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2009 Metal–organic frameworks issue

Published on 16 March 2009 on http://pubs.rsc.org | doi:10.1039/B804680H

Reviewing the latest developments across the interdisciplinary area of

metal–organic frameworks from an academic and industrial perspective
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Guest Editors Jeffrey Long and Omar Yaghi

Please take a look at the issue 5 table of contents to access

the other reviews.
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Industrial applications of metal–organic frameworksw

Alexander U. Czaja,*a Natalia Trukhanb and Ulrich Müllerb
Received 10th February 2009
First published as an Advance Article on the web 16th March 2009
DOI: 10.1039/b804680h

New materials are prerequisite for major breakthrough applications influencing our daily life, and
therefore are pivotal for the chemical industry. Metal–organic frameworks (MOFs) constitute an
emerging class of materials useful in gas storage, gas purification and separation applications as
well as heterogeneous catalysis. They not only offer higher surface areas and the potential for
Published on 16 March 2009 on http://pubs.rsc.org | doi:10.1039/B804680H

enhanced activity than currently used materials like base metal oxides, but also provide shape/size
selectivity which is important both for separations and catalysis. In this critical review an
overview of the potential applications of MOFs in the chemical industry is presented.
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Furthermore, the synthesis and characterization of the materials are briefly discussed from the
industrial perspective (88 references).

Introduction scaffold-like materials using Cu(I) centres and tetracyano-

Already in 1965, roughly three decades before the commonly
assumed birth year of metal–organic frameworks (MOFs),
Tomic mentioned materials which would nowadays be called
MOFs, metal–organic polymers or supramolecular structures.1
Bi- and trivalent aromatic carboxylic acids were used to form
frameworks with zinc, nickel, iron, aluminium, thorium
and uranium. Some interesting features of MOFs, like high
thermal stability and high metal content were already
reported. Also in 1965, Biondi et al. reported on Cu(II)
tricyanomethanide being a crystalline, polymeric compound.2
In 1990, Hoskins and Robson reported on the design of
a
Chemicals Research and Engineering, GCC/PZ, BASF SE,
California NanoSystems Institute, University of California,
Los Angeles, 570 Westwood Plaza, Los Angeles, CA 90095, USA.
E-mail: alexander.czaja@basf.com
b
Chemicals Research and Engineering, GCC/PZ, BASF SE,
67056 Ludwigshafen, Germany
w Part of the metal–organic frameworks themed issue.
tetraphenylmethane.3
Interest in the field was again kindled by the group of O. M.
Yaghi, which published the structure of MOF-5 in late 1999,4
and the concept of reticular design, with totally different
carboxylate linkers, in 2002.5–7
Numerous reviews summarize the fast growing research
efforts in the field. The most comprehensive ones are by
S. Kitagawa,8 O. M. Yaghi,9 and G. Férey.10 The review by
Gérard Férey is also highly recommended as an introduction
to the concepts applied in MOF research.
Structures, properties and possible applications of MOFs as
storage media were studied.9,10 Comparisons with oxides,
molecular sieves, porous carbon and heteropolyanion salts
have been made by Barton and co-authors.11 Nowadays
several hundred different MOFs have been identified. The
self-assembly of metal ions, which act as coordination centres,
linked together with a variety of polyatomic organic bridging
ligands, has resulted in tailored nanoporous host materials
as robust solids with high thermal and mechanical stability.

Alexander Czaja, born 1977 in Natalia Trukhan, born 1978 in

Nürnberg, Germany. 1997:
studied chemistry at the
Friedrich-Alexander Univer-
sity Erlangen-Nürnberg. 2005:
Dr. rer. nat. in the group of
Prof. Dieter Sellmann/Prof.
Horst Kisch (thesis on compe-
titive catalysts for nitrogen
fixation); subsequently joined
BASF SE (Ammonia Labora-
tory) as a research manager,
working on heterogeneous
oxidation catalysis and high
Alexander U. Czaja throughput catalyst screening.
2008: BASF scholar at the
University of California in Los Angeles, currently working
on catalysis with metal–organic frameworks (MOFs) in
collaboration with Prof. Omar Yaghi.
Petropavlovsk-Kamchatskij,
Russia. 1995: studied chemis-
try at Novosibirsk State
University, Department of
Natural Sciences. 2003: PhD
in the group of Dr Kholdeeva
on speciality ‘‘Kinetics and
Catalysis’’ (thesis on the
selective oxidation of organic
substrates over mesoporous
titanium- and vanadium-
silicates). 2004: Postdoc
at Stuttgart University,
Natalia Trukhan Germany, with Prof. Roduner
supported by an Alexander
von Humboldt Fellowship. 2005: research manager at
BASF SE. Research activity: zeolite and MOF synthesis and
applications.

