Metal-organic frameworks – synthesis and applications

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INDUSTRIAL CATALYSIS
AND SEPARATIONS
Innovations for Process Intensification
Edited by
K. V. Raghavan, PhD, and B. M. Reddy, PhD
Apple Academic Press
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Industrial catalysis and separations: innovations for process intensication/edited by
K.V. Raghavan, PhD, and B.M. Reddy, PhD.
Includes bibliographical references and index.
ISBN 978-1-926895-96-3 (bound)
1. Catalysis--Industrial applications. 2. Green chemistry. 3. Chemical processes.
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CHAPTER 3
METAL ORGANIC FRAMEWORKS–
SYNTHESIS AND APPLICATIONS
RADHA KISHAN MOTKURI, JIAN LIU, CARLOS A FERNANDEZ,
SATISH K NUNE, PRAVEEN THALLAPALLY, and B. PETE MCGRAIL
CONTENTS
3.1 Introduction ......................................................................................... 63
3.2 Synthesis and Characterization ...........................................................65
3.3 Sorption applications ........................................................................... 68
3.3.1 Gas Storage and Separation ..................................................... 68
3.3.2 Hydrogen Storage and Separation ........................................... 68
3.3.3 Methane Storage ...................................................................... 70
3.3.4 Carbon Dioxide Capture From Flue Gas ................................. 71
3.3.5 Water Sorption Studies for Adsorption Cooling
Applications .........................................................................................75
3.3.6 Harmful Gas Removal ............................................................. 76
3.4 Heterogeneous Catalysis, Sensor and Other Applications ..................78
3.4.1 Framework Activity ................................................................. 78
3.4.2 Organic or Pseudo-Organic Linkers as Active Sites ...............80
3.4.3 Catalysis with Tailored Microenvironment ............................. 80
3.4.4 MOFS for Sensing Applications ..............................................83
3.4.5 MOF Sensors Based on Piezoresistivity .................................83
3.4.6 Gravimetric-Based MOF Sensors ...........................................84
3.4.7 Surface Acoustic Wave-Based MOF Sensors: ........................ 85
Chapter 3. METAL ORGANIC FRAMEWORKS–SYNTHESIS AND APPLICATIONS
Radha Kishan Motkuri,* Jian Liu, Carlos A . Fernandez, Satish K . Nune, Praveen Thallapally, B . P. McGrail
Citation Information: “Industrial Catalysis and Separations Innovations for Process Intensification “ by K . V . Raghavan and B . M .
Reddy; Apple Academic Press 2014, Pages 61–103
Print ISBN: 978-1-926895-96-3; eBook ISBN: 978-1-4822-3426-8; DOI: 10.1201/b17114-6

62 Industrial Catalysis and Separations: Innovations for Process Intensification
3.5 Sensors Based on MOF Optical Properties ......................................... 86
3.5.1 Photoluminescence (PL)-Based MOF Sensors .......................86
3.5.2 Solvatochromism/Vapochromism ...........................................86
3.6 MOFs for Oil Spill Cleanup ................................................................ 88
3.7 Conclusions ......................................................................................... 92
Keywords ...................................................................................................... 93
Acknowledgments .........................................................................................94
References ..................................................................................................... 94

Metal Organic Frameworks–Synthesis and Applications 63
3.1 INTRODUCTION
Porous materials have received enduring interest in chemical science because
of their suitability for many applications, including host materials for molecu-
lar separation and storage, catalysis, molecular sensing, magnetism, and drug
delivery systems. These porous solids are broadly classified into two major
categories: (i) amorphous and (ii) crystalline. Porous amorphous solids (e.g.,
plastics, gels) do not exhibit any ordered repeated units within their structures,
but it is beneficial to work with them as they are usually less expensive and
easy to prepare. Their primary disadvantages are the potentially wide range
of molecular architectures with nonpredictable channels or topologies and the
lack of long-range order that results in low mechanical stability. In contrast,
the porous crystalline solids are more advantageous because of their ordered
structures with reproducible pores/channels and topologies, which give them
high thermal and mechanical stability. Nanoporous silica and zeolites are
characteristic examples of such ordered porous solids that have predictable
structural features with reproducible pores/channels, dimensions, and topolo-
gies. These porous solids are subdivided into three categories based on their
pore size. According to the International Union of Pure and Applied Chem-
istry, the porosity of crystalline solids is usually given by the diameter of the
pore size and is categorized as microporous (5–20 Å), mesoporous (20–500
Å), and macroporous (>500 Å) [1].
The inorganic microporous zeolites, both natural and synthetic, construct-
ed from aluminosilicates have been extensively studied for decades for a
wide variety of applications. Natural zeolites, which are predominantly ocean
based, have various uses, but their application is limited due to the difculty
in eliminating impurities. However, synthetic zeolites have been used exten-
sively for catalytic applications, adsorption, and separation because they can
be systematically tailored under controlled conditions to meet user require-
ments. For example, zeolite 4Å (Na12Al12Si12O48) with pore size of 4Å was
commercially used as a drying agent, while zeolite ZSM-5 served as a crack-
ing agent. Similarly, Silicalite-1 was extensively used as a porous sorbent for
removal of gasoline from drinking water [2]. Although zeolites have been
widely used, they possess a number of drawbacks that limit their utility. The
disadvantages include difculty in controlling the synthesis conditions, the
very limited number of structure and channel topologies (178 to date), and the

64 Industrial Catalysis and Separations: Innovations for Process Intensification
fact that they are not easily changeable covalently bonded crystalline struc-
tures.
In the last decade, a new class of porous solids called metal-organic
frameworks (MOFs) or porous coordination polymers (PCPs) was discov-
ered. These porous solids exhibit unique and outstanding properties such as
the largest pore volumes and highest surface areas known [3]. The tunable
nanoporosity of MOFs places them far ahead of zeolites and other metal ox-
ides. MOFs are considered as organic analogs of inorganic zeolites in, which
oxygen atoms are replaced by rigid organic ligands/linkers that bridge the
inorganic ions or ion clusters that self-assemble into one-, two-, and three-
dimensional frameworks [4]. The advantage of this class of materials is that
by carefully choosing the building blocks such as inorganic metal ions and
organic ligands, it is possible to tailor the structures, pore sizes, and their to-
pologies [5]. Because of the large selection of transition and lanthanide metal
ions with diverse coordination geometries and the possibility of creating an
even larger number of organic linkers via synthetic organic chemistry, an im-
mensely diverse range of MOF framework architectures can be generated [6].
The schematic representations of the general classication of porous solids
are shown in Fig. 3.1.
FIGURE 3.1 Schematic representations of the general classification of porous solids. A
typical construction procedure for MOFs is given in the bottom panel [7]. (Reproduced
from Li, J. R. et al., Chem Rev 112, 869–932 (2012), with permission).

Metal Organic Frameworks–Synthesis and Applications 65
The coordination polymers were discovered in the 1950s [8], and their
discovery was followed by work reported by Jacobson [9], Bujoli [10], and
Férey [11]. However, the major interest in these materials was boosted in the
late 1990s by a pioneering material chemist Omar Yaghi and his co-workers.
Yaghi and his team have been the most prolic group in synthesizing rigid
coordination networks with metal cations and organic ligands. They started
by replacing the 4,4′-bipyridine moieties with multidentate carboxylates li-
gands and named the resulting neutral frameworks as MOFs [12]. Amongst
them, MOF-5 is the well studied in the literature and its structure aided the
development of new concepts in design and tuning of MOFs. Later, because
of the unique and outstanding properties of these architectures, an exponential
increase in publications related to the development of new materials and their
applications was observed. The historical developments in MOF synthesis are
summarized in Fig. 3.2 [6].
FIGURE 3.2 Historical developments in MOF synthesis [6]. (Reproduced from Stock,
N. et al., Chem Rev 112, 933–969 (2012), with permission).
3.2 SYNTHESIS AND CHARACTERIZATION
The synthesis of MOFs is a moderately young field, and its evolution from
well-developed solid-state/zeolite chemistry is noteworthy. Different types
of synthesis methods were reported in the literature such as classical hydro
(solvo) thermal synthesis, microwave heating [13], diffusion [14], ultrasonic
[15], mechanochemical [16], electrochemical synthesis [17], and more recently

66 Industrial Catalysis and Separations: Innovations for Process Intensification
spray-drying [18]. However, conventional hydrothermal or solvothermal
heating of organic, inorganic precursors dissolved in a suitable solvent system
in closed vessels under autogeneous conditions was well studied for major
MOF synthesis. Both compositional parameters, such as solvent, pH, and mo-
lar concentration, and process parameters, such as temperature, pressure, and
reaction time, will play a large role in the formation of framework structures.
In a clear solution of dissolved reactants, the concentration gradient needs to
be adjusted to exceed the critical nucleation concentration that enables the
formation of crystal growth. The concentration gradient can be achieved by
various methods, including changing the temperature of the system, solvent
evaporation, layering, or slow diffusion of two or multiple solutions contain-
ing the reactants. Along with the powders, various morphologies such as thin
films, membranes, and composites have been successfully synthesized for
various applications (Fig. 3) [6].
FIGURE 3.3 Various synthesis methods and morphologies in MOFs [6]. (Reproduced
from Stock, N. et al., Chem Rev 112, 933–969 (2012), with permission).

