REVIEW

pubs.acs.org/CR

Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various

MOF Topologies, Morphologies, and Composites†
Norbert Stock* and Shyam Biswas
Institut f€ur Anorganische Chemie, Christian-Albrechts-Universit€at zu Kiel, Max-Eyth-Str. 2, 24118 Kiel, Germany

CONTENTS List of Acronyms and Abbreviations 964

1. Introduction 933 References 965
1.1. Historical Developments 935
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2. Conventional Synthesis 935

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1. INTRODUCTION
2.1. Reaction Scaleup 936
3. Systematic Investigations of MOF Synthesis 937 The synthesis of metal-organic frameworks (MOFs) has
attracted immense attention during the last 2 decades due to
3.1. High-Throughput Methods 937
the possibility to obtain a large variety of aesthetically interesting
3.2. Ex Situ and In Situ Studies of MOF structures that could also be of great interest for applications in a
Crystallization 939 number of fields related to porous materials. This includes the
4. Alternative Synthesis Routes 941 more traditional areas of storage, separation, and catalysis, which
4.1. Microwave-Assisted Synthesis 942 are based on the pore size and shape as well as the host
guest
interactions involved. In addition, biomedical applications or the
4.2. Electrochemical Synthesis 944 use as sensor materials are currently intensively investigated.
4.3. Mechanochemical Synthesis 945 Extensive reviews have been published that also partially cover
4.4. Sonochemical Synthesis 946 the synthesis of MOFs.1
4
5. Various Aspects of MOF Synthesis 948 Regarding the synthesis of MOFs, often the term “design” has
been used. There have been controversial discussions about this
5.1. Solvents and Structure-Directing Agents 949 term and an interesting personal view has been given recently.5
5.1.1. Solvents 949 The more stringent definition of “design”, which implies “to
5.1.2. Structure-Directing Agents 949 create, fashion, execute, or construct according to plan”
(Webster’s Dictionary),6 generally is not applicable in MOF
5.2. Mineralizers 950
synthesis. Nevertheless, the definition and its implications have
5.3. Precursor Approach 950 helped to promote the field. The knowledge of possible topol-
5.4. In Situ Linker Synthesis 951 ogies, the functionality of multitopic organic linker molecules, as
5.5. Control of Catenation 952 well as the understanding of typical metal coordination environ-
ments or the formation conditions of typical inorganic building
6. MOF Crystals, Films/Membranes, and Composites 953
blocks (sometimes termed as bricks) help one to understand and
6.1. Crystal Size and Morphology 953 direct the synthesis efforts. The main goal in MOF synthesis is to
6.1.1. Compositional and Process Parameters 954 establish the synthesis conditions that lead to defined inorganic
6.1.2. Temperature Program 955 building blocks without decomposition of the organic linker. At
6.1.3. Additives 956 the same time, the kinetics of crystallization must be appropriate
to allow nucleation and growth of the desired phase to take place.
6.1.4. Reverse Microemulsions 957 These complex relationships explain why only for selected
6.2. Thin Films and Membranes 957 examples isoreticular series of MOFs could be obtained and
6.2.1. Direct Growth 958 why for the discovery of the majority of MOFs still exploratory
6.2.2. Layer-By-Layer Growth 960 syntheses are mandatory. To speed up the discovery of MOFs,
6.2.3. Secondary Growth 960 high-throughput methods, which were at first developed in
pharmaceutical research, have been developed (section 3.1).
6.2.4. Chemical Solution Deposition 961
The concepts of miniaturization and parallelization in combina-
6.3. Composites 961 tion with the automation within the workflow allow not only
6.3.1. MOF-Organic Matrix Composites 961 speeding up the discovery of MOF but also facilitate synthesis
6.3.2. MOF-Inorganic Matrix Composites 962 optimization as well as the extraction of reaction and structural
7. Conclusions and Future Prospects 963
Author Information 963 Special Issue: 2012 Metal-Organic Frameworks
Biographies 963 Received: August 4, 2011
Acknowledgment 964 Published: November 18, 2011

r 2011 American Chemical Society 933 dx.doi.org/10.1021/cr200304e | Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

Figure 1. Overview of synthesis methods, possible reaction temperatures, and final reaction products in MOF synthesis.

trends. While these methods are very helpful in relating reaction Why are different syntheses methods necessary for MOFs?
conditions to the formation of MOFs, they do not result in a Starting from the same reaction mixtures, they can lead to
deeper understanding of the crystallization processes. Therefore, different MOFs. They may have a strong impact on reac-
detailed ex and in situ studies have been performed to shed more tion time, yields, or particle size and morphology, or may be
insight on the formation of MOFs (section 3.2). differently well suited for the implementation in large-scale
The historical development of the still relatively young field of processes.
MOFs is an excellent example of interdisciplinary research that Figure 1 summarizes the scope of this review. An account is
has evolved during the last 2 decades (section 1.1). Develop- given on the different synthesis methods that have been applied
ments in the more molecule-based field of crystal engineering led in the last 20 years. Thus, in addition to room temperature
coordination chemists at the beginning of the 1990s to focus on synthesis, conventional electric (CE) heating, microwave (MW)
the assembly of organic and inorganic building blocks in order to heating, electrochemistry (EC), mechanochemistry (MC), and
form porous structures.7 Since weak interactions between the ultrasonic (US) methods have been employed. Conventional
building blocks were anticipated, rather mild reaction conditions step-by-step methods as well as high-throughput methods have
were applied (section 2). At the same time, chemists with a been employed in some of the studies, and these will also be
background in the synthesis of zeolites and zeolite-related covered in this review. There have been various objectives
materials started to look at the use of organic molecules not regarding the morphology of the MOF products. In addition
only as structure-directing agents but also as reactants to be to the crystal size or shape, thin films, membranes, and various
incorporated in as a part of the framework structure.8 For these other shapes made of MOFs have been reported, which require
studies, elevated reaction temperatures are generally employed the application of different synthesis methods.
(section 2). These different scientific backgrounds explain the Although we take already a very restricted definition for the
diverse synthetic methods employed in MOFs synthesis nowa- class of compounds labeled MOFs, i.e., 3D framework struc-
days by various groups around the world, especially regarding tures that exhibit porosity and/or guest exchange properties, it
reaction temperatures and reactors. They also explain the variety is still not possible to review the syntheses of all the MOFs
of synthetic methodologies and strategies adopted in the field of presented in the literature. Thus, most conventional syntheses
MOF synthesis. Coordination chemistry has accounted for are not covered, but concepts and nonstandard investigations
introducing electrochemical and mechanochemical synthesis as are summarized.
well as concepts like the precursor approach or in situ linker We will not cover the activation of MOFs, although this is an
synthesis. On the other hand, from zeolite chemistry the con- extremely important step to unlock the full potential of MOFs.
cepts of solvothermal reaction conditions, structure-directing Well-activated MOFs are also crucial for postsynthetic modifica-
agents, mineralizers, as well as microwave-assisted synthesis or tion reactions, in order to diminish the number of side reactions
steam-assisted conversion have been also introduced.9 that can take place. This rapidly expanding field, which relates
934 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

Figure 2. Historical developments in the synthesis of porous MOFs. Details of the different synthetic issues can be found in the respective sections
(cf. contents). The dates given refer to the synthesis of porous MOFs, whose porosity was demonstrated by sorption experiments or solvent exchange
experiments.

more to organic solid-phase synthesis, will also not be covered, for the mixed-linker compounds was published in 2001.25 In 2002,
but a number of reviews have recently been published.10 Over the the family of MOFs was extended to imidazolate-based compounds
last years, many reviews and perspectives have been published in that are nowadays known as zeolitic imidazole frameworks
the field of MOFs. Information has been taken from these (ZIFs).26,27 Although there is a large number of exciting compounds
sources as well as from the primary literature. that need to be mentioned, this section will be concluded by
providing a list of MOFs that are currently investigated due to their
1.1. Historical Developments high stability: e.g., Ni
CPO-27,28 UiO-66,29 Cr
MIL-100,30
The still relatively young field of MOF synthesis has been Cr
MIL-101,31 MIL-125,32 CAU-1,33 and ZIF-8.34 Historical
recognized to have evolved from the fields of coordination and developments taking into account the different synthetic issues
solid-state/zeolite chemistry. Coordination chemistry has a covered in this paper are summarized on a time line in Figure 2.
long history of investigating compounds that were labeled as
coordination polymers11 since they were formed by connection 2. CONVENTIONAL SYNTHESIS
of metal ions as connectors and organic ligands as linkers.1
4
This area was first reviewed in 1964.12 The interest in porous The term conventional synthesis is usually applied to reac-
coordination polymers surfaced much later, although some tions carried out by conventional electric heating without any
complexes such as Prussian blue compounds and Hofmann parallelization of reactions. The reaction temperature is one of
clathrates had been known to show reversible sorption proper- the main parameters in the synthesis of MOFs, and two tem-
ties. Thus, the interest in porous coordination polymers and perature ranges, solvothermal and nonsolvothermal, are nor-
MOFs started only around 1990. In 198913 and 1990,7 the mally distinguished, which dictate the kind of reaction setups
seminal work by Hoskins and Robson set the basis for the that have to be used. Although a common definition of
future of MOFs. In their paper, they already envisioned what solvothermal reactions has not been established,35 we use the
has been subsequently shown by many scientists around the one by Rabenau,36 i.e., reactions taking place in closed vessels
world:14 the formation of a large range of crystalline, micro- under autogenous pressure above the boiling point of the
porous, stable solids, possibly using structure-directing agents, solvent. Accordingly, nonsolvothermal reactions take place
with ion-exchange, gas sorption, or catalytic properties that below or at the boiling point under ambient pressure, which
further allow introducing functional groups by postsynthetic simplifies synthetic requirements. The latter reactions can
modification. further be classified as the ones at room-temperature or the
The term MOF was popularized by Yaghi et al. around 199515,16 ones taking place at elevated temperatures.
for a layered Co
trimesate that showed reversible sorption proper- As exemplified by the work of Hoskins and Robson,7 early
ties. In 1997, a 3D MOF was reported by Kitagawa et al. that work has mainly relied on low-temperature routes. Thus, a
exhibited gas sorption properties at room temperature.17 In 1999, precipitation reaction followed by recrystallization or the slow
the syntheses of MOF-518 and HKUST-119 were reported that in evaporation of the solvent was reported. These methods are well-
the following years and up to now are among the most studied known to grow simple molecular or ionic crystals, since it is
MOFs. Starting in 2002, Ferey et al. reported on nonflexible as well possible to tune the reaction conditions, i.e., the rate of nuclea-
as flexible porous MOFs, i.e., MIL-4720 and MIL-5321/MIL-88,22 tion and crystal growth. To grow crystals from clear solutions, the
respectively. The concept of isoreticular chemistry23 was made concentration of the reactants has to be adjusted in a way that the
popular in 2002 for a series of Zn dicarboxylates but has also been critical nucleation concentration is exceeded. This is commonly
extended to other materials. Especially, the mixed-linker compounds achieved by changing the temperature or by evaporating the
[M2(dicarboxylate)2(diamine)] (M = Zn, Cu) have shown to be a solvent. Once particles exceeding the critical radius are formed,
versatile class, and numerous studies have been carried out by crystal growth takes place. Methods such as solvent evaporation
varying the two organic components.24 The first structural model of a solution of reactants, layering of solutions, or slow diffusion
935 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

Table 1. Summary of MOFs That Have Been Synthesized in Larger Amounts

MOF comment STYa (kg m‑3 d‑1) ref

MOF-2 organic solvent, open vessel, 87% yield (Zn) 52

MOF-5 organic solvent, open vessel, 91% yield (Zn) 52
IRMOF-8 organic solvent, open vessel, 15% yield (Zn) 52
Al
MIL-53 commercially available as Basolite A100 160 49, 55
HKUST-1 solvothermal batch synthesis 51
commercially available as Basolite C 300 225 49, 55
organic solvent, electrochemical synthesis 52, 56
continuous synthesis; microwave-assisted heating 2000 46, 47, 50
Fe
BTC commercially available as Basolite F300 20 49, 55
ZIF-8 commercially available as Basolite Z1200 100 49, 55
[Mg(O2CH)2] commercially available as Basosiv M050 >300 49, 55
Fe
MIL-100 hydrothermal reaction, 10 L reactor >120 48, 50
hydrothermal reaction, 100 L reactor 300 57
a
Space
time yields given in this table are not based on the reactor volume, but on the volume of the reaction mixture.

of reactants into each other lead to concentration gradients that need to be taken into account: (1) availability and cost of the
allow the formation of MOFs. Concentration gradients can also starting materials, (2) synthesis conditions (low temperature,
be accomplished using temperature as a variable, i.e. by apply- ambient pressure), (3) workup procedure, (4) activation process,
ing a temperature gradient or slow cooling of the reaction (5) necessity of obtaining high yields, (5) avoiding large amount
mixture. Often large crystals suitable for structure determina- of impurities, and (6) using only small amounts of solvents. The
tion are obtained by these methods. latter plays an important role and the use of organic solvents in
Some prominent MOFs have even been obtained at room synthesis, workup, and activation are preferentially avoided. High
temperature by just mixing the starting materials; these are, for space
time yields (STY) σP (in kg m
3 s
1), i.e., “the mass of a
example, MOF-5, MOF-74, MOF-177, HKUST-1 or ZIF-8.37
39 product formed per volume of the reactor and time”,54 need to be
This method is sometimes termed as direct precipitation reaction accomplished, which should be as high as possible. The exclusion
and shows that the crystallization of some MOFs must take place of anions such as nitrate, perchlorate, or chloride during the
on a short time-scale. Surprisingly, some of these MOFs, e.g. ZIF- synthesis mixtures that often pose challenges on the process
8, show good thermal and chemical stabilities. Variation of the control and the reactor layout has led to the development of
reaction temperature has a strong influence on the product electrochemical synthesis procedures (section 4.2).
formation and often more condensed/dense structures are ob- The efforts in recent years have resulted in the scaleup of well-
served at higher temperatures.40,41 An increase of reaction tem- known MOFs in good space
time yields, such as MOF-5,
perature is also necessary in some systems to attain suitable Al
MIL-53, HKUST-1, ZIF-8, and Fe
MIL-100 and some
crystallinity and reaction rates, especially if kinetically more inert products are also commercially available (Table 1).
ions are used. Nevertheless, the temperature can also have a strong The reported scale-up procedures do not comply with most of
influence on the morphology of the crystals,42 and prolonged the criteria for industrial-scale syntheses. Thus, MOF-2 was
reaction times can even lead to the degradation of the MOF.43 obtained in 87% yield, based on Zn, starting from 52.2 g of
Zn(NO3)2 3 4H2O and 24.9 g of H2BDC in a mixture of organic
2.1. Reaction Scaleup solvents, i.e., NMP, chlorobenzene, and DMF, by adding 30 g of
Although a large number of different MOFs as well as many triethylamine at 70 °C.52 MOF-5 was synthesized in 91% yield,
potential applications have been reported in the literature, the based on Zn, at 130 °C by reaction of 193 g of Zn(NO3)2 3 4H2O
synthesis up-scaling to the gram-scale or larger and the large- and 41 g of DEF.52 Large crystals of the isoreticular compound
scale production of these materials have surprisingly been IRMOF-8 could be isolated in 15% yield based on Zn or 91%
neglected. Most of the reports on scaled-up reactions can be yield based on H2NDC by reacting 67.4 g of Zn(NO3)2 3 4H2O
found in patents,44
48 but some have also been published, and 7.5 g of H2NDC in 883 g of DEF.52 The continuous
with varying amounts of details, in the scientific literature.49,50 electrochemical synthesis of HKUST-1 in methanol was scaled
The first successful scaleup was demonstrated for HKUST-1 up to the 100-g scale per batch (see also section 4.3).56
on the 80 g scale,51 and subsequently MOF-5 was synthesized A detailed report on the batch scale-up synthesis of Fe
MIL-
on a 50 g scale.52 Recently, a press release was issued on “the 100 will be published soon.48,50 Thus, it was possible to accomplish
first industrial-scale MOF synthesis” and the testing of the the HF-free synthesis of well-crystalline Fe
MIL-100 in Teflon-
material for natural gas storage in heavy-duty vehicles. 53 The lined autoclaves (V = 10 L, 160 °C) by changing the metal source
identity of the MOF was not disclosed. from elemental Fe to Fe(NO3)3 3 9H2O and by using high
The challenges for the use of MOFs in industrial applications concentrations of starting materials. Activation was accomplished
lie in their inherent properties as well as their production. by treatment with NH4F, and a STY > 120 kg m
3 d
1 was
Requirements of the MOFs that must be fulfilled include high obtained. For synthesis up-scaling to a 100 L reactor, a STY of 300
porosity, thermal and chemical stability, as well as sustainability. was even accomplished.57
Laboratory syntheses, which were established in the search of The synthesis of HKUST-1 was first scaled up to the 80-g scale
new MOFs, must also be adapted. Hence, the following issues by using a batch reactor.51 The systematic investigation of different
936 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

Table 2. Summary of High-Throughput Investigations of Porous MOFs

MOF comment ref

Imidazolate-Based MOFs
ZIFs 9600 microreactions lead to 25 different Co- and Zn-containing ZIFs, 34
10 mixed-linker ZIFs, 16 new compositions and structures,
and five new topologies; fully automated HT methodology
Carboxylate-Based MOFs
Fe
MIL-53
NH2; investigation of solvent; influence of pH, reaction temperature, 63
Fe
MIL-88B-NH2; Fe
MIL-101
NH2 overall concentration for scaleup
MOF-5; HKUST-1 influence of metal salt, reaction time, and temperature on phase purity, 42
crystal size, and morphology
Al
MIL-53
NH2 investigation of the influence of solvents for Al-based MOFs 64
CAU-1 investigation of the influence of solvents for Al-based MOFs; 33
new inorganic brick; methanol as solvent and reactant
Al
MIL-101
NH2 investigation of the influence of solvents for Al-based MOFs; DMF as solvent 33
MIL-121 influence of starting pH on the selective formation of MIL-118, -120, and -121; 65
Al
MIL-53
(COOH)2
CAU-4 investigation of the influence of solvents for Al-based MOFs; 66
use of DMF and synthesis optimization; [Al(BTB)]
Cr
MIL-101-NDC isoreticular to Cr
MIL-101 with mesoporous cages; acetic acid as additive improves crystallinity 67
Ni
HKUST-1 [Ni3(BTC)2(Me2NH)3]; investigation of Ni paddle wheel containing MOFs 68
Ni
MOF-14 [Ni3(BTB)2(HMIm)1.5(H2O)1.5]; investigation of Ni paddle wheel containing MOFs 68
[Ni2(BDC)2(DABCO)] investigation of Ni paddle wheel containing MOFs; discovery and optimization of polymorphs 68
Phosphonate-Based MOF
[NaLa(H4L)] [NaLa((HO3P)2CH-C6H4
CH(PO3H)2)]; anionic open framework; 69
alkaline metal ions as structure-directing agent
Tetrazolate-Based MOF
Fe
BTT fully automated HT methodology; open Fe2+ sites, sodalite-type MOF 61

solvent mixtures, the reaction temperature, and the influence 3.1. High-Throughput Methods
of stirring resulted in a procedure that yielded after 18 h at 383 K High-throughput (HT) methods for solvothermal syntheses
a product that showed after activation a specific surface area of are a powerful tool to accelerate the discovery of new compounds
964 m2 g
1, which is far below the values reported for other and to optimize syntheses procedures.34,58 Large amounts of data
HKUST-1 products. On the basis of results obtained by MW- are generated that allows one to establish crystallization fields
assisted heating,50 a continuous MW-assisted synthesis of and to extract relevant reaction trends. This in turn can con-
HKUST-1 was developed,46,47 and using a total solvent tribute to a better understanding of the role of individual reaction
volume of 9 L a STY of 2000 kg m
3 d
1 was achieved.57 It parameters on the product formation. HT methods are closely
has to be kept in mind that there are limitations regarding connected with the concepts of automation, parallelization, and
reactor design utilizing MW-assisted heating. Currently a 50-L miniaturization. Thus, parallel reactors, often based on the 96
MWreactor is being realized.57 well-plate format, have been employed, which can hold reaction
mixtures ranging from a few microliters to a few milliliters. In
order to facilitate the synthesis—handling of small amounts of
3. SYSTEMATIC INVESTIGATIONS OF MOF SYNTHESIS starting materials in different ratios—as well as the rapid
To investigate the formation of MOFs, many parameters, such as characterization of products, at least a minimum degree of
compositional (molar ratios of starting materials, pH, solvent, etc.) automation is necessary. But also fully automated HT setups
and process parameters (reaction time, temperature, and pressure), have been described.59 In addition to automated liquid handling,
are varied. This can be done in a serial way, but it is a time- the fully automated dosing in the milligram-range has also been
consuming process that is still used for most of the synthetic demonstrated.60,61 The proof of concept for the successful
investigations. High-throughput methods have been shown to be application of HT methods in solvothermal syntheses was first
the ideal tool to accomplish this cumbersome task. Thus, they demonstrated for zeolites in the late 1990s.62 Since then a large
present a new and more systematic way to establish the fields of number of inorganic
organic hybrid compounds as well as
formation (section 3.1). Nevertheless, their application does not MOFs (Table 2) have been discovered and optimized. Most of
shed any light on the reaction mechanism or the formation of the latter are metal
carboxylates, but also imidazolate-, phos-
intermediate phases. Thus, recently in situ and ex situ investigations phonate- and tetrazolate-based compounds were investigated.
under solvothermal conditions have been carried out that demon- Most of the reported studies focus on the discovery and synthesis
strate the fast crystallization of selected MOFs (section 3.2). optimization, i.e., the crystallinity or crystal size. Characterization of
937 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