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c The Royal Society of Chemistry 2009
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Interestingly, unlike other solid matter, e.g. zeolites, carbons 1. Synthesis

and oxides, a number of coordination compounds are known
to exhibit high framework flexibility and shrinkage/expansion
due to interactions with guest molecules.8 The most striking
difference to state-of-the-art materials is probably the total
lack of non-accessible bulk volume in MOF structures.
Although high surface areas are already known from activated
carbons and zeolites as well, it is the absence of any dead
volume in MOFs which principally gives them, on a
weight-specific basis, the highest porosities and world record
surface areas. It was reported, for example, that in the case of
MOF-177 the surface area reaches 5640 m2 g1 12 and for
MIL-101 up to 5900 m2 g1.13 Of course, properties like the
Published on 16 March 2009 on http://pubs.rsc.org | doi:10.1039/B804680H
Usually, the synthesis of MOFs is straightforward, using
well-soluble salts as the source for the metal component, e.g.
metal nitrates, sulfates or acetates. The organic ingredients,
which mostly are mono-, di-, tri- and tetracarboxylic acids,
are supplied in a polar organic solvent, typically an amine
(triethylamine) or amide (diethylformamide, dimethylformamide).
After combination of these inorganic and organic components
under stirring, the metal–organic structures are formed by
self-assembly at temperatures starting at room temperature
and up to solvothermal conditions at 200 1C within a few
hours. A typical scheme of a semi-technical process is given in
Fig. 1, where the scale-up synthesis of lightweight Mg-MOF

drastically increased velocity of molecular traffic through these

open structures are closely related to the regularity of pores in (Basolite M050) with formic acid as linker is shown as an
nanometre size as well. example. The scheme indicates not only the different steps of
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Thus, the combination of such unbelievable levels of preparation but also recycling of the solvent and further
porosity, surface area, pore size and wide chemical inorganic– processing of the dried powder into shaped material. Some
organic composition has recently brought these materials to details about preparing shaped bodies from MOF materials
the attention of many researchers both in academia and (Fig. 2) are published.17,18
industry, with over 1000 publications on ‘‘metal–organic It should be pointed out, however, that the filtering and
frameworks’’ and ‘‘coordination polymers’’ per annum.8 drying of metal–organic compounds in the wet processing
In this review, we focus on the topics of synthesis, steps need to be carried out very carefully, as—due to
characterisation and application of MOF materials from an their high porosity and surface area—MOFs may easily carry
industrial point of view. Whenever possible, comparison is
made to state-of-the-art applications in order to outline
possibilities of processes which might be beneficially run by
using MOFs. Recent findings, like the electrochemical reactivity
of MIL-53(Fe) with a promise for application in Li-based
batteries,14 the first completely new class of scintillation
materials using Zn-MOFs with stilbene dicarboxylic acid as
linker15 and the storage and delivery of pharmaceuticals by
MOFs,16 are acknowledged and may find application in
industry some time. However, they would go beyond the scope
of this review which focuses on the application in chemical
industry.

Ulrich Müller, born 1957 in Fig. 1 Simplified flow diagram of industrial metal–organic frame-
Katzenelnbogen, Germany. work synthesis procedures via solvothermal (Mg-MOF) and electro-
1977: studied chemistry in chemical (Cu-EMOF) routes.
Mainz (thesis on the synthesis
of large zeolite crystals and
sorption properties) and
received his PhD in the
group of Prof. K. K. Unger;
research activities at CNRS
‘Tian&Calvet’, Marseille,
ILL Grenoble, and with G. T.
Kokotailo, Univ. Pennsylvania.
1989: BASF SE: zeolite
synthesis and application in
Ulrich Müller catalysis and adsorption.
1999: Senior Scientist, zeolite
catalysis: CFC-free polyurethane foams, catalysts for crop
protection agents, chemical intermediates, sorptive olefin feed-
stream purification, piloting of propylene epoxidation catalysts.
1999: Synthesis, scale-up, modification and testing of various
metal–organic framework compositions. 2005: BASF Research
Director. Fig. 2 Shaped bodies made from MOF materials.