Metal Organic Frameworks–Synthesis and Applications 67
In contrast to zeolites, MOFs have signicantly weaker bonds (e.g., co-
ordinative and hydrogen bonds) between the organic–inorganic connections.
These weaker connections are responsible for MOF structural exibility un-
der external stimuli such as temperature [19], mechanical pressure [20], elec-
tric eld, magnetic eld, light, gas [21], and liquid/vapor [22] sorption. More
specically, sorption-induced structural deformation or “breathing” has been
studied extensively to determine its effect on chemical, structural, and topo-
logical changes in MOFs in the presence or absence of the guest [23]. The
different phases of a exible MOF, MIL-53, resulting from increasing the
amount adsorbed are shown in Fig. 3.4 [24]. Recently, it has been demon-
strated that postsynthetic modication methods successfully showed the pos-
sibility to tune the exibility in the material for tailored dynamic behavior in
MOFs [25].
FIGURE 3.4 Different phases of dynamic (flexible) metal-organic framework MIL-53
by increasing the amounts adsorbed. (Reproduced from Llewellyn, P.L. et al., J Am Chem
Soc 131, 13002–13008 (2009), with permission) [24].
Scalability is an important issue for any material for industrial applica-
tions. Large-scale synthesis of MOFs for industrial applications was success-
fully performed by BASF by considering the classical solvothermal synthetic
approach, which is generally used in industrial production of zeolites [26].
In large-scale synthesis (kilotons/year), the availability and cost of reactants
and the space–time-yield (STY) of synthesis play a crucial role. The higher
the STY value (kg of MOF per m3 of reaction mixture per day of synthesis),
the greater the feasibility for MOF production, industrially. The inorganic
salts (nitrates, oxides, sulfates) are readily available and inexpensive, while
the organic linkers are usually expensive and become a signicant compo-
nent of the raw material costs. The STY values for Basolite M050 (Mg(II)/
formic acid) and Basolite A520 (Al(III)/fumaricacid) are >3000 kg/(m3 D)

68 Industrial Catalysis and Separations: Innovations for Process Intensification
while Basolite Z1200 (ZIF-8) has 160 kg/(m3 D). The typical zeolites that
produced by BASF has a STY value of 50–150 kg/(m3 D) respectively [26].
Various characterization techniques have been successfully used to study
the MOFs, most notably single crystal and powder X-ray diffraction (XRD)
studies for getting the crystal morphology, arrangement of atoms and pore
structure; BET and pore size distribution studies for getting the informa-
tion of surface area and pore width and volume; Infrared spectroscopy stud-
ies for getting the information of functional groups in the MOFs structures;
Thermogravimetric analysis for getting information of stability and optimal
activation temperature ; Gas adsorption studies for getting the information
of gas storage capacities, gas adsorption selectivities, and diffusivities of gas
molecules in MOFs.
3.3 SORPTION APPLICATIONS
3.3.1 GAS STORAGE AND SEPARATION
MOFs are widely considered as promising novel adsorbents for gas storage
and separation due to their high surface areas, tunable pore size and structures,
and versatile chemical compositions [28, 29].
3.3.2 HYDROGEN STORAGE AND SEPARATION
Hydrogen is considered to be one of the best alternative fuels to fossil fuels
because of its high energy density, nonpolluting combustion products, and
natural abundance. However, H2 is an extremely volatile gas under ambient
conditions, resulting in a volumetric energy density that is much too low for
practical applications. The goal therefore is to design lightweight materials
that can reversibly and rapidly store H2 near ambient conditions at a density
equal to or greater than liquid hydrogen. MOFs have attracted considerable
attention in the H2 storage area in recent years because of their high working
capacities [27].
One of the rst MOFs investigated for H2 storage was the cubic carbox-
ylate-based framework MOF-5 or IRMOF-1, IRMOF-6, and IRMOF-8 (Fig.
3.5) [28]. With complete activation, MOF-5 can adsorbs 7.1 wt% H2 at 77
K and 40 bar and 10.0 wt% at 100 bar. The latter value is corresponding to
a record volumetric storage density of 66 g L–1, which is near the density of
liquid H2 at 20.4 K and 1 bar [29]. This MOF material is the best cryogenic
storage material currently known. In addition, it was demonstrated that H2 can

Metal Organic Frameworks–Synthesis and Applications 69
be loaded into MOF-5 within 2 min, and the sample can maintain a revers-
ible capacity for at least 24 cycles [30]. Researchers have reported hydrogen
storage data for more than 150 other microporous MOFs since MOF-5 was
investigated as a novel adsorbent for H2 [31]. Various strategies have been
adopted to improve H2 adsorption in MOFs. Open metal coordination sites (or
unsaturated metal centers) in the structures of MOFs can increase the interac-
tion between H2 molecules and MOFs, resulting in an improved performance.
This was rst demonstrated in the MOF Mn3[(Mn4Cl)3(BTT)8]2, which con-
tains open Mn2+ coordination sites and exhibits an isosteric heat of adsorption
of 10.1 kJ mol-1 at zero coverage [32].
FIGURE 3.5 MOFs, topologically the isoreticular MOFs (IRMOFs), are based upon an
augmented simple cubic net (the boron net in CaB6), while MOF-177 is based upon the
augmented form of the (3,6)-coordinated net qom. The large pore of each structure is
represented by a yellow sphere with diameter defined by the distance between the van der
Waals surfaces of the framework atoms. Atom colors: C, black; O, red; Zn, blue tetrahedra;
H, omitted [28a]. (Reproduced from Rowsell, J.L.C. et al., Angew Chem Int Edit 44, 4670–
4679 (2005), with permission).
In addition, surface area plays an important role in H2 adsorption on solid
materials. As a general rule, the maximum or saturated adsorbed amount of
gas on a solid surface is dependent on its surface area [27a]. When the pres-
sure of H2 is not high enough to reach its saturated adsorption, the amount of
the adsorbed H2 is determined mainly by the interactions between molecules
and MOF structures that can be positively related with the heats of adsorp-
tion [33]. Pore size can also affect the interaction between H2 molecules and
MOFs. It was found that MOFs having small pores with walls of high curva-
tures interact with H2 molecules more strongly than large-pore MOFs [34].
The ideal pore size is slightly larger than the kinetic diameter of H2 (2.8 Å) for
low-pressure adsorption because, under that condition, H2 molecules can

70 Industrial Catalysis and Separations: Innovations for Process Intensification
interact with a larger portion of the framework, which increases the interac-
tion energy between the frameworks and H2 molecules [34b].
MOFs have displayed outstanding performance for cryogenic H2 storage
at 77 K and pressures up to 100 bar. Improvements in gravimetric capac-
ity and in volumetric storage density are possible, provided advances in the
synthetic chemistry. The challenge is to design ligands or surface functional
groups that will lead to a high density of strong open metal sites, which are
capable of binding more than one H2 molecule with a binding enthalpy of
about 20 kJ mol–1. Thus, the creation of MOFs for practical applications in H2
storage is still a difcult yet engaging challenge [27b].
On the other hand, MOFs are also promising adsorbents for the purication
of H2 due to their tunable porous structures. Molecular sieving using MOFs
has been used to separate H2 and CH4 due to their different kinetic diameters
(H2: 2.8 Å; CH4: 3.8 Å) [35]. In addition, Long’s group has recently studied
some representative MOFs, including MOF-177, H3[(Cu4Cl)3-(BTTri)8], and
Mg-MOF-74, for separating CO2 and H2 via pressure swing adsorption [36].
These measurements were performed under conditions (at 313 K and pres-
sures up to 40 bar) close to practical application for precombustion CO2 cap-
ture. These MOFs showed excellent separation performances, with evaluated
CO2/H2 selectivities between 2 and 860 on an 20:80 CO2/H2 gas mixture. In
addition to experimental observations, molecular simulations have been used
to investigate the separation of H2, CO2, and CH4 using MOFs [37].
3.3.3 METHANE STORAGE
Natural gas, which consists mainly of CH4, is widely employed as feedstock
for synthesis gas in many countries. It is currently stored as compressed natu-
ral gas (CNG) at 207 bar in pressure vessels, requiring an expensive multi-
stage compression. An attractive alternative to CNG is adsorbed natural gas
(ANG), in, which the gas is stored as an adsorbed phase in a porous solid at
a lower pressure [38]. To promote the vehicular application of methane, the
U.S. DOE has set the target for methane storage at 180 v(STP)/v under 35 bar,
near ambient temperature, with the energy density of ANG being comparable
to that of CNG currently used. An ideal material for CH4 adsorption should
have not only a large accessible surface area but also a large pore volume, a
low framework density, and strong energetic interactions between the frame
work and CH4 molecules. GCMC simulation has been used as a screening
tool to identify new candidates for methane storage and to guide the design
of new materials.

