Chapter 3

Chapter 3
Materials, Experimental Methods, and Instruments
3.1. Chemicals
All the chemicals used in this work were used as received without any
further treatments. The chemicals are listed in table 3-1:
Table 3-1 a list of chemicals used in this research project.
Name

Formula

Grade

Vendor

Chromium (III) nitrate

nonahydrate
2-amino terephthalic acid

Cr(NO3)39H2O

99%

SigmaAldrich Chemicals.

C6H3NH2(COOH)2

98%

SigmaAldrich Chemicals.

Hydrofluoric acid,

HF

48%

SigmaAldrich Chemicals.

N-methyl-2-pyrrolidone

C5H9NO

99.5%

SigmaAldrich Chemicals.

Sodium hydroxide

NaOH

98%

SigmaAldrich Chemicals.

N, N-dimethylformamide

C3HNO

99.8%

SigmaAldrich Chemicals.

Salicylaldehyde

C7H6O2

98%

SigmaAldrich Chemicals.

Zirconium(IV) chloride

ZrCl46H2O

99.99%

SigmaAldrich Chemicals.

1-pentanol

CH3 (CH2)4OH

99%

SigmaAldrich Chemicals.

Acetic acid

CH3CO2H

99%

SigmaAldrich Chemicals.

Anisole

CH3OC6H5

99.7%

SigmaAldrich Chemicals.

Acetic anhydride

CH3CO)2O

99.5%

SigmaAldrich Chemicals.

Toluene

C6H5CH3

99.5%

SigmaAldrich Chemicals.

Methane sulfonic acid

CH3SO3H

99%

ACROS Organics

Ammonium fluoride

NH4F

98%

ACROS Organics

Terephthalic acid

C6H(COOH)

98%

ACROS Organics

Ethanol

CH3CH2OH

, 99%

ACROS Organics

Ethyl acetate

CH3COOC2H5

99%

ACROS Organics

Dichloromethane

CH2Cl2

99%

ACROS Organics

3.2. Experimental Methods

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Chapter 3

3.2.1 Synthesis of the Investigated Materials

3.2.1.1 Synthesis of MIL-101(Cr)
Hydrothermal synthesis of MIL-101(Cr) from Cr (NO3)3.9H2O, TPA and
deionized water was in accordance with a described procedure [ K. Gedrich, R.
Kraehnert, and S. Kaskel, Chem. Commun., 2008, 41924194.. Typically, a Cr

(NO3)39H2O (6.0 g), terephthalic acid (3.76 g) and HF (0.75 ml) was
dissolved in 75 ml of H2O in Teflon beaker, then introduced into 150-ml
Teflon-line autoclave. The mixture was then heated in an oven at 220 C for 8
h. By the end of the reaction, the temperature lowered to the ambient
temperature and the developed green-colored powder was obtained by
filtration to remove the excess recrystallized terephthalic acid. The MIL101(Cr) was first activated by suspending into 300 ml water with stirring for 5
h at 70 oC and then separated using a fine pore fritted glass filter followed by
drying at 150 oC on standing overnight to take out powdered MIL-101(Cr)
[36]. The second activation for the same sample was carried out by soaking
the sample in 150 ml 30 mM NH4F and stirred for 10 h at 60 oC. Finally, the
solid product was separated by filtration and washed with hot water and then
vacuum dried at 80 C for 12h.
3.2.1.2. Synthesis of N-methyl-2-pyrrolidonium methyl sulfate (IL)
The Brnsted acidic IL (N-methyl-2-pyrrolidonium methyl sulfonate,
([NMP]+CH3SO3-] ) was prepared (Scheme 1) as described elsewhere [Z.
Du, Z. Li, S. Guo, J. Zhang, L. Zhu and Y. Deng, J. Phys. Chem. B, 2005, 109,
19542;

CN Pat. , CN 200610124650.2, 2006.] with slight modification.

Typically, 9.9 g of N-methyl-2-pyrrolidone (0.1 mol) was stirred with (15 mL)