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Table 1 Space–time–yield for MOF synthesis
Materials
Basolite A100 (Al-MOF) Al-terephthalate
Basolite C300 (Cu-BTC-MOF) Cu-benzene-1,3,5-tricarboxylate
Basolite F300 (Fe-EMOF) Fe-benzene-1,3,5-tricarboxylate
Basolite Z1200 (Zn-EZIF) Zn-2-methylimidazole
Basolite M050 (Mg-MOF) Mg-formate
Zeolite — 300–800
50 to 150 wt% of occluded solvent. This is an order of
magnitude higher than in a zeolite or base metal oxide
preparation. Therefore, it is advisable to first remove the large
Published on 16 March 2009 on http://pubs.rsc.org | doi:10.1039/B804680H
amount of adsorbed solvent under gentle conditions regarding
pressure and temperature, prior to high thermal activation.
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Furthermore, the crystallization of MOFs is an equilibrium
reaction between an inorganic base metal salt and an
organic acid. The preparation of, for example, MOF-5 is
stoichiometrically expressed as:
4[Zn(NO3)24H2O] þ 3[H2BDC] þ 8[OH]
# [Zn4O(BDC)3] þ 8[NO3] þ 23[H2O]
where H2BDC is terephthalic acid and Zn4O(BDC)3 is the
MOF-5 unit composition. It is clearly seen, that the
equilibrium can be shifted to the MOF-product side by
working on the concentration profiles of, for example, the
solvent, liberated water and nitrate, respectively. By taking
these equilibrium conditions into account, it became possible
to improve the MOF quality; i.e. to increase the surface area
from 2600 m2 g1 up to 3400 m2 g1.19
As the reaction can be easily driven in both directions, it is
obvious that the stability and integrity of MOFs in their use
depend on the polarity of the environment and the pH-value.
The conditions under which a material is stable have to be
considered on a case-by-case basis.
On a larger production scale, attention has to be paid
to safety issues whenever high nitrate concentrations are
involved, especially in addition to the build-up of large surface
area volumes in adiabatic reactor vessels. Thus, an alternative
salt-free procedure has been developed by BASF SE, using an
electrochemical route. Bulk metal sacrificial anodes are
oxidized in the presence of dissolved carboxylates in an
electrochemical cell (Fig. 1).20,21 Simple recovery of the formed
solid by filtration directly yields the final MOF powder
after drying. This procedure is especially beneficial for
MOF-structures containing open metal sites, as no anions
from added salts can block the access to the sites. By the same
method the successful synthesis of Zn-EZIF (electrochemically
made zeolite imidazolate framework) with 2-methylimidazole
as a linker was reported.22
It is necessary to note that an issue of prime importance for
scale-up production is space–time–yield (STY) (kg of MOF
per m3 of reaction mixture per day), which should be as high as
possible. In Table 1, the STY for some industrial MOFs in
comparison to zeolite production are presented.
A summary of some verified synthesis procedures for
laboratory and larger scale has been presented.21
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Langmuir surface area/m2 g1 Space–time–yield/kg m3 day1
1100–1500 160
1500–2100 225
1300–1600 20
1300–1800 100
400–600 4300
50–150
2. Characterization
As MOFs are both crystalline and highly porous materials,
most frequently X-ray diffraction (XRD) is used to characterize
the crystallinity and phase purity, adsorption measurements
are performed to check for the porosity, and more elaborate
studies make use of neutron scattering to determine sorption
sites.23 Commercially available equipment using nitrogen
sorption at 77 K or argon uptake at 87 K are applied and
equivalent surface areas are calculated according to, e.g., the
Langmuir equation. However, it should be considered that the
underlying model of independent, equivalent and non-infringing
sorption sites might be different on a molecular level. Many
reports have described localized rather than bulk volume
adsorption phenomena on metal–organic materials, with some
even clearly differentiating between various crystallographic
sites and adsorption strengths.23–26
For industrial applications, sorption studies are simply a
convenient and fast way to compare the higher sorption
capacities of MOFs over state-of-the-art sorbents, although
care has to be taken whenever applications might rely upon
gravimetric or volumetric uptake later on.
While mass transfer can heavily influence results in catalysis,
it is clearly necessary to have information at hand on the
crystal sizes and size distribution of the MOF samples, which
are routinely collected by scanning electron microscopy
(Fig. 3).
As the metal content reaches values between 20–40 wt%, it
is also desirable to check the local metal cluster arrangements
and environments using more elaborate methodology such as
extended X-ray adsorption fine structure (EXAFS), X-ray
adsorption near-edge structure (XANES) or X-ray photon
spectroscopy (XPS).
The adsorbates in the pores of MOFs can be investigated by
UV-VIS, IR- and Raman-spectroscopy.7
3. Applications of metal–organic frameworks
Only a limited number of possible applications have been
discussed for MOFs so far and, to the best of our knowledge,
none have been industrially realized as yet. However, taking
a closer look at specific properties, it becomes clear that
especially the high porosity and the absence of hidden volumes
in these new frameworks in principal render them quite useful
for volume specific applications like adsorption, separations,
purification purposes, and catalysis. Typical drop-in technologies
might use MOFs first, for example, substituting zeolitic
molecular sieves, activated carbons and base metal oxides in
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Fig. 3 Morphology of crystals from different MOF samples determined by SEM analysis.