Metal Organic Frameworks–Synthesis and Applications 71
A microporous PCN-14 MOF based on a predesigned anthracene deriva-
tive, 5, 5′-(9,10-anthracenediyl)-di-isophthalate, was synthesized for CH4 up-
take because it contains nanoporous cages as shown in Fig. 3.6. It has an
estimated Langmuir surface area of 2176 m2/g and an estimated pore volume
of 0.87 cm3/g. More important, PCN-14 MOF exhibits an absolute methane-
adsorption capacity of 230 v/v (28% higher than the DOE target of 180v/v
at ambient temperature s) and heats of adsorption of methane of around 30
kJ/mol. These results indicate that PCN-14 is a promising adsorbent for CH4
storage and can be used to store the fuel in the natural-gas-fueled vehicles.
FIGURE 3.6 The crystal structure of the PCN-14 MOF. (a) Squashed cuboctahedral cage
and (b) nanoscopic cage with 18 vertices, 30 edges, and 20 faces. Color scheme: C, gray;
Cu, turquoise; and O, red [39]. (Reproduced from Ma, S.Q. et al., J Am Chem Soc 130,
1012–1016 (2008), with permission).
3.3.4 CARBON DIOXIDE CAPTURE FROM FLUE GAS
The post combustion separation of CO2 from power plant flue gas is of great
interest to mitigate the global warming phenomenon [40]. The sorption of
CO2 using various MOFs and related porous materials is well documented in
the literature [21, 41]. The CO2 partial pressure in a typical flue gas is about
0.15 bar, which is much lower than atmospheric pressure. Therefore, it is im-
portant to study CO2 adsorption in MOFs at low pressures. Yazaydin and col-
leagues used both experiments and simulation to screen MOFs for the highest
CO2 capacities at about 0.1 atm [42]. They found that Mg/DOBDC and Ni/
DOBDC (also known as Mg-MOF-74 and Ni-MOF-74 or CPO-27-Mg and
CPO-27-Ni) have the highest CO2 capacities at 0.1 atm and 298 K, which are
5.95 mol kg–1 and 4.07 mol kg–1, as shown in Fig. 3.7.

72 Industrial Catalysis and Separations: Innovations for Process Intensification
FIGURE 3.7 Experimental CO2 uptake in different MOFs at 0.1 bar. Data were obtained
at 293–298 K [42]. (Reproduced from Yazaydin, A.O. et al., J Am Chem Soc 131, 18198
(2009), with permission).
Instead of the surface area or the free volume, the authors found that MOFs
such as Mg/DOBDC and Ni/DOBDC with a high density of open metal sites
are promising candidates for CO2 capture from ue gas in, which CO2 par-
tial pressure is about 0.1 atm. Caskey et al. [43] found that metal substitu-
tion in the DOBDC series can signicantly impact their CO2 capacities in
the low-pressure region. The metal substitution effect may be caused by the
differences in the ionic character of the metal–oxygen bonds in the DOBDC-
series MOFs. Liu et al. found that Ni/DOBDC has a higher CO2 capacity than
NaX and 5A zeolites at 0.1 atm, and 25°C. In addition, water does not affect
CO2 adsorption in the Ni/DOBDC as much as in NaX and 5A zeolites, and it
is much easier to remove water from Ni/DOBDC by heat regeneration [44].
Therefore, the Ni/DOBDC can adsorb more CO2 than traditional zeolites un-
der the same moist conditions.
Most ue gas is composed of N2, so it is important to have a MOF that
can selectively adsorb CO2 over N2. Motkuri et al. showed that Prussian blue

Metal Organic Frameworks–Synthesis and Applications 73
derivatives represent a class of highly stable ordered crystalline structures
that can selectively adsorb CO2 over N2, CH4, and water present in ue and
natural gas conditions [41]. Seven MOFs, including CuBTC, MIL-47 (V), IR-
MOF-1, IRMOF-12, IRMOF-14, IRMOF-11, and IRMOF-13, were studied
for the separation performance of CO2 over N2 by Liu and Smit using GCMC
simulations [45]. In all the MOFs they considered, CO2 is more preferentially
adsorbed than N2, with CuBTC showing the highest selectivity. Motkuri and
team found that pore size plays an important role in the selective adsorption of
CO2 over N2 [47]. The effect of the chemistry of the materials (i.e., effects of
the electrostatic interaction) becomes less evident compared to the effects of
pore size because both CO2 and N2 molecules have quadruple moments. As a
result, the electrostatic interactions will help increase the adsorption for both
of them. Wu et al. obtained a Li-modied IRMOF-1, chem-4Li MOF, by sub-
stituting all the hydrogen atoms with O–Li groups in the aromatic rings of IR-
MOF-1.The chem-4Li MOF was found to have an extraordinarily high CO2/
N2 selectivity of 395 (CO2:N2 = 15.6:84.4), which is two orders of magnitude
larger than that of the original IRMOF-1 [46]. This selectivity is caused by
the strong electrostatic interactions between the gas molecules and the lithium
atoms in the framework. Thallapally and co-workers synthesized eight dis-
similar metal-organic supramolecular isomers using one exible tetrahedral
organic linker, tectonic acid (TA), with different metals Zn, Cd, Co, Mg, and
Cu [22, 47]. In the MOF constructed with Zn, addition of auxiliary ligands
(pyrazine, 1, 4-diazabicyclo [2.2.2]octane or DABCO) yielded MOFs with no
pores to mesopores. It is interesting to note that the auxiliary ligand bipyri-
dineinvolved in the crystal formation resulted in a exible MOF formation,
TetZB (isomer A in Fig. 3.8) that showed a breathing phenomenon upon sorp-
tion of gasses/vapors. All other TA-based MOFs showed preferable sorption
of CO2 over N2, H2, and methane at room temperature.
Meanwhile, selectivity between H2O and CO2 is important for using
MOFs to separate CO2 from ue gas because a typical ue gas is saturated
with water vapor. Some research work shows that a small amount of water
can help enhance CO2 adsorption in HKUST-1 [48]. The enhanced CO2 up-
take is caused by interactions between the quadruple moment of CO2 and the
electric eld created by the coordinated water molecules. However, further
increasing the water loading on the HKUST-1 will result in considerable un-
coordinated water molecules that block pore space and cause the HKUST-1
to adsorb less CO2 than the dry sample. On the other hand, Liu et al. reported
that neither the HKUST-1 nor the Ni/DOBDC MOF can adsorb any signi-
cant amount of CO2 when water loadings are high, which means that the two

74 Industrial Catalysis and Separations: Innovations for Process Intensification
MOFs preferentially adsorb H2O over CO2 although water does not affect
CO2 adsorption in HKUST-1 and Ni/DOBDC as much as it does in tradi-
tional zeolites [44].
FIGURE 3.8 Eight metal-organic supramolecular isomers formed with the flexible
ligand TA with transition metals Zn, Cd, Co, Cu, and Mg. All the isomers showed the rigid
framework while structure A (TetZB) showed flexible framework towards guest sorption
[21, 22, 47]. Py = pyrazine, DB = 1,4-diazabicyclo[2.2.2]octane, and BP = bipyridine.
(The structures reproduced from Motkuri et al. in referenced RSC and ACS journals, with
permission).
A straightforward approach to reduce water adsorption in MOFs is to cre-
ate more hydrophobic MOF pores. This can be done by either postmodica-
tion synthesis of attaching hydrophobic moieties or generating MOFs with
hydrophobic ligands. Nune et al. reported the synthesis of thermally stable