by organic linkers to form a 12-connected net. The structure is

related to a cubic centered packing motive in which the octameric
units replace individual atoms. Thus, distorted octahedral and tetra-
hedral cages with effective accessible diameters of 1 and 0.45 nm,
respectively, are formed. On the basis of the results of the HT
investigation, the syntheses could be scaled-up to the 250 mL scale.
Other Al-containing MOFs that have been discovered by employ-
ing HT methods are MIL-12165 and CAU-4.66 MIL-121 is an
Al
MIL-53 analogue containing two extra noncoordinating car-
boxylic acid functions per ligand. It was discovered as the third
member in the chemical system Al(NO3)3 3 9H2O/H4BTEC/
H2O/NaOH during the detailed investigation of the influence of
the starting pH and the overall concentration on the phase
formation. The HT methods enabled the authors to establish
reaction conditions for the selective formation of the three
Figure 3. Influence of pH related to the formation of MOF-type Al compounds (MIL-118, -120, and -121), and on the basis of the
pyromellitate frameworks. Reproduced with permission from ref 65.
Copyright 2010 American Chemical Society.
data, synthesis
structure correlations could be established. Thus,
low pH favors the formation of corner-sharing [AlO6] polyhedra
as observed in MIL-118 and -121, while higher pH values lead to
the reaction products is routinely carried out by automated XRPD
edge-sharing, as observed in MIL-120. The increase of the starting
measurements, and the patterns are compared to databases contain-
pH leads to a higher degree of deprotonation of H4BTEC, and
ing simulated powder patterns of the known compounds in the
thus for MIL-121, -118, and -120, four, six, and eight carboxyl O
system under investigation. In addition, automated optical micro-
atoms are connected to Al3+ ions, respectively (Figure 3).
scopy has also been employed to identify products containing
One outstanding example of a stable and highly porous MOF
suitable single crystals.34
is Cr
MIL-101,31 a Cr terephthalate that has been the focus of
The first two studies, reported in 2008, dealt with ZIFs
many investigations. It contains two kinds of accessible cages
and amino-functionalized derivatives of Fe
MIL-53, -88,
with diameters of ∼29 and ∼34 Å. Replacing BDC2‑ by NDC2‑
and -101.34,63 In the study on ZIFs,34 9600 reactions were performed
ions has led to a isoreticluar compound with pore diameters of
in 96-well plates in the range of 65
150 °C. Nine imidazolate-
∼39 and ∼46 Å, denoted as Cr
MIL-101-NDC.67 Employing a
type linkers and mixtures thereof were reacted with zinc or cobalt
24-well high-throughput reactor system, the influence of chemi-
nitrate in mixtures of DMF and DEF at various concentrations
cal (solvents, starting materials, molar ratio, etc.) and process
and molar ratios of metal to linker. Although 16 new compounds
parameters (temperature and reaction time) was investigated.
and five new topologies were identified, only seven out of 16
More than 600 individual reactions were performed to determine
discovered ZIFs could be scaled up in order to permit bulk
the appropriate synthesis conditions for Cr
MIL-101-NDC.
characterization. The results of the 9600 reactions allowed
The temperature control (heating and cooling rate), the Cr3+
establishing the optimal synthesis conditions for ZIFs, i.e., a
source, the solvent as well as the presence of aliphatic acids play
concentration level of 0.20 M, a reaction time of 72 h, and an
an important role. Although the compound was unambiguously
isothermal temperature of 85 or 100 °C.
characterized, it is only obtained in combination with an X-ray
The influence of reaction temperature, molar ratios of starting
amorphous byproduct.
materials, overall concentration, and pH of the reaction mixture
One of the most abundant inorganic bricks in MOFs is the so-
as well as the role of the solvent was studied for the system Fe3+/
called paddle wheel unit. According to the CSD database, most of
H2BDC
NH2/base/solvent.63 Reactions were carried out in
the compounds containing paddle wheel units are based on Cu and
protic as well as aprotic reaction media, i.e. DMF, water,
Zn, but examples with other ions such as Mo, Fe, and Cr were also
acetonitrile, and methanol. The fields of formation of the three
reported. Prominent examples are the compounds HKUST-1,19
amino-functionalized Fe-based compounds MIL-53
NH2,
MOF-14,70 PCN-6,71 or mixed-linker materials with the com-
MIL-88
NH2, and MIL-101
NH2 could be determined, and
position [M2(dicarboxylate)2(diamine)].72,73 Recently, a sys-
up-scaling of the reaction products was demonstrated. The
tematic HT investigation of Ni-based paddle wheel containing
following parameters could be established to have the most
MOFs was conducted using H3BTC, H3BTB, and the mixed-
profound impact on the product formation: (a) reaction med-
linker system H2BDC/DABCO. Six new compounds were
ium, (b) reaction temperature, and (c) overall concentration. discovered: four porous Ni-based MOFs with paddle wheel
The thorough investigation of the corresponding system
building units and two compounds with dense layered structures.
containing Al3+ as the metal ion was also carried out.33,64
66
Al
MIL-53
NH2 was obtained when water was employed as the As a first step in the study, a comprehensive screening of
solvent.64 The optimal molar ratio (Al3+:H2BDC
NH2) as well compositional and process parameters allowed establishing the
as the optimal reaction temperature was determined, and on reaction conditions for the Ni analogue of HKUST-1. Applying
the basis of these results the scaleup was successfully performed. these reaction conditions and replacing H3BTC with the ex-
The
NH2 groups were shown to be accessible to postsynthetic tended tritopic linker H3BTB, the Ni analogue of MOF-14 was
modification reaction. Al
MIL-101
NH2 could be isolated using discovered. In the mixed-linker system H2BDC/DABCO, two
DMF and working under diluted conditions.33 When methanol pillared
layered structures with the composition [Ni2(BDC)2-
was employed as the solvent, a new, highly porous MOF denoted (DABCO)] were achieved. HT methods involving MW-assisted
as CAU-1 was discovered.33 This compound contains the new Al- heating as well as stirring of the reaction mixture allowed
based octameric brick [Al8(OH)4(OCH3)8]12+ that is connected establishing the synthesis condition for each polymorph.
938 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

Table 3. Summary of Ex Situ Studies of MOF Crystallization

MOF method investigation ref

MIL-89 EXAFS indication of the retention of inorganic brick over the complete crystallization process 75
[Mg2(Hcam)3 (H2O)3][NO3] ESI-MS detection of the inorganic brick in the supersaturated crystallization solution 76
M
MIL-53; V
MIL-47 XRPD influence of metal ions on crystallization kinetics of isostructural M(III)
BDCs (M = Cr, Al) 77
M
MOF-76 XRPD influence of metal ions on crystallization kinetics of isostructural lanthanide
BTCs (M = Ce, Tb, Y) 78
Fe
MIL-53 XRPD influence of heating methods (conventional electric, microwave, and ultrasound) on crystallization kinetics 79
ZIF-8 XRPD evaluation of crystallization kinetics by the Avrami model 80

Compared to the large number of carboxylate-based MOFs, To follow the crystallization, ex situ or in situ studies can be
there are only a few porous metal phosphonates known in performed. In ex situ investigations, the reaction is quenched
literature.69,74 Recently, the anionic flexible open-framework metal after certain time intervals. This and the following workup can
phosphonate [NaLa((PO3H)2CH
C6H4
CH(PO3H)2)], [NaLa- lead to changes in the nature of the sample and thus to
(H4L)] was reported.69 In a systematic study on the role of the alkaline nonreliable results. Nevertheless, ex situ studies can be more
metal ions on the product formation, Na+ was identified as the best easily carried out under laboratory conditions and are fairly
structure-directing agent for this framework. The molar ratios of the straightforward to conduct. In contrast, in situ studies require
starting materials, the reaction temperature, and the degree of dilution often the use of special equipment and synchrotron radiation, but
as well as influence of the order of addition of the metal ions to the the reactions are monitored continuously, which leads normally
reaction mixture were scrutinized in a very systematic way. This also to a better time resolution. Various methods have been
allowed the presence of a Na4(H4L)solv precursor complex in solution employed for these investigations. EXAFS spectroscopy, ESI-
to be proposed and the order of suitability for the alkaline ions to be MS, and XRPD measurements were used for the ex situ studies
determined. (Table 3), while EDXRD, SAXS/WAXS, SLS, SPR, and AFM
A fully automated HT methodology employing a solid- and measurements were employed for in situ studies (Table 4).
liquid-dispensing robotic module, optical monitoring of the An ex situ EXAFS study was carried out for the synthesis of
reaction progress, as well as automated workup and HT powder Fe
MIL-89.75 The trimeric brick [Fe3(μ3-O)(O2C
R)6]+ was
diffraction were used for the synthesis optimization of the detected over the complete solvothermal crystallization process.
tetrazolate-based compound Fe3[(Fe4Cl)3(BTT)8(CH3OH)4]2 ESI-MS measurements of a supersaturated crystallization solu-
(Fe
BTT).61 Although this compound is isostructural with tion for the synthesis of [Mg2(Hcam)3(H2O)3][NO3] allowed
Mn
and Cu
BTT, many optimization cycles were necessary the direct identification of the inorganic brick [Mg2(Hcam)3]+.76
to obtain a phase-pure compound. The final optimized condi- XRPD measurements were mostly used for ex situ studies of
tions were observed to be vastly different from those for MOF synthesis. The extent of reaction is obtained from the
Mn
BTT and Cu
BTT, high-lighting the benefit of HT relative intensities of the most intense Bragg reflections. Using
methods. Unfortunately, only the final synthesis procedure but this method, the influence of metal ions in the synthesis of
no details about the synthetic strategy or the observed trends isostructural metal(III)
BDCs77 and lanthanide
BTCs78 was
investigated. In both cases, the synthesis rate was found to be
were reported.
directly proportional to the lability of the metal ions (rCr
MIL‑53 <
The synthetic parameters are not only responsible for the
phase formation but they also present a way to influence the rAl
MIL‑53 < rV
MIL‑47; rCe
BTC > rTb
BTC > rY
BTC). The
deprotonation of the linkers is much faster than the complexation
crystal morphology. In a study on MOF-5 and HKUST-1, the
of the metal ions. The same group also investigated the influence
influence of the metal source, the compositional parameters,
of the heating method on the reaction kinetics of Fe
MIL-53.79
reagent concentrations, and pH as well as reaction temperature
Compared to CE heating, the use of US or MW irradiation
and time were recently investigated.42 The characterization of the
substantially accelerated the synthesis rate of Fe
MIL-53 (rUS >
samples was performed by X-ray powder diffraction and high- rMW . rCE). The acoustic cavitation, which leads to hot spots, is
resolution scanning electron microscopy. Attention was focused possibly responsible for the acceleration of US synthesis. The
on the phase purity and the crystal morphology of the resulting higher rates of MW synthesis may be attributed to the fast and
compounds. The metal acetates were identified as preferable uniform heating of the reaction solutions. In another ex-situ
starting materials to obtain well-developed small crystals. For study, the Avrami model was applied to describe the crystal-
HKUST-1, the optimal reaction conditions for phase-pure lization kinetics of ZIF-8 at room temperature.80 The Avrami
compound and X-ray quality crystals were determined by con- exponent suggested homogeneous nucleation and growth of
trolling the reactant concentration as well as reaction time and spherical particles.
temperature. In a time-resolved in situ EDXRD study, the influence of the
heating method (MW and CE heating) on the crystallization
3.2. Ex Situ and In Situ Studies of MOF Crystallization process of CAU-1
(OH)2 was investigated (Figure 4).81 Com-
Time-resolved investigations of MOF crystallization allow the plete crystallization was observed in the range of 10
280 min
detection of crystalline intermediates, the assessment of indivi- depending on the reaction temperature, and MW heating led to
dual reaction parameters, i.e., reaction rate constants and activa- shorter induction periods as well as shorter reaction times
tion energies, and formulating an idea about the crystallization compared to CE heating. A kinetic analysis of the data according
mechanism. Thus, the optimization of the synthesis conditions of to the Sharp
Hancock method suggested that the reaction
new compounds can be achieved. In addition, they can be used to mechanism varied with the heating method. The Avrami ex-
monitor and adjust the crystal size of the final product. ponents indicated a phase-boundary controlled reaction under
939 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

Table 4. Summary of in Situ Studies of MOF Crystallization

MOF method investigation ref

CAU-1
(OH)2 EDXRD evaluation of crystallization kinetics using the Avrami
Erofe’ev model; influence of heating methods 81
(conventional electric and microwave) on crystallization kinetics
HKUST-1 EDXRD evaluation of crystallization kinetics using the Avrami
Erofe’ev as well as Gualtieri model 43, 82
Fe
MIL-53 EDXRD evaluation of crystallization kinetics using the Avrami
Erofe’ev model; 82
detection and isolation of MOF-235 as an intermediate
MOF-14 EDXRD evaluation of crystallization kinetics using the Gualtieri model; 43
determination of solvothermal stability of the MOF
Al
MIL-101
NH2 SAXS/WAXS evaluation of the competitive formation of Al
MIL-53
NH2, Al
MOF-235
NH2, 83
and Al
MIL-101
NH2 employing the Gualtieri model
SAXS/WAXS evaluation of the competitive formation of Al
MOF-235
NH2 84
and Al
MIL-101
NH2 in the presence of Keggin polyanions employing the Gualtieri model
HKUST-1 SLS elucidation of crystal growth mechanism from a supersaturated crystallization solution 85
MOF-5 SLS elucidation of crystal growth mechanism from a supersaturated crystallization solution; 86
control of particle size by using a modulator
ZIF-8 SLS adjustment of particle size by adding modulators; 87
determination of the role of modulators in the crystallization process
HKUST-1 SPR indication of the formation of inorganic brick during layer-by-layer 88
growth by varying the Cu2+ ion source
HKUST-1 AFM elucidation of mechanism of crystal growth as well as nature of building units 89, 90

Figure 4. (a) Time-resolved in situ EDXRD data measured during the crystallization of CAU-1-(OH)2 at 125 °C using conventional heating. (b)
Comparison of induction and reaction times between microwave (blue) and conventional (black) heating for the crystal growth of CAU-1-(OH)2 in the
range 120
145 °C. Reproduced with permission from ref 81. Copyright 2011 Wiley-VCH Verlag GmbH & Co. KGaA.

CE heating and a diffusion-controlled reaction under MW heat- Employing in situ SAXS/WAXS measurements, the crystal
ing. In the EDXRD investigations of the solvothermal crystal- growth kinetics of product formation in the system Al3+/
lization of HKUST-1 and Fe
MIL-53, two different crystalliza- H2BDC
NH2/solvent was evaluated using the Gualtieri
tion scenarios were noticed.82 The crystal growth kinetics of model.83,84 In the first report, the influence of solvent, reactant
HKUST-1 was evaluated using the Avrami
Erofeev model by concentration, and reaction temperature was systematically
applying the Sharp
Hancock method. A classical nucleation- investigated.83 When the synthesis is carried out in DMF at
controlled reaction was observed, in which nucleation continued low reactant concentration, both Al
MIL-53
NH2 and
after crystallization had begun. The formation of Fe
MIL-53 Al
MIL-101
NH2 are observed. The increase of the reactant
occurred via the metastable precursor MOF-235, which could also concentration or the replacement of DMF by water as solvent
be isolated by quenching. In an EDXRD study of the solvothermal leads to the formation of Al
MIL-53
NH2. In the intermediate
crystallization of MOF-14 and HKUST-1,43 the former compound temperature range in DMF, Al
MOF-235
NH2 appears as a
was found to decompose at longer reaction times. Thus, the kinetically stable phase, which transforms into the thermodyna-
material possesses a lower solvothermal stability compared to mically stable Al
MIL-101
NH2 as the reaction temperature
HKUST-1. The kinetics of crystallizations of both MOFs was rises. The DMF facilitates the dissolution of H2BDC
NH2,
examined by the Gualtieri model, which allowed separation of the increasing the availability of the building blocks and thus favoring
nucleation and growth regimes. The occurrence of secondary the formation of Al
MOF-235
NH2. The intermediate
nucleation in MOF-14 prior to the decomposition was proposed Al
MOF-235
NH2 phase could be isolated by quenching the
by the kinetic analysis and proven by SEM images. reaction mixture at intermediate temperatures. In DMF/water
940 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

mixtures, the Al
MOF-235
NH2 phase is hydrolyzed and the growth followed a 2D “birth and spread” mechanism with the
Al
MIL-53
NH2 phase is formed at high temperatures. The occurrence of defects as well as isotropic growth steps. The same
fast formation of Al
MOF-235
NH2 is supported by the higher group later investigated the in situ growth of the {111} facet of a
rate of nucleation compared to crystal growth. In the second ∼0.6 μm sized, defect-free HKUST-1 crystal on OH-terminated
report, the encapsulation of Keggin polyoxometalate ions Au surface.90 In this case, the authors proposed a 2D step-by-step
(POMs) in Al
MIL-101
NH2 was confirmed by the dramatic growth mechanism. The height of the anisotropic growth steps
change of relative intensity of the Bragg peaks after the addition corresponded to d111 crystal spacing (1.5 nm). The difference in
of POM to the synthesis mixture.84 The crystal growth kinetics of growth mechanisms between the two studies was attributed to
Al
MIL-101
NH2 was almost unaffected by this addition. It the difference in crystal size and nature of solvent used for
has been inferred that the POM acts as nucleation sites and crystallization.
stabilizes the precursor MOF-235 phase that aggregates rapidly.
When the crystallization of Al
MIL-101
NH2 begins, such
agglomerates separate and finally the POM nuclei are encapsu- 4. ALTERNATIVE SYNTHESIS ROUTES
lated in the cages of Al
MIL-101
NH2. Chemical reactions require some form of input of energy, and
Static light scattering (SLS) measurements were used to only at temperatures close to 0 K do reactions stop. As described
monitor the crystal growth of HKUST-1 from a supersaturated in the previous sections, normally MOF syntheses take place in a
solution at room temperature.85 After a reaction time of 10 min, solvent and at temperatures ranging from room temperature to
the particle mass continued to increase linearly, but there was no approximately 250 °C. The energy is generally introduced using
further increase of the particle size. It has been concluded that the conventional electric heating, i.e., heat is transferred from a hot
nucleation is slow and continues while the particles grow fast (i.e., source, the oven, through convection. Alternatively, energy can
nucleation-controlled reaction). In a similar in situ SLS study on also be introduced through other means, for example by an
the crystallization process of MOF-5,86 the same group observed electric potential, electromagnetic radiation, mechanical waves
that both mass and size of the particles continued to increase (ultrasound), or mechanically.91 The energy source is closely
until precipitation took place. For MOF-5, the reaction is not related to the duration, pressure, and energy per molecule that
nucleation-controlled; the nucleation being faster compared to is introduced into a system,92 and each of these parameters
successive crystal growth. The particle size of MOF-5 was can have a strong influence on the product formed and its
adjusted by using p-perfluoromethylbenzoic acid as a capping morphology.
agent. Monodentate ligands, such as sodium formate, 1-methy- Why is it important to use different synthesis methods?
limidazole, or n-butylamine, were successfully employed as Obviously, different methods can lead to new compounds that
modulators to tune the size of ZIF-8 crystals in the range rom cannot be obtained otherwise. Furthermore, alternative routes
10 nm to 1 μm.87 The modulators acted as competitive ligands in can lead to compounds with different particle sizes and size
the coordination equilibria and bases in the deprotonation distributions as well as morphologies that can have an influence
equilibria during nucleation and crystal growth. Time-resolved on the material’s properties. For example, different particle sizes
in situ SLS investigations revealed that nanocrystal formation is in porous materials can influence the diffusion of guest mol-
characterized by continuous, comparatively slow nucleation and ecules, which has a direct impact on catalytic reactions or the
fast crystal growth. Focusing and defocusing of the particle size adsorption and separation of molecules. Small crystals may also
distribution was noticed at earlier and later stages of growth, be employed for the formation of membranes using a seeded
respectively. The growth of microcrystals took place by a growth procedure (section 6.2.3). Nanocrystalline, nontoxic
particle
monomer attachment mechanism, and a change of MOFs with high loading capacities are also envisioned for
crystal shape from cubes to rhombic dodecahedra occurred in biomedical application.93 For these objectives, sonochemical
later stages of growth. Indications for the occurrence of a and microwave-assisted methods have been applied. On the
coalescence mechanism during early stages of the growth were other hand, larger single crystals (in the 100 μm range) are
also obtained. necessary to routinely determine the structure and to establish
Surface plasmon resonance (SPR) spectroscopy was applied structure
property relationships.
to monitor the layer-by-layer growth of HKUST-1 thin films on Since many groups working in the field of MOFs envision their
OH- or COOH-terminated Au surface.88 Virtually no deposition commercial use, it is also important to establish facile, inexpen-
of MOF was detected when copper nitrate was used as a Cu2+ ion sive, rapid, and commercially viable routes. Fast reactions could
source. Using copper acetate, fast growth of the layer was lead to continuous syntheses, which are advantageous for large-
observed. This fact was rationalized considering that the scale production. Reducing reaction time and temperature would
[Cu2(CH3CO2)4(H2O)2] unit already contains the paddle- lead to more energy-efficient processes and less demanding
wheel structure and is more efficiently attached compared to synthesis equipment. Thus, a number of investigations have
the mononuclear Cu2+ species present in copper nitrate solution. recently been carried out to evaluate the influence of the
Atomic force microscopy measurements were also used to synthetic method on the formation of MOFs (section 3.2).
study the formation of HKUST-1. The step height on the {111} Crystallization rate, particle size, and sorption properties are just
facet of a HKUST-1 crystal should be multiples of 1.1 or 1.3 nm, a few variables that have been the focus of these studies.
if the crystal growth mechanism involves only attachment of the Comparison of these results show one problem in MOF science:
paddle wheel units. However, during the time-resolved in situ a very detailed characterization of all materials using comple-
AFM imaging using a ∼50 μm crystal, the measured heights were mentary characterization methods is mandatory, since already
not multiples of 1.1 or 1.3 nm, and many growth hillocks small changes in synthesis procedures can lead to compounds
exhibited steps of less than 1.1 nm.89 This suggests that the with immense diverging properties.94,95
actual growth species (possibly, solvated Cu2+ ions or BTC In the following sections, alternative synthesis routes are de-
units) are smaller than the expected inorganic brick. The crystal scribed where energy is introduced through microwave irradiation
941 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