existing plants to gain better performance in variable costs Usually, either distillation or pressure and/or thermal swing
without any fixed capital expenditure. adsorption–desorption are used to separate the mixtures.
Examples of existing technologies are nitrogen–oxygen (air),
3.1 Gas purification nitrogen–methane, and noble gas (e.g. Kr–Xe) separations,
some of which use zeolitic adsorbents.
One possible field where MOFs can be beneficially used might
Recently, the separation of Kr–Xe by pressure swing
be the removal of ppm-traces of sulfur components from
adsorption, as well as the purification of methane in natural
various gases. Especially MOF structures with accessible
gas were piloted on MOF-adsorbents.27,28
open metal sites are well suited to strongly (430 kJ mol1)
chemisorb electron-rich, odour-generating molecules, like
amines, phosphines, oxygenates, alcohols, water, or sulfur-
containing molecules.
One example, which was experimentally evaluated in
continuous breakthrough trials, is the removal of tetra-
hydrothiophene (THT, odorant) from natural gas. At room
temperature, traces of 10–15 ppm sulfur were fully captured
down to less than 1 ppm using an electrochemically prepared
shaped Cu-EMOF (Fig. 4) in a fixed bed reactor.21 The
overall capacity of the MOF material (70 g THT LMOF1)
outperformed, by about an order of magnitude, commercially
available activated carbon materials as adsorbents, namely
Norit (type RB4) and CarboTech (type C38/4).

3.2 Gas separation

In gas separation processes, the gas mixtures usually consist of
components having concentrations in the same order of Fig. 4 Feed stream purification and removal of tetrahydrothiophene
magnitude. This is in contrast to the gas purification processes. from natural gas using Cu-BTC-EMOF.

