroge-
neous). The seeds often are nano-crystals of the same MOF, as in
the works reported by Guerrero et al. [90] and Hu et al. [91]. Fal-
caro et al. [92], however, utilized poly-hydrate zinc phosphate
(a-hopeite) microparticles as nucleation seeds for growing inter-
grown crystals of MOF-5 on patterned supports.
 B. Valizadeh et al. / Polyhedron 145 (2018) 1–15
Electrochemistry is another strategy to synthesize MOF thin
films, in which MOF crystals are directly grown on the surface of
an electrode by electrochemical deposition. The electrode can be
metallic [93,94] or made of other conductive materials [95,96],
and MOF crystals can be formed on either anode or cathode elec-
trodes (Fig. 4). Anodic deposition involves the dissolution of the
metal electrode, e.g., Cu, Zn, Al, into metal ions upon applying a
voltage, which react with the ligands in the electrolyte solution
to form the MOF. In cathodic deposition, the generation of hydrox-
ide anions by the reduction of water or oxoanions such as NO–3 and
Fig. 4. Scheme of the anodic and cathodic electrochemical deposition of UiO-66.
Reproduced with permission from Ref. [99].
Fig. 5. LBL technique combined with the Langmuir-Blodgett method. Reproduced with permission from Ref. [75].
5
ClO4 creates a pH gradient near the electrode surface that allows
the direct growth of MOFs on the cathode [97]. The crystallinity
and thickness of the MOF films can be controlled by adjusting
the potential, electrolyte, solution concentration, and temperature.
The major advantage of electrochemical thin film synthesis over
other methods is that it is a rapid and continuous process under
mild reaction conditions; however, growing oriented MOF crystals
on substrates with this method is challenging due to the fast elec-
tron transport and random nucleation, and the films formed by this
method mostly contain randomly oriented crystals [98].
The LBL method is based on the controlled diffusion of the MOF
precursors from independent solutions. In the LBL method, the
substrate is consecutively immersed in separate precursor solu-
tions of the metal ions and organic ligand, with an intermediate
washing step using a pure solvent. The layers of MOF crystals form
on top of each other as the metal ions and ligand molecules diffuse
onto the surface and the washing step in between is to remove
unreacted materials from the formed layer. This method provides
a highly oriented and homogenous layer of crystals (e.g., Fe-MIL-
88B-NH2 and MIL-101(Cr)), with the thickness of the film con-
trolled by the number of cycles performed [100,101]. Makiura
et al. [75] coupled the LBL technique with the Langmuir–Blodgett
method to fabricate a preferentially oriented MOF nanofilm con-
sisting of metalloporphyrin building units on a solid surface
(Fig. 5).
6 B. Valizadeh et al. / Polyhedron 145 (2018) 1–15

Recently a new solvent-free hot-pressing (HoP) method has the surface of the substrate to form the first layer, followed by the
been introduced as a direct method of synthesis of MOF thin films growth of MOF thin films (Fig. 6). Several MOFs can be shaped into
[102,103]. Under applied temperature and pressure, the MOF com- thin films with this method, including the ZIF-8, ZIF-9, ZIF-67,
ponents can rapidly react with the functional groups anchored on MOF-5 and others. In addition, this method allows not only the

Fig. 6. Schematic presentation of the HoP method for MOF coating. Reproduced with permission from Ref. [102].

Fig. 7. (a) Schematic procedure of HKUST-1@Fe3O4 magnetic fluid and the transformation from magnetic fluid to gel, shaped bodies and a porous foam; (b) other foams
derived from representative MOFs achieved using this strategy. Reproduced with permission from Ref. [59].
 B. Valizadeh et al. / Polyhedron 145 (2018) 1–15 7

growth of a uniform single thin film but also the formation of a
multi-layer MOF coating on either flexible, flat or meshed
substrates.
Interfacial microfluid membrane processing is another method
for the generation of MOF thin films on hollow fiber substrates.
In this method, the MOF precursors are dissolved in two different
immiscible solvents and the MOF crystals are formed at the liq-
uid–liquid interface allowing the positional control of the thin film
formation [104,105]. Since the formed crystals at the interface act
as a barrier against the diffusion of precursors, the reaction is more
directed toward the voids between crystals resulting in a continu-
ous film. The thickness of the film can be controlled by adjusting
the temperature of the reaction to boost the formation of the dense
barrier layer at the interface.
two main stages. In the early stage of the reaction, the metal–li-
gand coordination leads to the assembly of MOF clusters, which
then polymerize or aggregate, thus leading to the nucleation and
formation of MOF nanoparticles. In the second stage, if the reaction
conditions favor the growth of crystals, it will lead to the crystal-
lization of MOFs in their bulk form. However, the reaction can be
perturbed by controlling factors such as temperature, metal-to-
ligand ratio, or concentrations, and gelation might occur. Based
on this strategy, They demonstrated a general pathway for the pro-
duction of a variety of metal–organic aerogels, which exhibit high
surface area, large pore volume and low density, while maintaining
the microporosity of crystalline MOFs in the overall gel matrix.
2.5. Paper sheet, hollow structures and other shapes

2.4. Foams and gels
The formation of MOFs into a standalone foam shape has rarely
been investigated, with the majority of reports focused on the
growth of MOF crystals on foam-like structures using different
methods such as dip coating and deposition [106–109]. Chen
et al. [59] has introduced a new method for fabricating magnetic
fluid of several MOFs from which MOF foams in different shapes
were formed (Fig. 7). Following this method, the MOF@Fe3O4
core–shell nanoparticles dispersed in carboxymethylcellulose
solution could be molded into different shapes and converted into
a foam form by freeze drying or into a gel form by a solvent-
induced hardening process.
Xero- and aero-gels are technically considered as foams, in
which the liquid in the gel has been removed (xerogel) or replaced
by a gas (aerogel), with no or minor structure changes [110]. Por-
ous gel materials can be easily used to shape solids in many differ-
ent forms. Despite this advantage, together with the high porosity
and low density, xero- and aero-gels based MOFs have not been
pursued mainly due to their high fragility [58,111–113]. Li et al.
[114] suggested that the formation of MOF gels can evolve in
MOFs with shapes such as paper sheet, monolith, and honey-
comb have been occasionally reported in the literature. MOF-based
paper sheets can be prepared by methods such as coating, crystal
growth, inkjet printing and pulp processing. In the coating method,
the pre-synthesized MOF crystals were dispersed in a solvent and
the solution was coated on the paper sheet [60] (Fig. 8(a)). The sol-
uble starch can also be added as the adhesive agent [115]. To grow
MOF crystals on the paper, Park et al. [116] reported the growth of
ZIF-8 nanocrystals on a carboxylate-functionalized paper by
immersing the paper in the MOF precursor solutions. The paper
functionalization with carboxylate functions was found to be a
key factor for the better coordination of metal ions and the growth
of ZIF-8. The inkjet printing method involves printing of the solu-
tion of MOF precursors on paper substrates by a nozzle [117]. Fur-
ther drying and solvent-assisted development steps lead to the
formation of MOF crystals (Fig. 8(d)). Besides papers, this method
also allows the fast printing of HKUST-1 on other flexible sub-
strates such as textiles and plastics [118]. Pulp processing involves
in-situ synthesis of MOFs in the presence of pulp fiber resulting in
the growth of MOF crystals on the fibers or the dispersion of pre-
synthesized crystals into pulp slurry. Using the former method,

Fig. 8. MOFs coating and inkjet printing on paper sheets. (a) Schematic representation of coating process for Mg-1,4,5,8-naphthalenediimide; (b) scheme of printing on the
coated paper by sunlight irradiation; (c) image of the printed paper; (d) schematic representation of HKUST-1 inkjet printing process; (e) HKUST-1 ink solution; (f) HKUST-1
printed pattern (the inset shows the original image). Reproduced with permission from Refs. [60,118].
8 B. Valizadeh et al. / Polyhedron 145 (2018) 1–15
Küsgens et al. [119] showed that the HKUST-1 crystals can be reg-
ularly distributed over the fiber surface.