Metal Organic Frameworks–Synthesis and Applications 75
metal-organic gels (MOGs) using near-supercritical processing conditions;
signicant CO2 uptake capabilities were observed for the rst time [49]. Yang
et al. synthesized some FMOFs in, which hydrogen atoms are replaced by
uorine atoms in all ligands [50]. FMOFs with uoro-lined or uoro-coated
channels or cavities have enhanced thermal stability and hydrophobicity com-
pared to their nonuorous counterparts. Farha et al. replaced the coordinated
solvent molecules in a three-dimensional MOF with various cavity modi-
ers, including pyridine and its derivatives [51]. The resulting tailored cavi-
ties show different adsorption properties, and this postsynthetic modication
method can be adopted to cover hydrophilic surfaces in some MOFs with
hydrophobic molecules, such as pyridine, to reduce H2O effects on CO2 ad-
sorption. An alternative engineering solution to mitigate water effects on CO2
adsorption in MOFs is to install a guard bed loaded with desiccants in front
of the main bed loaded with MOFs to remove most of the water and to take
advantage of the MOFs’ high CO2 capacities and selectivities.
3.3.5 WATER SORPTION STUDIES FOR ADSORPTION
COOLING APPLICATIONS
Technologies based on the sorption of water are detailed in the literature for
a number of applications, including adsorption-based heating and cooling,
air-conditioning systems, desiccant dehumidifiers, and freshwater production.
The main criterion is to find a best adsorbent–adsorbate (solid + vapor) pair
that effectively works on sorption principles. Because of water has the highest
mass-based evaporation enthalpy (2440 kJ/kg at 25°C), it would be a pre-
ferred adsorbate. Currently, inorganic zeolites and silicagel are widely used as
adsorbents for water sorption, but these sorbents suffer with water adsorption
at overly high relative pressures and also at high temperature for desorption,
resulting in a large footprint and high capital cost. An ideal working pair with
water would be a material that has high surface areas that can sorb huge water
molecules at low partial pressures and moderate sorbate–sorbent interactions
for low-temperature desorption in a cycle.
MOFs with extraordinary porosity in combination with tunable pore char-
acteristics make a suitable choice as adsorbent material. Janiak et al. dem-
onstrated a three-dimensional MOF, ISE-1, as an efcient adsorbent for heat
transformation cycles for refrigeration, heat pumping, and storage [52]. The
MOF ISE-1 has approximately 22 water molecules per formula unit with a
potential solvent volume of 1621 Å3 (52%) of the unit cell volume constructed
from benzene-1,3,5-tricarboxylate and 1,2-bis(1,2,4-triazol-4-yl)ethane. ISE-

76 Industrial Catalysis and Separations: Innovations for Process Intensification
1 demonstrated good water stability and achieved a loading spread of about
210 g/kg, which is larger than that of ve zeolites and silica gel that have
been used in commercial heat pump applications. The stability and loading
spread features may be due to the less hydrophilic nature of ISE-1 compared
to silica and zeolites, which release water molecules (desorption) at lower
temperature and lower partial pressures. The Janiak research group recently
also successfully used a thermally stable porous MIL-100 (Fe, Al) for wa-
ter adsorption/desorption of up to 0.75 g of water vapor per gram of MOF.
Because of very good cycle stability and suitable hydrophilicity, MIL-100
proved itself a valuable addition to the pool of sorption materials used in heat
pumps or sorption chillers [53]. Henninger et al. compared the water sorption
capacities of HKUST-1 with that of zeolites and silica gel and showed that
the highest water uptake for driving temperature of 95°C was mesoporous
aluminophosphate AlPO-18 (0.253 g/g), while at 140°C, HKUST-1 showed
a highest water uptake of 0.324 g/g [54]. They also showed the rst results on
integral heats of adsorption in the cycle. Ferey et al. have demonstrated that
hierarchically porous MIL-100 and MIL-101 with mesoporous cages behave
as advanced water adsorbents applicable to energy-efcient dehumidication
systems that showed superior performance over commercial adsorbents such
as zeolite NaX, SAPO-34, and silica gel [55]. On a large-scale evaluation,
a honeycomb rotor coated with these MOFs showed huge sorption uptakes,
even at 40°C, as well as high desorption rates below 80°C and almost two
times higher efciency in energy consumption for adsorptive dehumidica-
tion applications in commercial/residential buildings.
3.3.6 HARMFUL GAS REMOVAL
Harmful gasses in the environment pose a growing international security
threat. Effective capture of these gasses is critical to protect lives and the envi-
ronment [56]. Pioneering work has been published on the performance of six
different MOFs such as MOF-5, IRMOF-3, MOF-74, MOF-177, MOF-199,
and IRMOF-62 for dynamic adsorption capacities for eight harmful gasses:
sulfur dioxide, ammonia, chlorine, tetrahydrothiophene, benzene, dichloro-
methane, ethylene oxide, and carbon monoxide and compared the same with
BPL carbon respectively [56a]. The dynamic adsorption capacity of each
MOF for each gas has been determined using a kinetic breakthrough method
and compared with that of a Calgon BPL-activated carbon. Pore functional-
ity was found to play a dominant role in determining the dynamic adsorp-
tion performance of the MOFs. For example, MOF-199, which featured a

Metal Organic Frameworks–Synthesis and Applications 77
reactive functionality, outperformed BPL carbon in all cases except chlorine
while MOF-74 and IRMOF-3 outperformed in sorption of sulfur dioxide and
ammonia respectively [56a].
In addition, various MOFs and their composites have been used to remove
H2S, SO2, NH3, CO, NO, and benzene [57]. For efcient adsorptive removal,
both the pore structures and open metal sites and functional groups of adsor-
bents are of great importance. The open metal sites of MOFs have been reported
many times as the active sites for the removal of various toxic gasses. Petit and
Bandosz reported composites of MOFs and a graphitic compound (graphite or
graphite oxide, GO) for the adsorptive removal of NH3, H2S, and NO2 under
ambient conditions [58]. The open metal sites of porous MOFs coordinated
with the oxygen groups of GO led to the formation of a new pore space in the
interface, resulting in increases of more than 12% (for NH3), 50% (for H2S), and
4% (for NO2) in the adsorption capacity for the GO/Cu-BTC composite.
A uorinated MOF, FMOF-2 obtained from 2,2′-bis(4-carboxyphenyl)
hexauoropropane and zinc nitrate hexahydrate, was also reported for the ad-
sorptive removal of toxic acidic gasses [59]. FMOF-2 was quite stable for the
adsorption of SO2 and H2S and has adsorption capacities of 14.0% and 8.3%
for SO2 and H2S, respectively, at room temperature and 1 bar. Fernandez et
al. showed that FMOF-2 also manifests “breathing” behavior during SO2 and
CO2 adsorption, an uncommon feature in, which the framework structure ex-
pands and contracts upon adsorption and desorption of guest molecules [59,
60]. In addition to chemically toxic gas adsorption, the removal of radioactive
gases such as Xe and Kr using MOFs has also been investigated. Thallapally
et al. found that the Ni/DOBDC has a Xe adsorption capacity 10% higher than
that of activated carbon at room temperature and 1 bar [61]. Meek et al. found
that the uptakes of Xe and Kr can be affected by the linker polarizability from
their results on a series of mono halogenated isoreticular MOFs [62].
Several MOFs and a benchmark-activated carbon sample were studied as
adsorbents to separate low-concentration Xe and Kr from air [63]. Both the
Ni/DOBDC and the HKUST-1 can selectively adsorb Xe and Kr from air,
even at concentrations at the parts-per-million level. The Ni/DOBDC has a
Xe capacity of 9.3 mmol/kg when the concentration of Xe is 1000 ppm in
air. More important, the Ni/DOBDC is able to separate 400-ppm Xe from 40-
ppm Kr mixture in air with a Xe/Kr overall selectivity of 7.3. The high Xe/Kr
selectivity is due mainly to the strong unsaturated metal centers in the crystal
structures of the Ni/DOBDC. In addition, the uniform cylindrical pores in
the Ni/DOBDC are believed to be favorable to maximize the Xe/Kr selectiv-
ity [64]. Nevertheless, Fernandez et al. demonstrated for the rst time that a