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Fig. 5 N2- and H2-adsorption isotherms (Mg-MOF, Basolite M050)
indicating a molecular sieving effect.
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Interestingly, even small pore MOFs have been described
which are able to separate molecules by size or kinetic
diameter,29–33 e.g., while water uptake occurs, slightly larger
molecules such as N2, O2, CO2, and methane are occluded
from adsorption.30 To demonstrate this concept, the adsorption
isotherms of nitrogen and hydrogen for the small-pore
Mg-MOF (Basolite M050) are shown in Fig. 5. Preferential
adsorption of hydrogen over nitrogen is observed.
CO2 separation is of great interest due to the awareness of
global warming over the past years. MOFs were considered as
CO2 adsorbents.10,34,35 Currently, elimination of CO2 from
low pressure flue gases as emitted, for example, by fossil fuel
burning power plants is done very effectively by gas scrubbing.
The partial pressure of CO2 in these streams lies between
60 and 130 mbar. The separation is done using the reversible
stoichiometric reaction (chemisorption) of CO2 with an amine
in aqueous solution (amine wash) at room temperature. CO2
in MOFs is physisorbed in the same temperature region. Due
to the lower energy of adsorption for the physisorption
process, MOF adsorbents, e.g. MIL-53(Cr),36 need a higher
CO2 partial pressure to reach sufficient adsorption capacities
(Fig. 6). This shows that MOFs currently can only be
effectively used in CO2 separation at high pressure. However,
Fig. 6 Adsorption isotherms of carbon dioxide on MIL-53(Cr) in
comparison to carbon dioxide removal from flue gas by amine wash.
1288 | Chem. Soc. Rev., 2009, 38, 1284–1293
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even under these conditions they do not perform as well as an
amine scrubber.
3.3 Gas storage
Due to the unique structure of MOFs and especially due to the
absence of dead volume, it becomes possible to increase the
volumetric specific gas storage above previously known levels.
This effect can be very pronounced and depends on the type,
temperature and pressure of the gas, as well as on the specific
MOF material being used.
The mechanism of increased storage in MOF-filled gas
cylinders over empty gas bottles is easy to understand, once
the underlying principles are considered. The filling of a
conventional gas cylinder is simply applying physical effects
depending on the pVT-characteristic of the gas under
investigation. Considering MOF-filled gas cylinders, the above
mentioned effect is overlaid by an additional adsorption effect
inside the MOF. As these frameworks are free of dead-volume,
there is almost no notable loss of storage capacity due to space
blocking by non-accessible volume. Summarizing, pVT-filling
plus adsorption contribute to an enhanced volumetric storage
capacity.
The uptake curves resulting from this effect are shown in
Fig. 7 for the storage of CH4 at room temperature and
pressures up to 200 bar in gas cylinders filled with different
MOF materials. A non-linear uptake behaviour can be
monitored as the pressure is increased. Release of the gas
follows the same curve when the valves are opened and the
pressure is reduced. At a pressure of 150 bar, it is clearly seen
that about 35% more capacity is reached over the state-of-
the-art filling curve. It should be noted that the benefit of
enhanced capacity with MOF-filled vessels can only occur if
the gas is in a true gaseous state and not in the liquid-phase.
Furthermore, the density of the liquid phase is the limiting case
for the storage capacity of the MOF. Graphically speaking, a
MOF cannot compress gas to a higher density than its liquid
state density.
Recently, exceptionally high uptakes of even acetylene were
reported by Kitagawa, in this case clearly exceeding the
packing density usually obtained in today’s storage devices.37
The greatest challenge is, of course, the storage of hydrogen.
The underlying possibility to use hydrogen as a fuel for mobile
or portable fuel-cell applications raises a very high interest in
Fig. 7 CH4-storage in MOFs (prototype trials).
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hydrogen storage possibilities. MOF-storage for hydrogen
works fully reversibly, avoids complicated heat treatments,
and recharging proceeds within seconds or minutes. This
clearly is an advantage over, e.g., metal hydrides as storage
materials. In MOF-5 even the distinct locations of adsorbed
hydrogen molecules have been elucidated using inelastic
neutron scattering,23 while density functional theory (DFT)
studies have proposed a storage capacity of 16–20 molecules of
H2 per Zn4O-cluster.26
The need for alternative fuel sources and energy carriers
together with target values by the US Department of Energy
was recently reviewed.38 Storage data are reported of up to
7.5 wt% of hydrogen on MOFs, (e.g. MOF-177) at 9 MPa and
77 K.12,27,37 Many other research groups look into this
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challenge as well. 3.8 wt% hydrogen capacity has been
reported by Férey’s group on MIL-5339 derived from aluminium
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salts and terephthalic acid. Pillaring with secondary amine
linkers (triethylenediamine) as a strategy was employed by
Kim40 and Seki,41 which resulted in hydrogen uptakes up to
2.0 wt% at 0.1 MPa and 87 K. Similar values were achieved
with MOF-505 by Yaghi’s group,42 where Cu-paddle-wheels
are connected by 3,3 0 ,5,5 0 -biphenyltetracarboxylic acid.
Doubly interpenetrated nets of zinc frameworks built by
NTB-linkers (4,4 0 ,400 -nitrilotrisbenzoic acid) by Suh43 were
reported to reach 1.9 wt% of hydrogen uptake at 77 K.
However, it is not yet known whether large surface area
materials like MOF-177,7 MIL-10044 or MOF-5 and isoreticular
compounds,4–6 or materials with an average surface area of
between 1000 to 1500 m2 g1 39,43 or even small pore
MOFs24,33 will be the most promising storage media. Neither
can it be concluded whether divalent or trivalent metal
clusters45 are the most favourable ones. Nevertheless, a
comparison to NaX-zeolite very clearly indicates the superior
behaviour of MOFs over conventional microporous inorganic
media.46
From our results on prototype equipment (77 K and up to
40 bar) it can be seen how different MOF materials contribute
differently to volume-specific hydrogen storage (Fig. 8).
MOF-177 demonstrates the most promising results for the
selected MOFs. This data from a large scale prototype
compares reasonably well with the literature.38
Fig. 8 H2-storage capacities for different MOFs (prototype trials).
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For many volume-limited mobile and portable fuel-cell
applications it will be industrially much more relevant to
compare storage data on a volume-specific rather than a
weight-specific storage capacity. Typically, the packing
densities of MOF powders are around 0.2 to 0.4 g cm3
increasing to 0.5–0.8 g cm3 when shaped into tablets or
extrudates. The density of this material is so low that weight
limitation for an application, generally, is not relevant. This is
in contrast, of course, to the alternative use of metal hydrides
as storage media.
The most important issue here is the amount of hydrogen
which, on a reasonable time-scale, can be discharged from the
storage media. Within this context, MOFs really have a fully
reversible uptake- and release-behaviour. As the storage
mechanism is based predominantly on physisorption, there
are no huge activation energy barriers to be overcome when
liberating the stored hydrogen. A simple pressure reduction by
controlling valve opening is sufficient to draw off hydrogen
from MOFs within a few seconds.
Energy density values of 1.1 kW h L1, as requested in the
European hydrogen and fuel cell Strategic Research Agenda
and Deployment Strategy,47 are equivalent to a volumetric
hydrogen stored capacity of about 33 g H2 L1. As has been
demonstrated, this value can be reached by storing hydrogen
in MOF-177 at 77 K at a moderate pressure of 40–50 bar.
However, due to the low degree of interaction between
hydrogen molecules and its low heat of adsorption, until
now significant storage capacity at room temperature has
not been reached.
Getting better information on the preferred adsorption sites
for hydrogen in MOF structures should principally enable the
prediction of storage capacities. In this respect, molecular
modelling tools might become as important as elaborate
experimental synthesis efforts.46 Depending on the temperature
range of a possible application, highly porous MOFs might be
favourable for low temperatures, whereas rather small pore
materials,24,33 or highly attractive and flexible ones,39,48 could
be favourites for room temperature hydrogen storage.
More recent reports have addressed biomimetic approaches,
like Co4(m4-O)(carboxylate)4 units49 being related to the structure
of active centres like Fe in haemoglobin. Such materials have
quite high sorption enthalpies of 10 kJ mol1 for hydrogen
and similarly very high enthalpies for O2, CO or CH4.
3.4 Heterogeneous catalysis
3.4.1 Relevance. Due to its crucial role in many chemical
processes, heterogeneous catalysis is one of the key elements of
our industrialized society, and thus has direct impact on the
global economy. It is reported that approximately nine-out-
of-ten chemical processes utilize heterogeneous catalysts.50
The global catalyst market is estimated to be between
15–20 billion USD annually. Approximately half of this
market is geared directly towards the chemical industry
and the rest is divided between environmental and refinery
applications. The annual combined worth of the products
obtained from industrial catalytic processes (including refinery
operations) is estimated to be at a multi-trillion USD level.
Therefore, it can be stated that the value created by utilizing
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Table 2 Summary of catalytic reactions employing MOFsa

MOF type Reaction type Reactants Ref.