MOF-based monoliths can offer certain advantages compared to
the MOF powders, including high robustness, easy handling, and
low flow resistance. The monoliths can be formed as a composite
with inorganic or organic polymers [120], or as a pure MOF mate-
rial itself [113]. Pure MOF monoliths might exhibit superior perfor-
mance over composite MOF monoliths for applications that utilize
or rely on the MOF properties, e.g., gas adsorption [121]. Reports on
shaping MOFs into monoliths based on extrusion and pressing
[113], gelation [122], coating [61,123], and 3D-printing [121] have
been noticed. Thakkar et al. [121] used a 3D-printing method to
fabricate MOF monolith contactors for gas adsorption and showed
that these structured adsorbents can improve the adsorption kinet-
ics due to tunable structure, channel size, and density (Fig. 9).
Growing MOF crystals into hollow structures is another
approach of shaping MOFs. Several methods have been reported
for the synthesis of hollow MOF structures including templating,
Ostwald ripening, etching, and spray drying. Templating is the
most utilized method in which the MOF crystals are carefully
grown on templates and the hollow structure is achieved by
removing the template from the structures [124–126] (Fig. 10
(a)). Sacrificial templating is another approach to synthesize hol-
low MOF crystals in which the template acts as the metal source
that deteriorates during the reaction to form the MOF around itself
leaving the MOF crystal empty inside [127]. Templating methods
usually involve tedious process of growing the crystals and remov-
ing the templates. Therefore, template-free methods such as Ost-
wald ripening, chemical etching, interfacial synthesis and spray
drying have been developed to synthesize hollow MOF structures.
In Ostwald ripening, the hollow structure is formed by diffusion of
small crystals from the center of the aggregate particle toward the
surface [128,129]. Huo et al. [128] investigated the time-depen-
dent development of ferrocenyl coordination polymer micro-
spheres into hollow microstructures with microporous walls
through Ostwald ripening (Fig. 10(b)). Chemical etching is the pro-
cess of hollowing out the MOF crystals by adding an acid solution
at an intermediate temperature under sonication [130,131] (Fig. 10
(c)). The etching process requires careful control over synthesis
Fig. 9. Two-solution-based procedure for 3D-printing of MOF-74(Ni) and UTSA-16(Co). Bentonite clay and poly(vinyl alcohol) were used as the binder and plasticizer,
respectively. Reproduced with permission from Ref. [121].
conditions and selective etching agents to prevent structure col-
lapse and particle degradation [132]. In the interface synthesis
method, two immiscible solutions are used; one contains the metal
ions while the organic ligands are in the other solution. By releas-
ing droplets of one solution into the other, the MOF crystals are
formed on the surface of the droplets (interface between two
phases), which are in the form of hollow spherical superstructures.
Ameloot et al. [133] developed a continuous flow process for inter-
facial synthesis of hollow MOF capsules (Fig. 10(d)). In spray dry-
ing, the MOF precursors are dissolved in an appropriate solvent,
and the solution is sprayed into a hot gas environment. The high
temperature atmosphere causes the fast evaporation of the sol-
vent; the reaction occurs, and the crystals form on the surface of
the droplets with the shape of a thin spherical hollow shell [62]
(Fig. 10(e)). Among the methods mentioned above, the spray dry-
ing and interfacial synthesis are promising for scaling up the
MOF powder synthesis due to the facile, rapid and continuous pro-
cesses which they rely on.
3. Shaped MOFs in action
Shaping MOFs into a specific form is highly dependent on the
targeted application, and in this regard the use of MOFs in the crys-
talline powder form is often not favorable. The technology used for
each application is crucial in determining the efficient shape
required. Hence, in this section, we will discuss different aspects
of shape engineering of MOFs based on their applications.
3.1. Capture, storage, and separation
Due to the structural tunability and porous nature of MOFs,
they are considered as ideal candidates for gas capture, storage,
and separation. The concentration of CO2 in the atmosphere has
risen sharply in the past decades, which has an impact on global
warming and climate change [134]. Therefore, over the last 5–10
years, several synthetic strategies have been followed to design
and synthesize MOFs that can selectively capture CO2 in air or in
different dry or wet gas streams (e.g., flue gas, natural gas, biogas).
 B. Valizadeh et al. / Polyhedron 145 (2018) 1–15
Fig. 10. Hollow MOF synthesis procedures. (a) Template synthesis of MIL-100(Fe)
on polystyrene spheres templates; (b) iron-based ferrocenyl hollow MOF by
Ostwald ripening method; (c) formation of hollow MIL-100(Fe) crystals by acid
etching; (d) interfacial synthesis of HKUST-1 capsules; (e) spray drying method for
the synthesis of hollow MOF superstructures. Reproduced with permission from
Refs. [62,125,128,130,133].
MOFs are also ideal candidates for the storage of hydrogen or
methane, which can be then used as fuels for stationary and trans-
portation applications. The use of MOFs for the separation of gas
mixtures [135] is also of great importance for many industrial pro-
cesses such as in hydrogen purification against other gases includ-
ing N2, CO, CO2, or hydrocarbons, natural gas sweetening, and
hydrocarbon separation [136]. Although MOFs show high promise
in this research area, their use for gas storage, capture and separa-
tion applications as in the form of powder is not practical and
therefore, they must be appropriately shaped [137].
The technology for gas capture or storage requires low cost,
high durability, and high capacity of adsorbent materials. The huge
potential of MOFs for natural gas vehicles, chemical storage and
9
transportation depends on their high capacity and low density.
MOF foams and sponge-like structures are promising candidates
due to their high meso- and micro-porosity and light weight nat-
ure. The high MOF loading, availability of the MOF pores in the
foam structure, the uptake capacity and the kinetics of adsorp-
tion/desorption play an important role for this application [138].
The membrane-based process is a mature technology for gas
and liquid separation owing to its simplicity, low-energy consump-
tion, easy control, and facile scale-up [139]. Many organic poly-
meric membranes are available as their cost is low, they are
processable and mechanically robust. However, for these mem-
branes, there is a trade-off between permeability and selectivity,
also known as the Robeson upper bound [140,141]. In recent years,
mixed matrix membranes (MMMs), which often comprise a poly-
mer matrix and a porous filler, have been introduced to overcome
this limit. Porous fillers such as zeolites have been utilized to form
MMMs; however, the poor affinity between the inorganic fillers
and the organic polymer phase affects the performance of the
membranes [142]. When MOFs are used as the porous filler, the
organic ligands in MOFs can be modified to improve the interac-
tions occurred between the filler and the polymer phase [143],
avoiding the incompatibility that might cause the presence of
non-selective interphase voids [140]. Therefore, there is an exten-
sive on-going research on MOF-composite membranes for gas sep-
aration [144,145]. MOFs as a standalone membrane have also been
a subject of research, however they suffer from fragility and com-
plex fabrication processes, which complicate the scale-up of the
MOF membranes to the large surface areas [17].
The adsorption beds such as packed and fluidized beds are ideal
for liquid and gas separation. In these beds, the volumetric adsorp-
tion capacity, e.g., the high amount of the adsorbent in the bed vol-
ume is favorable; therefore, granules and pellets are good options
due to the high density of MOFs packed in a small volume. The size
and mechanical stability of the granules and pellets are of great
importance. Small particles with high mechanical stability are pre-
ferred in order to decrease the void fraction in the bed and to pre-
vent particles from abrasion and crushing due to the fluid flow and
column weight. Monoliths are also a favorable choice due to their
lower pressure drop and higher mechanical stability compared to
beads [61]. The typical examples of using MOF absorption bed
were demonstrated by Kim et al. [66], who used an adsorption col-
umn packed with MIL-100(Fe) beads for the separation of sulfur
hexafluoride from N2 stream; and Finsy et al. [69] illustrated the
separation of CO2/CH4 mixtures with MIL-53(Al) pellets.
Filter technology can also benefit from the tunable selectivity of
MOFs for the capture and immobilization of different pollutants.
Growing MOFs on pulp [119], polymer [146] and cotton fibers
[147], which can be easily fabricated into filter sheets and papers
allows the utilization of MOF filters. The MOFs grown directly on
paper sheets and meshed substrates have been utilized as a filter
for selective capture of pollutants such as dyes and particulate
matters from liquid and gas streams, respectively. Park et al.