Table 5. Summary of Studies Dealing with the Microwave-Assisted Synthesis of Porous MOFs
MOF comment ref

Metal(III)
Carboxylate-Based MOFs
Cr
MIL-100 first MW synthesis of MOFs 100
Fe
MIL-100 nanoscale particles; imaging and drug delivery 101
Cr
MIL-101 nanoscale particles; benzene sorption 102
nanoscale particles 103
Fe
MIL-101 nanoscale particles 104
Fe
MIL-101
NH2 nanoscale particles; imaging and drug delivery 104
nanoscale particles; imaging and drug delivery 101
Fe
MIL-88A CE, MW and US synthesis; nanoscale particles 105
Fe
MIL-53 CE, MW and US synthesis; ex-situ crystallization study 79
CAU-1 CE and MW synthesis; in situ crystallization study 81
V
dicarboxylates isoreticular frameworks with MIL-47 topology 106
growth on polyacrylonitrile 107
[Ce2(PYDC)2(HPYDC) (H2O)2]Cl lanthanide-based MOF 108
Metal(II)
Carboxylate-Based MOFs
IRMOF-n IRMOF-1 109
112
IRMOF-1; 32 statistical design used for synthesis optimization; 113
consecutive application of US and MW irradiation
IRMOF-1 film 114
IRMOF-1 membrane 115
IRMOF-2, -3 110
IRMOF-16-(OH)2; activation by supercritical CO2 116
MOF-177 CE, MW, and US synthesis 117
HKUST-1 systematic study of Cu
trimesates 118
comparison with other synthesis methods 119
kinetics of crystallization 120
activation by supercritical CO2 121
Ni
glutarates phase-selective and rapid crystallization 122
Ni
CPO-27 epoxidation catalysis 123
[M3(NDC)3(DMF)4] M = Co, Mn 124
[Mg2(BTEC)(H2O)4] single-crystal-to-single-crystal transformation; 125
selective gas sorption
[Cu2(OBA)2(DMF)2] dynamic framework 126
Azolate-Based MOFS
ZIF-7 and -8 ZIF-8 powder 127
ZIF-8 membrane 128
ZIF-7 membrane 129
[Co4O(BDPB)3] catalytic oxidation 130
[Zn5Cl4(BBTA)3] triazolate-based MOF; selective gas sorption 131
[Zn5Cl4(BTDD)3] triazolate-based MOF; hydrogen sorption 132
Mixed-Linker MOFs
[Zn2(NDC)2(DPNI)] selective gas sorption 133
[Ni2(BDC)2(DABCO)] 3 (DMF)4 3 (H2O)4 phase selectivity, polymorphs 68

(microwave-assisted synthesis, section 4.1), application of an electric as well as solution-based syntheses, for examples of zeolites9 and
potential (electrochemistry, section 4.2), mechanically (mechano- MOFs, have also been described. The latter has been recently
chemistry, section 4.3) or through ultrasound (sonochemistry, summarized in a perspective covering nonporous coordination
section 4.4). polymers as well as MOFs.99 Here, we present a short summary
of the work presented in ref 99 and focus on the most recent
4.1. Microwave-Assisted Synthesis examples.
Introduction of energy using microwave irradiation is a well- Microwave-assisted synthesis relies on the interaction of
established method in synthetic chemistry96 but has been mainly electromagnetic waves with mobile electric charges. These can
used in organic chemistry.97,98 Nevertheless, solid
solid reactions be polar solvent molecules/ions in a solution or electrons/ions in
942 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

a solid. In the solid, an electric current is formed and heating is crystallization study were carried out on Fe
MIL-5379 and CAU-
due to electric resistance of the solid. In solution, polar molecules 1
(OH)2,81 respectively. In both cases, MW irradiation resulted in
try to align themselves in an electromagnetic field and in an faster reaction rates compared to CE heating. Six isoreticular
oscillating field so that the molecules change their orientations V
dicarboxylates having MIL-47 topology were synthesized under
permanently. Thus, applying the appropriate frequency, collision similar MW conditions (200 °C, 10 min, VCl3 as metal salt).106
between the molecules will take place, which leads to an increase Later, the same group studied the direct growth of MIL-47 on
in kinetic energy, i.e., temperature, of the system. Due to the polyacrylonitrile as a function of MW irradiation time.107 In contrast
direct interaction of the radiation with the solution/reactants, to the above-mentioned studies on nanocrystals, X-ray quality
MW-assisted heating presents a very energy efficient method of single-crystals of [Ce2(PYDC)2(HPYDC)(H2O)2]Cl were ob-
heating. Thus, high heating rates and homogeneous heating tained in 20 min at 200 °C by applying MW irradiation.108
throughout the sample is possible. Attention must be paid to A wide variety of metal(II)
carboxylate-based MOFs were
the choice of appropriate solvents and selective energy input, synthesized by applying MW irradiation. IRMOF-1 and HKUST-1
since starting materials may strongly interact with the MW are among the most studied materials. In the earliest study, cubic
radiation. microcrystals of IRMOF-1 with the length of 2
4 μm were
Microwave ovens suited for materials syntheses allow one to obtained in 9 min at 95 °C in 27% yield.109 In another report, both
monitor temperature and pressure during the reaction and thus size and regularity of the cubic microcrystals (4 ( 1 μm) of IRMOF-1
allow a more precise control of reaction conditions. Nevertheless, decreased up to 1 μm with reducing the concentration of H2BDC
transfer of the syntheses to MW ovens from different vendors is in the starting solution.110 The size of the microcrystals did not
often critical, since these differ in their specifications. MW- change remarkably when the reaction time was varied from 25 s to 1
assisted MOF syntheses have mainly focused on (1) the accel- min. The MW synthesis of the microcrystals of IRMOF-2 and -3
eration of crystallization and (2) the formation of nanoscale was also described, but the adjustment of crystal size was demon-
products, but it has been also used (3) to improve product purity strated only for IRMOF-1. In a recent report on IRMOF-1, the
and (4) for selective synthesis of polymorphs. This is due to the MW-assisted method yielded higher quality crystals with better CO2
direct heating of the solvents and the higher nucleation rate that adsorption properties, compared to the ambient pressure dynamic
have been observed. Table 5 summarizes the investigations that CE synthesis.112 A ramped-temperature MW synthesis led to
deal with MW-assisted synthesis of MOFs. crystals with higher crystallinity compared to a constant temperature
MW-assisted synthesis of MOFs has often been carried out at experiment. In a systematic study on microscale IRMOF-1 (20
25
a temperature above 100 °C with reaction times rarely exceeding μm), the increase in MW irradiation time, power level, and
1 h. Only a few reports describe the systematic variation of concentration of the substrates beyond an optimal condition led
compositional and process parameters (solvent, irradiation time, to a reduction in synthesis time at the expense of crystal quality.111 In
reaction temperature, power level, molar ratio of the reactants, another work, uniform IRMOF-1 microcrystals (5
15 μm) were
reactant concentration, etc.) in order to optimize the reaction synthesized by applying a consecutive combination of US and MW
conditions. In general, MW irradiation allows faster synthesis of irradiation.113 This combined two-step technique resulted in smaller
smaller crystals compared to CE heating. and more regularly shaped crystals, compared to CE synthesis. Thin
Several metal(III) carboxylate-based MOFs (M = Fe, Al, Cr, films and membranes of IRMOF-1 were also deposited on porous
V, Ce) have been prepared by MW-assisted synthesis route. The alumina by using MW irradiation.114,115 Oriented but poorly
first MW synthesis of MOFs dealt with Cr
MIL-100.100 The intergrown films of IRMOF-1 crystals were grown on graphite-
compound was synthesized in 4 h at 220 °C under MW coated alumina by the direct growth method.114 In another study,
irradiation with 44% yield, which is comparable with that of continuous and ordered membranes of IRMOF-1 were deposited
CE synthesis. The analogous Fe compound was prepared in 30 on α-alumina by employing the crystals produced by direct growth
min at 200 °C.101 The MW-assisted synthesis of nanoscale as seeds for secondary growth.115 In the MW synthesis of microscale
Cr
MIL-101 was demonstrated in two reports.102,103 In the IRMOF-16
(OH)2 (20 μm), the crystal quality as well as porosity
earlier report, the dimensions of the nanoparticles increased from of the material improved with an increase in irradiation time.116 The
40
80 to 70
90 nm and became more homogeneous in size effect of the heating method was investigated for the synthesis of
with increasing reaction time.102 In the later report, the use of HF microscale MOF-177 (5
50 μm).117 Both crystallinity and poros-
was avoided, and nanocrystals of Cr
MIL-101 with sizes of ity of the material prepared by MW irradiation were inferior to those
∼50 nm in 37% yield were obtained by lowering the reactant obtained by US and CE synthesis. The MW synthesis of HKUST-1
concentration or increasing the pH of the reaction mixture.103 was systematically investigated in four reports, and the results were
However, the particle size was not affected by the reaction time. compared with other synthesis methods.118
121 In the first report
Nanocrystals of Fe
MIL-101 having an average diameter of on HKUST-1, the results of MW and CE syntheses were
∼200 nm were synthesized by using DMF as the solvent at compared.118 MW-assisted heating was found to be the method
150 °C in 10 min.104 The formation of nanocrystals of amino- of choice to rapidly synthesize HKUST-1 crystals in the range of
functionalized Fe
MIL-101 was investigated in two reports.101,104 10
20 μm in high yields (∼90%) within 1 h. The crystal size
In the first report,104 only small amounts of BDC
NH2 were increased with MW irradiation time and reactant concentration. In
incorporated in the mixed-linker nanocrystals synthesized in DMF the second report on HKUST-1, the compound was obtained using
at 150 °C in 10 min. In the later report,101 octahedral nanocrystals six different synthetic routes (static and dynamic CE, MW, US, EC,
of 173 ( 60 nm containing exclusively BDC
NH2 were prepared and MC conditions).119 The results show that MW-assisted synth-
in water at 60 °C in 5 min. In a systematic study showing the effect esis is the best method to produce crystalline HKUST-1 in a short
of compositional and process parameters on nanoscale Fe
MIL- time (30 min) associated with high purity, high micropore volume
88A formation, only MW-assisted hydrothermal synthesis ensured (0.79 cm3 g
1), and quantitative yield. In the third report on
the fast synthesis of small (<100 nm) and monodispersed nano- HKUST-1, the crystallization kinetics was investigated by ex situ
particles with high yields.105 An ex situ and a time-resolved in situ XRPD measurements.120 A comparison between MW and CE
943 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

Table 6. Summary of Studies Dealing with the Electrochemical Synthesis of Porous MOFs
MOF comment ref

Zn
and Cu
carboxylates patent; first electrochemical synthesis; systematic investigation of Zn, Cu, Mg, Co 56
as anode materials and 1,3,5-H3BTC, 1,2,3-H3BTC, H2BDC, and H2BDC-(OH)2 as linkers
Zn
imidazolates patent; synthesis of [Zn(MIm)2] and [Zn(BIm)2] 134
HKUST-1 synthesis; gas purification, storage and separation 52
comparison with other synthesis methods 119
synthesis; isobutene
isobutane separation 135
patterned film growth 136
patterned film growth by galvanic displacement 137

synthesis suggests that the acceleration in MW synthesis is due to a In another work, one of the polymorphs of the pillared
layered
highly increased pre-exponential factor of the Arrhenius equation [Ni2(BDC)2(DABCO)] framework was synthesized by employing
rather than decreased activation energy. In the fourth report on a high-throughput MW-assisted method.68 A combination of MW
HKUST-1, MW irradiation led to an increase in the porosity of the irradiation, low overall concentration, stirring of the reaction mix-
material compared to CE heating.121 The influence of pH, reaction tures, and an excess of DABCO yielded the phase-pure polymorph
temperature, and heating method was investigated for the synthesis of [Ni2(BDC)2(DABCO)] 3 (DMF)4 3 (H2O)4.
two Ni-glutarates. The formation of the cubic phase [Ni20(GLU)20-
(H2O)8] occurred at low pH, low temperature, and especially under 4.2. Electrochemical Synthesis
CE heating. In contrast, the tetragonal phase [Ni22(GLU)20(OH)4- The electrochemical synthesis of MOFs was first reported in
(H2O)10] was formed at high pH, high temperature, and especially 2005 by researchers at BASF.56 Their main objective was the
with MW irradiation.122 In the MW synthesis of Ni
CPO-27, the exclusion of anions, such as nitrate, perchlorate, or chloride,
effect of irradiation time and reaction temperature on the porosity and during the syntheses, which are of concern to large-scale produc-
morphology of the compound was investigated.123 The crystallinity as tion processes. Rather than using metal salts, the metal ions are
well as the porosity of the material decreased with an increase in continuously introduced through anodic dissolution to the
reaction temperature. However, the variation of reaction temperature reaction medium, which contains the dissolved linker molecules
(90
130 °C) or irradiation time (2
60 min) had negligible effect and a conducting salt. The metal deposition on the cathode is
on the crystal size (22
28 nm). In a study on [M3(NDC)3(DMF)4] avoided by using protic solvents, but in the process H2 is formed.
(M = Co, Mn), MW irradiation led to 5
20 μm sized crystals with a Another option is the use of compounds such as acrylonitrile,
narrow size distribution, whereas CE heating resulted in 50
200 μm acrylic, or maleic esters that are preferentially reduced. Other
sized single-crystals.124 In contrast to the above-mentioned reports on advantages of the electrochemical route for industrial process are
micro- or nanosized crystals, single-crystals of [Mg2(BTEC)- the possibility to run a continuous process and the possibility to
(H2O)4]125 and [Cu2(OBA)2(DMF)2]126 were obtained under obtain a higher solids content compared to normal batch
MW irradiation. Whereas a phase-pure synthesis of the former reactions. Studies dealing with the electrochemical synthesis of
required a careful adjustment of pH or reaction temperature, the porous MOFs are listed in Table 6.
latter could only be obtained in multistep MW irradiation mode. To date the electrochemical formation of microcrystalline
The MW-assisted synthesis of azolate-based MOFs has been powders and films was reported. Researchers from BASF have
described in only a few reports. Rhombic dodecahedral shaped performed the pioneering work and have established synthesis
crystals (∼20 μm) of the imidazolate-based ZIF-8 were synthesized procedures for some Cu- and Zn-based MOFs.56 In their study
at 140 °C in 4 h.127 The ZIF-8 crystals obtained by MW irradiation various combinations of anode materials (Zn, Cu, Mg, Co) and
showed a larger specific surface area compared to the material linkers [1,3,5-H3BTC, 1,2,3-H3BTC, H2BDC, and H2BDC

synthesized under CE heating. Membranes on ZIF-7 and -8 were (OH)2] as well as different experimental setups were reported,
also prepared by using MW radiation. In a report of ZIF-8, a dense, which also allowed the up-scaling of the syntheses. From these
crack-free membrane was deposited on bare titania using the direct combinations, four Cu- or Zn-containing compounds with high
growth method.128 In another report, high-quality membrane of porosity were obtained. The HKUST-1 product was tested for its
ZIF-7 was grown on α-alumina by a secondary growth technique.129 use in gas purification, i.e., removal of tetrahydrothiophene from
In order to produce a seed layer prior to secondary growth, natural gas, H2 storage, and the separation of Kr
Xe mixtures.52
α-alumina was dip-coated with dispersions containing presynthe- This work was further extended to the chemistry of ZIFs.134
sized nanocrystals and PEI. The pyrazolate-based compound Synthesis procedures were reported that led to the formation of
[Co4O(BDPB)3] was synthesized at 155 °C in 2 min under MW [Zn(MIm)2] and [Zn(BIm)2] showing specific surfaces of 1746
radiation.130 The small, uniform crystals synthesized by MW and 465 m2 g
1, respectively. Studies by other groups have
irradiation exhibited higher catalytic activity in cyclohexene oxida- exclusively focused on the electrochemical synthesis of HKUST-1.
tion, compared to the material obtained by CE heating. The MW In a comparative study on the influence of the synthesis
synthesis of two triazolate-based MOFs, [Zn5Cl4(BBTA)3]131 and procedure on the properties of HKUST-1, the compound was
[Zn5Cl4(BTDD)3],132 was accomplished at 155 °C in 10 and 30 synthesized using solvothermal, ambient pressure, and electro-
min, respectively. chemical routes in pure ethanol and ethanol/water mixtures.119
Two mixed-linker MOFs were synthesized under MW irradiation. Although XRPD investigations demonstrated that in all cases
The microwave sample of [Zn2(NDC)2(DPNI)] shows slightly HKUST-1 was formed, TG experiments, elemental analyses,
lower capacity for CO2 and CH4 compared to the sample prepared and sorption experiments showed the inferior quality of the
by CE heating, but it has much higher selectivity of CO2 over CH4.133 electrochemically synthesized product. This was explained by
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Table 7. Summary of Studies Dealing with the Mechanochemical Synthesis of Porous MOFs
MOF comment ref

Carboxylate-Based MOFs
[Cu(INA)2] first report; solvent-free synthesis; known phase 144
[Cu(INA)2]; HKUST-1 array approach: 12 metal salts and five organic linkers; 145
solvent-free synthesis, known and unknown phases
HKUST-1 formation and properties 146
evaluation of competitive formation of Cu-BTC phases 119
yields and properties 147
H2 storage 148
MOF-14 yields and properties 147
[Ln(BTC)(H2O)] homo- and hetero-Ln MOFs (Ln = Y, Sm, Gd, Tb, Dy, Er, Yb) 149