MOF as classical catalyst support
Ag@[Zn4O(BDC)3] (MOF-5) Epoxidation Propylene þ O2 53
Pt@[Zn4O(BDC)3] (MOF-5) H2O2 synthesis H2 þ O2 54
Cu@[Zn4O(BDC)3] (MOF-5) Methanol synthesis Syngas 55
Pd@[Zn4O(BDC)3] (MOF-5) Hydrogenation Cyclooctene þ H2 55
Link as active centre
Ti(OiPr)4[Cd3Cl6(L1)3]4DMF6MeOH3H2O Addition to ZnEt2 þ aromatic aldehydes 56, 57
Ti(OiPr)4[Cd3(NO3)6(L1)4]7MeOH5H2O carbonyls
Ti(OiPr)4[Cd(L1)2(H2O)2][ClO4]2DMF4MeOH
3H2O
[Rh2(M21TCPP)2] (M21 ¼ Cu, Ni, Pd) Hydrogenation Propene þ H2 58
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1-Butene þ H2 59
[Zn2(BPDC)2(L2)]10DMF8H2O Epoxidation 2,2-Dimethyl-2H-chromene þ 60
2-(tert-butylsulfonyl)iodosylbenzene
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SBU (secondary building unit) as active centre

[Zn3O(L3-H)](H3O)2(H2O)12 (D-POST-1) Transesterification Acetic acid 2,4-dinitrophenyl ester þ EtOH 61
[Sm(L4-H2)(L4-H3)(H2O)4](H2O)x Esterification Meso-2,3-dimethylsuccinic anhydride þ MeOH 62
[Cu(bpy)(H2O)2(BF4)(bpy)] Alcoholysis of Epoxide þ alcohol 63
epoxides
[Zn4O(BDC)3] (MOF-5) Alkoxylation Dipropylene glycol þ PO, methyl dipropylene 64
glycol þ EO, acrylic acid þ EO
Zn-DHBDC-MOF, Zn-BTC-MOF Polyalkylene PO þ CO2 65
carbonate
formation
[Ln(OH)(H2O)(naphthalenedisulfonate)], Oxidation Linalool þ H2O2 66
Ln ¼ Nd, Pr, La
[In4(OH)6(BDC)3] Oxidation Methylphenylsulfide, 67
(2-ethylbutyl)phenylsulfide þ H2O2
[Cu3(BTC)2] Oxidation Polyphenols þ H2O2 68
[Sc2(BDC)3] Oxidation Methylphenylsulfide þ H2O2 69
[Sc2(BDC)2.5(OH)], 70
[Y2(BDC)3(H2O)2]H2O, [La2(BDC)3(H2O)2]H2O
[Pd(2-pymo)2] Oxidation Cinnamyl alcohol þ air 71
[Rh2(H2TCPP)2]BF4 Oxidation Alcohol þ air/O2 72
[Cu2(trans-1,4-cyclohexanedicarboxylate)2]H2O Oxidation Alcohol þ H2O2 72
[Cu(2-pymo)2] Oxidation Tetralin þ air 73
[Co(PhIM)2]
[In2(BDC)3(bpy)2], [In2(BDC)2(OH)2(phen)2], Acetalization Benzaldehyde þ trimethylorthoformate 74
[In(BTC)(H2O)(bpy)], [In(BTC)(H2O)(phen)]
[Sc2(BDC)2.5(OH)], [Y2(BDC)3(H2O)2]H2O, 70
[La2(BDC)3(H2O)2]H2O
[Cu3(BTC)2] Cyanosilylation Benzaldehyde þ cyanotrimethylsilane 75
[Cd(4,4 0 -bpy)2(H2O)2](NO3)2(H2O)4 Cyanosilylation Benzaldehyde, aromatic imines þ 76, 77
cyanotrimethylsilane
[Sm(L4-H2)(L4-H3)(H2O)4](H2O)x Cyanosilylation Benzaldehyde þ cyanotrimethylsilane 62
Mn3[(Mn4Cl)(BTT)8(MeOH)10]2 Cyanosilylation Aromatic aldehyde þ cyanotrimethylsilane 78
[Zn4O(BDC)3] (MOF-5) Addition to alkynes 4-tert-butylbenzoic acid þ C2H2, MeOH þ 79
propyne
Ti-(2,7-dihydroxynaphthalene)-MOFs Ziegler–Natta Ethylene, propylene 80
polymerization
[Pd(2-pymo)2] C–C coupling 4-Bromoanisole þ phenylboronic acid 71
[Cu3(BTC)2] Isomerization a-Pinene oxide 81
[Cu3(BTC)2] Cyclization Citronellal 81
[Cu3(BTC)2] Rearrangement 2-Bromopropiophenone 81
[Rh2(L5)] Hydrogenation Ethylene, propylene þ H2 82
[Rh(BDC)], [Rh(fumarate)] H–D exchange, Propylene þ H2 83
hydrogenation
[Ru(1,4-diisocyanobenzene)2]Cl2 Hydrogenation 1-Hexene þ H2 84, 85
[In4(OH)6(BDC)3] Hydrogenation 1-Nitro-2-methylnaphthalene, 67
nitrobenzene þ
H2
[Ru2(BDC)2], [Ru2(BPDC)2], [Ru2(BDC)2(dabco)], Hydrogenation Ethylene þ H2 86
[Ru2(BPDC)2(dabco)]
[Rh2(fumarate)2], [Rh2(BDC)2], [Rh2(H2TCPP)2] Hydrogenation Ethylene þ H2 58
H–D exchange Propylene þ H2
[Pd(2-pymo)2] Hydrogenation Octane/cyclododecene þ H2 71