78 Industrial Catalysis and Separations: Innovations for Process Intensification
MOF material can selectively capture and separate Kr from Kr/Xe mixtures
at moderate temperature via a temperature gating mechanism on a copper-
based uorinated MOF [65]. MOFs have shown great application potential in
the gas capture and separations area, which will help in evaluating the MOFs
for sorption, separation-related applications, and selective single-component
sorption/separation applications, respectively.
3.4 HETEROGENEOUS CATALYSIS
Although MOF-based catalysis was proposed and experimentally proven in
the last decade, substantial experimental exploration with considerable prom-
ise in catalysis has been reported very recently [66]. The use of MOFs as cata-
lysts for industrial processes may still be far into the future, but it is likely that
the growing opportunities demonstrated on the laboratory scale may trigger
interest in scaling up for industrial use. The low thermal and chemical stability
of MOFs, certainly limit their use in vapor-phase reactions (reactions carried
out above 300°C) in industrial processes such as oil refining or petrochemi-
cal processes in, which zeolites are currently used. However, in liquid-phase
reactions, MOFs can compete with or even outperform the existing zeolites,
particularly the reactions carried out under mild conditions [67]. The main
advantage of MOFs is their versatility in chemical composition, organic and
inorganic building units, and the bifunctional metal/acid sites for insertion
using isoreticular chemistry. MOFs can complement zeolites to perform the
reactions at lower temperature s. As heterogeneous catalysts, the three known
possibilities for building catalytic activity are (1) framework activity (2) en-
capsulation of active species, and (3) postsynthesis modification.
3.4.1 FRAMEWORK ACTIVITY
One of the most widely explored strategies for configuring MOFs as hetero-
geneous catalysts is to take advantage of the exchangeable coordination posi-
tions around the metal ions. Another methodology would be to introduce the
organic linker with acidic or basic groups as the active sites. Recently, the
structural defects around the metal nodes also were explored for catalytic ap-
plications [68]. The framework activity is further divided into acidic and basic
sites, as discussed below.
3.4.1.1 LEWIS ACID CATALYSIS
The porous material [Cu3(btc)2(H2O)3], also known as HKUST-1, contains
large cavities. The copper metal is coordinated to water molecules that can

Metal Organic Frameworks–Synthesis and Applications 79
be removed easily under heat treatment, leaving open metal centers (Cu(II)
sites act as Lewis acidic centers) [69]. Jacobs et al. investigated the behav-
ior of HKUST-1 as a Lewis acidic catalyst by examining three sets of re-
actions, including isomerization of (i) alpha-pinene oxide (ii) rearrange-
ment of alpha-bromoacetal, and (iii) cyclization of citronellal. Based on the
experimental data and product selectivities, they concluded that HKUST-1
works primarily as a Lewis acid catalyst [70]. Kaskel et al. evaluated the
Lewis acidity of both HKUST-1 and large-pore MIL-101 having the formu-
la [Cr3F(H2O)2O(bdc)3] on cyanosilyzation of benzaldehyde and concluded
that the Cr(III) sites in MIL-101 showed greater activity than Cu(II) sites in
HKUST-1. Moreover, the catalytic sites in MIL-101 are immune to the un-
wanted reduction of benzaldehyde during the reaction [71]. Long et al. used
a manganese-based MOF with the formula Mn3[(Mn4Cl)3BTT8(CH3OH)10]2
(H3BTT = 1,3,5-benzenetris(tetrazol-5-yl) having a three-dimensional pore
structure with a pore diameter of 10 Å having two Mn+2 sites. The MOF ac-
tively engaged in Lewis acid catalytic conversion of selected aldehydes and
ketones with cyanotrimethylsilane to the corresponding cyanosilylated prod-
ucts with conversion yields above 90%, one of the highest yields reported in
metal-organic frameworks (Fig. 3.9). The same MOF also was shown to cata-
lyze the Mukiyama aldol reaction, which generally requires stronger Lewis
acidic sites than cyanosilyzation reactions [72]. In another report, Gandara et
al. documented highly Lewis acidic In (III) sites in a two-dimensional MOF
that catalyzed acetalization of benzaldehyde with trimethyl orthoformate [73].
FIGURE 3.9 (Left) A portion of the crystal structure of Mn3[(Mn4Cl)3BTT8(CH3OH)10]2
(H3BTT = 1,3,5-benzenetris(tetrazol-5-yl) showing the two different types of Mn+2
sites exposed in 10-Å-wide channels. Site I is five-coordinate, while site II is only two-
coordinate; the separation between them is 3.4 Å. (Right) Lewis acid catalyzed conversion
of selected aldehydes and ketones with cyanotrimethylsilane to the corresponding
cyanosilylated products. Orange, green, gray, and blue spheres represent Mn, Cl, C, and
N atoms, respectively [72]. Reproduced from Horike, S. et al., J Am Chem Soc 130, 5854
(2008), with permission).

80 Industrial Catalysis and Separations: Innovations for Process Intensification
3.4.1.2 BRØNSTED ACID CATALYSIS
Ferey et al. reported the Brønsted acid catalysis reaction on Friedal-Crafts
benzylation using two different MIL-100 cations, Fe and Cr. Although the
structure is identical [M3OF0.85(OH)0.15(H2O)2(btc)2] in both cases, the Fe-based
MIL-100 showed superior performance over that the Cr-based MIL-100 and
even surpassed the reported HY and HBEA zeolites [74]. In MIL-100(Cr+3),
the Cr-OH sites showed medium Brønsted acidic strength as confirmed by
low-temperature CO chemisorption studies [75].
3.4.2 ORGANIC OR PSEUDO-ORGANIC LINKERS AS ACTIVE
SITES
The metal complexes with functionalized ligands such as porphyrin building
blocks as organic linkers reported the catalytic active in oxidation reactions.
The porphyrinocarboxylate frameworks constructed from both Mn(III) and
Zn (II) successfully showed for olefin epoxidation reactions [76]. Here, the
metal coordinated to the porphyrin nitrogens performed as active sites when
compared to inorganic nodes of the MOF. Amino-functionalized MOFs such
as IRMOF-3 and [ZnF(Am2Taz)] synthesized from corresponding 2-ami-
noterepthalic acid and 3,5-diamino-1,2,4-triazole (Am2Taz) with zinc has
been successfully used as base catalysts in the Knoevenagel reaction. Both
MOFs showed the activity toward Aza-Michael condensation reactions at
25°C with a turnover number (TON) of 1.4 h–1 and 0.15 h–1 and fatty methyl
ester transesterification with a TON of 3.3 h–1 and 0.3 h–1 at 130°C, respec-
tively [77].
3.4.3 CATALYSIS WITH TAILORED MICROENVIRONMENT
Prepared post synthetic modifications of MOFs as described below have led
to the creation of a new microenvironment inside their porous network for
accelerating the rates of specific reactions and enhancing the selectivity to the
desired product.
3.4.3.1 ENCAPSULATION OF ACTIVE SPECIES
The encapsulation of active species such as metal complexes or metal
nanoparticles (MNPs) inside the porous MOFs is of growing interest in the
catalysis community because MOFs can provide a large pore volume that can
accommodate guest molecules. Here the MOF porous framework is used as a

Metal Organic Frameworks–Synthesis and Applications 81
support or host for the catalytic species, which was positioned in the cavity by
noncovalent interactions using a ship-in-a-bottle or bottle-around-the-ship ap-
proach [68, 78]. The encapsulation of MNPs inside MOFs can be achieved by
a stepwise process of particle infiltration followed by decomposition. Here,
the pore size, shape, and channel structure govern the size and shape of the
nanoparticle. It has also been reported that simple grinding of the organome-
tallic complex and MOF could result in the encapsulation inside the MOF for
aerobic oxidation of alcohols [79].
BASF is industrially producing MOF-5 mainly for encapsulating plati-
num, palladium, copper, and gold nanoparticles for catalysis applications.
The Pd@MOF-5 is used as a heterogeneous catalyst in hydrogenation reac-
tions, specically hydrogenation of cyclooctene, while Cu@MOF-5 is used in
methanol production from syngas [80].
Another example is encapsulation of metal porphyrins into the MOF cavi-
ties to be used for oxidation of cyclohexane to corresponding cyclohexanol and
cyclohexanone. The reactivity was comparable to that of reactions carried out
using a free metal porphyrin complex [81]. The mesoporous MOFs, chromium
(III) terephthalate Cr-MIL-101 [82], and iron anologue Fe-MIL-101 [83] have a
rigid zeotype crystal structure with quasi-spherical cages of 2.9 and 3.4 nm and
have been demonstrated to have very good encapsulation capabilities. Because
of their high thermal stabilities, huge surface areas, and large pore volumes,
these materials played a greater role as host materials for active species. Khold-
eeva et al. showed the encapsulation of polyoxometalates [PW11TiO39]5– and
[PW11CoO39]5–, which accelerates the oxidation of alpha-pinene to correspond-
ing alcohol and ketones using hydrogen peroxide (Fig. 3.10) [84].
FIGURE 3.10 The catalytic activities of polyoxotungstate-encapsulated MIL-101
(PWx/MIL101) for selective oxidation of alkenes with aqueous hydrogen peroxide [85].
(Reproduced from N. V. Maksimchuk, N.V. et al., Inorg Chem 49, 2920–2930 (2010), with
permission).

