METAL ORGANIC FRAMWORKS
Materials for Gas Storage
Nouran A. El Badawi
Report 3
Nanochemistry 5205
Fall 2016
Table of Contents
1. Introduction ...................................................................................................................... 2
2. Synthesis........................................................................................................................... 3
3. Applications ..................................................................................................................... 5
References................................................................................................................................ 8
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1. Introduction
Metal organic frameworks (MOFs) are class of synthetic micro-meso crystalline porous solid
compounds that were first manufactured in the 1990’s. They were believed to be only man-made
until last August when a group of Canadian scientists found them naturally existing in rare minerals
from the coal mines of Siberia [1]. Studies on manufacturing and modifying such compounds have
gained so much interest. This is because they have high surface areas, thermally stable, and their
pore sizes and framework structures and functionality could be designed according to their target
applications [2, 3]. In order to call a material MOF, it should have a set of criteria including a
well-defined crystalline structure with strong bonds between metal centers (atoms or ions) and
organic ligands that could extend in a 2 or 3 dimensions [4]. Figure 1 shows examples of different
structures of MOFs.
Figure 1 Structures of metals carboxylates as examples of MOFs in different arrangements: (a) the
square with two terminal ligands, (b) the octahedral (zinc acetate) cluster, and (c) the trigonal prismatic
oxo-centered with three terminal ligands. Blue spheres are metals, black spheres are carbons, and red
spheres are oxygen [4]
From the figure above, it can be interpreted that according to the type of the ligands and metal
centers, different arrangements can be formed where the ligands are known to self-assemble
around the metal centers [5]. The connectivity across the networks was found to be the main
criterion that affect the properties of the MOFs since it determines the strength and the shape of
structures [4]. That is why in the synthesis of the MOFs, it was important to have a method to
predict how connections and assemblies would take place. This required the introduction of the so
called Secondary Building Units (SBU) concept. SBUs are sets of geometrical arrangements of
inorganic groups linearly connected together by organic groups to form a framework [4]. These
arrangements were first used to predict the shape of zeolites, then the concept has expanded to
include the predictions of MOFs assemblies.
There are dynamic structural properties of MOFs due to the idea of organic-inorganic
connections unlike the pure inorganic connections found in zeolites for example. Such dynamic
properties gave the structures flexibility to contract, expand, swell, or compress. Figure 2 shows
different MOFs with different flexibilities [6].
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Figure 2 Flexibility of different MOFs [6]
The structural flexibility is attributed to the kinds of bonding between the organic-inorganic
connection including coordination bonds, π-π stacking and/or hydrogen bonds. This allowed the
structures of MOFs to flexibility respond to chemical, mechanical, and thermal stress/strains.
Depending on the type of the framework and its constituents, the allowable degrees of freedom
can vary to include stretching, bending and rotational motions. In figure 2, flexibilities included
axial rotation, bending, swelling due to “guest” molecules (will be explained in the next section),
and negative thermal expansion which is a rare phenomenon that happens to very few solids
including MOFs and zeolites [6].
Manipulating the structures of MOFs opened a wide area of research for various applications.
According to the type of metal centers and ligands attached, MOFs could be used in gas storage
and/or separation. They could also be used in catalysis and photocatalysis. Moreover, applications
that involve fluorescence, chromatography, drug delivery, energy storage and conversion, as well
as magnetism were also studied [3, 5, 7].
2. Synthesis
Since connectivity is responsible for the structure and consequently the functionality of the
frameworks, maintaining the structure of the building blocks becomes a key factor during
synthesizing MOFs. This includes selecting synthesis conditions that are mild enough to preserve
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the structure of the frameworks and their functionality, while being strong enough to allow the
formation of a metal-ligand bond to form high quality fine crystals [4]. The general method used
is usually solvothermal precipitation technique. Typically, the precursors of the building blocks
are diluted in a solution with solvents such as water, alcohols, acetone, N,N-dimethylformamide
(DMF), and/or acetonitrile, and the solution is heated up in a sealed vessel, Teflon-based, in which
pressure starts accumulating, the nucleation starts taking place [4, 8]. The type of solvent used
depends on both the metal centers and the ligands types. It’s worth mentioning though that the
precursors don’t necessarily have to be soluble in the solvent used since the high temperature of
the reaction medium that exceeds the boiling point of the solvents facilitates their solubility
anyway [4]. Inside the reaction medium, and during the frameworks nucleation and self-assembly,
the reversibility of the bond formation and structural rearrangements allow the crystals to grow
with minimal defects, thus obtaining a single crystalline form as shown in figure 3.