1290 | Chem. Soc. Rev., 2009, 38, 1284–1293 This journal is 

c The Royal Society of Chemistry 2009

Table 2 (continued)
MOF type Reaction type
Active centre introduced by post-synthesis modification
[Ni(L-aspartate)bpy0.5]HCl0.9MeOH0.5 Methanolysis of epoxides
[Cu(L-aspartate)bpy0.5]HCl
[Cu(D-aspartate)bpy0.5]HCl
[Cu(L-aspartate)bpe0.5]HCl
[Cu(D-aspartate)bpe0.5]HCl
Cr3(F,OH)(en)2O(BDC)3 (ED-MIL-101) Knoevenagel condensation
Cr3(F,OH)(en)2O(BDC)3 (ED-MIL-101) Heck coupling
Published on 16 March 2009 on http://pubs.rsc.org | doi:10.1039/B804680H
Downloaded by Pennsylvania State University on 27 May 2012
a
Abbr.: BDC ¼ 1,4-benzenedicarboxylate, BTC ¼ 1,3,5-benzenetricarboxylate, bpy ¼ 4,4 0 -bipyridine, phen ¼ phenanthroline, BPDC ¼
biphenyldicarboxylate, DHBDC ¼ 2,5-dihydroxy-1,4-benzenedicarboxylate, TCPP ¼ 5,10,15,20-tetrakis-(4-benzoate)-porphyrin, 2-pymo ¼
2-hydroxy-pyrimidinolate, PhIM ¼ phenylimidazolate, H3BTT ¼ 1,3,5-benzene-tristetrazol-5-yl, bpe ¼ 1,2-bis(4-pyridyl)ethane, en ¼ ethylene-
diamine.
catalysts is approximately three orders of magnitude higher
than the amount invested in them.
Shape and size selectivity is a vital consideration for many
industrial catalytic processes, and it is typically attained by
utilizing catalysts of nanoporous nature. The selectivity can be
based on the shape/size of the reactant, product or intermediate.
In order to provide such shape/size selective behaviour, the
catalyst must have uniform pores with molecular dimensions.
Uniform porosity is the outcome of a highly ordered structure,
such as MOFs, where pores/channels are part of the building
blocks (i.e., repetitive units). Each MOF has the potential to
offer unique structural and chemical features that can be
beneficial for an industrial application.
The most remarkable characteristic of MOFs relevant
for catalysis, which makes them unique, is the lack of
non-accessible bulk volume (‘‘dead volume’’). Furthermore,
due to the very open architecture, the self diffusion coefficients
of molecules in the pore system are only slightly lower than in
the bulk solvent.51 This means that mass transport in the pore
system is not hindered. In addition, the ordered structure
offers the opportunity to spatially separate active centres. As
a result of their high surface areas, MOF-based catalysts
contain a very high density of fully exposed active sites per
volume.52 This characteristic results in enhanced activity, and
thus a more effective catalytic system.
3.4.2 Different approaches towards MOF catalysts.
Approaches towards heterogeneous catalysis with MOFs fall
into three categories. The first, and most straightforward
approach is the use of the material as the carrier for an active
mass. This concept is well known for classical catalysts,
e.g. platinum on carbon. Patents by BASF SE53,54 show that
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c The Royal Society of Chemistry 2009
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Reactants Ref.
Cis-2,3-epoxybutane 87
Benzaldehyde þ ethyl cyanoacetate 88
Iodobenzene þ acrylic acid 88
silver and platinum on MOF-5 are catalytically active. With
Ag@MOF-5 the epoxidation of propylene with molecular
oxygen was achieved. Pt@MOF-5 is active in the synthesis
of hydrogen peroxide from the elements. The group of Fischer
in Bochum, Germany used MOF-5 as a carrier for copper,
palladium and gold.55 Cu@MOF-5 was active in the synthesis
of methanol from synthesis gas. Pd@MOF-5 was used for the
reduction of cyclooctene with hydrogen. Au@MOF-5 proved
to be too labile to do any catalysis with. Remarkable is the
method of preparation employed. The metal precursors were
introduced by chemical vapour deposition (CVD).
The second approach is fixation of catalytically active
species in the framework. This can be done by modifying
known catalysts in a way so that they are capable of forming
MOF frameworks. Knowledge about the catalytic activity
existed before (a priori) the formation of the MOF. Therefore,
this approach can be termed the a priori approach to MOF
catalysis. For that type of catalyst, it is important to set the
results from the catalytic test into the context of the results for
catalysis experiments with the free linker as catalyst. The work
by Hupp et al.60 on manganese salen complexes for epoxidations
illustrates that exemplary. The reaction rate for the epoxidation
was only slightly lower for the MOF catalyst compared to the
homogeneous one. Additionally, there was no deactivation of
the MOF-based catalyst during the reaction, because the
active centres were spatially separated from each other at fixed
positions, limiting the amount of side reactions that could
result in catalyst deactivation. This can be considered the first
unequivocal description of a ‘‘MOF effect’’ in catalysis.
Third, coordination species can be generated in and
stabilised by the framework which are either completely
unknown in the homogeneous complex chemistry of the metal
Chem. Soc. Rev., 2009, 38, 1284–1293 | 1291