82 Industrial Catalysis and Separations: Innovations for Process Intensification
3.4.3.2 POST SYNTHETIC MODIFICATION
A new synthetic strategy of incorporating active functional groups using a
postsynthetic modification approach has been proposed recently as an alter-
native to presynthetic approaches discussed above. Cohen et al. used this ap-
proach to modify the amino functional groups in IRMOF-3 with alkyl anhy-
drides [86]. The amino groups within MOFs have been synthetically modified
using carboxylic acid or isocyanates to introduce various functions. Similarly,
Ferey et al. introduced thermally stable amino groups into MIL-101 frame-
work to the unsaturated Cr (III) coordination centers that open new oppor-
tunities for introduction of organic functional groups [87]. He showed the
successful introduction of ethylenediamnie (EDTA) (ED@MIL-101) and
diethylenetriamine (APS@MIL-101) into the MIL-101 framework. The free
terminal NH2 groups hanging in the cavities showed Bronsted basicity in the
Knoevenagel condensation reactions with 99.3% selectivity. Using a similar
approach, Corma et al. introduced a Au(III) complex with a Schiff base, and
the material showed superior activity and selectivity in domino-coupling reac-
tions [88]. The catalyst is completely recyclable and showed higher catalytic
activity when compared to gold-based homogeneous and supported catalysts.
Eddaoudi et al. demonstrated a versatile platform by encapsulation of free-
base porphyrin in a large pore of an In-HImDC-based rho-ZMOF, which post-
synthetically modified by various transition metals to produce a wide array of
encapsulated metalloporphyrins in MOFs and successfully tested for oxida-
tion reactions (Fig. 3.11) [89].
FIGURE 3.11 (a) Eight-coordinate molecular building blocks that could be represented
as tetrahedral building units (b) [H2TMPyP]4+ porphyrin (c) crystal structure of rho-ZMOF,
schematic representation of [H2TMPyP]4+ porphyrin ring enclosed in rho-ZMOF α-cage
(drawn to scale) (right) catalytic oxidation of cyclohexane at 65°C (right) [89]. (Reproduced
with permission from Alkordi, M.H. et al., J Am Chem Soc 130, 12639 (2008)).

Metal Organic Frameworks–Synthesis and Applications 83
3.4.4 MOFS FOR SENSING APPLICATIONS
A sensor is a device that responds to a physical or chemical stimulus (e.g.,
heat, light, sound, pressure, chemical vapor) and transmits a resulting im-
pulse. As described earlier MOFs have high surface area and porosity, struc-
tural diversity, flexibility, and physical and chemical tailorability that render
them excellent candidates for sensing applications. In MOF-based sensors, the
MOF responds to external stimulation such as gravimetric, mechanical, opti-
cal or environmental changes by manifesting a change in structure and prop-
erties or by showing a guest-dependent response. Although the latter is the
most common case, an example of structural change was observed in MOF-5.
The framework volume of MOF-5 changes with external temperature, show-
ing a linear negative thermal expansion (–16 x 10–6 K–1) between 4 K and
600 K. This expansion is due to the large-amplitude transverse vibration of
the carboxylate groups. A large number of examples of MOF-based sensors
show the guest-dependent response [90]. MOF samples have displayed opti-
cal, magnetic, or electronic responses based on the interactions between the
framework structure and a guest molecule, which opens up a large number of
applications of MOFs as sensing devices [91].
Depending on their response mechanism or route, MOF sensors can be
classied into three groups: piezoresistive response, mass response, and opti-
cal response. The rst relies on the stress induced by a guest molecule and
takes advantage of the structural exibility of MOF materials. Mass response
takes advantage of the large surface area and available volume capacity of the
pores to produce an important change in host mass when capturing a given an-
alyte. Optical responses, including photoluminescence quenching, emission
wavelength shifts, or simple color changes due to a guest-induced change in
MOF optical absorption spectrum, are reported on extensively in the litera-
ture.
3.4.5 MOF SENSORS BASED ON PIEZORESISTIVITY
Sensors based on piezoresistive MOFs are promising sensing devices for de-
tecting gas molecules and small organic molecules. One of the attractive fea-
tures of MOF materials is the structural flexibility. A number of MOF materials
exhibit expansion and contraction of the crystal lattice induced by guest–host
interactions. This property can be evidenced by “gating effects” and “breath-
ing effects” due to expansion and contraction of the framework upon incorpo-
ration of guest molecules. The unit cell dimensions of some MOFs can vary

84 Industrial Catalysis and Separations: Innovations for Process Intensification
by as much as 10% when molecules are adsorbed within their pores [92].
Therefore, transduction mechanisms in, which distortions in a MOF thin film
creates stress at the interface with a second material can be used to recognize
and measure a number of analytes. By depositing a MOF film on the surface
of a static microcantilever, stress at the cantilever surface results in bending
that can be detected by means of a built-in piezoresistive sensor [93]. In this
fashion, MOFs can show effective recognition chemistries for a variety of
gases and vapors provided they interact with the MOF pore.
An example is HKUST-1, which, although small, shows adsorption-in-
duced distortions when water, methanol, or ethanol are reversibly adsorbed.
Allendorf et al. showed this property when a thin lm of HKUST-1 was inte-
grated with a microcantiveler surface [94]. The time-dependent responses to
H2O are shown in Fig. 3.12. It was also demonstrated that the sensor responds
to CO2 when the MOF layer is dehydrated. The stress in this case was due to
the coordination of CO2 with unsaturated copper sites in HUKST-1. Because
the framework distortions were quite small, the group concluded that higher
sensitivities can be achieved using more exible MOFs.
FIGURE 3.12 Temporal response of the cantilever piezoresistive sensor to water vapor
diluted in N2 (room temperature, 1 atm) [94]. (Reproduced with permission Allendorf,
M.D. et al., J Am Chem Soc 130, 14404 (2008), with permission).
3.4.6 GRAVIMETRIC-BASED MOF SENSORS
Thin films of MOF materials can also be applied on quartz crystal micro-
balances (QCMs). In this fashion, it is possible to take advantage of the
extremely high sensitivity to mass changes on the QCM surface when an ana-
lyte interacts with the cavities of the MOF. Detection limits on the order of

Metal Organic Frameworks–Synthesis and Applications 85
the nanogram scale have been demonstrated [95]. MOF thin films grown on
a QCM substrate can be widely adopted as a device to probe mass changes
due to gas or vapor adsorption/desorption in the highly porous sorbent mate-
rial. Liu et al. successfully used a stepwise liquid-phase epitaxial method to
synthesize two homochiral thin films of [Zn2(±)cam2dabco]n (where ±cam =
(1R,3S)—(±)-camphoric acid, and dabco = 1,4-diazabicyclo(2.2.2)octane)
on self-assembled monolayers (SAMs) functionalized QCM substrates [96].
In another example, coating a QCM substrate with HKUST-1 showed to de-
tect humidity variations via adsorption/desorption of water molecules on the
sorbent film [97].
3.4.7 SURFACE ACOUSTIC WAVE-BASED MOF SENSORS:
Surface acoustic wave (SAW) sensors [93] are robust devices extensively em-
ployed for chemical sensing. Depositing MOF materials on the sensor surface
can then be useful for detecting and measuring vapors and gases. A frequency
shift of acoustic waves traveling parallel to the MOF surface, which are gen-
erated by an oscillator can be used to detect gas or vapor sorption. By grow-
ing a HKUST-1 film using a layer-by-layer (LBL) method on the quartz of
96.5-MHz devices, Robinson and collaborators reported humidity detection
using SAWs (Fig. 3.13) [98]. Fast and reproducible detection on frost points
(FP) as high as 10°C and as low as −70°C (2.6 ppmv and 12,300 ppmv at an
atmospheric pressure of 625 Torr, respectively) can be obtained. In addition,
the group demonstrated three orders of magnitude better response to humidity
using HKUST-1 as compared to the same coating on QCMs [97, 99]. The in-
fluence of film thickness on the SAW sensor response also was reported. Op-
timum coupling occurred between the MOF film and SAW surface; hence, the
highest response of the HKUST-1 SAW sensor to water vapor was obtained
for LBL coatings between 40 and 50 cycles (150-to 180-nm film thickness).
FIGURE 3.13 Humidity detection (left) and a molecular model of Cu3(BTC)2 (HKUST-1)
SAWs with water molecules (right) [98]. (Reproduced from Robinson, A.L. et al., Anal
Chem 84, 7043 (2012), with permission).