Figure 3 Steps of solvothermal precipitation technique for MOFs fabrication [9]
Manipulation of reactions conditions such as pH, temperature, solvent types and polarities, as
well as precursors concentrations and their rate of introduction into the medium plays a vital role
in the crystals yield and quality [10]. For example, introducing one of the precursors slowly into
the reaction medium slows the rate of nucleation and crystalline formation, thus giving the crystals
the time to reconstruct with minimal defects. Furthermore, the selection of the solvent types is
crucial because some solvents may play a competitive role with the ligands in coordination with
the available metal sites. Sometimes, to adjust solvents polarity and manipulate the kinetics of
solvent ligand competition over the metal sites, mixed solvents could be used [4]. Solvent
molecules can also play another role in crystalline formation by acting as “space-filling” inside the
frameworks such that they stabilize the crystals and allow their growth in defined channels that
reduces the possibility of defects [4, 10]. That’s why, it’s very important to examine the stability
of the frameworks after the “guest” solvent molecules are removed. The most common methods
of examination are using powdered X-ray diffraction (PXRD), as well as thermogravimetric
analysis (TGA). PXRD will give the crystalline conformation of the dried MOFs, while TGA will
give the weight loss difference between the desorption of the remaining solvent molecules and the
MOF decomposition.
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It’s noteworthy that the only limitation for converting MOFs into mass production is that their
synthesis can sometimes take days which is not efficient for industry. A new technique was
introduced to reduce the time called microwave assisted solvothermal precipitation. In this
technique, the digestion step takes place in the presence of a microwave source which speeds up
the process [11]. However, if a high yield is desired without much concern of high crystalline
quality, increasing precursors concentrations and promoting the agitation of the solution could
reduce the reactions time significantly giving a higher yield [4].
3. Applications
One of the most common types of applications for MOFs is gas storage. The idea of gas
storage depends on the adsorption of the gas molecules onto a given surface. This makes porous
materials with high surface areas very rich field for experiments. The most important factor of
course is the permanent porosity of the used material which is a property that MOFs have.
Isotherms for gas adsorption on MOFs have been well established, which represents the quantity
of the gas adsorbed as the function of pressure. Such technique is commonly used in estimation
the pore sizes, and surface area of the materials. It’s also used to estimate the types of pores present
(micro, meso, or macro). Typically, a Type I isotherm with no hysteresis was found to be the most
common in MOFs. Type I isotherms are produced when the gas molecules form a monolayer on a
surface with micropores of sizes less than 2 nm [4, 12]. Figure 4 shows different type I isotherms
for different structures of MOFs.
Figure 4 Type I isotherms showing different quantities of gas adsorbed on different structures [4]
From the figure above, it is clear that different types of structures have different adsorption
capacities. It’s important to note that the notations MOF-177, MOF-5, MOF-2 are used to identify
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different conformations in the 3D, and there is a huge database for identifying each structure and
giving it a three lowercase bold letters followed by numbers [13].
An example of gas storage application is for hydrogen. This has been studied extensively for
different MOFs structures since they have high specific surface areas and their structures can be
tailored. For example, a gas cylinder used for hydrogen storage filled with MOFs was found to
uptake more hydrogen molecules than when it is empty. This is because hydrogen physisorbes on
the MOF surfaces in a denser storage rearrangement compared to its gaseous form. Moreover,
there is no volume loss for storage capacity due to MOF crystals, since the material is highly
porous and all pores are accessible for the gas [14].
One example used to store hydrogen molecules is MOF-74 shown in figure 5. MOF-74 was
prepared from the precursors Zn(NO3)2.4H2O and dihydroxyl-1,4-benzenedicarboxylic acid
dissolved in DMF, isopropanol and water. Nucleation was allowed to take place in a solvothermal
precipitation manner [15].
Figure 5 MOF-74 extended crystalline conformation with Zn cations centers [16]
The BET surface area of the MOF-74 was measured and found to be as high as 820 m2/g of
the sample. Hydrogen adsorption on the surface was measure at low pressure (100 mbar), and it
was found to be very high compared to other known materials used in hydrogen adsorption. To
understand how this dense storage capacity takes place, the crystals with the physisorbed
hydrogens (Deuterium was used instead of hydrogens for easier characterization) was
characterized using neutron powder diffraction (NPD) technique. It is a diffraction technique,
similar to XRD, but uses neutrons instead of X-rays since they have much shorter wavelengths,
and therefore can characterize very small molecules such as adsorbed deuterium on the MOF
surface. The results indicated that the intermolecular spacing between D2-D2 molecules were
shorter than that of solid D2. This could be attributed to the fact that the packing density of the
molecules on the surface increased due to the interaction between the deuterium molecules and the
MOF surface inside the tubular structure as shown in figure 6 [15].
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Figure 6 D2 adsorbing along the axis of the MOF-74 structure in a densely packed conformation. The
green balls are of D2 molecules [15]
Different experiments have been carried out for other types of gas storage and separation. This
included hydrocarbons, mostly methane gas [17], and CO2/methane, CO2/N2 and CO2/H2 gases
separation [18, 19]. Furthermore, some research focused on the magnetic properties of the metal
centers in some MOFs to extract certain types of pesticides from water [20]. The field is rich and
tailoring the structures of MOFs could lead to better performance properties.
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