Chapter 3

ethyl acetate in a 50 mL round flask. After that, 9.6 g of methane sulphonic

acid (0.1 mol) in 15 mL ethyl acetate was added drop wise within 30 min in an
ice bath. The reaction continued for extra 4 h at ambient temperature. Finally,
ethyl acetate was taken away under diminished pressure at 80 oC till the initial
volume added.
3.2.1.3. Synthesis of IL/ MIL- 101(Cr) catalysts
The impregnation reaction encapsulation technique was used to
encapsulate N-methyl-2-pyrrolidonium methyl sulfonate IL onto MIL-101(Cr)
framework. In typical synthesis, 2.0 g of IL was diluted with 10 times volume
of ethyl acetate was added to 1 g of MIL-101(Cr) suspended in 10 mL ethyl
acetate under stirring for 4 h at 45C. Then, the solvent was removed under
vacuum at 80 C and stirring of 150 rpm. The obtained gel was extracted in
soxhlet extractor using ethanol/toluene (1:1) as co-solvent, and the weight of
the obtained solid was determined to explore the maximum capacity of MIL101(Cr). To maximize the ratio of IL occluded in MIL-101(Cr) pores, different
loading of IL behind maximum capacity are prepared and donated as X%
MIL-101(Cr) where X (5, 10, 15, 20) indicates the percent ratio of the ionic
liquid on MIL-101(Cr).
3.2.1.4 Synthesis of Amine-Functionalized MIL-101(Cr)
As indicated by the advanced technique [Y.
RSC Advances, 2012, 2, 64176419],

Lin, C. Kong, and L. Chen,

the amino- MIL-101(Cr) was synthesized

by dispersion of 2-aminoterephthalic acid (360 mg, 2 mmol), Chromic nitrate

hydrate (800 mg, 2 mmol), and sodium hydroxide (200 mg, 5 mmol) in
deionized water (15 ml) and blended for 5 minutes, then the mixture was

Chapter 3

poured into 50 ml Teflon-lined stainless steel autoclave and heated at 150 C

for 12 h. The autoclave was then left to chill off to room temperature. The
green powder was separated by centrifugation. The unreacted 2aminoterephthalic acid was washed in hot alcohol at 100 C for 24 h in an
autoclave. Finally, the products were dried at 80 C in air, and denoted (NH 2MIL-101).
3.2.1.5 Preparation of NH2-MIL-101-Sal
As described in literature [Z.
A: General 466 (2013) 98104.],

Sun, G. Li, H. Liu, L. Liu, Applied Catalysis

0.2 mL salicylaldehyde wa added to 30 ml

ethanol containing 0.3 g of the prepared amino-MIL-101

(NH 2-MIL-101).

The blend was heated under reflux at 80 C with mixing for 10 h, a short time
later; the blend was filtrated and washed with copious ethanol. Lastly the
product was dried under vacuum at 80 C over night, and denoted (NH 2-MIL101-Sal).
3.2.1.6 Preparation of NH2-MIL-101-Sal-Zr (IV)
0.5 g amino-MIL-101-Sal (NH2-MIL-101-Sal) was added to dry
CH2Cl2 (30 ml). Then excess 0.3 g, Zirconium (IV) chloride, was added. The
reaction mixture was stirred under N2 for 6 h at room temperature. The final
product was filtrated and washed with ethanol, and then dried under vacuum
at 80 C over night, and denoted (NH2-MIL-101-Sal-Zr).
3.2.2 Exploration of the Catalytic Performance of the
Prepared Materials
3.2.2.1 Esterification reaction

Chapter 3

The esterification reaction was carried out using certain percent of

catalyst (1, 2, 3, 4, 5 and 10%). Typical, a mixture of acetic acid and the
desired alcohol (amyl/ 1-octanol) were stirred and heated to achieve the
reaction temperature (30, 60, 80 and 100 C). The activated catalyst (preheated at 150 C for 6 h) was then added and the mixture was stirred. Samples
of the mixture were then collected at intervals of time (1, 2, 3, 4, 5, and 6 h.).
The reaction mixture were then collected and analyzed by means of GC
(Varian Technologies, model 3800 GC, capillary column DHA-100).
For illustration of the effect of alcohol, different alcohols are used at the
optimum conditions of the reaction. The reusability test was operated by
repeating the test at the optimum conditions of the reaction.
3.2.2.2 FriedelCrafts acylation
FriedelCrafts acylation of anisole with acetic anhydride was carried
out by mixing (20 mmol) anisole, (5 mmol) acetic anhydride followed by
magnetically stirred and heated to achieve the reaction temperature (80120oC). Then activated catalyst with the desired ratio was added and the
mixture stirred for 1h at the required temperature. After the reaction
completion, the catalyst was separated from the reaction temperature by
centrifugation. Finally, the reaction mixture was analyzed using GCMS. The
conversion was calculated depending on gas chromatographic analysis of the
remaining acetic anhydride.
3.2.2.3 Knoevenagel Condensation
In a typical reaction Knoevenagel condensation was carried out using a
mixture of benzaldehyde and ethyl cyanoacetate with molar ratio of (1:2) in
5

Chapter 3

toluene as the optimized conditions in literature [ Y.