Imidazolate-Based MOFs
[Zn(EIm)2] dense and porous ZIFs; ILAG; ZnO as starting material; metal salts as 150
structure-directing agents
[Co3Cl6(L0 )2] tripodal imidazole frameworks; manual grinding 151
Mixed-Linker, Pillared-Layered MOFs
[Zn2(FMA)2(BPY)]; [Zn2(FMA)2(BPE)] ZnO as starting material; LAG 152
[Zn2(FMA)2(BPY)] varying amount of AcOH and H2O in the pores; solvent-free grinding 153
[Zn2(BDC)2(BPY)]; [Zn2(BDC)2(DABCO)] ZnO as starting material; LAG of Zn terephthalates with BPY or DABCO 154
[Zn2(BDC)2(DABCO)] ZnO as starting material; ILAG; polymorphs; salt inclusion; anion as structure-directing agent; 155
additives enhance MOF formation

the incorporation of linker molecules and/or the conducting salt lists all the reports on MOFs obtained by mechanically activated
in the pores during crystallization. synthesis.
The formation of films and patterned coatings of HKUST-1 The interest in mechanically activated MOF synthesis is due to
has also been reported.136 Careful adjustment of the reaction multiple reasons. One important point is environmental issues.
conditions allowed the growth of films in the range of 2
50 μm. Reactions can be carried out at room temperature under solvent-
By extending the reaction time, self-completing growth of uni- free conditions, which is especially advantageous when organic
form HKUST-1 films was demonstrated. The method was solvents can be avoided.141 Short reaction times, normally in the
extended to Cu-patterned substrates and a Cu-coated QCMB range of 10
60 min, can lead to quantitative yields, and generally
sensor. The latter was shown to be suitable to monitor the products containing small particles are obtained. Moreover, in
adsorption of water vapor. Patterned growth by anodic oxidation some cases metal salts can be replaced by metal oxides as a
is only possible if continuous electrical contact of the complete starting material, which results in the formation of water as the
metallic pattern to the power source must be guaranteed. An only side product. For example, ZnO has recently been shown to
alternative method based on a galvanic replacement reaction was be suitable for the synthesis of pillared
layered MOFs and
reported for the patterned growth of HKUST-1 on glass ZIFs.152,154,155 In contrast, metal oxides are rarely used in
slides.137 A pattern of metallic Cu was deposited on a glass solvent-based reactions due to their low solubility.
substrate. Spin-coating of a reaction solution containing H3BTC, First studies were performed under solvent-free conditions.144,145
DMSO, and AgNO3 led to the oxidation of Cu by the Ag+ ions. The use of organic reactants with a low melting point and hydrated
Evaporation of the solvent resulted in the formation of dense metal salts, preferentially the ones containing basic anions, were
films of small intergrown octahedral crystallites with sizes shown to be advantageous. Thus, well-crystalline compounds were
between 100 and 200 nm. Sonication of the coated substrates
obtained using metal acetates or carbonates. As a result, acetic acid is
did not lead to a significant loss of crystallites, which demon-
often observed as the byproduct that is present in the pores, but it
strates the strong adherence of the crystals.
can easily be removed by thermal activation. The addition of minute
4.3. Mechanochemical Synthesis amounts of solvents, the so-called liquid-assisted grinding (LAG),
Mechanical force can induce many physical phenomena has been shown to have profound advantages.152 It leads to the
(mechanophysics) as well as chemical reactions.138 In mechano- acceleration of mechanochemical reactions, which is probably due
chemical synthesis, the mechanical breakage of intramolecular to an increase of mobility of the reactants on the molecular level.
bonds followed by a chemical transformation takes place. Me- At the same time, the liquid can exert structure-directing proper-
chanochemistry has a long history in synthetic chemistry139 and ties. Recently, the extension of the method to ion- and liquid-
it has recently been employed in multicomponent (ternary and assisted grinding (ILAG) was demonstrated to be highly efficient
higher) reactions to form pharmaceutically active cocrystals and for the selective construction of pillared
layered MOFs, and it
in inorganic solid-state chemistry, organic synthesis, and polymer was shown that the ions as well as solvents exert a structure-
science, just to name a few.140
142 Its use for the synthesis of directing effect.150,155
porous MOFs was first reported in 2006144 and results of selected The following paragraphs summarize the results on mechno-
mechanochemial studies were summarized recently.143 Table 7 chemical synthesis reported so far. The first investigation dealt
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with the solvent-free grinding of Cu(OAc)2 3 H2O and isonico- influence on the phase formation, and the results illustrate that
tinic acid.144 Treatment of the starting materials for 10 min in a ILAG assists the construction of porous as well as nonporous
20 mL steel reactor containing a steel ball led to a highly materials. By variation of the reaction time, the time-dependent
crystalline and single-phase product of [Cu(INA)2] with acetic ZIF transformation was demonstrated. Thus, short reaction
acid and water molecules in the pores.144 These can be removed times led to a more open structure, which was stepwise trans-
by thermal activation to yield the guest-free porous compound. formed to finally yield the Zn imidazolate with qtz topology. In
Interestingly, the grinding was only required to initiate the addition to this detailed study, another paper reports the
reaction. As proven by XRPD experiments, a sample that was mechanochemical formation of a MOF containing a tripodal
ground for just 1 min yielded in the course of 6 h a single-phase imidazole linker.151 The focus of the work is on the solvothermal
product. The same group also reported a systematic study on synthesis, but by using a pestle and mortar one of the porous
solvent-free mechanochemical syntheses using 60 mixtures be- compounds was also obtained.
tween 12 metal salts (Ni, Cu, or Zn with various counterions) Zn-based, mixed-linker MOFs with the composition [M2(di-
and five carboxylate-based organic linker molecules.145 On the carboxylate)2(diamine)] exhibit pillared
layered structures, i.e., 2D
basis of XRPD results, 38 mixtures resulted in crystalline metal carboxylate sheets containing inorganic paddle wheel units are
products, and 29 reactions were quantitative. Two porous pillared by ditopic amines.24,73 LAG of ZnO, fumaric acid, BPY, or
compounds ([Cu(INA)2] and HKUST-1) as well as other BPE in the presence of DMF, methanol, ethanol, or 2-propanol
known and previously unknown coordination polymers were yielded the corresponding pillared
layered structures.152 Starting
obtained. Due to the large amount of data, the reaction trends from a mixture of zinc acetate, fumaric acid, and BPY, the synthesis
mentioned in the previous paragraph could be established. was repeated in the absence of a solvent, and the interpenetrated
The mechanochemical synthesis of HKUST-1 has also been structure was refined using Rietveld methods.153 The product
studied in detail. Five publications deal with the formation and contains varying amounts of disordered acetic acid and water
properties of the resulting products.119,145
148 Starting from a molecules in the pores, which can be thermally removed.
stoichiometric ratio of Cu2+ to H3BTC (3:2), solvent-free The reactivity of MOFs under mechanochemical reaction con-
grinding as well as LAG resulted in the desired product. Cu ditions has also been investigated.154 Thus, the mechanochemical
salts, grinding conditions (time and frequency), presence/ab- synthesis and grinding-induced transformation of three different
sence of a solvent, and nature of the solvent (DMF, methanol, nonporous solvated Zn terephthalates were demonstrated, showing
H2O/ethanol) were studied. Copper acetate was shown to be the the lability of the compounds under grinding conditions. These
starting material of choice and LAG led to better crystalline compounds were also used as starting materials to synthesize
products with better sorption properties. The pores of the pillared
layered MOFs through the reaction with BPY or DABCO.
products contain residual reactants and/or acetic acid and water Direct mechanochemical synthesis starting from ZnO or Zn5-
molecules, which was proven by TG and TG
MS measure- (CO3)2(OH)6 or direct immersion of the nonporous Zn terephtha-
ments as well as spectroscopic methods. The guest molecules lates in a solvent containing DABCO or BPY were generally not
could be removed by washing followed by thermal treatment, but successful. Surprisingly, the formation of two pseudopolymorphs of
thermal treatment alone led only to small specific surface areas pillared
layered compounds in the system ZnO/H2BDC/DABCO/
(SBET). Thus, the SBET values differ substantially for the opti- DMF was observed upon addition of several weight percent of
mized products of the different studies (739,148 1364,146 1421,119 alkaline metal nitrate or ammonium nitrate.155 In addition to the
and 1713147 m2 g
1). Interestingly, the products obtained by acceleration of the reaction, a structure-directing effect was observed
short grinding times exhibit mesoporosity,146,147 which was which is probably due to the salt inclusion within the MOF
proven by SAXS and sorption experiments. In one of the studies structure. Thus, the pillared
layered MOF based on a square
on HKUST-1, the BTC linker was replaced by the extended BTB grid was preferentially obtained using KNO3, NH4NO3, Na2SO4.
linker and the Cu carboxylate denoted as MOF-14 was also (NH4)2SO4, or K2SO4, giving quantitatively a pillared
layered
obtained by ball milling.147 MOF based on a hexagonal (Kagome) grid.
LAG of mixtures of H3BTC with seven rare-earth carbonates
in the presence of DMF gave a series of isostructural products 4.4. Sonochemical Synthesis
with the composition [Ln(BTC)(H2O)] (Ln = Y, Sm, Gd, Tb, Sonochemistry deals with the chemistry that takes place
Dy, Er, Yb), which have previously also been obtained from upon application of high-energy ultrasound to a reaction
solvothermal reactions.149 Activation using methanol followed mixture. Fundamental principles of sonochemistry and its
by thermal treatment led to porous structures. Switching the use for the synthesis of nanomaterials can be found, for
solvent from DMF to water resulted in the formation of a example, in refs 156 and 157, but a basic summary is presented
nonporous coordination polymer, while changing the starting in the following paragraphs.
material from the rare-earth carboxylates to the oxides and Ultrasound is cyclic mechanical vibration with a frequency
acetates led to new, so far unidentified phases. between 20 kHz, the upper limit of human hearing, and 10 MHz.
Imidazolate-based compounds have also been synthesized by Since the wavelength is much larger than molecular dimensions, no
mechnochemical synthesis.150,151 While the reaction of HIm direct interaction between ultrasound and molecules can be re-
with ZnO or ZnCl2 led only to nonporous Zn(Im)2, LAG of ZnO sponsible for chemical reactions, but when high-energy ultrasound
in the presence of DMF was shown to yield quantitatively ZIF-4 interacts with liquids, cyclic alternating areas of compression (high
and ZIF-8 in the presence of HIm and HMIm, respectively.150 pressure) and rarefaction (low pressure) are formed. In the low-
Since ILAG had been shown to accelerate the formation and pressure region, the pressure drops below the vapor pressure of
direct the phase formation,155 various combinations ZnO/RIm/ the solvent and/or the reactants and small bubbles, i.e. cavities,
solvent/ammonium salts were investigated (RIm = HIm, HMIm are formed. The bubbles grow (tens of micrometers) under the
and HEIm). The synthesis of ZIFs was facilitated in the presence alternating pressure through the diffusion of solute vapor into the
of the ammonium ions. All components were shown to have an volume of the bubble. Thus, ultrasonic energy is accumulated. Once
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Table 8. Summary of Studies Dealing with the Sonochemical Synthesis of Porous MOFs
MOF comment ref

Ditopic Linker
MOF-5 variation of reaction time and temperature as well as power level 159
32 statistical design used for synthesis optimization; consecutive application of US and MW irradiation 113
IRMOF-9 and -10 control of catenation and its effect on CO2 adsorption; role of power level in US synthesis 160
Fe
MIL-53 crystallization kinetics using CE, MW, and US methods; combination of MW 79
and CE heating for nucleation/crystal growth; temperature control; variation of power level
Fe
MIL-88A nanoparticles; flexible porous MOF; CE, MW, and US synthesis 105
Tritopic Linker
[Zn3(BTC)2] synthesis of nanoparticles; selective sensing of organoamines 161
HKUST-1 time-dependent formation in DMF/ethanol/water mixture 162
rapid room temperature synthesis; amount of DMF determines nature and morphology of reaction product 163
competitive formation with [Cu2(BTC)(OH)(H2O)] using six synthesis methods 119
[Ln(BTC)(H2O)] (Ln = Ce, Tb, Y) short reaction time; particle size; luminescence 78
MOF-177 comparison among CE, MW, and US syntheses; short reaction time; high yield; 117
small particles; improved sorption properties
PCN-6 and -60 control of catenation and its effect on CO2 adsorption; role of power level in US synthesis 160

the bubbles reach their maximum size, they become unstable and are often obtained by sonochemical syntheses, were also anticipated
collapse. This process of bubble formation, growth, and collapse is to be of advantage for their application. Systematic studies were
called cavitation and it leads to the rapid release of energy with carried out focusing on the role of reaction time and temperature,
heating and cooling rates of >1010 K s
1, temperatures of ∼5000 K, power level, and solvent. Short reaction times at ambient pressure
and pressures of ∼1000 bar. Thus, these “hot spots” present rather were reported to lead to high yields of the desired product.
unusual conditions of short duration of extremely high temperature Nevertheless, comparisons of the results must be regarded with
and pressures inside the collapsing bubble as well as in its vicinity caution due to the following reasons. The different studies were
(ring of ∼200 nm). At a little larger distance, intense shear forces are carried out using different equipment, i.e., ultrasonic cleaning baths
observed. There are a large number of parameters that govern the that have normally lower power intensities or direct immersion of
formation of cavities and the intensity of their collapse, and only a high power ultrasonic horns. In addition, reaction setups differ and
fraction of the input energy is transformed into cavitation. In sometimes they were not even reported. This is critical since the
addition to the acoustic frequency and intensity (based on the power introduced into the reaction system will strongly depend on
equipment used), parameters such as the choice of liquid (vapor the detailed setup. Some authors claim that room temperature
pressure, viscosity, and chemical reactivity), the temperature, or the syntheses were carried out. This may be true at the start of the
gas atmosphere play an important role. Volatile organic solvents are reaction, but depending on the equipment used, a larger or smaller
often not an effective medium for sonochemistry because the high increase of temperature will occur in the reaction mixture. While in
vapor pressure reduces the intensity of cavitational collapse and some cases the reaction temperature was monitored or even
hence the resulting temperatures and pressures.91 regulated by external cooling, in other cases the reaction tempera-
In the case of a solid surface in its vicinity, cavitation leads to ture was not measured at all. The comparison of results obtained by
the formation of microjets which clean, erode, or activate the sonochemistry or by other synthetic methods was also frequently
surface. Agglomerations of smaller particles are dispersed. In a reported. In some studies, the comparison is not valid, since
homogeneous liquid, chemical reactions can take place within optimized sonochemically synthesized products were compared
the cavity (extreme conditions) at the interface (intermediate to nonoptimized conventionally synthesized products. In addition,
temperatures and pressures) or in the bulk media, where intense the formation of nanoparticles is claimed in some of the papers, but
shear forces are present. The extreme conditions and intense the results were only supported by a few TEM micrographs. To
shear forces (see mechanochemistry) can lead to the formation prove the formation of nanoparticles, additional characterization
of molecules in an excited state, bond breakage, and the forma- methods such as light-scattering techniques must be employed, as
tion of radicals that will further react. At the same time, nicely shown in the study of MIL-88A.105
ultrasonication will improve dissolution of the starting materials. Only a few studies are exclusively concerned with the sono-
Sonochemistry has been extensively used in organic synthesis158 chemical synthesis of MOFs, but the results are mostly compared
and the synthesis of nanomaterials.156 Starting in 2008, it was also with others obtained by MW-assisted, electrochemical, mechano-
applied to the investigation of MOFs but it is still largely chemical, or conventional synthesis. It is striking that up to now
unexplored. Table 8 summarizes the studies undertaken for the only known MOF structures have been sonochemically synthe-
sonochemical synthesis of MOFs. sized and that these compounds (e.g., MOF-5,38 MOF-177,38
The primary goal of sonochemical synthesis in MOF science was HKUST-1119) can also be obtained under mild conditions or
to find a fast, energy-efficient, environmentally friendly, room- even at room temperature.
temperature method that can easily be carried out. This is of special The first sonochemical investigations dealt with the synthesis
interest for their future application, since fast reactions could allow of Zn carboxylates.161 [Zn3(BTC)2] was obtained from an
the scaleup of MOFs. In addition, nanocrystalline particles, which aqueous solution of zinc acetate and H3BTC in a mixture of
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ethanol and water at room temperature in an ultrasonic bath. The and 40 °C to yield well-crystalline particles in the 2
3 μm range.
only variable investigated was the reaction time. Compared to the On the basis of N2 sorption experiments, these compounds also
solvothermal synthesis, which was carried out at 140 °C for 24 h, showed improved physical properties. Interestingly, the synthesis
milder reaction conditions and faster reactions were reported. rates for the three isostrucutral compounds differ substantially.
However, optimization of the solvothermal synthesis to shorten The crystallization kinetics was established, and the nucleation
reaction time or reduce reaction temperature was not tested. The and crystal growth rate were shown to correlate with the lability
size and morphology of the reaction product varied with reaction of the metal ions.
time. Short reactions led to spherical particles in the 100
200 nm The use of the tritopic extended linker H3BTB in sonochem-
range, while reactions for 30 and 90 min resulted in long needles ical synthesis was described in the synthesis of the well-known
with a diameter of up to 900 nm. Zn-based compound MOF-177.117 Using NMP as the solvent, a
High-quality MOF-5 crystals in the 5
25 μm range were high yield (95.6%) of 5
50 μm-sized crystals was obtained
obtained within 30 min in a horn-type reactor using NMP as the within 40 min. Sonication time and power level were shown to
solvent.159 Starting from a clear solution, the reaction time and have a strong influence on the product properties, and optimiza-
power level were varied. After 8
30 min, the product formed and tion of these parameters led to high-quality crystals matching the
the temperature was measured to be between 129 and 164 °C, highest reported SBET values for MOF-177.
depending on the power applied. At low power levels, phase- In a comprehensive kinetic study on the synthesis of Fe
MIL-
impure samples were observed. Reaction times above 10 min and 53, sonochemical reactions were carried out at various tempera-
working at higher power levels led to the deterioration of the tures using an ultrasonic horn. The temperature was kept
previously formed samples. Detailed characterization and com- constant and the reaction time was varied to investigate the
parison with a conventionally synthesized sample showed almost crystallization process. High crystallization rates were observed.
identical physical properties. In a more recent report on MOF-5, Unexpectedly, the crystal size was found to be almost indepen-
a very similar study was undertaken in DMF as the solvent, dent of reaction time or temperature, but dependent on the
starting again from clear solutions.113 A temperature-regulated synthesis method (CE, US, MW). Thus, small, well-shaped
ultrasonic bath and microwave-assisted heating were consecu- crystals with homogeneous morphologies were observed for
tively used in a two-step process. Reactions were carried out at the sonochemically synthesized compound.
different temperatures for varying reaction times. Products with a Several synthetic routes were investigated for the synthesis of
narrow size distribution containing small particles (5 μm) could Fe
MIL-88A with the goal to obtain monodisperse nanoparti-
be obtained. However, the best samples were inferior to the ones cles in a high yield. The study uses a number of characterization
obtained by using NMP as the solvent and ultrasonication methods to determine the particle size and polydispersity, such as
exclusively. TEM, SEM, and dynamic light scattering. Different parameters,
Three studies were reported on the synthesis of HKUST- such as temperature (0, 20, and 50 °C), time (0.5, 1, 1.5, and 2 h),
1.119,162,163 The first report investigated the influence of re- concentration, and pH (addition of acetic acid or NaOH), were
action time starting from copper acetate and H3BTC in a evaluated, and an ultrasonic bath was used. Unfortunately, no
mixed-solution of DMF/EtOH/H2O.162 Using an ultrasonic information about the power input was given. The systematic
bath and varying the reaction time, the desired product was study shows that the particle size increases as a function of
obtained already after 5 min as a nanocrystalline (10
40 nm) concentration, reaction time, and temperature and that the
powder. Increasing the reaction time led to larger crystals crystallization rate increases with pH. Thus, by working at
(50
200 nm) and higher yields, but long reaction times resulted 0 °C, adding acetic acid, and using dilute conditions, mono-
in their partial decomposition. Only blurred TEM micrographs disperse small particles (<200 nm) were obtained. Unfortu-
give a hint about the sizes and size distribution of the particles, nately, the yield was lower than 5%.
which seem not to contain well-shaped crystals. Another study The most recent article demonstrates the unexpected influ-
confirms these findings.163 Using the same starting materials and ence of the ultrasonic power level on the product formation.160
the three solvents, the amount of DMF was increased stepwise Two examples of interpenetrated and noninterpenetrated struc-
and the reaction time was varied. In contrast to conventional and tures, i.e., PCN-6/PCN-60 and IRMOF-9/IRMOF-10, are pre-
MW-assisted heating, DMF was necessary for the formation of sented. While at lower power levels the noninterpenetrated
HKUST-1. This was explained by a possible deprotonation of structure is obtained, intermediate power levels led to mixtures
H3BTC by DMF. After 1 min, a phase-pure and highly crystalline and higher power levels to phase-pure interpenetrated structure
product was obtained. Short reaction times led to smaller and of the corresponding MOF. For all four compounds, small, well-
more homogeneous products (200
400 nm) compared to long shaped particles were obtained (1.5
2 μm for PCN-60 , 4.5
6
reaction times, when agglomeration was observed. The concen- μm for PCN-6, and ∼5
20 μm for IRMOF-9 and -10).
tration of DMF was found to have a strong influence on the
physical properties of the product. In contrast to these studies,
the third report concerns the successful synthesis of HKUST in a 5. VARIOUS ASPECTS OF MOF SYNTHESIS
mixture of EtOH and H2O, while a product of poor quality is As mentioned in the Introduction, concepts from zeolite
formed in pure DMF.119 The physical measurements of all the chemistry were also used in MOF synthesis. Whereas struc-
optimized materials show that the specific surfaces (SBET) are ture-directing agents and mineralizers play an important role in
smaller (1100,162 1156,163 and 1253119 m2g
1) compared to the zeolite science, they have been less frequently used in the
best materials. In the another study using the BTC3‑ as the linker, synthesis of MOFs. On the other hand, approaches that are
the isostructural compounds [Ln(BTC)(H2O)] (Ln = Ce, Tb, based on coordination chemistry have been proven suitable for
Y) were synthesized.78 The Tb compound was previously the formation of MOFs. This includes the precursor route as well
obtained by conventional heating, but the reaction time and as the in situ linker synthesis. A phenomenon that is often
temperature could be significantly reduced to 20 min between 25 observed with MOF structures is catenation. On the basis of the
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reaction procedures, catenated and noncatenated MOFs can be synthesis in water led to a nonporous closed structure that could
sometimes selectively obtained. In the following sections, the use not be opened, while the synthesis in DMF as a solvent resulted
of solvents and structure-directing agents (section 5.1), minera- in the open-pore modification called DUT-4 that also showed no
lizers (section 5.2), precursors (section 5.3), as well as the in situ flexibility.171
linker synthesis (section 5.4) and the selective synthesis of Solvents can also act as ligands during the synthesis. In a study
catenation polymorphs (section 5.5) will be covered. on Zn benzobistriazolates, the variation of amide solvents (DMF
vs DMA) led to two structurally different MOFs.131 While the
5.1. Solvents and Structure-Directing Agents product synthesized in DMF could be activated to yield a porous
The solvent is one of the most important parameters in the structure, the synthesis in DMA yielded a product with DMA
synthesis of MOFs, which has been investigated to a lesser extent coordinated to the metal ion. Removal of DMA led to the
in zeolite synthesis.63 Although most often no direct interaction decomposition of the structure. Similarly, the variation of amide
with the framework is observed, solvents are almost always solvents in the amide/water solvent mixtures resulted in two
incorporated in the as-synthesized MOF structures and thus similar yttrium
organic frameworks with different spatial ar-
act as space-filling molecules. Structure-directing agents (SDAs) rangement of the BTC linkers around the Y3+ centers and 1D
have been mostly used in the field of zeolite synthesis,164 where channels (along the a-axis), which are occupied by coordinated
they act as counterions for charge balance, as space-filling or occluded solvent molecules.172
molecules, or as “true” templates, in the case of well-defined Hydrolysis of the solvent has been observed especially in the case
host
guest interactions. SDAs have also been employed for the of organic amides under solvothermal conditions.173,174 In a study
preparation of porous MOFs, but it is often hard to identify the on the synthesis of MOF-5 and in another study, concerning the use
role of the solvent as pore-filling molecule (SDA) or as pure of ZnO in the synthesis of Zn terephthalates under acidic conditions,
reaction medium. hydrolysis of DEF led to the formation of diethylammonium ions,
One challenge in the use of organic structure-directing agents, which were, together with the solvent, incorporated in the final
such as amines and ammonium ions, is their removal/exchange structure (H2NEt2)2[Zn3(BDC)4] 3 3DEF. Thus, this compound
after the synthesis. This is due to strong host
guest interactions exhibits an anionic framework structure.
that lead to structural collapse upon removal of the guest The use of room temperature ionic liquids (ILs) or deep
molecules. Numerous examples of amine-templated compounds eutectic solvents (DESs), which can act both as a solvent and a
have been described, but most often the removal of the guest SDA, is called ionothermal synthesis.175,176 ILs are well-suitable
molecules was not reported.165
168 for the dissolution of the inorganic components required for the
5.1.1. Solvents. The influence of solvents on the product synthesis. The lack of a detectable vapor pressure of ILs is also an
formation has been addressed in few systematic studies. As advantage. A DES is a mixture of two or more compounds that
presented in section 3.1, high-throughput methods have been has a melting point lower than that of either of its constituents.
used to study the systems Fe3+/H2BDC
NH2/solvent and Al3+/ DESs exhibit also unusual solvent properties that are very similar
H2BDC
NH2/solvent.33,63 In both systems, the reaction to those exhibited by the ionic liquids. A number of coordination
medium has a profound impact on the product formation. This polymers have been obtained using ILs and DESs.175,176 Re-
was shown to be due to the polarity of the solvent and the cently, the group of Morris and Bu demonstrated that chirality
solubility of the organic linker and its protolysis properties. Thus, can be induced in the framework that is built up of nonchiral
in acetonitrile as well as in methanol, at low temperatures, only building blocks. Chiral ILs were used, but these were not
Fe
MIL-88B
NH2 was observed. With DMF only structures observed in the final structure.177
179 The removal of the ionic
based on the trimeric inorganic brick [Fe3(μ3-O)(O2C
R)6]+, component was not reported, but the authors expected the
i.e., Fe
MIL-88B
NH2 and Fe
MIL-101
NH2, were isolated, collapse of the frameworks upon removal of the guest molecules.
while the reaction in water led to Fe
MIL-53
NH2 in most of In relatively rare cases, the framework contains the neutral
the cases. The systematic investigation on the influence of component of the DES, the removal of which imparts porosity
different solvents on the analogous Al3+ system was carried to the material. Thus, though an increasing number of MOFs (all
out with aluminum nitrate and chloride.33 Aluminum nitrate of them are not cited here) has been synthesized so far under
led in all cases to the formation of Al
MIL-53
NH2 using ionothermal conditions, the permanent porosity of only one
DMF, methanol, and water as the solvent. The use of aluminum compound, a samarium terephthalate,180 was proven by sorption
chloride in DMF resulted in the formation of both Al
MIL- analysis.
53
NH2 and Al
MIL-101
NH2. The reactions performed in 5.1.2. Structure-Directing Agents. Space filling by un-
methanol yielded a completely new MOF denoted as CAU-1, reacted linker molecules in addition to the solvent is quite often
[Al4(OH)2(OCH3)4(BDC
NH2)3] 3 xH2O, in which the sol- observed in as-synthesized MOF products. Depending on the
vent acted also as a reactant. In a similar study, the effect of flexibility of the framework, the guest molecules can have a strong
solvent on the Cr3+/H3BTC/solvent system was demonstrated.169 influence on the pore dimension. Thus, M
MIL-53 (M = Fe, Al, Cr)
Cr
MIL-100 was obtained as a pure phase using water as a can switch reversibly from a narrow pore (NP) into a large pore (LP)
solvent. The addition of small amounts of methanol to the form with up to 60% variation of their unit cell volume without
aqueous synthesis mixture led to the coexistence of Cr
MIL- altering the framework topology.21,181,182 The Cr- and Al-based
100 and Cr
MIL-96. Use of more methanol resulted in the compounds show similar thermal and host
guest behavior. The
formation of phase-pure Cr
MIL-96. However, if water was as-synthesized (AS) materials contain guest terephthalic acid
omitted, Cr
MIL-96 with poor crystallinity was obtained. The molecules and adopt the LP form. Removal of the guest
influence of the solvent was also observed for isoreticluar molecules by thermal activation leads to the high-temperature
compound based on the MIL-53 topology, [Al(OH)(NDC)], form, which is identical to the LP form. Upon cooling down to
denoted as Al
MIL-69 or DUT-4.170 While MIL-53 exhibits a room temperature, the compounds adsorb water from air and
highly flexible structure, [Al(OH)(NDC)] is rigid. Thus, the transform into the NP form. In case of the M
MIL-88 and -89
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Chemical Reviews REVIEW