[116] used ZIF-8 and ZIF-67 grown on cellulose paper sheets as a
filter to remove methyl orange and methyl blue dye pollutants
from aqueous solutions. Chen et al. [103] fabricated MOF-based fil-
ters (MOFilters) by growing ZIF-8, ZIF-67, and Ni-ZIF-8 on a variety
of filter substrates using roll-to-roll hot pressing method (Fig. 11).
3.2. Catalysis
Heterogeneous catalysis is a field in which MOFs have shown
promising results owing to their high surface areas and tunable
pore surface functionalities. MOFs are crystalline materials allow-
ing for the homogenous distribution of one or more active sites.
In addition, it is also possible to attach functional groups and mod-
ulate the pore sizes by applying isoreticular chemistry that can
10 B. Valizadeh et al. / Polyhedron 145 (2018) 1–15

overcome diffusion and pore size limitations [148]. However, con-
cerns such as stability and cost of MOFs still remain, and MOF
catalysis studies have been focused more on fine chemical synthe-
sis than for bulk chemistry.
Shaping MOF powders into various forms is crucial for catalytic
applications at the industrial scale. Catalysis using MOF powders or
nanoparticles as the active catalysts can be severely affected by the
agglomeration, catalyst loss and pipe clog that would inevitably
occur when flushing with fluids during catalytic cycles [59,149].
Therefore, depositing or growing MOF nanocrystals on shaped bod-
ies such as honeycomb- or monolith-shaped substrates is a good
solution that can dramatically increase the conversion and yield
of the catalytic reactions. Sachse et al. [150] performed a continu-
ous flow liquid-phase catalytic reaction with HKUST-1 catalyst
nanoparticles grown on a macro-/mesoporous silica monolith sub-
strate, which showed low pressure drop in a highly selective cat-
alytic reaction due to the synergy of properties of both materials.
The excellent binding of MOF crystals on the substrate is crucial
to prevent material loss especially when it comes in contact with
solvents.
Another approach is the encapsulation of molecular or nanopar-
ticle catalysts in hollow MOF structures; in this case, the MOFs act
as the substrate, which can restrict the catalyst agglomeration and
prevent the poisoning of the catalyst [151]. A wide range of tech-
niques have been used for encapsulating nanoparticles in MOF
templates [152] such as chemical vapor deposition [153], solid
grinding [154], liquid impregnation [155], encapsulating pre-syn-
thesized nanoparticles [156], self-sacrificing template [157], and
emulsion-based interfacial synthesis [158]. The spray drying tech-
nique was recently used for the preparation of hollow MOF super-
structures with encapsulated catalyst [159]. A typical example of
encapsulation of a nanoparticle catalyst within the pores of MOFs
was reported by Kuo et al. [157], where the authors presented
the use of yolk-shell Pd nanocrystal@ZIF-8 structures for hydro-
genation of alkenes (Fig. 12). Different from the core–shell nanos-
tructures, in which the shell is directly on the metal surface, the

Fig. 11. Roll-to-roll hot pressing synthesis of MOFilters on variety of substrates for particulate matter removal. Reproduced with permission from Ref. [103].

Fig. 12. Schematic presentation of nanoparticle encapsulation in hollow MOF structure by a sacrificial templating method. Reproduced with permission from Ref. [157].
 B. Valizadeh et al. / Polyhedron 145 (2018) 1–15
cavity between the core and the shell in yolk-shell nanostructures
allows better interactions between the reactants and the surface of
the nanoparticle catalyst. In addition, the microporous shell pro-
vides molecular-size selectivity; consequently, large alkene mole-
cules cannot diffuse through the pore apertures of the ZIF-8
shell, and only the small ones are hydrogenated.
MOF gels usually lose their integrity in the liquid phase but they
have shown good catalytic activities in gas phase reactions [58].
The transparency of a few gels allows them to be utilized in photo-
catalysis. Rechberger et al. [112] designed a photoreactor for the
selective photoreduction of CO2 to methanol using a 3D translu-
cent TiO2–Au nanoparticle-based aerogel monolith, which retain
its structure upon the reaction. MOF foams acting as a cup reactor
have also shown interesting performances for liquid-phase cat-
alytic reactions by improving the kinetics and facilitating the recy-
cling process [59]. Membrane reactors have a massive potential in
catalytic applications as MOF thin films can play the roles of the
catalyst and the membrane at the same time [160]. The MOF mem-
brane is usually selective to the reaction product and therefore by
removing the product from the reaction medium, the reaction con-
version is improved.
3.3. Sensing
Chemical sensing is one of the growing and promising applica-
tions of MOFs due to their ability to adsorb/capture different ana-
lytes in the gas phase and in solution [11]. The high selectivity,
high sensitivity, and short response time are important criteria
for good chemical sensors, and MOFs can play a significant role
with their flexible functionalities that can considerably affect these
parameters. The selectivity of the sensor depends on the selectivity
of the MOF, which in turn depends on its pore size, functional
groups, and open metal sites. The sensitivity depends firstly on
the ability of MOFs to capture the targeted molecule(s) and on
their loading capacity, and secondly on the efficiency of signal
transduction. The response time depends on the kinetics of adsorp-
tion of the molecule and rate of diffusion into the MOF pores [24].
Signal transduction is one of the major challenges in MOF sensors.
There are a large number of luminescent MOFs reported as stan-
dalone sensors that produce a signal such as turn-on or turn-off
luminescence intensity or color change upon adsorption of guest
molecule(s) [26–29,25,161]. Other means of signal transduction
such as the changes in the electrical or mechanical property of
the MOF can also be used. For example, Allendorf et al. [162]
demonstrated the use of an HKUST-1 layer deposited on gold-
coated microcantilevers that incorporate a built-in piezoresistive
sensor for gas detecting. In general, for sensors that are based on
electrical and mechanical signal transduction, the close bind at
physical interface between the MOF and the transducer is impor-
tant. Therefore, MOF thin films coated on a transducer are often
used, which improves the contact of the crystals with the surface
(Fig. 13). Depending on the MOF and the thickness of the layer, dif-
ferent methods of thin film synthesis such as LPE [163,164] and
Fig. 13. Schematic representation and SEM image of piezoresistive microcantilever. Reproduced with permission from Ref. [167].
11
LBL synthesis [165] have been used. In general the thinner the
MOF layer, the faster the diffusion and consequently the faster
the response. Therefore, synthesis conditions must be carefully
controlled. In addition, surface treatment has also been performed
to improve the crystal adhesion to the surface [100,166].
3.4. Biomedicine and drug delivery
The application of MOFs in medical research, mostly in drug
delivery, relies on the ability of MOFs to capture and release the
drug molecules in a controlled fashion. In drug delivery, the high
porosity and the tunable structure of the MOFs are used to design
particles capable of adsorbing specific drugs in their pores and
releasing it inside the body by a triggering stimulus such as pH
or temperature change [168–170].
MOFs as nanocrystals can be utilized for oral or intravenous
administration. There are a large number of reports on MOF
nanocrystals loaded with a variety of different drugs such as busul-
fan [171], ibuprofen [172], doxorubicin [173], methotrexate [174],
azidothymidine triphosphate and cidofovir [42]. However, for this
application, the stability and compatibility of MOFs in the biologi-
cal environment are crucial; encapsulation methods, for instance
with a silica shell, have been used to improve the stability and to
control the release of the drug from MOFs [42,175,176]. On the
other hand, the encapsulation of drugs and biomolecules into the
hollow MOF structures is another method for drug loading in
which the release of the molecules is not only due to the desorp-
tion from the pores but also due to the diffusion through the
MOF surface and perhaps the gradual collapse of the hollow struc-
ture [131,177]. Spray drying is a method that has been widely used
in pharmaceutical industry for encapsulation [178]. Due to its abil-
ity to form hollow MOF structures in an instantaneous reaction,
this method is highly promising for the encapsulation of drugs,
especially of thermally sensitive compounds, within MOFs hollow
structures [62].