86 Industrial Catalysis and Separations: Innovations for Process Intensification
3.5 SENSORS BASED ON MOF OPTICAL PROPERTIES
3.5.1 PHOTOLUMINESCENCE (PL)-BASED MOF SENSORS
PL-MOFs are the most widely explored type of MOF sensing devices. The
popularity of luminescence over other transduction mechanisms are a con-
sequence of several key elements, including very high detection limits that
can reach molecular level. In addition, there is no need for film fabrication or
other processing, so conventional solvothermal synthesis is used to produce
PL-MOFs. A very important advantage over other PL sensors is the porosity
of MOFs. In addition, the possibility of adjusting MOF sorption properties of-
fers a high degree of molecular specificity. As an example, Li et al. prepared a
luminescent Ln-based MOF displaying efficient turn-on triggered by solvent
vapors, showing good selectivity for DMF vapor [100].
In another example, Lanet al. reported the detection of trace nitroaro-
matic explosives (DNT, 2,4-dinitrotoluene and DMNB, 2,3-dimethyl-2,3-
dinitrobutane) in the vapor phase using a highly luminescent MOF material
[Zn2(bpdc)2(bpee)]n (bpdc = 4,40-biphenyldicarboxylate; bpee = 1,2-bipyri-
dylethene) thin lm where they described the sensing process as a redox
quenching mechanism [101].
3.5.2 SOLVATOCHROMISM/VAPOCHROMISM
A visible change in a material’s color is one of the simplest means of trans-
ducing a sensing signal. Solvatochromism and vapochromism refers to a large
shift in the absorption spectrum of a material in response to a change in the
identity of the solvent or vapor. As in any other optical active material, MOFs
constructed from ligands that are chromosphors should behave in a similar
fashion in the presence of vapors. The electronic transition responsible for
the coloration entails charge transfer (i.e., a change in dipole moment upon
excitation from the ground electronic state to the excited electronic state of
the chromophoric component of the material) in a MOF material, the organic
linker. If the ground state has the larger dipole moment, hypsochromic shifts
(blue shifts) occur with increasing solvent polarity. On the other hand, if the
excited state possesses a larger dipole moment than the ground state, it is pref-
erentially stabilized by polar solvents, and bathochromic shifts (red shifts) are
observed with increasing solvent polarity.
A square shaped nanotubular MOF with the stoichiometry [[(WS4Cu4)-
I2(dptz)3]·DMF]n (124·DMF) in, which each WS4
2− anion chelates four Cu(I)
cations was synthesized by Lu et al. and its optical properties studied. The

Metal Organic Frameworks–Synthesis and Applications 87
sorbent material shows individual WS4Cu4
2+ units that are paired up by pyr-
azines that exhibit π−π interactions at an interplanar distance of 3.578(2)
Å. Also, each Cu(I) center is tetrahedrally coordinated. The 5.4-× 5.3-Å
nanotubes along the c-axis contain DMF guests and, once DMF is removed,
immersion of the MOF into various organic solvents manifested signicant
color changes. The group described a negative solvatochromic effect with a
solvent-induced absorption band shift of 245 nm between CH3CN and CHCl3
(Fig. 3.14) [102].
FIGURE 3.14 (Left) The perspective view of the nanotubular structure of [(WS4Cu4)
I2(dptz)3]n. Right: The UV−vis spectra and photograph of the inclusion compounds 1
solvent [102]. Reproduced from Lu, Z.Z. et al., J Am Chem Soc 133, 4172 (2011), with
permission).
As another example, Long et al. showed that exposing CO2
+-based MOFs
to various vapors could shift the optical absorption across the visible region
[103]. The explanation was a change in coordination environment from the
as-synthesized octahedral to a tetrahedral geometry. Lee et al. proposed a
similar color change mechanism on a MOF material that detects chloride ions
derived from chlorine-containing vapors or gasses. The MOF contains CO2
+
nodes coordinated to 1,2,4,5-tetra(2H-tetrazole-5-yl)-benzene (TTB) struts as
well as Br-anions [104]. The as-synthesized material is characterized by a
visible absorption peak at 475 nm, suggesting octahedral coordination of the
CO2
+ centers. Interestingly, exposure of the MOF material to chlorine-con-
taining gasses, including HCl, SOCl2 (COCl)2, and COCl2 (phosgene) show
color changes from red to blue [104]. The blue color, which is due to a new

88 Industrial Catalysis and Separations: Innovations for Process Intensification
absorption at 670 nm was attributed to tetrahedrally coordinated CO2
+. To
explain the change in metal coordination geometry, it was hypothesized that
the Br-is replaced with Cl-originating from the reactive gasses.
3.6 MOFS FOR OIL SPILL CLEANUP
The world energy dependence on fossil energy continues to increase. Petro-
leum is the largest source of primary energy production in the world. The
world petroleum consumption of 87,135,100 barrels/day (2010) poses a
daunting task to use aggressive methods for producing and transporting the
crude oil by various means including pipeline, ship, or barge to the rest of the
world from production sites [105]. Production, transportation, and storage of
oil present the risk of oil spill.
The rst commercial oil spill dates back to 1967 in the United Kingdom;
the most recent but not the worst (BP Deepwater Horizon Oil spill in the Gulf
of Mexico) occurred in 2010, and its cleanup cost is estimated to be over
$20 billion [106]. Oil spills not only cause nancial burden but also pose an
environmental damage risk. Oil is highly hydrophobic, does not mix with
water, and forms a thick slick or droplets that oat on water. With time the
oil eventually becomes spreadout. Although no two oil spills are considered
the same due to their location, weather conditions, and oil type, current oil
spill cleanup methods include three main methods of response (i) booming
(ii) skimming, and (iii) centrifuge in, which physical collection is routine (see
Ref. [1], of Chapter 8). Use of dispersants that break the oil to speed up the
natural biodegradation and burning of oil are considered as potential alterna-
tives. However, the use of dispersants and burning often results in adverse
effects on the environment. One another approach is to use the porous sorbent
that can effectively absorb the oil [107, 108]. A porous sorbent for oil spill
cleanup should have the following characteristic properties: (i) high rate of
adsorption/absorption (ii) oil retention, and (iii) ease of application. Currently
used sorbents include sand, organic clays, and cotton bers. These adsorbents
are cheap and easy to apply; however, they suffer from their afnity toward
water, limiting their performance during cleanup.
In general, to be effective for oil cleanup, a porous material should be
hydrophobic and olephilic. MOFs with excellent porosities and hydrophobic-
ity are likely to be efcient hydrocarbon absorbers at low to high concentra-
tions. Focusing on the potential industrial importance, Motkuri et al. recently
reported for the rst time breathing and adsorption of hydrocarbons using a
novel exible MOF (TetZB) [22]. They observed framework expansion and