series (M = Fe, Cr), the ratio between the volumes of NP and LP not lead to a total decomposition of the crystal structure.192 The
forms can reach even more than 300%.183 use of H3PW12O40 as a template was also studied in the synthesis
Benzene was observed to act as a SDA in the synthesis of of Al
MIL-101
NH2.84 In-situ SAXS/WAXS measurements
pillared
layered MOFs. Depending on the presence or ab- demonstrated that the POM ions act as nucleation sites. They
sence of hydrophobic benzenze molecules in the hydrother- also stabilize the precursor phase Al
MOF-235
NH2, but this
mal reaction among Co2+ ion, H2NDC, and BPE, two different has almost no effect on the kinetics of the crystallization of
MOFs were obtained,184 in which the benzene-templated Al
MIL-101
NH2.
structure had larger pores and more favorable host
guest Surfactants and swelling agents have been used as SDAs, in
interactions than the nontemplated one. analogy to mesostructured zeolite synthesis, to get hierarchically
Organic amines as SDAs were introduced in the synthesis of micro- and mesoporous MOFs. Triblock copolymers P123 and
In-based MOFs.185 Thus, the different SDAs HHPP, HIm, and F127 in ethanol were used to synthesize hierarchically micro-
H2DACH were reacted with In3+ ions and 4,5-imidazoledicar- and mesoporous Al
MIL-53 with two types of mesopore
boxylic acid to form the zeolitic MOFs rho-ZMOF, sod-ZMOF, diameters.193 The formation of the larger (5.4
7.6 nm) and the
and usf-ZMOF, respectively. In the resulting anionic frameworks, smaller (4.0 nm) pore diameters was attributed to block copo-
protonated HHPP, HIm, and H2DACH species acted as charge- lymers and solvent. It was presumed that ethanol reacts with 1,4-
balancing templates. The organic counterions in rho-ZMOF benzenedicarboxylic acid under the synthesis conditions and that
could be ion exchanged by Na+ ions and subsequent thermal the resulting organic product acts as a different surfactant
activation was accomplished. In another report, two zeolitic Cd- creating smaller mesopores. In another study, the surfactant
based MOFs incorporating the four-connected organic linker cis, CTAB and the swelling agent TMB were employed to create
cis-1,3,5-cyclohexanetricarboxylate were synthesized using piper- mesoporous HKUST-1.194 An increase in CTAB/Cu2+ molar
azine and isopropanolamine as templates. In this case, the ratio enhanced the meosopore diameter from 3.8 to 5.6 nm. A
organic counterions were exchanged by K+ ions prior to thermal further increase in the mesopore diameter up to 31 nm was
activation.186 Piperazine was also employed in order to prepare a achieved by carefully optimizing the TMB/CTAB molar ratio.
zeolite-like MOF [Co5(Im)10]. Though not observed in the
5.2. Mineralizers
crystalline structure, the piperazine apparently served as SDA,
In addition to helping solubilize the starting materials under
since parallel reactions with different SDAs resulted in different
the reaction conditions, mineralizers, such as fluorides, added to
networks.187 Furthermore, a precipitate isolated after 12 h at
the reaction mixtures in the correct quantities favor the formation
room temperature prior to solvothermal reaction exhibited an IR
of well-crystalline phases of desired zeolites. Similarly, in the
spectrum with a distinctive signature for an
NH stretch.
synthesis of carboxylate-based MOFs with trivalent metal ions,
Tetramethylammonium (TMA) ions as SDA were used in the
for example, Cr
MIL-53,21 Fe
MIL-53-X [X = CH3, NH2,
synthesis of lanthanide tris(2-carboxyethyl)isocyanurates.188,189
(OH)2, (COOH)2],195 MIL-71,196 M
MIL-96 (M = Al,197
In the formation of isostructural 2D network structures using
Cr169), M
MIL-100 (M = Cr,30 Fe198), and Cr
MIL-101,31
different lanthanides, TMA acted as a so-called “structure-
fluoride was used as a mineralizing agent to increase the crystal-
blocking agent” that stops the formation of the 3D structure.
linity and to promote the crystal growth of the final product. In
Thus, in absence of the TMA ions, isostructural 3D frameworks
M
MIL-100 (M = Cr, Fe) and Cr
MIL-101, the fluoride ions
were produced.
are incorporated as terminal ligands at the trimeric metal clusters.
Inorganic templates such as alkaline metal ions or Keggin
Fluoride coordinates with the V3+ ions, forming corner-sharing
POM anions have also been investigated in the synthesis of
[VO2(OH)2F2] octahedra in MIL-71.196 The complete re-
MOFs. The role of the alkaline metal ion was studied in the
placement of the OH
ions of Al
MIL-53, [Al(OH)(BDC)],
system La3+/[(H2O3P)2CH
C6H4
CH(PO3H2)2]/NaOH/
by F
ions yielded the analogous compound [Al(F)(BDC)].199
H2O, and Na+ was identified to be the best structure-directing
Noteworthily, a significant drop in the BET surface area of the as-
agent for the anionic flexible open-framework metal phospho-
synthesized Cr
MIL-101 material was observed with an increase
nate [NaLa((PO3H)2CH
C6H4
CH(PO3H)2)].69 Keggin
in fluoride concentration in the reaction solution.200 It has been
ions were employed in the synthesis of HKUST-1190
192 and
proposed that fluoride ions strongly interact with Cr-trimers,
Al
MIL-101
NH2.84 In the room-temperature synthesis of
thus inducing nucleation of Cr
MIL-101 during the hydrother-
HKUST-1 in water, no MOF product formed in absence of the
mal reaction. Other studies were also conducted to increase
POM H3PW12O40.190 The synthesis also failed if H3BTC was
crystallinity. Thus, TEOS and H2O2 have been used in order to
added prior to POM. On the basis of the importance of the
synthesize Al
MIL-96197 and MOF-5,37,201 respectively. The
preparation sequence, it was presumed that Cu2+ ions arrange
role of these additives was not explained.
around the POM before coordinating with BTC. In the final
framework structure, the POM ions reside in the smaller cages, 5.3. Precursor Approach
since their geometry matches with the cage dimensions. Experi- MOF structures are obtained by a self-assembling process
mental evidence was provided in favor of the molecular mecha- starting usually from isolated metal ions that assemble together
nism for the spatial arrangement of Cu2+ ions surrounding the with the linker molecules forming the inorganic brick. An
template. In another study,191 evidence was presented that the alternative route is the use of molecular inorganic precursors,
formation of HKUST-1 is significantly accelerated by adding the so-called “precursor approach”. This involves the use of
Keggin POM ions to the synthesis solution. The use of EPR, prebuilt polynuclear coordination complexes comprising struc-
XANES, and pH measurements presented evidence of changes in tures and functions similar to or identical with the inorganic
the Cu2+ speciation upon addition of H3PW12O40. This enables bricks constituting the MOF. The polynuclear “precursors” must
paddle wheel formation and crystallization of HKUST-1 at room maintain their structural integrity in the reaction media.
temperature. The POM-encapsulated HKUST-1 was shown to The exchange of the monotopic linkers of the precursors with
exhibit improved thermal stability. Steaming at up to 483 K did polytopic linkers having similar functionalities can generate 3D
950 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

frameworks. The replacement of the acetate ligand of a trinuclear

oxo-bridged basic iron(III) acetate by ditopic fumarate, NDC,
and trans,trans-muconate enabled the syntheses of MIL-88A,
MIL-88C, and MIL-89, respectively.202,203 However, no syn-
thetic details were provided for MIL-88C. Notably, the EXAFS
spectra recorded from crystallization solutions, amorphous inter-
mediates, and crystalline products collected at different reaction
times were very similar, demonstrating that the iron(III) acetate
building units remained intact during crystallization of MIL-89.75
The same group also substituted the monocarboxylate ligand of
the zirconium methacrylate oxocluster [Zr6O4(OH)4(OMc)12]
with dicarboxylates (trans,trans-muconate and BDC), leading
to Zr dicarboxylates exhibiting the UiO-66 architecture
(Figure 5).204 The UiO-66 analogous structure with trans, Figure 5. Zirconium
dicarboxylates (right) synthesized from [Zr6]
trans-muconate was obtained using the Zr methacrylate oxo- methacrylate oxocluster (left) by applying the precursor approach.
cluster precursor as well as ZrCl4. In a similar study, tetra- Color codes: Zr, green polyhedra; C, gray; O, red. Reproduced with
nuclear oxo-centered basic zinc and beryllium acetates, permission from ref 204. Copyright 2010 Royal Society of Chemistry.
[(M4(μ4-O)(OAc)6)], were used as precursors to produce
Zn
MOF-5 and Be
MOF-5, respectively.205 Since the ana- Hydrolysis of esters and nitriles to the corresponding carbox-
logous Co compound is not available, cobalt oxopivalate, ylates was employed to synthesize several MOFs. The ester
which contains polynuclear complex ions composed of two trimethyl 1,3,5-benzenetricarboxylate was hydrolyzed in situ and
[Co4O]6+ building units, was employed to prepare the iso- the BTC3‑ ions were incorporated into M
MIL-96 (M = Al,197
morphous Co
MOF-5. The cobalt as well as the beryllium Ga,211 In212) and Al
MIL-100.213 The in situ hydrolysis of the
compound has not been obtained by another synthesis route same ester led to the formation of two MOFs constructed from
up to now. Y3+ ions and BTC3‑ linkers.172 The rho-type zeolitic MOF
Exchange of a terminal ligand by a bridging ligand of different [Cd(PYMC)] was obtained by in situ hydrolysis of the nitrile
functionality can also lead to the formation of MOFs. The 2-pyrimidinenitrile.214 Using the imidazolate 4-amide-5-imidate
replacement of the labile axial solvent molecules of the molecular linker, generated in situ by partial hydrolysis of 4,5-dicyano-2-
complex [Cu2(CDC)2(DMA)(EtOH)]6 with the ditopic linker methylimidazole, a Zn
imidazolate MOF was synthesized.215 A
BPY yielded a polyhedron-based MOF.206 The polyhedron- careful adjustment of the acidity of the reaction mixture was
based MOF dissembled back into the molecular complexes in required to achieve the selective hydrolysis.
the presence of monotopic pyridine ligands, confirming the [2 + 3]-Cycloaddition reaction of an azide with nitriles in
transformation as reversible. The chelating nitrate ligands of presence of a Lewis acid generates tetrazolates. The in situ
the tetrahedral symmetrical precursors [M5(BTA)6(NO3)4- formed tetrazolates were employed as linkers for the construc-
(H2O)x] (M2+ = Zn, Co, Ni; x = 1, 4) were exchanged by either tion of a large variety of nonporous terazolate-based frame-
dicarboxylates (BDC, BDC
NH2, and BPDC) or TCNQ works.216 However, by using the 5-methyl-1H-tetrazole (MT)
radical anion, respectively, resulting in 3D MOF structures.207,208 linker, formed in situ via cycloaddition of acetonitrile with Na
The precursor approach presents many advantages compared azide in the presence of Cd2+ ions, the porous Cd-based MOF
to the conventional synthesis, such as the control of the nature [Cd(Cl)(MT)] was prepared.217
and topology of the final product and the possibility to use milder Decarboxylation of esters and carboxylate ions was applied to
synthetic conditions (for example, lower temperature).204 The prepare Cu- and Cd-based MOFs. The in situ formation of
proof of the precursor concept is experimentally very demanding, unfunctionalized tetrazolate (TZ) by decarboxylation of ethyl
but due to the large number of known metal carboxylate tetrazolate-5-carboxylate was used to synthesize MOFs of com-
precursors, it might offer a versatile route to many new MOFs.209 position [M5(TZ)9][NO3] (M2+ = Cu,218 Cd219). The linker
Care must be taken due to the insolubility206 or hydrolytic 1,2,3-benzenetricarboxylic acid underwent decarboxylation fol-
instability of the precursor compounds. lowed by hydroxylation to produce 2-hydroxyisophthalic acid
(HIP), which enabled the synthesis of the mixed-linker MOF
5.4. In Situ Linker Synthesis [Cu3(HIP)2(PYZ)2].220
Traditionally, MOFs are prepared by reactions of presynthe- Oxidation reactions of three types were used to synthesize porous
sized or commercially available linkers with metal ions. An MOFs. The mixed-linker MOF [Eu2(μ2-PZDC)(μ4-PZDC)(OX)-
alternative approach termed as “in situ linker synthesis”, in which (H2O)4] was synthesized via in situ oxidation of 5-methylpyrazine-
the specified organic linkers are generated in the reaction media 2-carboxylic acid using HNO3 as an oxidant.221 The in situ oxidation
in situ from the starting materials, is attracting increasing interest of dimethyl sulfoxide in the presence of nitrate ions led to sulfate
in recent years. For the preparation of coordination compounds ions, which were incorporated in the structure of PCN-17, [Yb4(μ4-
and coordination polymers, a wide variety of in situ organic H2O)(TATB)8/3(SO4)2].222 In order to prepare PCN-46, the
transformation reactions were applied, which include oxidation, same group has employed 5,50 -(buta-1,3-diyne-1,4-diyl)diisophtha-
decarboxylation, hydrolysis, hydroxylation, cycloaddition, sub- lic acid (H4BDI), formed in situ through the oxidative coupling of
stitution, alkylation, acylation, amination, formation, or cleavage 5-ethynylisophthalic acid (H2EI) (Figure 6).223 It has been postu-
of C
C, S
S, and C
S bonds, and so on.210 Only a few reaction lated that the combination of H2EI bearing terminal acetylene
types have been employed for the synthesis of porous MOFs, i.e., groups with a slight excess of Cu2+ salt, which is readily reduced
the hydrolysis, [2 + 3]-cycloaddition, decarboxylation, oxidation, to Cu+ ion under solvothermal conditions, generates the homo-
and dimerization of the starting materials. coupled diisophthalic acid H4BDI. However, the exact chronological
951 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

Figure 6. The linker 5,50 -(buta-1,3-diyne-1,4-diyl)diisophthalic acid

(b), which is formed in situ under solvothermal conditions from
5-ethynylisophthalic acid (a), is incorporated in the PCN-46 framework
(c). Reproduced with permission from ref 223. Copyright 2010 Royal
Society of Chemistry.

sequence of events, such as the coupling of the precursors, the Figure 7. Phase-pure synthesis of the catenation isomers PCN-6 and -60
deprotonation of the diisophthalic acid, and the formation of the upon adjusting the ultrasonic power level. One benzoate moiety of each
MOF, has not been deciphered. TATB linker in the PCN-6 structure has been omitted for simplicity.
Dimerization of L-aspartic acid resulted in meso-iminodisucci- Reproduced with permission from ref 160. Copyright 2011 Royal
nate (IDS), which was used to synthesize the mixed-linker MOF Society of Chemistry.
[Zn2(IDS)(BPY)].224
In situ linker synthesis has many advantages over conventional the possibility of forming a sublattice in the voids of non-
synthetic routes. This “one-pot” approach precludes the neces- catenated structures as they are being formed. On the other
sity of synthesizing the linkers, thus simplifying tedious synthesis hand, higher temperatures afford more thermodynamically
and purification steps. The slow release of the in situ generated stable and denser catenated structures.
linkers in presence of metal ions can lead to the growth of better MOF-5 is also known in an interpenetrated as well as a
crystalline products or even larger single crystals. Moreover, the noncatenated form. In a study on the catenated form of MOF-5,
approach provides alternative pathways to MOFs with in situ the synthesis parameters were optimized by systematically vary-
synthesized linkers, which are inaccessible or not easily obtained ing the amount of water, temperature, time, and molar ratio of
by conventional synthetic methods. It should be mentioned that the reactants.228 In this case dilution of the reaction mixture did
the discovery of some of the in situ synthesized linkers is not lead to the noncatenated form of MOF-5. The solvent or
serendipitous.216 template effect was suggested as the controlling factor for the
catenation behavior of MOF-5. Recently, the pH of the reaction
5.5. Control of Catenation solution was found to be a key factor for the phase-pure synthesis
The self-assembly of multiple separate frameworks within of the catenated form of MOF-5.229
each other, which is known as framework catenation, is a well- Ultrasonic power level was adjusted in order to develop a
documented phenomena in MOF chemistry. Catenation is rapid, phase-pure synthesis route for PCN-6 and PCN-60
divided into two types: interpenetration and interweaving.225 (Figure 7).160 Employing this strategy, the control of catenation
In interpenetrated MOF structures, frameworks are maximally in the US synthesis of IRMOF-9 (catenated) and IRMOF-10
displaced from each other; in interwoven MOF structures, the (noncatenated) pair was demonstrated. In both the cases,
distance between both frameworks is minimized. Catenation noncatenated and catenated isomers were synthesized at lower
enhances the rigidity of the material at the expense of its porosity. and higher sonication power levels, respectively. Unfortunately,
However, there exits no established synthetic route to control the mechanistic implications of such power levels on the catena-
catenation. For a given combination of inorganic building units tion are not understood.
and organic linkers, catenation has sometimes been regulated by Additives were used to control the catenation of MOFs
changing the conventional solvothermal reaction conditions in a containing paddle wheel units. Employing oxalic acid as an
trial-and-error fashion. additive to the reactants, the noncatenated forms of PCN-60
Dilution of the synthesis mixtures or lowering the reaction and MOF-HTB0 were obtained instead of the catenated forms
temperature can be employed as a route to avoid catenation. The PCN-6 and MOF-HTB.230 However, the role of the additive was
noncatenated (IRMOF-10, -12, -14, -16) and the catenated not explained.
(IRMOF-9, -11, -13, -15) forms of the IRMOF-n series of com- A layer-by-layer (LBL) approach, completely different from
pounds were synthesized in dilute and concentrated reaction solu- the above-mentioned strategies involving bulk synthesis, was
tions, respectively.226 In another report, a systematic variation of applied to synthesize thin films of noncatenated form of MOF-
concentration as well as temperature affording control over the 508a, [Zn(BDC)(BPY)0.5], at room temperature.231 In the LBL
synthesis of a noncatenated form of [Cd(BPY)(BDC)] 3 3DMF 3 method, a pyridyl-terminated Au surface was alternatively im-
3H2O and its catenated form [Cd(BPY)(BDC)] was carried out.227 mersed in two different solutions: one containing metal salt and
Similar to the previous report, the noncatenated form of the frame- the other containing a mixture of the organic linkers. The
work was obtained from dilute reaction solution, whereas concen- substrate was rinsed in between the immersion steps to remove
trated reaction solution resulted in its catenated form. Moreover, the unreacted or physisorbed reactants. The pyridyl-terminated Au
noncatenated and the catenated forms of the frameworks were surface, which acts as a nucleation site and mimics the BPY
prepared in low and high temperatures, respectively. The authors linkers, probably lifts the equivalence of the two catenation
explained the influences of concentration and temperature based on isomers. However, the factors controlling the preferential for-
the following hypotheses. The dilution of a reaction solution reduces mation of the particular isomer remain unclear.
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Chemical Reviews REVIEW

Figure 8. Summary of strategies for manipulating the crystal growth, i.e., size and morphology of MOF crystals.