Shaping MOFs into a thin film is an approach for the construc-
tion of medical patches for topical administration. Several biocom-
patible polymers such as gelatin, polyethylene glycol, poly(vinyl
alcohol) can be used for the shaping of MOF crystals as thin layers.
Márquez et al. [179] fabricated biocompatible composite patches
using MIL-100 nanoparticles combined with gelatin and poly(vinyl
alcohol) (Fig. 14) for the loading and release of caffeine and ibupro-
fen, which showed a good degree of slow and progressive release of
drugs on the simulated skin. Growing MOFs on paper sheets and
textile is another approach for fabrication of MOF patches and
band aids loaded with drugs.
Apart from drug delivery application, MOFs have also been used
for imaging and analytical applications in biomedicine. The pho-
toactivity of MOFs and their ability to encapsulate paramagnetic
metal ions and photoactive compounds have been used to utilize
MOF nanoparticles for magnetic resonance imaging (MRI)
[180,181], optical imaging [175,182] and X-ray computed tomog-
raphy imaging [183,184]. Recently MOFs coated on paper sub-
12 B. Valizadeh et al. / Polyhedron 145 (2018) 1–15

Fig. 14. Biocompatible polymer-MIL-100 composite patches, PVA: poly(vinyl alcohol), GEL: gelatin, CAF: caffeine. Reproduced with permission from Ref. [179].

strates have been used to improve sensitivity of paper spray mass
spectrometry for quantitative analysis of drugs. Wang et al. [115]
successfully used UiO-66(Zr), MIL-53(Al), and ZIF-8 to improve
the lower limit of quantitation for the detection of several anti-
psychotic drugs such as clozapine, amisulpride, quetiapine, risperi-
done and aripiprazole in human blood samples.
3.5. Electronics
Applications of MOFs in electronic and electric devices depend
on the conductive properties of MOFs. Since most MOFs are insula-
tors, the construction of MOF-based electrical devices is limited,
and usually involves the growth of MOF crystals in micro scale
on electronic chips and surfaces [185]. With the development of
thin film synthesis methods and pattern printing, controlled syn-
thesis of nano- and micro-size single crystals and films on chips
has been performed and several MOFs have shown promising per-
formances [52]. It is worth mentioning here that electrochemical
sensors could also be considered as electronic devices as they
transduce the chemical response to electrical signals, which have
been discussed previously in the Section 3.3. The liquid–liquid
[186] and air–liquid [187] interfacial syntheses were used to pre-
pare thin films of semiconductive MOFs on silicon substrate to
form a field effect transistors (Fig. 15a). The LPE method was also
utilized for fabrication of a ZIF-8 [188] and HKUST-1 [189] layer
on rigid and flexible substrates in a multilayer resistive memory
device, which showed chemically-mediated resistance-switching
property due to interaction of guest molecules with the MOF struc-
ture (Fig. 15b). On the other hand, the insulating MOFs were also
used as low dielectric constant insulators in microelectronic chips.
ZIF-8 is one of the promising MOFs for this application due to its
hydrophobicity, good mechanical properties and low dielectric
constant in the form of a polycrystalline thin film [190].
4. Conclusions and future outlook
Owing to their versatile structures and tunable pore shapes,
sizes, and functionalities, large surface areas, low densities, ability

Fig. 15. (a) Schematic fabrication of a MOF-based porous field effect transistor and (b) structure of the ZIF-8 based flexible memory devices and photograph of the devices on
a wrist strap. Reproduced with permission from Refs. [187,188].
 B. Valizadeh et al. / Polyhedron 145 (2018) 1–15 13

to selectively interact with molecules, amenability for post-syn- [16] Y.S. Lin, Curr. Opin. Chem. Eng. 8 (2015) 21.
[17] E. Adatoz, A.K. Avci, S. Keskin, Sep. Purif. Technol. 152 (2015) 207.
thetic functional modification of their surfaces and capacity to effi-
[18] Y. Lin, C. Kong, Q. Zhang, L. Chen, Adv. Energy Mater. 7 (2017) 1601296.
ciently encapsulate active species, MOFs are considered as the [19] M. Ranocchiari, J.A. van Bokhoven, Phys. Chem. Chem. Phys. 13 (2011) 6388.
most attractive porous materials for a plethora of applications. [20] J. Gascon, A. Corma, F. Kapteijn, F.X. Llabrés i Xamena, ACS Catal. 4 (2014) 361.
However, in order to realize their true potential, MOFs have to be [21] A.H. Chughtai, N. Ahmad, H.A. Younus, A. Laypkov, F. Verpoort, Chem. Soc.
Rev. 44 (2015) 6804.
produced in large-scale and industrially tested. The large-scale [22] Y. Zhao, Z. Song, X. Li, Q. Sun, N. Cheng, S. Lawes, X. Sun, Energy Storage
production of MOFs as a crystalline powder is well developed for Mater. 2 (2016) 35.
launching industrial-scale production; however, shaping MOFs [23] Y.-B. Huang, J. Liang, X.-S. Wang, R. Cao, Chem. Soc. Rev. 46 (2017) 126.
[24] L.E. Kreno, K. Leong, O.K. Farha, M. Allendorf, R.P. Van Duyne, J.T. Hupp, Chem.
into different forms is an essential requirement for their use in Rev. 112 (2012) 1105.
industrial applications. Through a deep understanding and careful [25] Z. Hu, B.J. Deibert, J. Li, Chem. Soc. Rev. 43 (2014) 5815.
control of the chemistry of MOFs, several methodologies have been [26] Y. Yu, X.M. Zhang, J.P. Ma, Q.K. Liu, P. Wang, Y.B. Dong, Chem. Commun. 50
(2014) 1444.
reported for the direct or indirect shaping of MOFs in different [27] B.J. Deibert, J. Li, Chem. Commun. 50 (2014) 9636.
forms. Granules, pellets, thin films, foams, gels, paper sheets and [28] S. Khatua, S. Goswami, S. Biswas, K. Tomar, H.S. Jena, S. Konar, Chem. Mater.
hollow structures are amongst the most popular architectures that 27 (2015) 5349.
[29] Y. Yu, J.P. Ma, C.W. Zhao, J. Yang, X.M. Zhang, Q.K. Liu, Y.B. Dong, Inorg. Chem.
MOF crystallites can be shaped into. The majority of reports con- 54 (2015) 11590.
cerning MOFs shaped into granules, pellets and monoliths are [30] S.E. Miller, M.H. Teplensky, P.Z. Moghadam, D. Fairen-Jimenez, Interface
based on packing beds for gas separation applications, whilst MOFs Focus 6 (2016) 20160027.
[31] D. Wang, Q. Tan, J. Liu, Z. Liu, Dalton Trans. 45 (2016) 18450.
shaped into thin films can act as filter papers for the separation of
[32] X. Liu, W. Fu, E. Bouwman, Chem. Commun. 52 (2016) 6926.
different molecules. Hollow MOF structures have shown good per- [33] M. Andrzejewski, A. Katrusiak, J. Phys. Chem. Lett. 8 (2017) 279.
formance towards catalysis since they can be used to encapsulate [34] L.R. Mingabudinova, V.V. Vinogradov, V.A. Milichko, E. Hey-Hawkins, A.V.
active species. MOF foams, membranes, thin films and gels have Vinogradov, Chem. Soc. Rev. 45 (2016) 5408.
[35] W. Zhang, R.G. Xiong, Chem. Rev. 112 (2012) 1163.
additionally displayed promise towards catalytic applications. Thin [36] M. Kurmoo, Chem. Soc. Rev. 38 (2009) 1353.
film based MOFs have been tested and frequently used for sensing, [37] A.D. Katsenis, E.K. Brechin, G.S. Papaefstathiou, Metal-organic frameworks:
drug delivery and electronic applications. derived from single molecule magnets, in: Encyclopedia of Inorganic and
Bioinorganic Chemistry, John Wiley & Sons Ltd, 2011.
Although shaped MOFs have shown great promise in several [38] A. Morozan, F. Jaouen, Energy Environ. Sci. 5 (2012) 9269.
areas, the classical powder processing methods, e.g., granulation [39] S. Horike, D. Umeyama, S. Kitagawa, Acc. Chem. Res 46 (2013) 2376.
and palletization, affect the intrinsic properties of MOFs in most [40] P. Ramaswamy, N.E. Wong, G.K. Shimizu, Chem. Soc. Rev. 43 (2014) 5913.