Metal Organic Frameworks–Synthesis and Applications 89
contraction upon uptake and release of hydrocarbons. Although framework
expansion properties in exible MOFs are not of interest for cleanup appli-
cations, they have potential uses in sensing and other applications. In gen-
eral, typical hydrocarbon sorption experiments are conducted on gravimet-
ric analyzers (Intelligent Gravimetric Analyzer (IGA), Hiden Instruments or
duPont Model 990 TGA). Variable-temperature powder x-ray diffraction of
TetZB has revealed that there is framework distortion (probably by contrac-
tion) by removing the coordinated solvent on metals. Figure 3.15 illustrates
the adsorption and desorption of hydrocarbons on TetZBat room temperature.
TetZB exhibits an open structure when the solvent is removed after activa-
tion. Upon exposure to the hydrocarbons, the narrow pores in the framework
are saturated, while at high relative pressures, the framework undergoes ex-
pansion by opening access to the large pores [22].
FIGURE 3.15 Structure of flexible MOF TetZB (left) and their hydrocarbon uptake
measurements (right) [22]. (Reproduced from Motkuri, R.K. et al., Chem Commun 47,
7077 (2011), with permission).
While addressing hydrocarbon sorption properties of MOFs, there has
been intense debate on the commensurate adsorption of hydrocarbons using
MOFs; the mean number of adsorbed hydrocarbon molecules relates to the
symmetry of the framework topology, which is nearly impossible in routinely
studied/used zeolites [109]. Jing Li et al. reported that adsorption capacity
and location of molecules are specically controlled by cavity size, shape,
symmetry, and channel features such as channel segment [109]. Three differ-
ent adsorption mechanisms have been offered for the sorption and separation
of hydrocarbons: (1) equilibrium (2) steric, and (3) kinetic. In some com-
plex materials, it is possible that one or more mechanisms may operate at the
same time. The equilibrium sorption and separation mechanism relies on

90 Industrial Catalysis and Separations: Innovations for Process Intensification
the difference in the relative quantities of various hydrocarbons; the size and
shape of the pores in the adsorbate contribute to the steric mechanism, and the
difference in the rate of adsorption of different hydrocarbons contribute to the
kinetic mechanism [109].
Generally, MOFs have high afnity toward water, limiting their applica-
tions; however, the recent Deepwater Horizon oil spill devastation has in-
creased awareness of the need for new adsorbents. Signicant efforts have
been devoted to develop new hydrophobic MOFs with high thermal stability,
high selectivity, and fast regenerability. A prominent approach to circumvent
this problem is the utilization of postsynthetic modication (PCM) of MOFs to
produce moisture resistant and superhydrophobic MOFs [110]. This approach
garnered signicant attention because it is an important tool to chemically
modify or introduce various functional groups to produce new MOFs with
completely new chemical and physical properties. It means chemical modi-
cation is performed on the nal MOF materials rather than in the precursor
used for MOF construction. This approach is particularly attractive because
(1) the use of solvothermal conditions for MOF synthesis limits the presence
of functional groups on the ligand and (2) unlike any inorganic porous mate-
rials, MOFs have organic component that can be functionally modied, ren-
dering change in physical and chemical properties [110]. To circumvent the
posed by water-unstable MOFs, Yang et al. recently developed stable MOFs
using novel ligands that contain peruorinated groups (Fig. 3.16) [111]. These
new MOFs (FMOFs) are hydrogen free and uorine rich, not only bestowing
greater stability but also offering favorable hydrocarbon sorption properties
while inducing hydrophobic characteristics. FMOF-1 is the rst known MOF
with an exceptional hydrophobic nature while offering afnity for typical aro-
matic hydrocarbons and aliphatic oil components. To the best of our knowl-
edge, this nding is denitely a signicant scientic achievement, considering
the fact that many known MOFs are not stable in the presence of water or they
uptake very large quantities of water that compromise the uptake of hydro-
carbons during cleanup. Water adsorption isotherms clearly illustrate that the
FMOF-1 is signicantly hydrophobic, while routinely studied/used inorganic
porous materials such as activated carbon and zeolite-5A are hydrophilic, ab-
sorbing water even at very low relative humidity [111]. FMOF-1 is not only
hydrophobic but also very stable under aggressive conditions. FMOF-1 has
been soaked in distiled water for several days; powder X-ray diffraction im-
ages of soaked materials resemble the untreated material, indicating the ex-
ceptional stability.

Metal Organic Frameworks–Synthesis and Applications 91
FIGURE 3.16 (Left) Building blocks of FMOF-1 (middle) water sorption studies in
FMOF-1, BPC-Carbon and Zeolite-5A; (right) water and hydrocarbon sorption studies in
FMOF-1 [111]. (Reproduced from Yang, C. et al., J Am Chem Soc 133, 18094 (2011), with
permission).

92 Industrial Catalysis and Separations: Innovations for Process Intensification
In addition to oil cleanup, MOFs have been extensively investigated for
hydrocarbon separation applications due to the fact that currently available
separation strategies are energy-intensive processes and are contributing to
the largest segment of industrial production costs [112]. A recent report using
the exible feature that we reported earlier unveils the exceptional selectivity
of exible MOFs based on the differences in their gate opening pressure [22,
113]. The selectivity depends on the chain length of the hydrocarbon and its
specic interaction with framework [113].
3.7 CONCLUSIONS
Although the synthesis of MOFs was initially established for making new
compounds with interesting properties, the field has matured well and is slow-
ly widening its scope. The surface areas and pore properties of MOFs demon-
strate that these materials have large applicability in both fundamental and in-
dustrial arenas. The chemical versatility, pore tunability and tailoring of active
sites will lead to a broader range of applications. Although the conventional
hydro/solvothermal synthesis was well used in MOF synthesis, alternative
and new methods such as electro, mechano, sonochemical, and microwave-
assisted synthesis are just emerging in this area. However, greater care must
be taken while considering the crucial points in the synthesis, specifically the
reaction conditions and input energy requirements. Recent developments of
high-throughput methods may provide the tools needed in establishing the
standard synthetic protocol for each MOF, but establishing these protocols
takes time. With the developments in myriads of MOFs and their applications,
it is time to take them from the laboratory to the industrial world and focus on
applying this knowledge to industrial scenarios for real-world applications.
Although there is some progress in scale-up of MOFs for industrial produc-
tion and use, much still needs to be learned from zeolite chemistry for com-
mercial success.
In gas capture and separation-related topics, the current status of MOF
research is focused primarily on exploring new materials for single sorption
properties that cannot be viewed as new sorbent materials for practical sepa-
ration applications. The breakthrough experiments with mixed gases (includ-
ing vapors) will be a valuable means for better understanding the materials
for long-term potential and applicability. In the heterogeneous catalysis area,
MOFs still are unable to compete with zeolites in high-temperature reactions,
but these materials are capable of replacing zeolites in catalysis reactions that
use mild reaction conditions in ne chemical and enantio-selective synthesis.

Metal Organic Frameworks–Synthesis and Applications 93
MOF materials can respond to external stimulation in a number of ways
including changes in structure, as well as in their optical or mechanical prop-
erties, which can be employed for the fabrication of a number of sensing de-
vices. Although some examples have been shown, their application in this area
is still in the early stage. Because MOFs offer very attractive properties, there
is a great potential for developing novel MOF-based sensors whose detection
limits will depend on the type of stimulation the material is responsive to. An-
other attractive feature of MOFs is that their physical and chemical properties
can be altered by postsynthesis modication; a technique not possible in any
other class of porous inorganic materials thus will help in developing suitable
materials for required applications.
Most of the current technological options for the recovery and separa-
tion of industrially important gases including CO2 and H2 entail the forma-
tion of molecular complexes, through physical and/or chemical interactions,
that must then be reversed through signicant energy input, which is wasteful
both thermodynamically and dynamically. While continued improvement in
the above technologies can be expected with further R & D, the new options
with novel materials like MOFs and their analogs could provide signicant
breakthroughs in intensication of both chemical processes and separations
by tuning to vary cavity size and functionalizations to create a more effective
microenvironment inside their porous structure and to enhance accessibility
and interactions with molecules conned within the tailored environment.
As there is a great deal of exibility in tailoring their structural framework
and functionalizations, it is likely that MOFs will play much more important
role in the future to achieve higher level of process intensication leading to
greener process.
KEYWORDS
•Adsorption chiller
•CO2 capture
•Gas capture and separation
•Heterogeneous catalysis
•Metal-organic frameworks
•Oil spill cleanup
•Sensing applications, sensors
•Water sorption

94 Industrial Catalysis and Separations: Innovations for Process Intensification
ACKNOWLEDGMENTS
R. K. Motkuri would like to thank Dr. K.V. Raghavan for the support over the
years. This review was not possible without support from U.S. Department of
Energy’s office of Advanced Research Projects Agency for Energy (ARPA-e)
under Building Energy Efficiency through Innovative Thermodevices (BEET-
IT) program. Pacific North-west National Laboratory is a multiprogramming
laboratory operated by Battelle Memorial Institute for the U.S. Department of
Energy under contract DE-AC05–76RL01830.
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INDEX