6. MOF CRYSTALS, FILMS/MEMBRANES, AND improve biocompatibility has also been described. Thus, nanoparticles
COMPOSITES of [Gd2(BDC)3(H2O)4] were coated with the copolymer poly-
Manipulation of the size and shape of the crystals is an (N-isopropylacrylamide)-co-poly(N-acryloxysuccinimide)-co-poly-
emerging area in MOF research, since such manipulation is a (fluorescein O-methacrylate).240 Silica-coating of Fe
MIL-101
NH2
means of optimizing the physical properties of the solids for was accomplished with a solution of Na
silicate under solvother-
mal conditions.104 Nanorods of [Ln2(BDC)3(H2O)4] (Ln = Eu,
specific applications.232 For example, nanosized MOF crystals
Gd, Tb), which were obtained from a synthesis in a reverse
have been studied to investigate the influence of the particle size
microemulsion, were directly coated by treatment with TEOS at
on the diffusion, i.e., the rate of adsorption. In addition, nano- room temperature.241 The thickness of the silica shells increased
sized MOF crystals can be used for the fabrication of thin films or upon prolongation of reaction time.
membranes.233
236 Notably, MOF thin films or membranes with
well-defined porosity and chemical tunability are promising 6.1. Crystal Size and Morphology
candidates for smart membranes, catalytic coatings, and chemical Different strategies have been adopted to manipulate the
sensors.233 Nanoscale MOF particles have also been employed in size and morphology of MOF crystals in the micro/nano
magnetic resonance imaging237 and drug delivery.238 Beside thin regimes (Figure 8). They involve variations that are related to
films and membranes, MOF composites of different shapes have any of the following issues: (1) compositional and process
been prepared to easily handle and integrate them in gas storage/ parameters, (2) temperature program, (3) additives, and (4)
separation, catalytic, and biomedical systems. In the following reverse microemulsions.
paragraphs, the adjustment of crystal size and morphology Compositional parameters that can be adjusted to manipulate
(section 6.1) as well as the synthesis of films/membranes the size and shape of MOF crystals include solvent, pH, metal
(section 6.2) and composites (section 6.3) will be discussed. source, reactant concentration, or molar ratio of the reactants.
In addition to the results in the following sections, few other Process parameters, such as time, temperature, pressure, and
studies were reported that do not fit into the above categories. heating source, can also have a strong influence on the crystal size
Therefore, these results are summarized in this paragraph. For the and shape. In general, both US and MW synthesis produce
synthesis of an amorphous Fe
MIL-100 aerogel with dual micro- relatively small and homogeneous crystals as compared to CE
and mesoporosity, the MOF gel was synthesized by vigorous stirring synthesis. Except this, no other general trends can be deduced
of the reactants in ethanol at room temperature.239 However, no about the control of crystal size by variation of compositional and
detailed synthesis procedure was reported. An excess amount of process parameters, which have to be fine-tuned for each system
starting materials was removed by Soxhlet extraction, and the ad- in a trial-and-error approach. Temperature programs, which have
sorbed ethanol was exchanged with supercritical CO2 to yield the an influence on the relative nucleation and crystal growth rates,
final aerogel. The densities of the aerogels increased with increasing have been also employed to synthesize nanoscale MOFs starting
concentration of the starting solution. Drying the gels slowly at low from supersaturated crystallization solutions. Various additives
temperatures for several days yielded the corresponding xerogels. have been tested: thus, polymers can adsorb at certain crystal
Aging of the gels prior to Soxhlet extraction led to xerogels with faces and slow down nucleation rates. Molecular blocking agents
increased surface areas. Coating of MOF nanoparticles in order to have been shown to slow down the crystal growth by adsorption
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Chemical Reviews REVIEW

on certain crystal faces. Capping agents can be used to stop US irradiation time and concentration of the reactants deterio-
crystal growth, while modulators have been used to control the rated the crystal quality. The decrease in crystal quality was
size and morphology of MOF crystals. The use of modulators attributed to high temperatures generated by the prolonged
relies on the addition of monodentate ligands (modulators), irradiation time. However, the replacement of the commonly
having the same chemical functionality as the multidentate used solvent DEF by low-cost NMP increased the crystal quality.
linkers, to the reaction mixture. The modulators compete with This was ascribed to the higher vapor pressure produced by the
the organic linkers in order to coordinate with the metal more volatile DEF compared to NMP, reducing the intensity of
ions during nucleation and crystal growth. Thus, the size and cavitational collapse and hence the resulting temperatures
morphology of the resulting crystals are greatly influenced. and pressures. In another work, microscale MOF-5 crystals
Microemulsions are thermodynamically stable mixtures of a (5
15 μm) were synthesized by using US and MW-assisted
hydrophobic liquid, water, and a surfactant, often in the presence heating consecutively, and the results were compared to reaction
of a cosurfactant, often short chain alcohols. They form sponta- products obtained by CE heating.113 In this study, CE heating led
neously upon mixing of the starting materials. In case the to less regularly shaped crystals. The crystal size decreased with
dispersed phase is water and the continuous phase is the organic increasing ultrasonic bath temperature and sonication time. This
phase, these mixtures are called reverse microemulsions. The was attributed to the combined effects of US and MW irradiation,
starting materials are usually dissolved in the aqueous phase and which promoted uniform and fast nucleation.
the collision between droplets or the application of an external Microscale MOF-177 was obtained in a variety of shapes
stimulus (temperature, MW or US radiation) induces crystal- (filaments, rods, needles, cuboids, cubes) using CE heating.242 A
lization. Thus, the nanodroplets act as “nanocontainers”. The size low temperature (90 °C) and a short reaction time (24 h)
and number of nanodroplets within the microemulsion can be favored the growth of well-dispersed cubic crystals (10
25 μm).
tuned by varying the molar ratio (W) of continuous phase to A slow cooling rate (0.1 °C min
1) enabled the formation of rod-
surfactant. By changing the value of W, the size and morphology shaped crystals (length ∼ 60 μm, diameter ∼ 10 μm) that were
of the crystals can be adjusted. less aggregated than those obtained without applying any cooling
6.1.1. Compositional and Process Parameters. Micro- program. However, a detailed investigation demonstrating the
and nanoscale MOF-5 were prepared in several reports at room precise control of the morphology was not performed. In another
temperature or by using CE heating, MW and US irradiation. In work on MOF-177, the US synthesis yielded microsized crystals
the room temperature synthesis, nanoscale (70
90 nm in (5
20 μm), which were smaller in size compared to those
diameter) MOF-5 and a new phase (100
150 nm in diameter) prepared by using CE heating (0.5
1.5 mm) or MW irradiation
were produced when triethylamine (TEA) was directly added (5
50 μm).117 The size of the sonochemically synthesized
into a DMF solution containing the reactants.37 Spherical crystals remained invariant to the reaction time. It has been
(30
45 nm in diameter) and wire-shaped (∼100 nm in dia- reasoned that the significantly accelerated nucleation in US
meter) nanocrystals with reduced sizes were synthesized when synthesis quickly depletes the reagent concentration below the
the direct-mixing approach occurred within a liquid crystalline critical nucleation concentration.
phase (nonionic surfactant, polyoxyethylene(4) lauryl ether or The influence of the reaction parameters on the crystal size of
Brij30) or in the ordered cylindrical channels (diameter 100 nm) HKUST-1 was systematically investigated in two reports.42,118
of an anodic alumina membrane, respectively. In the CE synthe- The choice of the metal salt has a strong influence on the crystal
sis of microscale MOF-5, the profound effect of the Zn salt on size. Thus, the use of acetate as the counterion led to smaller
the morphology of the microcrystals was demonstrated.42 Em- crystals, which was related to the change in nucleation rate.
ployment of zinc nitrate and zinc oxide led to strongly intergrown Increasing the reaction temperature leads to the formation of
big cubic crystals (>100 μm), whereas in the case of zinc acetate, Cu2O as a side product. Only low reaction temperatures (348 K)
smaller well-defined cubic crystals were formed (<10 μm). This resulted in octahedrally shaped crystals (∼15 μm) while higher
was assigned to the higher nucleation rate when starting with zinc temperatures led to crystals with less-defined faces and edges.
acetate, resulting in higher basicity compared with zinc nitrate, The overall concentration of the reaction mixtures was also
and better solubility of the Zn source compared with zinc oxide. investigated. At low concentrations, intergrowth of truncated
In the MW synthesis of microscale MOF-5 (4 ( 1 μm), both size octahedral crystals was observed. Intermediate concentrations
and regularity of the cubic shaped crystals decreased down to led to well-defined octahedra and high concentrations to less
1 μm by reducing the concentration of H2BDC in the starting defined irregular products. In another report, the results of MW
solution.110 By varying the reaction time from 25 s to 1 min, the and CE syntheses were compared.118 While the crystal size
size of the microcrystals did not change remarkably. The reduc- increased at prolonged reaction time in the MW synthesis, the
tion in size has been attributed to the quick depletion of the reverse was observed in the CE synthesis. The crystal size also
available reactants during the crystal growth. In another study increased in both cases when higher concentrated solutions were
concerning the MW synthesis of microscale MOF-5 (20
25 μm), used. MW-assisted heating was found to be the method of choice
the increase in irradiation time, power level, and concentration to rapidly synthesize HKUST-1 crystals in the range of 10

of the substrates beyond an optimal condition led to a reduc- 20 μm in high yields (∼90%) within 60 min.
tion in synthesis time at the expense of crystal quality.111 It Nanoscale ZIF-8 (∼50 nm) was synthesized in methanol at
has been speculated that the excess Zn clusters, formed at room temperature, using an excess of HMIm relative to the Zn
increased MW heating time, competes with the BDC linkers in source.39 The product contained agglomerated, nonuniform,
the preformed crystals. Thus, the BDC linkers dissolve back in rhombic dodecahedrally shaped crystals. It was assumed that
solution, causing defects in the crystal faces. In the US synthesis the excess linker molecules in the protonated form acted as a
of microscale MOF-5 (5
25 μm), the formation of platelike stabilizing agent for the colloidal particles. Focusing and
crystals as an impurity was suppressed by increasing the power defocusing of the particle size distribution was observed at
level.159 Similar to the MW synthesis of MOF-5,111 an increase in earlier and later stages of growth, respectively.87 In another
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Chemical Reviews REVIEW

Figure 9. TEM images of Fe
MIL-88A crystals synthesized by MW-assisted heating at various reaction temperatures and reaction times. Reproduced
with permission from ref 105. Copyright 2011, Royal Society of Chemistry.

report, nanoscale ZIF-8 (∼85 nm) was prepared by using a dissolution and deprotonation of H2BDC and thus formation
molar ratio HMiM: Zn(NO3)2 3 6H2O of 70 and replacing of Cr trimers, leading to an increase in nucleation rate and as a
methanol by water.243 Variation of the molar ratio was shown consequence to a decrease in particle size.
to reduce the crystal size, but it had little effect on the Microscale PCN-6 and -60 (1.5
2 μm for PCN-60 , 4.5
6 μm
morphology of the crystals. Thus, the size of the crystals for PCN-6), which are formed in the Cu2+/TATB3‑/DMF
decreased from ∼85 nm to ∼50 nm when the molar ratio was system, increased in size with an increase in sonication power
increased from 70 to 100. level.160 A mixture of crystals of two different sizes was obtained
Fe
MIL-53 crystal size varied with the synthesis method at an intermediate power level. It has been proposed that the
applied.79 Starting from identical reaction mixtures, CE heating smaller, larger, and mixed crystal sizes belong to PCN-60
as well as US and microwave irradiation were employed. While (noncatenated), PCN-6 (catenated), and their mixtures, respec-
CE heating led to large, irregular-shaped crystals of varying size, tively. A similar effect of the sonication power level was found on
MW-assisted heating and US radiation resulted in well-shaped the crystal sizes of IRMOF-9 and -10 (∼5
20 μm for both),
crystals with crystal sizes around 1 and 0.5 μm, respectively. suggesting that catenation seemingly produced bigger crystals.
Nanoscale MIL-88A was synthesized by using various synthe- 6.1.2. Temperature Program. Three studies have dealt with
sis methods, i.e., static hydro/solvothermal synthesis, dynamic the synthesis of the nanocrystals of IRMOF-1, IRMOF-3, and
ambient pressure synthesis, sonochemical as well as microwave- HKUST-1 by using temperature programs and additives. The
assisted hydrothermal conditions.105 Reaction parameters such nanocrystals of IRMOF-186 and HKUST-185 were synthesized
as solvent, pH, reaction time, and temperature as well as overall in three steps: (a) incubation of the reaction solution, (b) initiation
concentration were studied. Optimized reaction conditions of nucleation by heating at a high temperature, and (c) initiation
yielded relative large crystals for common hydrothermal synthe- of growth by cooling down to low temperature. The combination
sis (250 nm). Sonochemistry resulted in particles of around of faster nucleation (b) and comparatively slow crystal growth
100 nm but only in small yields. The best results were obtained (c) for MOF-5 led to homogeneous nanocrystals. However, for
by MW-assisted heating. Particles smaller than 100 nm were HKUST-1, the nucleation continued also at lower temperatures
obtained in high yield that also showed a narrow particle size and thus overlapped with the crystal growth. Thus, crystal growth
distribution (Figure 9). up to 200 nm in particle size within 10 min was observed, but
Nanoscale Cr
MIL-101 was prepared in water using HF continuous new nucleation was proven by SLS measurements
and MW-assisted heating.102 The dimensions of the particles and SEM images.
increased (from 40
80 to 70
90 nm) and became more homo- The influence of the presence of a surfactant (CTAB) to
geneous in size with increasing reaction time. Later, the research- regulate the nucleation was also investigated.244 The steps for the
ers avoided the use of HF, and nanocrystals of Cr
MIL-101 with preparation of the monodisperse nanocrystals of IRMOF-1 and -3
sizes of around 50 nm were obtained by lowering the reactant with regular shape and uniform size of 200
300 nm included
concentration or increasing the pH of the reaction mixture.103 (a) incubation of the reaction solution at a lower temperature,
However, the particle size was not affected by the reaction time. (b) addition of the CTAB to decrease the rate of nucleation, (c)
The decrease in particle size with lowering of the reactant initiation of growth at a higher temperature, and (d) increment of
concentration is not easy to understand, but the authors attrib- growth rate by adding TEA.244 Step a led to the formation of
uted it to a faster rate of nucleation compared with that of inorganic building units. Its exclusion led to crystals with poor
crystal growth. It was also argued that high pH promoted monodispersity and crystallinity. Nucleation (b) and crystal
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Chemical Reviews REVIEW

growth (c) were influenced by the addition of CTAB as the

surfactant, and upon addition of the amine (d), rapid growth was
accomplished. Surprisingly, replacing TEA with other amines in
step d resulted in products with various crystal shapes. Thus,
addition of decylamine or piperidine led to relatively large
crystals with rodlike or octahedral shapes, respectively. Lowering
the reactant concentration resulted in spherical and flower-
shaped crystals.
6.1.3. Additives. The polymer PVSA was added as an
additive in different concentrations in the crystallization of
[Cu2(PZDC)2(PYZ)] at room temperature to tune the size
(mean sizes in the range 1
100 μm) and shape of the result-
ing crystals (Figure 10).245 Larger crystals have been obtained
with an increase in PVSA/Cu2+ molar ratio, which is opposite to
the conventional route for size tuning of crystals using additives.
The addition of PVSA to the reaction mixture led to a slow rate of Figure 10. Control of crystal size for the preparation of [Cu2(PZDC)2-
nucleation and consequently provided larger crystals. The direc- (PYZ)]. Reproduced with permission from ref 245. Copyright 2006
tion of crystal growth upon addition was also influenced and American Chemical Society.
larger amounts of PVSA resulted in crystal growth parallel to the
ac-plane and thus to the formation of platelets. The micropore time increased the number of nanocubes and the aspect ratio of the
volumes of the products were independent of crystal size. However, nanorods, demonstrating oriented attachment growth mechanism.
the elongation of the 1D channels, which are parallel to the a-axis in This mechanism was also supported by the fact that the aspect ratio
the larger crystals, decreased the rate of adsorption. of the nanorods increased at higher concentrations of all the
A blocking agent like pyridine was added in the solvothermal reactants.
synthesis of In
MIL-53 to manipulate the morphology of the In the CE synthesis of nanoscale MIL-88A the addition of
microsized crystals. The employment of 0, 1, 2, and 25 equiv of acetic acid had the reverse effect. The increasing of the concen-
pyridine resulted in long rod, short rod, lump, and disk-shaped tration resulted in a decrease of particle size.105
crystals, respectively.246 It has been argued that control of the Acetic acid or benzoic acid as a modulator was added to
crystal shape is achieved through a crystal growth blocking event regulate the size and morphology of isoreticular Zr-based MOFs
involving the interaction of blocking agents with particular facets with UiO-66, -67, and -68 structures.248 Without modulation, the
of MOFs and the simultaneous crystal growth interruption in a MOFs were obtained as microsized aggregates of nanocrystals.
specific direction. Thus, the crystal growth rate in a certain By adding increasing amounts of the modulator, Zr
BDC
direction was manipulated by using a variable amount of the samples evolved from aggregated small crystals to separated
blocking agent. octahedrally shaped nanocrystals of increasing size. For Zr

Modulators have been employed to adjust the size and shape BPDC, increasing the amount of the modulator resulted in the
of MOF crystals in seven reports.86,87,105,247
250 Mostly mono- formation of individual octahedral microcrystals. Upon addition
carboxylic acids and their salts were used for the synthesis of of suitable amounts of benzoic acid, single crystals of Zr

metal carboxylates, but N-heterocycles and alkylamines were also TPDC
NH2 were obtained. An increase in the amount of
employed for the synthesis of ZIFs. modulator presumably decreased the rate of nucleation, resulting
Acetic acid was added as a modulator in the CE synthesis under in fewer nuclei and hence larger crystals.
reflux conditions of nanosized, pillared
layered [Cu2(NDC)2- Lauric acid (LA, C11H23
COOH) was used as a modulator in
(DABCO)] to control the morphology of the crystals.247 Lower the MW synthesis of HKUST-1 to tune the size of the crystals in
concentration of acetic acid induced rapid crystallization, producing the nano- to microscale range.249 Nanocrystalline powder with
intergrown nanocrystals with low crystallinity. A higher concentra- less defined morphology was obtained in the absence of the
tion of acetic acid decelerated the rate of crystallization and modulator. Lower as well as higher concentrations of LA in
facilitated the formation of well-dispersed nanorods with high butanol (BuOH) led to globular and cubic nanocrystals, respec-
crystallinity. Notably, Cu
NDC and Cu
DABCO interactions tively. The replacement of LA by acetic acid (AcOH) generated
predominate in the [100] and [001] directions, respectively, in the less-defined crystals of different sizes. The change of solvent to
tetragonal framework. Acetate ions compete with NDC ions, ethanol led to highly intergrown nanoparticles, regardless of the
disturbing Cu
NDC interaction and thus inhibiting crystal growth modulator (LA or AcOH). Thus, the combination LA/BuOH
in the [100] direction. However, Cu
DABCO interaction, which was selected for further studies. For a given LA/BuOH ratio,
remains unaffected in presence of acetic acid, favors crystal growth in lowering of the reactant concentration decreased the sizes of the
the [001] direction. Therefore, the aspect ratios of the nanorods cubic nanocrystals. At a fixed reactant concentration, increasing
increased at higher concentration of acetic acid. The formation of the LA content promoted the growth of larger crystals. Small
the nanorods was shown to be even more complicated, since fused nanoparticles, cubic nanocrystals, and cubic microcrystals
nanoparticles with a size of around 5 nm, nanocubes with an were received at lower, intermediate, and higher concentrations
average size of around 80 nm, and nanorods with different length of LA, respectively. Whereas the higher concentration of LA
but diameters of approximately 80 nm were observed (Figure 11). decelerated the rate of nucleation, leading to larger crystals with
Thus, an oriented attachment mechanism was proposed, in which greater polydispersity, the reverse was true at lower concentra-
the initially produced nanoparticles assemble to nanocubes, which tion. This tendency has also been observed using a polymer
subsequently assemble to nanorods at later stages of the reaction. At additive (compare Figure 10).245 The sorption capacity of the
an optimal concentration of acetic acid, prolongation of reaction small fused nanoparticles or cubic microcrystals was significantly
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Chemical Reviews REVIEW