[41] L. Sun, M.G. Campbell, M. Dincă, Angew. Chem. Int. Ed. 55 (2016) 3566.
cases. Therefore, the methodologies used to shape MOFs require [42] P. Horcajada, T. Chalati, C. Serre, B. Gillet, C. Sebrie, T. Baati, J.F. Eubank, D.
further research optimization in order to prevent the collapse of Heurtaux, P. Clayette, C. Kreuz, J.-S. Chang, Y.K. Hwang, V. Marsaud, P.-N.
the MOF structure, pore blocking and relieve diffusion limitations Bories, L. Cynober, S. Gil, G. Ferey, P. Couvreur, R. Gref, Nat. Mater. 9 (2010)
172.
of shaped bodies by imposing optimum void fractions between pri- [43] P. Horcajada, R. Gref, T. Baati, P.K. Allan, G. Maurin, P. Couvreur, G. Férey, R.E.
mary powders. Composite fabrication, as a post-synthetic method Morris, C. Serre, Chem. Rev. 112 (2012) 1232.
for shaping MOF crystallites can be a promising approach for the [44] M.-X. Wu, Y.-W. Yang, Adv. Mater. 29 (2017), 1606134-n/a.
[45] I. Mihad, S. Rana, A.H. Ghaleb, Curr. Med. Chem. 24 (2017) 193.
improvement of the properties of the final shaped products. In
[46] M. Rubio-Martinez, C. Avci-Camur, A.W. Thornton, I. Imaz, D. Maspoch, M.R.
addition, current methods dealing with the synthesis of MOFs in Hill, Chem. Soc. Rev. (2017).
different shapes for device fabrication are not sufficiently devel- [47] http://www.sigmaaldrich.com/technical-documents/articles/materials-
oped yet, and they mostly involve complicated, tedious and expen- science/metal-organic-frameworks.html, in.
[48] A. Betard, R.A. Fischer, Chem. Rev. 112 (2012) 1055.
sive multi-step processes. There is thus a great opportunity to [49] J.R. Li, J. Sculley, H.C. Zhou, Chem. Rev. 112 (2012) 869.
explore this field further and develop device fabrication methods [50] N. Stock, S. Biswas, Chem. Rev. 112 (2012) 933.
towards more facile and flexible routes. [51] S.M. Iveson, J.D. Litster, K. Hapgood, B.J. Ennis, Powder Technol. 117 (2001) 3.
[52] P. Falcaro, R. Ricco, C.M. Doherty, K. Liang, A.J. Hill, M.J. Styles, Chem. Soc. Rev.
43 (2014) 5513.
Acknowledgements [53] U.-H. Lee, A.H. Valekar, Y.K. Hwang, J.-S. Chang, Granulation and shaping of
metal-organic frameworks, in: S. Kaskel (Ed.), The Chemistry of Metal-
Organic Frameworks: Synthesis, Characterization, and Applications, Wiley-
KCS and TNN thank Swiss National Science Foundation (SNF) for VCH Verlag GmbH & Co. KGaA, 2016.
funding under the Ambizione Energy Grant n.PZENP2_166888. The [54] H. Wu, T. Yildirim, W. Zhou, J. Phys. Chem. Lett. 4 (2013) 925.
authors thank Mr. Andrzej Gładysiak for helpful discussions over [55] J. Ren, N.M. Musyoka, H.W. Langmi, A. Swartbooi, B.C. North, M. Mathe, Int. J.
Hydrog. Energy 40 (2015) 4617.
the preparation of this review. [56] M.A. Moreira, J.C. Santos, A.F. Ferreira, J.M. Loureiro, F. Ragon, P. Horcajada, K.
E. Shim, Y.K. Hwang, U.H. Lee, J.S. Chang, C. Serre, A.E. Rodrigues, Langmuir 28
References (2012) 5715.
[57] Y.-N. Wu, F. Li, H. Liu, W. Zhu, M. Teng, Y. Jiang, W. Li, D. Xu, D. He, P. Hannam,
G. Li, J. Mater. Chem. 22 (2012) 16971.
[1] O.M. Yaghi, H. Li, J. Am. Chem. Soc 117 (1995) 10401.
[58] B. Bueken, N. Van Velthoven, T. Willhammar, T. Stassin, I. Stassen, D.A. Keen,
[2] H.-C. Zhou, J.R. Long, O.M. Yaghi, Chem. Rev. 112 (2012) 673.
G.V. Baron, J.F.M. Denayer, R. Ameloot, S. Bals, D. De Vos, T.D. Bennett, Chem.
[3] A. Schoedel, M. Li, D. Li, M. O’Keeffe, O.M. Yaghi, Chem. Rev. 116 (2016) 12466.
Sci. 8 (2017) 3939.
[4] A.J. Howarth, A.W. Peters, N.A. Vermeulen, T.C. Wang, J.T. Hupp, O.K. Farha,
[59] Y. Chen, X. Huang, S. Zhang, S. Li, S. Cao, X. Pei, J. Zhou, X. Feng, B. Wang, J. Am.
Chem. Mater. 29 (2017) 26.
Chem. Soc. 138 (2016) 10810.
[5] H. Furukawa, K.E. Cordova, M. O’Keeffe, O.M. Yaghi, Science 341 (2013).
[60] B. Garai, A. Mallick, R. Banerjee, Chem. Sci. 7 (2016) 2195.
[6] M. Eddaoudi, D.B. Moler, H. Li, B. Chen, T.M. Reineke, M. O’Keeffe, O.M. Yaghi,
[61] P. Küsgens, A. Zgaverdea, H.-G. Fritz, S. Siegle, S. Kaskel, J. Am. Ceram. Soc. 93
Acc. Chem. Res. 34 (2001) 319.
(2010) 2476.
[7] B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629.
[62] A. Carne-Sanchez, I. Imaz, M. Cano-Sarabia, D. Maspoch, Nat. Chem. 5 (2013)
[8] S. Kitagawa, R. Kitaura, S.-I. Noro, Angew. Chem. Int. Ed. 43 (2004) 2334.
203.
[9] S.L. James, Chem. Soc. Rev. 32 (2003) 276.
[63] S. Cantor, L. Augsburger, S. Hoag, A. Gerhardt, Pharmaceutical Granulation
[10] C. Janiak, Dalton Trans. (2003) 2781.
Processes, Mechanism and the Use of Binders, 2008.
[11] A. Gładysiak, T.N. Nguyen, J.A.R. Navarro, M.J. Rosseinsky, K.C. Stylianou,
[64] J. Kim, S.-H. Kim, S.-T. Yang, W.-S. Ahn, Microporous Mesoporous Mater. 161
Chem. A Eur. J. 23 (2017) 13602.
(2012) 48.
[12] B. Rungtaweevoranit, C.S. Diercks, M.J. Kalmutzki, O. Yaghi, Faraday Discuss.
[65] D. Bazer-Bachi, L. Assié, V. Lecocq, B. Harbuzaru, V. Falk, Powder Technol. 255
201 (2017) 9.
(2014) 52.
[13] S. Ma, H.-C. Zhou, Chem. Commun. 46 (2010) 44.
[66] P.-J. Kim, Y.-W. You, H. Park, J.-S. Chang, Y.-S. Bae, C.-H. Lee, J.-K. Suh, Chem.
[14] K. Sumida, D.L. Rogow, J.A. Mason, T.M. McDonald, E.D. Bloch, Z.R. Herm, T.-H.
Eng. J. 262 (2015) 683.
Bae, J.R. Long, Chem. Rev. 112 (2012) 724.
[67] F. Akhtar, L. Andersson, S. Ogunwumi, N. Hedin, L. Bergström, J. Eur. Ceram.
[15] M. Shah, M.C. McCarthy, S. Sachdeva, A.K. Lee, H.-K. Jeong, Ind. Eng. Chem.
Soc. 34 (2014) 1643.
Res. 51 (2012) 2179.