Luan, Y. Qi, H. Gao , R. S.

Andriamitantsoa , N. Zheng and G. Wang, J. Mater. Chem. A, 2015, 3, 17320. ].

The reaction temperature was maintained at 40 C, and catalyst was of 4% wt.

The conversion was monitored by GC.
For the reuse test the catalyst, the catalytic reaction was repeated under
the same reaction conditions in toluene for 2 h using the recovered catalyst.
3.3. Instruments for Characterization and Tools
a variety of characterization techniques and combinations of different
methods need to be applied in order to study and understand how MOFs
behave in different environments.
3.3.1 Powder X-ray Diffraction (XRD)
X-rays are electromagnetic radiation with a wavelength much shorter
than visible light.A crystal consists of a group of atoms arranged in a
particular pattern that repeats itself in all three dimensions in space. The
structure of a crystal is best described using a 3-dimensional array of lattice
points. Analysis of the XRD data for crystal-structures is governed by the
Braggs Equation (Eq. 1), [Douglas A. Skoog FJH, Stanley R. Crouch.
Instrumental Analysis. Brooks/Cole; 2007], which describes the relationship
between the angles at which diffracted X-rays constructively interfere and the
lattice spacing of the crystal structure, d, and is illustrated in Figure 2.1.

n=2d sin
Where n represents integer values, the wavelength of the incident radiation,
and is the angle of incidence.
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Chapter 3

Figure () Geometry of Braggs Law [Douglas A. Skoog FJH, Stanley R.

Crouch. Instrumental Analysis. Brooks/Cole; 2007]
Powder X-ray diffraction is a rapid analytical and non-destructive
analytical technique to determine if the material synthesized is crystalline or
amorphous form and to verify that it contains no impurities. In addition,
powder X-ray not only can be used for crystal quantitative analysis, but also
could determine the lattice parameter, grain size and miller index precisely.
The resulting XRPD pattern can be regarded as a fingerprint of a
crystalline phase. A crystalline phase can be identified by comparing the
positions and the relative intensities of the diffraction peaks with already
known compounds. If there is no pattern that matches the synthesized sample,
a new phase may have been made.
X-ray diffractograms were obtained on a XPERT X-ray diffractometer,
operating with CuK radiation ( = 0.1542 nm), X-ray radiation (X-ray
generator current and voltage set at 40 mA and 45 kV). The diffractograms
were recorded in the 2 range of 1.8 to 20 with a 2 step size of 0.02 and a
step time of 10 s.

Chapter 3

3.3.2 Fourier-Transform Infrared Spectroscopy (FT-IR)

Fourier-Transform Infra-Red (FT-IR) spectroscopy is a valuable
analytical technique for structure analysis and functional group identification
of materials. The basic principle of infrared spectroscopy is vibrations of
molecules in a sample can absorb infrared radiations with specific
wavelengths. Every material possesses unique infrared spectrum decided by
its structures and symmetry. Thus, infrared spectroscopy could be used for
qualitative analysis. When studying MOFs with FT-IR one looks for
coordination modes between metal and linker as well as functional groups
positioned at the linkers. The presence of water and solvent can also be
observed.
FT-IR spectra of the pure materials and pyridine-adsorbed samples were
carried out using ATI unicam (Mattson 936) Bench Top spectrometer. Samples
were prepared by mixing a 10% (w/w) dispersion of prepared materials in
dried, pre-ground KBr after adjustment of the sample height to obtain the
maximum interferogram signal. Prior to the pyridine adsorption, small
portions of the calcined samples were degassed under vacuum at 150 C for 2
h followed by suspending in dry pyridine. Then the excess pyridine was
removed by evaporation.

3.3.3 Surface Area and Pore Size Distribution

Nitrogen sorption was the primary method used to characterize the
porous solids studied; therefore, presentation of this technique will be broad. A

Chapter 3

crystal structure may show that a MOF possesses porosity but the permanent
porosity of a material needs to be proven by adsorption and desorption
isotherms. The porosity of the material must be characterized in order to know
its capacity to be used in certain applications. An isotherm can give
information about the kind of pores that exist (micro- or mesopores), surface
area, pore volume and pore size distribution. Before all these parameters can
be measured accurately, the pores or channels ought to be emptied from guest
molecules as much as possible without destroying the structure.
The type of porosity the material can be determined from the
appearance of the collected isotherms by comparing it with the various types
of physisorption classified by IUPAC (Figure 2.11).[ K. S. W. Sing, D. H.
Everett, R. A. W. Haul, L. Moscou, R. A. Pieroti, J. Rouquerol, T.
Siemieniewska. Pure Appl. Chem. 57, (1985).]