Figure 11. Proposed growth mechanism for [Cu2(NDC)2(DABCO)] nanorods. The growth process of nanocubes is a consequence of nanoparticle
aggregation-mediated crystal growth. The selective coordination modulation on the (100) surfaces of the nanocubes induces the oriented attachment
leading to the growth of nanorods in the [001] direction. Reproduced with permission from ref 247. Copyright 2009 Wiley-VCH Verlag GmbH
& Co. KGaA.

higher than the ill-defined nanocrystalline powder and was 6.1.4. Reverse Microemulsions. CTAB/isooctane/1-hex-
comparable to the microcrystals produced by static CE heating. anol/water microemulsions were used to prepare uniform nano-
The sudden increase in adsorption at high relative pressure, rods of [Ln2(BDC)3(H2O)4] (Ln = Eu, Gd, Tb) at room
observed for nanoparticles but absent for microcrystals, was temperature in 84% yield.251 Higher water/CTAB molar ratios
attributed to the condensation of the adsorptive in the space led to particles with higher aspect ratios, resulting from a decrease
between the nanoparticles (textural porosity). of nucleation sites within the microemulsion droplets. The
Sodium carboxylates were used as modulators in the CE synthesis particle size also decreased with lowering of reactant concentra-
of nanoscale [Ln(BTC)(H2O)] (Ln = Dy, Eu, Tb).250 The tion. Luminescent nanorods were synthesized by using Eu3+ and
crystallinity of the compounds increased in presence of the mod- Tb3+ ions as dopants in the Gd-based compound. Although a
ulators. Rod-shaped microcrystals were obtained in the absence of high yield was observed, the method required high volumes of
the modulators, while the addition of sodium formate resulted in solvents. Moreover, the removal of the surfactants from the
uniform, bean-shaped nanocrystals. Smaller nanocrystals were nanoparticle surface required harsh conditions or multiple
obtained when sodium acetate was used. However, sodium oxalate washing steps.
led to needle-shaped microcrystals. The influence of the additive on The nonaqueous AOT/n-heptane/DMF microemulsion sys-
the crystal morphology was not explained. tem was employed to synthesize nanorods of [Zn(IP)(BPY)] at
Ligands with different functionalities (carboxylate, N-hetero- room temperature.252 The compound exhibits a flexible inter-
cycle, and alkylamine) were employed as modulators to tune the digitated layered structure. US irradiation was mandatory to
size and shape of ZIF-8 crystals. A rapid room-temperature induce fast nucleation in the microemulsion and thus to control
synthesis was developed that allowed the synthesis of nanocryst- the crystal growth. Absence of US irradiation resulted in a gel-like
amorphous material. At a molar ratio of DMF to AOT (W) of 1,
als (10
65 nm) and microcrystals (∼1 μm).87 The addition of
nanocrystals having dimensions of ∼300 nm  50 nm  15 nm
n-butylamine to a reaction solution containing excess of the
were observed, which were larger than the microemulsion
bidentate ligand HMiM resulted in spherical nanocrystals, droplets. The nanoparticle growth was therefore explained by
whereas rhombic dodecahedrally shaped microcrystals were aggregation of the growing nanocrystals followed by the coordi-
obtained by adding 1-methylimidazole or sodium formate to nation of AOT on the crystal surface, thus changing the crystal
the same solution. It was surmised that the modulators acted as growth behavior. The morphology of the particles was unaffected
competitive ligands in the coordination equilibria and that the upon variation of reaction time. Increasing W led to larger
bases influence the deprotonation equilibria during crystalliza- nanorods, but at W > 3, nonuniform particles resulted due to
tion. The growth of microcrystals was proposed to be dominated instability of the microemulsion. The adsorption properties of the
by a particle-monomer attachment mechanism, although coales- resulting MOFs depend strongly on the synthesis procedure.
cence of nanocrystals during early stages of growth is also While the overall adsorption capacity was identical for nanocryst-
indicated by the results of the SLS measurements. ZIF-8 nano- als and bulk microcrystals synthesized using CE heating, the shape
crystals exhibited a type-H2 hysteresis loop in the adsorption
of the sorption isotherms varied considerably. This is probably
desorption isotherm at high relative pressure, originating from due to the adsorption of surfactant on the crystal surface. At the
interparticle mesopores (textural porosity). same time, nanocrystals were shown to exhibit faster adsorption
While modulators, which are usually added to the reaction due to shorter diffusion lengths compared to the bulk material.
solution from the beginning, influence the crystal growth, other
additives, termed as capping agents, prevent the crystal 6.2. Thin Films and Membranes
growth.105,247,249 Thus, the size of the growing nanocrystals of Various functionalized and nonfunctionalized substrates such
MOF-5 was adjusted by adding p-perfluoromethylbenzoic acid in as silica, alumina, titania, graphite, or nylon have been used
a supersaturated mother solution at room temperature.86 to deposit thin films and membranes. Especially continuous,
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Figure 12. Layer-by-layer growth of HKUST-1 thin films on COOH-terminated support. The substrate is repeatedly immersed in solutions of
Cu(OAc)2 and H3BTC, with an intermediate washing between successive steps. Reproduced with permission from ref 275. Copyright 2008 Royal
Society of Chemistry.

Figure 13. Comparison between direct and secondary growth methods for the preparation of MOF thin films under solvothermal conditions.
Immersion of the bare or seeded supports in the reaction solution and subsequent solvothermal treatment lead to discontinuous or continuous films,
respectively.

well-intergrown, and oriented films are of interest, which could which is a nontrivial task. Moreover, the repetitive process of
be useful for efficient gas/liquid separation applications. For the immersion/washing cycles is time-consuming. The full description
use in sensors, the preparation of patterned films is also of of the method is summarized in several review articles.233
235,254
interest.136,137,253 Different strategies have been described in the Secondary or seeded growth offers a better control over
literature to fabricate thin films or membranes of MOFs. These thickness and orientation of the film or membrane, compared
can be categorized as follows: (1) direct growth, (2) layer-by- to direct growth (Figure 13). Prior to secondary growth, the
layer growth, (3) secondary growth, and (4) chemical solution substrate is coated with a seed layer, and the most versatile
deposition. seeding method is spin- or dip-coating. The seeded supports are
Direct growth techniques rely on the immersion of the then immersed in a reaction solution of the particular MOF, and
supports in the reaction solutions containing the metal salts thin films or membranes on the seeded surface are produced in a
and linkers. Application of CE or MW-assisted heating generates procedure similar to direct growth. Due to the pre-existence of
nucleation sites on the supports, thus enabling the growth of nuclei on the support surface, the influence of the surface
crystals on the substrate. These crystals can intergrow to form chemistry is eliminated. More often, secondary growth is used
films having a thickness of several micrometers. Alternatively, prepare membranes, since direct growth does not lead to good
supports can be immersed in preheated reaction mixture in which coverage of crystallites on bare substrates.
nucleation has occurred and crystallization is about to begin. For The chemical solution deposition route for the preparation of
both methods, it has been observed that the preparation of thin films employs stable dispersions of nanocrystals that are
continuous thin films on bare substrates is difficult due to poor spin- or dip-coated on the substrates. Films with increasing
heterogeneous nucleation. Therefore, chemical modifications of thickness can be prepared by multiple depositions. This method
the supports turn out to be indispensable for high quality films. is simple, rapid, and cheap. Because of its low-cost and the
The layer-by-layer (LBL) approach (Figure 12) for the growth of possibility of large-area processing, this technique is also used in
MOF thin films at room temperature involves repeated cycles of industry.
immersion of a substrate in solutions of the metal salt and solutions of 6.2.1. Direct Growth. Direct growth of MOF thin films was
organic linker. Between successive deposition steps, the substrate is demonstrated on flat substrates, as well as on beads. The
rinsed with an appropriate solvent to remove unreacted or physi- substrate-free direct growth at liquid
liquid interface of two
sorbed reaction components. Compared to direct growth, the LBL immiscible solvents was also shown that resulted in free-standing
method leads to homogeneous, nanoscale films with precise control films and capsules.
of orientation and thickness for each single step. However, the LBL Unfunctionalized substrates were used for the direct growth of
route includes the prefunctionalization of substrates with SAMs, thin films of only a few MOFs.128,255
257 Alumina or graphite was
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used as a substrate to grow thin films of [Mn(HCO2)2].255 Since The α-alumina substrate was pretreated with a solution of the
only poor coverage was observed, Al2O3 was treated under basic imidazole linker at 200 °C, which resulted in strong covalent
conditions (NaOH) and graphite was partially oxidized in air. The bonds between the linker and the substrate.261 For the prepara-
pretreatment led to even lower crystal densities, but changing the tion of continuous membranes of ZIF-7, -8, -22, and -90, the
reaction conditions, i.e., replacing formic acid with sodium formate, titania and α-alumina supports were functionalized with APTES,
resulted in an improved coverage due to more favorable electrostatic which created fixed nucleation sites on the supports, act-
attraction between oxidized graphite and the [Mn(HCO2)2] nuclei. ing as covalent linker molecules between the ZIFs and the
SEM images demonstrated the intergrowth of the MOF crystals supports.262,263 For ZIF-90, it was hypothesized that the ethoxy
into the porous graphite. Dense, crack-free films of M
CPO-27 groups of APTES reacted first with the hydroxyl groups of
with M = Co2+, Ni2+, and Mg2+ were synthesized by applying alumina, which was followed by the condensation of the amine
the direct growth method on bare alumina.256 When the metal groups of APTES with the aldehyde groups of imidazole-2-
source was changed to Zn2+ or Mn2+ salts, only large individual carboxaldehyde.
crystals were deposited on the surface in a discontinuous fashion. Surface modification employing SAMs has been extensively
This suggested a strong effect of the nature of the cation on the used for the direct growth of MOF thin films.264
271 Depending
growth mechanism and binding to the substrate. The influence of on the functional groups of the SAM, oriented growth was
the surface chemistry on the crystal growth of the three MOFs observed in most cases. The orientation depends on the crystal
[Zn2(BDC)2(DABCO)], MOF-5, and HKUST-1 was also structure of the MOFs and specific interactions of the surface
investigated.265,266 MOF-5 and HKUST-1 did not grow on un- with the inorganic bricks or the growing nuclei. However, mostly
functionalized silica but did on nonfunctionalized c-sapphire discontinuous films were obtained. To accomplish direct growth,
(c-Al2O3). Compared to silica, c-sapphire is more basic and therefore the SAM-modified substrates were either directly immersed in
could promote the growth of MOF crystals due to better deproto- the reaction mixture or in a filtered preheated solution of
nation of the carboxylic acids. Changing to ALD-alumina, which is the starting materials, which supposedly contained nuclei of
amorphous and more basic compared to silica, increased surface the desired MOF phase. In addition, diffusion of the starting
coverage of all the three MOFs. Only [Zn2(BDC)2(DABCO)] materials through a polymer gel was reported.
could also be grown on silica, probably due to the basic DABCO In the preparation of thin films of MOF-5 on a bifunctional
linkers, which favored H-bonding interactions. The crystals of CF3-/COOH-terminated Au surface, the crystals grew only on
HKUST-1 showed an oriented growth mode on both c-sapphire COOH-terminated parts.264 Comparative studies on unfunctio-
and COOH-terminated silica. In a report on ZIF-8, a dense, crack- nalized, CF3- and COOH-terminated Au surfaces revealed that
free membrane was deposited on bare titania using the direct growth well-adherent films were formed only in the later case. The same
method and MW irradiation.128 The so-called contra-diffusion group also reported a similar selective growth of films of MOF-5,
method was employed in order to fabricate a continuous and HKUST-1, and [Zn2(BDC)2(DABCO)] on CF3- and COOH-
compact film of ZIF-8 on an organic polymer as the support. terminated c-sapphire and silica.265,266 The difference between
Individual solutions of the metal salt and the linker are separated by a CF3- and COOH-terminated surfaces was attributed to the
porous nylon membrane, and crystallization occurs on membrane ability of the latter to mimic the carboxylate-based organic linker.
surfaces via diffusion of both starting materials.257 The reactant Highly oriented thin films of HKUST-1 were obtained after 8
concentration was systematically varied and the growth was re- days at room temperature on a COOH- and OH-terminated Au
peated to improve the quality of the film, but only on the zinc nitrate surface,267,268 while the CH3-terminated Au substrate yielded
side was a continuous film accomplished. nonoriented crystals due to the absence of specific interactions.
Modified substrates were more often used for the direct The same researchers also synthesized highly ordered thin films
growth of thin films of MOFs.114,258
263 MOF-5 films were of MIL-88B on a COOH-terminated Au surface.269 The selective
deposited on porous alumina, which was coated with a thin formation of Fe
MIL-88B over Fe
MIL-53 was ascribed to the
conductive layer of graphite, under MW irradiation.114 The possible symmetry transfer between hexagonally ordered SAMs
authors argued that the strong interaction between graphite layer and the hexagonal structure of MIL-88B. The growth of CAU-1
and MW radiation resulted in a rapid temperature increase in on OH-, COOH-functionalized gold surface at room tempera-
alumina, which enhanced direct growth of MOF-5 on alumina. ture starting from pretreated crystallization solutions was also
However, oriented but poorly intergrown crystals were pro- investigated.270 While oriented growth is independent of the
duced. In another report on MOF-5, a continuous, well-inter- reaction conditions for the COOH-terminated surface, crystal
grown MOF-5 membrane was grown on porous α-alumina disk orientation at the OH-terminated SAM can be tuned by changing
that was treated with a H2BDC solution prior to solvothermal the synthesis procedure. In a recent report on the synthesis of
reaction.258 The use of almost dehydrated zinc nitrate improved oriented nanoscale films of HKUST-1 and MIL-88B at room
the quality of the film, and the crystal size was found to decrease temperature, the same group used the gel-layer approach, in
with lowering of the reactant concentration. In a recent study on which the gel layer containing the COOH-functionalized Au
the direct growth of thin films of MOF-5, the surface of alumina substrate and the metal salt was covered with the solution
was modified by depositing a drop of a suspension containing α- containing the linker molecules.271 Slow diffusion of the reac-
hopeite [Zn3(PO4)2 3 4(H2O)] microparticles, which acted as tants through the gel layer produced thin films on the modified
nucleation sites.259 For the direct growth of continuous films of Au surface. The film thickness was adjusted by lowering the
HKUST-1, an oxidized Cu net was used, which provided reactant concentration.
homogeneous nucleation sites as well as Cu2+ ions.260 The Patterned films of HKUST-1 have been described in three
syntheses of thin films of ZIFs have been described in four reports. By modifying the bulk electrochemical synthesis of
reports. In order to prepare continuous, well-intergrown films of HKUST-1,52 densely packed films of this MOF were grown on
ZIF-7 and -8, sodium formate was added to the reaction mixture a Cu anode, a patterned Cu, or a Cu-coated Au electrode.136 The
to enable the complete deprotonation of the linker molecules. crystal size decreased upon increasing of voltage or lowering of
959 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

water content in the synthesis mixture. For the synthesis of a

patterned film of HKUST-1 on a nonconducting substrate, the
same group has used the galvanic displacement method, which
precludes the need of voltage supply and interconnectivity
among the metallic patterns as opposed to anodic oxidation.137
The spin-coating of a solution containing AgNO3 and H3BTC on
a Cu surface, patterned on glass, ensured the release of Cu2+ ions
upon reduction of Ag+ ions. Subsequently, the reaction of Cu2+
ions with H3BTC molecules during evaporation of the solvent
yielded patterned films. In another study, patterned polydi- Figure 14. (a) Top- and (b) cross-sectional view the ZIF-8 membrane
methylsiloxane stamps were used to generate patterned films synthesized by secondary growth technique. Reproduced with permis-
of oriented crystals of HKUST-1 by evaporation of the solvent sion from ref 278. Copyright 2011 American Chemical Society.
from the reaction mixture confined under the protrusions of the
stamp.253 areas of a bifunctional CH3-/COOH-terminated Au surface.275
Beads were also used as substrates. Thin films of SIM-1 and Applying the same method, thin films of HKUST-1 were
ZIF-7 were grown on α- or γ-alumina beads using the direct prepared on flexible polyester fabrics.276
growth method.272 SIM-1 is isostructural to ZIF-8 but contains Employing the LBL technique, the same group was able to
4-methyl-5-imidazolecarboxaldehyde instead of 2-methyimida- deposit thin films of the highly oriented noncatenated form of
zole. Since ZIF-8 crystals did not grow on γ-alumina under [Zn(BDC)(DABCO)0.5], on a pyridyl-terminated Au surface
similar conditions, it was postulated that the linker in SIM-1 is (see section 4.5).231 The isoreticular Zn- and Cu-based com-
attached to the alumina surface, probably through bond forma- pounds with various dicarboxylate ions and dinitrogen pillar
tion to the C(2)-atom of the linker molecule. ligand molecules were obtained. Surprisingly, the orientation of
Direct growth at a liquid
liquid interface, termed as interfacial the film was observed to depend on the sequence of addition of
or biphasic synthesis, has led to the formation of thin films and/ the reactants. In the case of a two-step process, i.e., addition of
or hollow capsules of HKUST-1 and ZIF-8.273 The method takes an equimolar mixture of both ligands, growth along the [001]
advantage of the preferential solubility of the metal salts and direction was observed while the three-step process with con-
linkers in water and organic solvents, respectively. Free-standing secutive addition of all three components resulted in the deposi-
thin films of HKUST-1 and ZIF-8 were obtained at the interface tion along the [100] direction on COOH-terminated SAMs.277
between two immiscible liquids by layering an organic solution 6.2.3. Secondary Growth. Several preparative strategies
(typically 1-octanol) of the linker on top of the aqueous solution have been developed to deposit a seed layer on the substrate
of the metal salt at room temperature. Nucleation occurred at the prior to secondary growth. Those are (1) spin- or dip-coating,
liquid
liquid interface. For the synthesis of hollow capsules of (2) direct growth, (3) rubbing, and (4) LBL growth.
HKUST-1, aqueous droplets containing the metal salt were Spin- or dip-coating of a dispersion of as-synthesized or
added to a coflowing stream of the organic solution of linker presynthesized crystals on the substrates can be used to produce
flowing through hydrophobic tubing. In this case, nucleation a seed layer. For the preparation of seed layers of ZIF-7 and -8,
took place inside the droplets. Concentrated solutions of the α-alumina was dip-coated with dispersions containing presynthe-
reactants were used to avoid a reduction in crystallization rate sized nanocrystals and PEI (Figure 14).129,278,279 Later, the same
due to reactant depletion near the interface. The selection of group added PEI in the reaction solution during the room
copper acetate decreased the preparation time when compared temperature synthesis of ZIF-7 to obtain a stable colloidal
to copper nitrate. The addition of an organic amine base dispersion, which was dip-coated on alumina.280 PEI supposedly
accelerated the MOF formation by deprotonation of the linker. enhanced the attachment between the seeds and the support via
A small amount of the water-soluble emulsifier polyvinyl alcohol, H-bonding. In all cases, continuous and oriented membranes
which was added to the interior phase, avoided coalescence of the were produced. In a study on HKUST-1, dip-coating of an
droplets and was also incorporated in the capsule wall, enhancing α-alumina substrate in a dispersion of preformed seeds led to poor
mechanical stability of the capsules. Exchanging 1-octanol with crystal densities in the resulting membrane.281 Spin-coating of
cyclohexanol had a negligible influence. However, the addition of the support with a dispersion of a 1D Cu(II)-BTC coordination
ethanol to the aqueous droplets increased the thickness of polymer or an amorphous MOF material, followed by secondary
capsule walls, possibly due to the formation of less well-defined growth, resulted in the formation of HKUST-1 films. These
interface as the ethanol diffused out. exhibited improved crystal coverage; however, membrane-qual-
6.2.2. Layer-By-Layer Growth. The LBL preparation was ity coatings of HKUST-1 were not obtained.
developed and demonstrated for thin films of HKUST- Direct growth, which often leads to poor crystal densities on
188,274
276 and the mixed-ligand, pillared
layered MOFs substrates, can be used to create a seed layer for secondary
[M(L1)(L2)0.5] (M = Zn, Cu; L1 = BDC, BDC-F4, NDC; growth. Thus, repeated direct growth was employed at room
L2 = DABCO, BPY).231,233 The stepwise formation of HKUST-1 temperature for the fabrication of continuous and ordered thin
was investigated on differently functionalized SAMs on a Au films of [Cu2(PZDC)2(PYZ)]282 and ZIF-8.283 In a similar way,
surface employing SPR spectroscopy. Highly oriented growth continuous films of MOF-5115 and ZIF-8261 were prepared.
was observed for substrates with different functionalization, such During secondary growth, the bases EDIPA and sodium formate
as COOH or OH. The growth rate depends on the surface were added to the starting mixtures of MOF-5 and ZIF-8,
termination as well as the metal source. Copper acetate was respectively. EDIPA led to the deprotonation of H2BDC and
observed to be the Cu source of choice, which was explained by thus prevented dissolution of the MOF-5 seeds. Analogously,
the presence of paddle wheel units in the starting solution.88 Film sodium formate ensured the complete deprotonation of HMiM
growth was also selectively observed on COOH-functionalized in the synthesis of ZIF-8. The same group also prepared hybrid
960 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