14 B. Valizadeh et al. / Polyhedron 145 (2018) 1–15

[68] D. Liu, J.J. Purewal, J. Yang, A. Sudik, S. Maurer, U. Mueller, J. Ni, D.J. Siegel, Int. D. Maspoch, R. Mas-Ballesté, J.L. Segura, F. Zamora, Chem. – Eur. J. 21 (2015)
J. Hydrog. Energ. 37 (2012) 6109. 10666.
[69] V. Finsy, L. Ma, L. Alaerts, D.E. De Vos, G.V. Baron, J.F.M. Denayer, Microporous [118] J.L. Zhuang, D. Ar, X.J. Yu, J.X. Liu, A. Terfort, Adv. Mater. 25 (2013) 4631.
Mesoporous Mater. 120 (2009) 221. [119] P. Küsgens, S. Siegle, S. Kaskel, Adv. Eng. Mater. 11 (2009) 93.
[70] G.W. Peterson, J.B. DeCoste, T.G. Glover, Y. Huang, H. Jasuja, K.S. Walton, [120] Q.-L. Zhu, Q. Xu, Chem. Soc. Rev. 43 (2014) 5468.
Microporous Mesoporous Mater. 179 (2013) 48. [121] H. Thakkar, S. Eastman, Q. Al-Naddaf, A.A. Rownaghi, F. Rezaei, ACS Appl.
[71] D. Crawford, J. Casaban, R. Haydon, N. Giri, T. McNally, S.L. James, Chem. Sci. 6 Mater. Interfaces 9 (2017) 35908.
(2015) 1645. [122] M. Wickenheisser, A. Herbst, R. Tannert, B. Milow, C. Janiak, Microporous
[72] D. Zacher, O. Shekhah, C. Woll, R.A. Fischer, Chem. Soc. Rev. 38 (2009) 1418. Mesoporous Mater. 215 (2015) 143.
[73] J. Gascon, S. Aguado, F. Kapteijn, Microporous Mesoporous Mater. 113 (2008) [123] E.V. Ramos-Fernandez, M. Garcia-Domingos, J. Juan-Alcañiz, J. Gascon, F.
132. Kapteijn, App. Catal. A 391 (2011) 261.
[74] Y.-S. Li, H. Bux, A. Feldhoff, G.-L. Li, W.-S. Yang, J. Caro, Adv. Mater. 22 (2010) [124] H.J. Lee, W. Cho, M. Oh, Chem. Commun. 48 (2012) 221.
3322. [125] A.-L. Li, F. Ke, L.-G. Qiu, X. Jiang, Y.-M. Wang, X.-Y. Tian, Cryst. Eng. Comm. 15
[75] R. Makiura, S. Motoyama, Y. Umemura, H. Yamanaka, O. Sakata, H. Kitagawa, (2013) 3554.
Nat. Mater. 9 (2010) 565. [126] M. Pang, A.J. Cairns, Y. Liu, Y. Belmabkhout, H.C. Zeng, M. Eddaoudi, J. Am.
[76] M. Li, M. Dinca, Chem. Sci. 5 (2014) 107. Chem. Soc. 135 (2013) 10234.
[77] R. Ameloot, L. Stappers, J. Fransaer, L. Alaerts, B.F. Sels, D.E. De Vos, Chem. [127] H. Kim, M. Oh, D. Kim, J. Park, J. Seong, S.K. Kwak, M.S. Lah, Chem. Commun.
Mater. 21 (2009) 2580. 51 (2015) 3678.
[78] S. Hermes, F. Schröder, R. Chelmowski, C. Wöll, R.A. Fischer, J. Am. Chem. Soc. [128] J. Huo, L. Wang, E. Irran, H. Yu, J. Gao, D. Fan, B. Li, J. Wang, W. Ding, A.M.
127 (2005) 13744. Amin, C. Li, L. Ma, Angew. Chem. Int. Ed. 49 (2010) 9237.
[79] E. Biemmi, C. Scherb, T. Bein, J. Am. Chem. Soc. 129 (2007) 8054. [129] Z. Shen, J. Liu, F. Hu, S. Liu, N. Cao, Y. Sui, Q. Zeng, Y. Shen, Cryst. Eng. Comm.
[80] C. Scherb, A. Schödel, T. Bein, Angew. Chem. Int. Ed. 47 (2008) 5777. 16 (2014) 3387.
[81] F. Hinterholzinger, C. Scherb, T. Ahnfeldt, N. Stock, T. Bein, Phys. Chem. Chem. [130] J. Koo, I.-C. Hwang, X. Yu, S. Saha, Y. Kim, K. Kim, Chem. Sci. 8 (2017) 6799.
Phys. 12 (2010) 4515. [131] H.-Y. Lian, M. Hu, C.-H. Liu, Y. Yamauchi, K.C.W. Wu, Chem. Commun. 48
[82] D. Zacher, A. Baunemann, S. Hermes, R.A. Fischer, J. Mater. Chem. 17 (2007) (2012) 5151.
2785. [132] M. Hu, S. Furukawa, R. Ohtani, H. Sukegawa, Y. Nemoto, J. Reboul, S. Kitagawa,
[83] M. Arnold, P. Kortunov, D.J. Jones, Y. Nedellec, J. Kärger, J. Caro, Eur. J. Inorg. Y. Yamauchi, Angew. Chem. Int. Ed. 51 (2012) 984.
Chem. (2007) 60. [133] R. Ameloot, F. Vermoortele, W. Vanhove, M.B.J. Roeffaers, B.F. Sels, D.E. De
[84] C. Carbonell, I. Imaz, D. Maspoch, J. Am. Chem. Soc. 133 (2011) 2144. Vos, Nat. Chem. 3 (2011) 382.
[85] C. Carbonell, K.C. Stylianou, J. Hernando, E. Evangelio, S.A. Barnett, S. [134] A. Schoedel, Z. Ji, O.M. Yaghi, Nat. Energy 1 (2016) 16034.
Nettikadan, I. Imaz, D. Maspoch, Nat. Commun. 4 (2013) 2173. [135] Z. Kang, L. Fan, D. Sun, J. Mater. Chem. A 5 (2017) 10073.
[86] A. Huang, W. Dou, J. Caro, J. Am. Chem. Soc. 132 (2010) 15562. [136] E.D. Bloch, W.L. Queen, R. Krishna, J.M. Zadrozny, C.M. Brown, J.R. Long,
[87] A. Huang, H. Bux, F. Steinbach, J. Caro, Angew. Chem. Int. Ed. 49 (2010) Science 335 (2012) 1606.
4958. [137] B. Smit, J.R. Reimer, C.M. Oldenburg, I.C. Bourg, Introduction to Carbon
[88] H. Guo, G. Zhu, I.J. Hewitt, S. Qiu, J. Am. Chem. Soc. 131 (2009) 1646. Capture and Sequestration, Imperial College Press, 2014.
[89] H. Ji, S. Hwang, K. Kim, C. Kim, N.C. Jeong, ACS Appl. Mater. Interfaces 8 (2016) [138] H. Li, M. Li, W. Li, Q. Yang, Y. Li, Z. Gu, Y. Song, Phys. Chem. Chem. Phys.: PCCP
32414. 19 (2017) 5746.
[90] V.V. Guerrero, Y. Yoo, M.C. McCarthy, H.-K. Jeong, J. Mater. Chem. 20 (2010) [139] W.J. Koros, G.K. Fleming, J. Membr. Sci. 83 (1993) 1.
3938. [140] B. Seoane, J. Coronas, I. Gascon, M.E. Benavides, O. Karvan, J. Caro, F. Kapteijn,
[91] Y. Hu, X. Dong, J. Nan, W. Jin, X. Ren, N. Xu, Y.M. Lee, Chem. Commun. 47 J. Gascon, Chem. Soc. Rev. 44 (2015) 2421.
(2011) 737. [141] S. Wang, X. Li, H. Wu, Z. Tian, Q. Xin, G. He, D. Peng, S. Chen, Y. Yin, Z. Jiang, M.