Nitrogen adsorption and desorption isotherms were measured at (-196

C) using a NOVA 3200 system (USA). Prior to the analysis, the samples were
degassed at 120 C for 12 h. The modeling technique utilized for surface area
prediction was the Brunauer Emmett Teller (BET) method which was
9

Chapter 3

developed for modeling of multilayer adsorption of gases at temperatures near

their condensation points and is more appropriate for MOFs than the
Langmuir method, which was developed for solely monolayer adsorption
modeling and will typically overestimate the available surface area of MOFs. ,
[ Brunauer S, Emmett PH, Teller E. Adsorption of gases in multimolecular
layers. Journal of the American Chemical Society. Jan-Jun 1938;60:309-319.]
3.3.4 Thermo-Gravimetric Analysis (TGA)
Thermo gravimetric analysis is used to study the thermal stability and
decomposition of compounds. It is understood that the measured mass of a
sample will change when it sublimates, vaporizes, decomposes or loses
crystalliferous water. If any of these processes take place, then the thermo
gravimetric curve will make a sharp decline. The sample weight loss is
measured as the temperature is elevated with a continuous heating rate in an
atmosphere inert gas, N2 or He. The resulting TG curve, in which the weight
in percentage is a function of the temperature, shows steps of weight loss.
All thermo gravimetric measurements were carried out in flowing
nitrogen or air using a TA-600 Instruments Inc. (USA) model TGA TA-600
simultaneous TGA-DSC analyzer. The weight change (TGA) patterns were
recorded as a function of temperature in the range from 35 to 500 C. The
instrument was equipped with an open platinum pan and an automatically
programmed temperature controller. The heating rate was adjusted
automatically during measurements to achieve the best resolution; its
maximum was 10 C min-1.
3.3.5 Electron Microscopy

10

Chapter 3

Electron microscopes are scientific instruments that use an electron gun

to generate the beam of energetic electrons. Whereas the light microscope uses
glass lenses to magnify and focus images, the electron microscope uses
magnetic lenses to magnify and focus images. This examination can yield
information about the topography (surface features of an object), morphology
(shape and size of the particles making up the object), composition (the
elements and compounds that the object is composed of and the relative
amounts of them) and crystallographic information (how the atoms are
arranged in the object).
3.3.5.1 Transmission Electron Microscope (TEM)
Transmission electron microscopy (HRTEM) images were obtained
using a JEOL 2011 electron microscope (Japan) operated at 200 kV. For the
TEM imaging, the sample powder dispersed in methanol by using ultrasonic
radiation for 5 min and deposited onto the carbon-coated copper grids.
3.3.5.2 Scanning Electron Microscope (SEM)
Field emission scanning electron microscopy (FESEM) was obtained on
Zeiss Leo Supra55 microscope. The samples for FESEM observations were
observed without any metal coating.

11

Chapter 3

Figure 1.5 Schematic diagram of a TEM instrument.

Figure 1.6 Schematic diagram of a SEM instrument.

3.3.4 Nuclear Magnetic Resonance (NMR) Spectroscopy

12

Chapter 3

Proton nuclear magnetic resonance (1H NMR) spectroscopy was

routinely

used

for

characterizing

synthesized

organic

linkers

and

functionalized linkers and for determining the product conversions during

catalytic studies. 1H NMR was performed on a 400 MHz NMR Bruker
spectrometer. The chemical shifts () are reported in ppm.
3.3.5 Mass Spectrometry (MS)
The synthesized organic linkers and functionalized linkers were
identified using high-resolution mass spectrometry (HRMS). The masses and
molecular formulas of the compounds are determined from the measured
mole-tocharge ratios (m/z). The measured value is considered accurate if it is
within an error range of 5 ppm. The purity of a sample cannot be detected with
this method. High resolution mass spectra were recorded on a Bruker
microTOF ESITOF mass spectrometer.
3.3.6 Carbon Hydrogen and Nitrogen Analyzer
Most elemental analyses such as C, H, N and S are based on redox
reaction. Samples are finely grounded, wrapped by a tin foil and delivered to
the combustion tube by an autosampler. A small amount of pure oxygen is
used to aid combustion of organic or inorganic samples. After combustion,
samples undergo further catalytic redox processes to convert C, H, and N to a
variety of detectable gases. The instrument used in my project for C, H, N and
other element determination is Leco True-Spec CHN Determinator. The
carrier gas is helium in 99.99% purity and the pressure is 35psi 10%. The
purity of the oxygen is 99.99% and the pressure is 35psi 10%. The furnace
used for combustion can be heated up to as high as 1050.

13