IRMOF-3/IRMOF-1 films using IRMOF-1 crystals as seeds and according to composites containing an organic (section 6.3.1) or
adding EDIPA in the reaction solution of IRMOF-3 during and inorganic matrix (section 6.3.2). Monoliths, membranes, fibers,
secondary growth.284 In another work concerning the prepara- or beads were used as the continuous phase. The section does not
tion of continuous membranes of Al
MIL-53, a uniform seed cover MOF-based composites where the MOF is the continuous
layer was synthesized on α-alumina, which acted as the inorganic phase. Numerous examples for these kinds of composites have
source in the reaction with the organic linker. Secondary growth been reported, which include also metals,296 magnetic particles,297
under hydrothermal reaction conditions led to the formation of CNTs,298 or polymers299 as the dispersed phase.
homogeneous, crack-free membranes.285 6.3.1. MOF-Organic Matrix Composites. Natural and
Rubbing the substrate surface with grounded presynthesized synthetic polymers were used for the formation of composites
crystals can also generate a seed layer. Using this route, dis- composed of an organic matrix and MOF crystals.
continuous films of [Mn(HCO2)2]255 and continuous films of One study on the use of a monolithic material has been
ZIF-8286 were obtained after secondary growth. In a study reported. HKUST-1 crystals were deposited within the inter-
regarding [Cu(HFIPBB)(H2HFIPBB)0.5], the α-alumina sur- connected voids of a monolithic macroporous hydrophilic poly-
face was modified with PEI before rubbing the seeds on the HIPE, which was obtained by polymerization of 4-vinylbenzyl
surface.287 Secondary growth led to well-intergrown and ordered chloride and divinylbenzene. Hydrophilization was mandatory to
films. obtain homogenously distribution of the crystals throughout the
LBL growth can also be applied to prepare a seed layer. Ap- monolith, which was easily detected by the light blue color of the
plying this approach, continuous and ordered thin films of composite material. The formation of the composite was accom-
[Cu(NDC)(DABCO)0.5] were formed on bare SiO2, Al2O3, plished by treatment of the activated monolith with the reaction
Ta2O5, and Si3N4.288 These films were used as a seed layer for the mixture followed by the solvothermal reaction.300 A HKUST-1
secondary growth of thicker films. monolithic structure (Figure 15a) was also manufactured in a
6.2.4. Chemical Solution Deposition. Spin-coating a sus- two-step process. Presynthesized crystals were first mixed with a
pension of presynthesized nanocrystals on ITO glass enabled the liquid binding agent and a plasticizer in a lab-scale kneader until
preparation of thin films of [Ln1
xTbx(BTC)].250 The resulting the molding batch appeared as homogeneous. In a second step,
films showed strong luminescence properties. Dip-coating was the molding batch was extruded to a monolithic structure.301
also used in order to synthesize high-quality optical thin films of Synthetic polymer
MOF composite membranes have been
Fe
MIL-89,289 Cr
MIL-101,290 and ZIF-8.291 In these cases, investigated using a polyimide (Matrimid) and a polysulfone
silicon wafers were dip-coated with colloidal dispersions of as- polymer as the matrix. Composite membranes of MOF-5 and
synthesized or presynthesized nanocrystals. The thickness and ZIF-8 with Matrimid were prepared by the solution blending
density of the ZIF-8 films were tuned by varying the withdrawal approach.302
304 A dispersion of preformed MOF-5 or ZIF-8
speed and the concentration of nanoparticles. For MIL-89, only was added to a solution of Matrimid in CHCl3. Dispersion of the
the use of the trimeric precursor [Fe3O(OAc)6(H2O)3] in MOF crystals was accomplished by sonication. The composite
combination with trans,trans-muconoic acid resulted in stable membrane was formed by evaporation of the solvent. Plastic
colloidal dispersions, which was deposited on the surface. The deformation of the composite membrane indicated strong inter-
thin films of Cr
MIL-101 or ZIF-8 displayed a dual hierarchical action between the polymer matrix and the MOF-5 nanocrystals.
porous structure due to the textural porosity. Appling the same approach, composite membranes of HKUST-1,
Instead of using flat substrates, the inner surface of a silica MIL-47, MIL-53, and ZIF-8 with Matrimid or polysulfone
capillary column was coated with thin films of Cr
MIL-101,292 were also produced.305,306 Better quality composite membranes
ZIF-n (n = 7, 8),293 and IRMOF-n (n = 1, 3).294 Suspensions of pre- were formed by pretreatment of the MOF crystals with the
synthesized nanocrystals of Cr
MIL-101, the ZIFs, or IRMOFs silylating agent N-methyl-N-(trimethylsilyl)trifluoroacetamide.
were first filled into the column under gas pressure and then In a similar study, ZIF-8
polysulfone membranes were also
pushed through the column at a steady speed to leave a wet coating
obtained by the solution blending approach.307 The CO2 diffu-
layer on the inner wall. To avoid acceleration of the suspension
sion properties of the composite membranes were studied, and
near the exit of the column, a buffer tube was attached to the
the ZIF-8 crystals were shown to improve the transport of the gas
column end as a restrictor. Before the GC separation experiments,
the columns were treated using different temperature programs. through the membrane.
Synthetic polymer fibers were also employed as the substrate,
6.3. Composites and the composites were obtained by electrospinning. In the first
Composites are multicomponent materials comprising multi- report, ZIF-8/polyvinylpyrrolidone (PVP) composite nanofibers
ple different (nongaseous) phase domains in which at least one were synthesized starting from a PVP solution with well-dis-
type of phase domain is a continuous phase.295 They are often persed ZIF-8 nanocrystals (Figure 15b).308 The diameter of the
used in industrial processes, since the composites combine the nanofibers in the fiber mat was adjusted by varying the polymer
properties of the phases and tuning of the properties is possible. concentration. Using other polymers like polystyrene and poly-
Thus, they have been studied, for example, to improve gas ethylene oxide allowed increasing the fibers’ stability. Higher
sorption properties or in gas separation. In addition, handling ZIF-8 loadings were achieved by tuning the synthesis parameters
of the composites is often easier compared to the crystalline and functionalizing the surface of the ZIF-8 nanocrystals with less
MOFs. Especially in catalysis, composites are of interest since the polar molecules. The second report describes the preparation of
catalytic activity of the dispersed phase is combined with superior MOF/polymer (MOF: HKUST-1, MIL-100; polymer: PS, PVP,
stability of the continuous phase, which also allows the easy polyacrylonitrile, polypropylene) composite fibers with different
recovery of the catalyst. mechanical stabilities.309 A small difference between particle size
In the following section composites will be described containing and fiber diameter led to a pearl necklace-like morphology with
the MOF as the dispersed phase. The sections are organized lower MOF loadings. Fortunately, particles in combination with
961 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
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Figure 15. Digital images of (a) HKUST-1 monolith, (b) ZIF-8/PVP fiber mat, and (c) HKUST-1/PAM beads. Reproduced with permissions from ref
301, 308, and 311, respectively. Copyright 2010 American Ceramic Society, 2011 Royal Society of Chemistry, and 2010 Royal Society of Chemistry,
respectively.

significantly smaller fibers resulted in a spiderlike morphology at together with preformed Cr
MIL-101 nanocrystals was dip-
higher MOF loadings. coated on the substrate. Dense, uniform coating was observed
Natural polymer fibers were also used to form composites. for optimized reaction conditions, i.e., rotating of the autoclave
Differently treated pulps were employed. Addition of the crystal- during the secondary growth step as well as the right choice of the
line powder of HKUST-1 to the pulp slurry was found to yield an size of seeds and the seeding procedure. The composite was tested
inhomogeneous distribution of the powder.310 Pulp fibers with in liquid-phase oxidation reactions and showed good stability. In
crystals homogeneously distributed over the surface area were the second study, a cordierite monolith was also used as the
obtained by the direct growth method. In these experiments, the substrate.301 Solvothermal synthesis of HKUST-1 resulted in low
degree of coverage increased with increasing lignin contents in crystal coverage on the cutting edges of the honeycomb structure.
the fibers. This was explained by the presence of carboxyl groups In order to enhance gas adsorption capacities of graphite oxide
in lignin. (GO), composites of MOF-5313 and HKUST-1314 were synthe-
PAM beads were used as a matrix, due to their hydrophilicity, sized by dispersing GO in the synthesis mixtures prior to the
in combination with HKUST-1 and Co
CPO-27311 with the solvothermal reactions. GO/MOF-5 composites with various
goal to enhance mechanical stability and facilitate handling ratios of the components were obtained. With increased GO
compared to bulk HKUST-1. Two methods were employed: content, a decrease in microporosity was observed. The compo-
formation under solvothermal conditions and immersion of the sites likely adopted lamellar structures constructed from alternat-
beads into preheated crystallization solutions. Using copper ing layers of GO and MOF, which was explained by possible
nitrate, HKUST-1/PAM composites (Figure 15c) were synthe- interactions between the epoxy groups on graphene and the oxide
sized under solvothermal conditions, and the presence of clusters in MOF-5. GO/HKUST-1 composites were also re-
HKUST-1 crystals within the beads was confirmed by SEM ported, and the porosity of the composite was claimed to exceed
images. Preswelling of the beads in an ethanol/water (1:1) that of the parent materials. Unfortunately, a specific surface of 900
mixture prior to solvothermal treatment led to growth of the m2/g of HKUST-1 for their material was reported by the authors ,
crystals only on the external surface, indicating a large barrier to which is far below the state of the art values known for HKUST-1.
diffusion compared to the rate of nucleation and crystal growth. Recently also the formation GO/Fe
MIL-100 composites was
The ratio of MOF:polymer could be adjusted by changing the also investigated. In these studies increasing amounts of an
concentration of the HKUST-1 reaction mixture. The immersion amorphous phase were observed with higher GO contents.315
procedure of untreated beads did not lead to the formation of Using a nonionic surfactant, the formation of hierarchical
HKUST-1 crystals. Therefore, pretreatment, i.e., preswelling of micro- and mesoporous HKUST-1/alumina and HKUST-1/
the PAM beads in a solution of copper acetate, was carried out silica composites was investigated. These were prepared by
and led to the formation of HKUST-1/PMA composites. applying MW irradiation to a dispersion containing starting
Independent of the pretreatment, solvothermally prepared materials of HKUST-1 and the alumina (boehmite) or silica
Co
CPO-27/PAM beads exclusively exhibited crystals on the (TEOS) source together with the triblock copolymer Pluronic
external surface. In addition to pure organic beads, composite P123.316 Microporosity as well as mesoporosity could be demon-
SiO2/PAM beads were also tested. Applying the immersion strated for the composites by sorption experiments, and the
method, HKUST-1 crystals were grown on SiO2/PAM beads. presence of HKUST-1 was confirmed by XRPD measurements.
6.3.2. MOF-Inorganic Matrix Composites. Four different Silica as well as alumina beads were also employed as sub-
types of inorganic matrices—graphite oxide (GO), silica, alumi- strates for the synthesis of HKUST-1 composites. Monodisperse
na, and cordierite or combinations thereof—were employed for mesoporous silica beads (Nucleosil 100-3) were impregnated
the formation of composites. with the starting mixture, and the solvent was evaporated.317
Two studies were reported on the coating of a cordierite The monodisperse MOF
silica composites were tested as the
monolith.301,312 Uniform coatings of Cr
MIL-101 nanocrystals HPLC stationary phase and showed good separation properties.
inside the macropores of a cylindrical cordierite monolithic were In another report,311 silica and SiO2/Al2O3 composite beads
accomplished by employing the secondary growth technique.312 were used. Two methods were employed: formation under solvo-
Two methods were employed: (a) a suspension of α-alumina was thermal conditions and immersion of the beads into preheated
dip-coated on the substrate prior to seeding with preformed crystallization solutions. No HKUST-1 growth was detected on
Cr
MIL-101 nanocrystals and (b) the suspension of α-alumina silica beads, but growth was observed using mixed SiO2/Al2O3
962 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

beads. This was attributed to the more basic properties of the A large variety of distinct preparative approaches, such as the use
alumina. No information regarding bead surface growth or of structure-directing agents, ionic liquids, biphasic solvent mixtures,
growth within the macropores of the beads was reported. molecular precursors, or in situ linker synthesis, have been under-
taken in the last 2 decades. The modulator approach or reverse
7. CONCLUSIONS AND FUTURE PROSPECTS microemulsion systems in combination with different energy
sources have shown to be useful to tune size and morphology of
Although MOF synthesis was originally set out for making MOF crystals. Most of these studies have dealt with a few proto-
new compounds and structures with interesting properties, typical MOFs. Considering that a wide variety of compounds are
the field has matured and is broadening its scope. This holds
available, future investigations must be extended to these and also to
for the synthesis methods applied as well as the areas of
the shaping of MOFs with potential applications. In addition to the
application. While conventional syntheses methods have been
most-studied thin films and membranes, other shaped composite
widely used, the fields of mechano-, sono-, and electrochemi-
cal synthesis as well as microwave-assisted syntheses are just materials could be envisaged for desired industrial applications.
emerging. They have demonstrated to be applicable for some Finally, we want to raise concern about the comparison of
compounds, often under milder reaction conditions, yielding results reported on the synthesis and characterization, especially
materials with different particle sizes and properties. This sorption properties, of MOFs. Great care must be exerted not
could be of interest for up-scaling of syntheses and the only to the synthesis but also to the activation and characteriza-
application of MOFs. However, mainly well-known com- tion in order to allow for reliable comparisons. Verification of
pounds have been reproduced by these alternative routes, results by different groups such as established in the zeolite
and the reproducibility of the synthesis procedures needs to be synthesis community in the book on “Verified Synthesis of
established. Great care must be exerted upon the actual input Zeolites” would benefit the synthesis community and the groups
of energy by the different synthetic procedures. Therefore, working on the application of MOFs.320
systematic studies under well-defined conditions need to be
performed. High-throughput methods are the ideal tools to AUTHOR INFORMATION
accomplish this task, but unfortunately, they are still not well- Corresponding Author
established in the MOF community. Their extension to the *E-mail: stock@ac.uni-kiel.de.
study of other reaction parameters or other synthesis methods
would definitely be beneficial. Thus, the reaction temperature Notes
†
can be systematically varied using a gradient oven. This setup Dedicated to Prof. Ferey on the occasion of his 70th birthday in
could be extended to higher reactions temperatures. While the July 2011.
HT methodology was recently extended to microwave-as-
sisted heating, setups can be envisioned, with different degrees BIOGRAPHIES
of miniaturization and parallelization, that would even allow
the HT investigation using sonochemical or mechnochchem-
ical syntheses. A method that has been much neglected,
probably due to the complexity of the equipment and the
chemistry involved, is the electrochemical synthesis of MOFs.
Especially when working at elevated reaction temperatures,
this method could lead to new MOFs structures with unusual
metals in uncommon oxidation states.
As shown, concepts from other research areas, and especially
from zeolite chemistry, have found their way in MOF synthesis,
but they need to be extended and pursued in more detail.
MOFs offer an even larger playground compared to zeolites.
For example, due to the variety of possible organic linkers,
some positively as well as negatively charged framework com-
pounds have been obtained. Thus, MOFs can be imagined that
contain zwitterionic linker molecules. In addition, the use of
charged linkers in combination with structure-directing agents Norbert Stock has received his Ph.D. degree in chemistry
could allow discovery of new compounds. Alternative synthesis with Prof. Schnick in 1998 at the University of Bayreuth and
methods applied in zeolite synthesis, such as dry-gel or steam- has spent the next 15 months as a postdoc in the groups of
assisted conversion, could be an easy candidate to obtain some Prof. Ferey, Prof. Cheetham, and Prof. Stucky at the Uni-
of the compounds as recently described for the first time.318 versity of Versailles and University of California at Santa
While expanding the variety of MOFs, there is also a need to Barbara. In 2000, he joined the group of Prof. Bein at the
learn more about the formation of these compounds. Systema- Ludwig-Maximilians University of Munich, where he finished
tic studies can help to identify specific parameters, but in situ his habilitation in 2004. In the same year, he became Professor
and ex situ methods comprising various analytical tools in com- at the Institute of Inorganic Chemistry at the Christian-
bination with theoretical methods are necessary to study the Albrechts-University in Kiel. His research interests are within
different stages of crystallization. These studies could not only help the field of inorganic
organic hybrid compounds. He has
to explain the crystallization, but they could even help in the been involved in the development and application of high-
synthesis of metastable polymorphs and/or MOFs with new or throughput methods for reactions under solvothermal condi-
improved properties.319 tions. Thus, he is interested in the discovery of new hybrid
963 dx.doi.org/10.1021/cr200304e |Chem. Rev. 2012, 112, 933–969
Chemical Reviews REVIEW

compounds, in understanding their formation, as well as in BPY 4,40 -bipyridine

setting up synthesis
structure relationships. BTA 1,2,3-benzotriazolate
BTB benzene-1,3,5-tribenzoate
BTC 1,3,5-benzenetricarboxylate
BTDD bis(1H-1,2,3-triazolo[4,5-b],[40 ,50 -i])dibenzo-
[1,4]dioxin
BTEC 1,2,4,5-benzenetetracarboxylate
BTT 1,3,5-benzenetristetrazolate
cam D-camphorate
CAU Christian-Albrechts University
CDC 9H-carbazole-3,6-dicarboxylate
CE conventional electric
CNT carbon nano tube
CPO coordination polymer of Oslo
CTAB cetyltrimethylammonium bromide
DABCO 1,4-diazabicyclo[2.2.2]octane
DACH 1,2-diaminocyclohexane
DEF N,N0 -diethylformamide
Shyam Biswas received his M.Sc. in chemistry from Indian DES deep eutectic solvent
Institute Technology Kanpur in 2006. He completed his Ph.D. in DMA N,N0 -dimethylacetamide
2010 from University of Ulm under the supervision of Prof. Dirk DMF N,N0 -dimethylformamide
Volkmer in the area of coordination compounds and coordina- DMSO dimethyl sulfoxide
tion polymers based on 1,2,3-triazolate ligands. He is currently a DPNI N,N0 -di-(4-pyridyl)-1,4,5,8-naphthalene tetracarboxy-
postdoc with Prof. Norbert Stock. His research interests include diimide
functional coordination compounds, catalytic and gas storage DUT Dresden University of Technology
properties of metal
organic frameworks. EC electrochemistry
EDIPA N-ethyldiisopropylamine
EDXRD energy-dispersive X-ray diffraction
ACKNOWLEDGMENT EI 5-ethynylisophthalate
Deutsche Forschungsgemeinschaft (DFG, SPP 1362 EIm 2-ethylimidazolate
“Porous Metal
Organic Frameworks”, grant agreement no. EPR electron paramagnetic resonance
STO 643/5-2) and European Union (Seventh Framework Pro- ESI-MS electron spray ionization
mass spectrometry
gramme FP7/2007-2013, grant agreement no. 228862) are EXAFS extended X-ray absorption fine structure
gratefully acknowledged for their financial support. The FMA fumarate
authors thank Tim Ahnfeldt (University of Kiel) and Prof. GLU glutarate
Paul Wright (University of St. Andrews) for helpful discus- GO graphite oxide
sions, and Lars-Hendrik Schilling (University of Kiel) for H2HFIPBB
drawing Figures 1 and 8. N.S. thanks Prof. Karl-Petter Lillerud 4,40 -(hexafluoroisopropylidene)bis(benzoic acid)
and the research team at the Norwegian National Centre of HIP 2-hydroxyisophthalate
Research inGAP (University of Oslo) for their hospitality and HIPE high internal phase emulsion
support during his sabbatical. HKUST Hong Kong University of Science and Technology
HPP 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine
LIST OF ACRONYMS AND ABBREVIATIONS HT high-throughput
2D two-dimensional HTB s-heptazine tribenzoate
3D three-dimensional IDS meso-iminodisuccinate
AFM atomic force microscopy IL ionic liquid
ALD atomic layer deposition ILAG ion- and liquid-assisted grinding
AOT dioctyl sulfosuccinate, sodium salt Im imidazolate
APTES 3-aminopropyltriethoxysilane INA isonicotinate
AS as-synthesized IP isophthalate
BBTA 1H,5H-benzo[1,2-d:4,5-d0 ]bistriazolate IRMOF isoreticular metal
organic framework
BDC 1,4-benzenedicarboxylic acid L [(HO3P)2CH
C6H4
CH(PO3H)2]
BDC
(OH)2 L0 1,3,5-trimethylimidazole-2,4,6-triethylbenzene
2,5-dihydroxybenzenedicarboxylate LA lauric acid
BDC
NH2 LAG liquid-assisted grinding
2-aminoterephthalate LBL layer-by-layer
BDI 5,50 -(buta-1,3-diyne-1,4-diyl)diisophthalate LP large pore
BDPB 1,4-bis[(3,5-dimethyl)pyrazol-4-yl]benzene MC mechanochemistry
BET Brunauer
Emmett
Teller MIL Material of Institute Lavoisier
BIm benzimidazolate MIm 2-methylimidazolate
BPDC 4,40 -bipyridinedicarboxylate MOF metal
organic framework
BPE trans-1,2-bis(4-pyridyl)ethylene MT 5-methyl-1H-tetrazole
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