[92] P. Falcaro, A.J. Hill, K.M. Nairn, J. Jasieniak, J.I. Mardel, T.J. Bastow, S.C. Mayo, D. Guiver, Energy Environ. Sci. 9 (2016) 1863.
M. Gimona, D. Gomez, H.J. Whitfield, R. Riccò, A. Patelli, B. Marmiroli, H. [142] G. Dong, H. Li, V. Chen, J. Mater. Chem. A 1 (2013) 4610.
Amenitsch, T. Colson, L. Villanova, D. Buso, Nat. Commun. 2 (2011) 237. [143] S.R. Venna, M. Lartey, T. Li, A. Spore, S. Kumar, H.B. Nulwala, D.R. Luebke, N.L.
[93] W.-J. Li, J. Lu, S.-Y. Gao, Q.-H. Li, R. Cao, J. Mater. Chem. A 2 (2014) 19473. Rosi, E. Albenze, J. Mater. Chem. A. 3 (2015) 5014.
[94] N. Campagnol, T. Van Assche, T. Boudewijns, J. Denayer, K. Binnemans, D. De [144] Y. Zhang, X. Feng, S. Yuan, J. Zhou, B. Wang, Inorg. Chem. Front. 3 (2016) 896.
Vos, J. Fransaer, J. Mater. Chem. A 1 (2013) 5827. [145] M.S. Denny Jr, J.C. Moreton, L. Benz, S.M. Cohen, Nat. Rev. Mater. 1 (2016)
[95] C. Hou, J. Peng, Q. Xu, Z. Ji, X. Hu, RSC Adv. 2 (2012) 12696. 16078.
[96] R. Ameloot, L. Pandey, M.V.d. Auweraer, L. Alaerts, B.F. Sels, D.E. De Vos, [146] Y. Zhang, S. Yuan, X. Feng, H. Li, J. Zhou, B. Wang, J. Am. Chem. Soc. 138 (2016)
Chem. Commun. 46 (2010) 3735. 5785.
[97] M. Li, M. Dincă, Chem. Mater. 27 (2015) 3203. [147] R.R. Ozer, J.P. Hinestroza, RSC Adv. 5 (2015) 15198.
[98] W.-J. Li, M. Tu, R. Cao, R.A. Fischer, J. Mater. Chem. A 4 (2016) 12356. [148] M. Ranocchiari, J.A.v. Bokhoven, Phys. Chem. Chem. Phys. 13 (2011) 6388.
[99] I. Stassen, M. Styles, T. Van Assche, N. Campagnol, J. Fransaer, J. Denayer, J.-C. [149] P. Falcaro, R. Ricco, A. Yazdi, I. Imaz, S. Furukawa, D. Maspoch, R. Ameloot, J.D.
Tan, P. Falcaro, D. De Vos, R. Ameloot, Chem. Mater. 27 (2015) 1801. Evans, C.J. Doonan, Coord. Chem. Rev. 307 (Part 2) (2016) 237.
[100] O. Shekhah, H. Wang, S. Kowarik, F. Schreiber, M. Paulus, M. Tolan, C. [150] A. Sachse, R. Ameloot, B. Coq, F. Fajula, B. Coasne, D. De Vos, A. Galarneau,
Sternemann, F. Evers, D. Zacher, R.A. Fischer, C. Wöll, J. Am. Chem. Soc. 129 Chem. Commun. 48 (2012) 4749.
(2007) 15118. [151] G. Prieto, H. Tuysuz, N. Duyckaerts, J. Knossalla, G.H. Wang, F. Schuth, Chem.
[101] D. Zacher, K. Yusenko, A. Bétard, S. Henke, M. Molon, T. Ladnorg, O. Shekhah, Rev. 116 (2016) 14056.
B. Schüpbach, T. de los Arcos, M. Krasnopolski, M. Meilikhov, J. Winter, A. [152] J. Yu, C. Mu, B. Yan, X. Qin, C. Shen, H. Xue, H. Pang, Mater. Horizons 4 (2017)
Terfort, C. Wöll, R.A. Fischer, Chem. – A Eur. J. 17 (2011) 1448. 557.
[102] Y. Chen, S. Li, X. Pei, J. Zhou, X. Feng, S. Zhang, Y. Cheng, H. Li, R. Han, B. Wang, [153] Y.K. Park, S.B. Choi, H.J. Nam, D.-Y. Jung, H.C. Ahn, K. Choi, H. Furukawa, J. Kim,
Angew. Chem. Int. Ed. 55 (2016) 3419. Chem. Commun. 46 (2010) 3086.
[103] Y. Chen, S. Zhang, S. Cao, S. Li, F. Chen, S. Yuan, C. Xu, J. Zhou, X. Feng, X. Ma, B. [154] T. Ishida, M. Nagaoka, T. Akita, M. Haruta, Chem. Eur. J. 14 (2008) 8456.
Wang, Adv. Mater. 29 (2017). [155] Y.K. Hwang, D.-Y. Hong, J.-S. Chang, S.H. Jhung, Y.-K. Seo, J. Kim, A. Vimont, M.
[104] A.J. Brown, N.A. Brunelli, K. Eum, F. Rashidi, J.R. Johnson, W.J. Koros, C.W. Daturi, C. Serre, G. Férey, Angew. Chem. Int. Ed. 47 (2008) 4144.
Jones, S. Nair, Science 345 (2014) 72. [156] G. Lu, S. Li, Z. Guo, O.K. Farha, B.G. Hauser, X. Qi, Y. Wang, X. Wang, S. Han, X.
[105] K. Eum, A. Rownaghi, D. Choi, R.R. Bhave, C.W. Jones, S. Nair, Adv. Func. Mater. Liu, J.S. DuChene, H. Zhang, Q. Zhang, X. Chen, J. Ma, S.C.J. Loo, W.D. Wei, Y.
26 (2016) 5011. Yang, J.T. Hupp, F. Huo, Nat. Chem. 4 (2012) 310.
[106] M.L. Pinto, S. Dias, J. Pires, ACS Appl. Mater. Interfaces 5 (2013) 2360. [157] C.H. Kuo, Y. Tang, L.Y. Chou, B.T. Sneed, C.N. Brodsky, Z. Zhao, C.K. Tsung, J.
[107] J. Ren, T. Segakweng, H.W. Langmi, B.C. North, M. Mathe, J. Alloys Compd. 645 Am. Chem. Soc. 134 (2012) 14345.
(2015) S170. [158] Y. Yang, F. Wang, Q. Yang, Y. Hu, H. Yan, Y.-Z. Chen, H. Liu, G. Zhang, J. Lu, H.-L.
[108] U. Betke, S. Proemmel, J.G. Eggebrecht, S. Rannabauer, A. Lieb, M. Scheffler, F. Jiang, H. Xu, ACS Appl. Mater. Interfaces 6 (2014) 18163.
Scheffler, Chem. Ing. Tech. 88 (2016) 264. [159] N. Gholampour, S. Chaemchuen, Z.-Y. Hu, B. Mousavi, G. Van Tendeloo, F.
[109] K.-Y. Andrew Lin, H.-A. Chang, J. Mater. Chem. A 3 (2015) 20060. Verpoort, Chem. Eng. J. 322 (2017) 702.
[110] A. Garai, W. Shepherd, J. Huo, D. Bradshaw, J. Mater. Chem. B 1 (2013) 3678. [160] W.L. Jiang, L.G. Ding, B.J. Yao, J.C. Wang, G.J. Chen, Y.A. Li, J.P. Ma, J. Ji, Y. Dong,
[111] M.R. Lohe, M. Rose, S. Kaskel, Chem. Commun. (2009) 6056. Y.B. Dong, Chem. Commun. 52 (2016) 13564.
[112] F. Rechberger, M. Niederberger, Mater. Horizons (2017). [161] W.P. Lustig, S. Mukherjee, N.D. Rudd, A.V. Desai, J. Li, S.K. Ghosh, Chem. Soc.
[113] A. Ahmed, M. Forster, R. Clowes, P. Myers, H. Zhang, Chem. Commun. 50 Rev. 46 (2017) 3242.
(2014) 14314. [162] M.D. Allendorf, R.J.T. Houk, L. Andruszkiewicz, A.A. Talin, J. Pikarsky, A.