or which are extremely sensitive. This will mean the active
centre is created from scratch or de novo. An example of this
approach is the free metal-site in fully activated Cu3(BTC)2
units in Cu-BTC-MOF. If the apical aquo-ligand is removed
from the molecular parent compound Cu2(CH3COO)42H2O,
the unsaturated Cu-centre will coordinate an oxygen donor
from a second complex fragment to form a m2-O bridge. In the
MOF, this way of saturation is prohibited by the framework
and the open metal sites are stable and highly reactive.
Another example for the de novo approach is the protonation
of chiral MOF frameworks and their usage as catalysts in the
enantioselective methanolysis of cis-2,3-epoxybutane.87
The classification of MOF catalysts to the a priori and
Published on 16 March 2009 on http://pubs.rsc.org | doi:10.1039/B804680H
de novo categories may not always be unequivocal. However,
it shows that for MOF catalysts one also should think outside
the realm of conventional complex chemistry. For example, in
Downloaded by Pennsylvania State University on 27 May 2012
a MOF structure the stabilization of highly reactive species,
like open metal-sites, is much easier than in the homogeneous
phase—see the example of Cu-BTC-MOF above. Due to the
self-organisation of simple (cheap) ligands and metal salts,
structural motifs can be realized that would require a huge
amount of sterically demanding decoration on the ligand
sphere of the transition metal in the homogenous phase. This
concept may also be applicable for other catalytically active
species.
In Table 2, a list of publications on MOFs as catalysts is
given. The classification in Table 2 is according to the nature
of the active centre or the way the catalyst was gained. Recent
publications on catalytic properties of MOFs make also use of
post-synthesis modification. Noteworthy is the modification of
MIL-101 by ethylenediamine to yield a basic catalyst that is
able to catalyze the Knoevenagel condensation of benzaldehyde
and ethyl cyanoacetate with a selectivity of 99.3% towards the
condensation product.88 Since the reaction takes place inside
the pore system, it can be hypothesized that a follow up
Michael addition of benzaldehyde and the large condensation
product is unfavourable. Therefore, the high selectivity is
directly linked to the structural features of the MOF.
Conclusions
It can be stated that MOF materials are of great interest to the
chemical industry. Promising fields of applications are gas
storage, gas purification, separations and catalysis. Gas
storage, gas purification and separation are the most mature
fields of research. Therefore, it is most likely that the first
application will come from one of these fields. However,
research on the catalytic properties of MOFs is gaining
momentum. Due to their unique properties, MOFs are likely
to give new impulses to catalysis research as a whole and may
also be beneficial for existing processes. All in all, as an
emerging class of porous materials, MOFs are being investigated
more and more. Consequently, an increasing number of new
materials are being discovered and novel applications are
being identified. Since there is virtually an infinite number of
possible combinations of linker molecules and metal ions, it
can be expected that academic and industrial research activities
in this field will continue to be vigorous.
1292 | Chem. Soc. Rev., 2009, 38, 1284–1293
View Online
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