[114] L. Li, S. Xiang, S. Cao, J. Zhang, G. Ouyang, L. Chen, C.Y. Su, Nat. Commun. 4 Choudhury, K.A. Gall, P.J. Hesketh, J. Am. Chem. Soc. 130 (2008) 14404.
(2013) 1774. [163] M. Drobek, J.H. Kim, M. Bechelany, C. Vallicari, A. Julbe, S.S. Kim, ACS Appl.
[115] H. Jiang, Q. Wang, H. Wang, Y. Chen, M. Zhang, ACS Appl. Mater. Interfaces 8 Mater. Interfaces 8 (2016) 8323.
(2016) 26817. [164] O. Yassine, O. Shekhah, A.H. Assen, Y. Belmabkhout, K.N. Salama, M.
[116] J. Park, M. Oh, Nanoscale 9 (2017) 12850. Eddaoudi, Angew. Chem. Int. Ed. 55 (2016) 15879.
[117] A. de la Peña Ruigómez, D. Rodríguez-San-Miguel, K.C. Stylianou, M. Cavallini, [165] X. Chong, K.-J. Kim, E. Li, Y. Zhang, P.R. Ohodnicki, C.-H. Chang, A.X. Wang,
D. Gentili, F. Liscio, S. Milita, O.M. Roscioni, M.L. Ruiz-González, C. Carbonell, Sens. Actuators B Chem. 232 (2016) 43.
 B. Valizadeh et al. / Polyhedron 145 (2018) 1–15
[166] N. Liu, Y. Yao, J.J. Cha, M.T. McDowell, Y. Han, Y. Cui, Nano Res. 5 (2012) 109.
[167] J.-H. Lee, R.T.J. Houk, A. Robinson, J.A. Greathouse, S.M. Thornberg, M.D.
Allendorf, P.J. Hesketh, SPIE Defense, Security, and Sensing, SPIE, 2010, p.
767927.
[168] P. Horcajada, C. Serre, M. Vallet-Regí, M. Sebban, F. Taulelle, G. Férey, Angew.
Chem. Int. Ed. 45 (2006) 5974.
[169] Q. Fang, J. Wang, S. Gu, R.B. Kaspar, Z. Zhuang, J. Zheng, H. Guo, S. Qiu, Y. Yan,
J. Am. Chem. Soc. 137 (2015) 8352.
[170] F. Balas, M. Manzano, P. Horcajada, M. Vallet-Regí, J. Am. Chem. Soc. 128
(2006) 8116.
[171] M.T. Simon-Yarza, T. Baati, A. Paci, L.L. Lesueur, A. Seck, M. Chiper, R. Gref, C.
Serre, P. Couvreur, P. Horcajada, J. Mater. Chem. B 4 (2016) 585.
[172] K.J. Hartlieb, D.P. Ferris, J.M. Holcroft, I. Kandela, C.L. Stern, M.S. Nassar, Y.Y.
Botros, J.F. Stoddart, Mol. Pharm. 14 (2017) 1831.
[173] R. Anand, F. Borghi, F. Manoli, I. Manet, V. Agostoni, P. Reschiglian, R. Gref, S.
Monti, J. Phys. Chem. B 118 (2014) 8532.
[174] R.C. Huxford, K.E. deKrafft, W.S. Boyle, D. Liu, W. Lin, Chem. Sci. 3 (2012) 198.
[175] K.M.L. Taylor-Pashow, J.D. Rocca, Z. Xie, S. Tran, W. Lin, J. Am. Chem. Soc. 131
(2009) 14261.
[176] M. Filippousi, S. Turner, K. Leus, P.I. Siafaka, E.D. Tseligka, M. Vandichel, S.G.
Nanaki, I.S. Vizirianakis, D.N. Bikiaris, P. Van Der Voort, G. Van Tendeloo, Int. J.
Pharm. 509 (2016) 208.
[177] I. Imaz, M. Rubio-Martinez, L. Garcia-Fernandez, F. Garcia, D. Ruiz-Molina, J.
Hernando, V. Puntes, D. Maspoch, Chem. Commun. 46 (2010) 4737.
[178] R. Vehring, Pharm. Res. 25 (2008) 999.
[179] A.G. Marquez, T. Hidalgo, H. Lana, D. Cunha, M.J. Blanco-Prieto, C. Alvarez-
Lorenzo, C. Boissiere, C. Sanchez, C. Serre, P. Horcajada, J. Mater. Chem. B 4
(2016) 7031.
[180] K.M.L. Taylor, W.J. Rieter, W. Lin, J. Am. Chem. Soc. 130 (2008) 14358.
[181] W.J. Rieter, K.M.L. Taylor, H. An, W. Lin, W. Lin, J. Am. Chem. Soc. 128 (2006)
9024.
[182] D. Liu, R.C. Huxford, W. Lin, Angew. Chem. Int. Ed. 50 (2011) 3696.
[183] K.E. DeKrafft, Z. Xie, G. Cao, S. Tran, L. Ma, O.Z. Zhou, W. Lin, Angew. Chem. Int.
Ed. 48 (2009) 9901.
[184] D. Liu, K. Lu, C. Poon, W. Lin, Inorg. Chem. 53 (2014) 1916.
[185] I. Stassen, N. Burtch, A. Talin, P. Falcaro, M. Allendorf, R. Ameloot, Chem. Soc.
Rev. 46 (2017) 3185.
[186] X. Huang, P. Sheng, Z. Tu, F. Zhang, J. Wang, H. Geng, Y. Zou, C.-A. Di, Y. Yi, Y.
Sun, W. Xu, D. Zhu, Nat. Commun. 6 (2015) 7408.
[187] G. Wu, J. Huang, Y. Zang, J. He, G. Xu, J. Am. Chem. Soc. 139 (2017) 1360.
[188] Y. Liu, H. Wang, W. Shi, W. Zhang, J. Yu, B.K. Chandran, C. Cui, B. Zhu, Z. Liu, B.
Li, C. Xu, Z. Xu, S. Li, W. Huang, F. Huo, X. Chen, Angew. Chem. Int. Ed. 55
(2016) 8884.
[189] L. Pan, Z. Ji, X. Yi, X. Zhu, X. Chen, J. Shang, G. Liu, R.-W. Li, Adv. Funct. Mater.
25 (2015) 2677.
[190] S. Eslava, L. Zhang, S. Esconjauregui, J. Yang, K. Vanstreels, M.R. Baklanov, E.
Saiz, Chem. Mater. 25 (2013) 27.
15
Bardiya Valizadeh was born in Shiraz, Iran. He received
his B.Sc. and M.Sc. degrees in chemical engineering from
the Amirkabir University of Technology (Tehran
Polytechnic) in Tehran, Iran. He started his Ph.D. in 2016
in LSMO group under the supervision of Dr. Kyriakos
Stylianou and Prof. Berend Smit at the Institute of
Chemical Sciences and Engineering, at EPFL Valais
Wallis. His research interests include materials design
and engineering for environmental- and energy-related
applications.
Dr. Tu N. Nguyen was born in Ha Noi, Vietnam. He
received his PhD from the University of Florida in 2014
under the supervision of Professor George Christou.
After postdoctoral work with Professor Vincent L. Pec-
oraro at the University of Michigan, he moved to EPFL
and is currently a Scientist within the LSMO group of
Professor Berend Smit. His current research interests
focus on metal-organic frameworks for sensing and
photocatalysis.
Dr. Kyriakos C. Stylianou was born in Larnaca, Cyprus.
He received his PhD from the University of Liverpool
under the supervision of Professor Matthew J. Rossein-
sky and co-supervision of Professor Darren Bradshaw.
Upon completion of his PhD, he was awarded with the
prestigious Marie Curie fellowship and collaborated
with Professor Daniel Maspoch at the Catalan Institute
of Nanotechnology and Nanoscience. At EPFL Valais, he
leads the synthetic activity of LSMO and the research
focus of his team is on the synthesis of new porous
materials for energy, environmental and sensing appli-
cations. In 2016, he was successful with the Ambizione
Energy grant from the Swiss National Science Foundation to investigate the
potential of MOFs as photocatalysts.