Preparation and Characterization of Metal Organic Framework (MOF)

Materials

by

Nor Azillah Binti Mamat@Azmi

15605

Dissertation submitted in partial fulfilment of

the requirement for the
Bachelor of Engineering (Hons)
(Chemical Engineering)

SEPTEMBER 2015

Universiti Teknologi PETRONAS

32610 Bandar Seri Iskandar

Perak , Darul Ridzuan

 CERTIFICATION OF APPROVAL

Preparation and Characterization of Metal Organic Framework (MOF)

Materials
by

Nor Azillah Binti Mamat@Azmi

15605

A project dissertation submitted to the

Chemical Engineering Programme
Universiti Teknologi PETRONAS
in partial fulfilment of the requirement for the
BACHELOR OF ENGINEERING (Hons)
(CHEMICAL ENGINEERING)

Approved by,

(Dr Chew Thiam Leng)

UNIVERSITI TEKNOLOGI PETRONAS

BANDAR SERI ISKANDAR, PERAK

September 2015

ii
 CERTIFICATION OF ORIGINALITY

This is to certify that I am responsible for the work submitted in this project, that the
original work is my own except as specified in the references and acknowledgements,
and that the original work contained herein have not been undertaken or done by
unspecified sources or persons.

NOR AZILLAH BINTI MAMAT@AZMI

iii
 ABSTRACT

One of the metal-organic framework (MOF) material known as MOF-2, with

the formula of Zn2 (BDC)2 (where Zn = zinc, BDC = benzenedicarboxylic acid) is
commonly synthesized at room temperature. In current project, MOF-2 was
synthesized using solvothermal method at higher temperature. The current project
attempted to study the effect of different temperature and time of synthesis on MOF-
2. Several characterization analysis have been performed on the MOFs samples to
determine the properties of MOF-2 that have been produced which included Scanning
Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR),
Thermal Gravimetric Analysis (TGA), and Particle Size Analyzer (PSA). The study
demonstrated differences as well as similarities of MOF-2 properties for different
synthesis parameters.

iv
 ACKNOWLEDGEMENTS

I would like to take this opportunity to thank my parents, Mr. Mamat@Azmi

Bin Yaacob and Ms. Fauziah Binti Haji Mohamed Zin for their continuous support
from the beginning until the end of the project. Besides my parents, I want to express
my utmost gratitude to my supervisor, Dr Chew Thiam Leng for guiding me
throughout the completion of this final year project. It would be very hard for me to
finish this project without his valuable guidance.

I am also very thankful to the coordinator, Dr Nurul Ekmi for keeping track on
final year project progress and frequently reminding the students regarding the
submission and providing all the necessary information on the final year project.
Endless appreciation to all laboratory technologists involved who have assisted and
helped me a lot during the experiment. Without their help, this project would not be
possible.

I also want to thank all my friends who have directly and indirectly aided me
and constantly supported me in completing this project. On top of that, thank you to
Chemical Engineering department and Universiti Teknologi Petronas for giving me
the opportunity to involve in this research project.

v
 TABLE OF CONTENTS

CERTIFICATION OF APPROVAL ii
CERTIFICATION OF ORIGINALITY iii
ABSTRACT iv
ACKNOWLEDGEMENT v
TABLE OF CONTENT vi
LIST OF FIGURES viii
LIST OF TABLES viii
CHAPTER 1: INTRODUCTION 1
1.1 Background 1
1.2 Problem Statement 2
1.3 Objectives 3
1.4 Scope of study 4
CHAPTER 2: LITERATURE REVIEW 5
2.1 Porous material 5
2.1.1 Metal Organic Frameworks (MOFs) 6
2.1.1.1 Synthesis Technology 7
2.1.1.2 Characterization Technique 7
2.1.1.3 MOF-2 8
CHAPTER 3: METHODOLOGY 10
3.1 Project Flowchart 10
3.2 Gantt Chart 11
3.3 Key Project Milestones 11
3.4 Material, Apparatus and Equipment 12
3.5 Synthesis of MOFs material 13
3.5.1 MOFs preparation 13
3.5.2 Characterization of MOFs 14
3.5.2.1 Fourier Transform Infrared 14
Spectroscopy (FTIR) 14
3.5.2.2 Scanning Electron Microscopy 14
(SEM)

vi
 3.5.2.3 Thermal Gravimetric Analysis 14
(TGA)
3.5.2.4 Particle Size Analyzer (PSA) 15
CHAPTER 4: RESULT AND DISCUSSION 16
4.1 Weight of the sample 16
4.2 Fourier Transform Infrared Spectroscopy 17
4.3 Scanning Electron Microscopy 19
4.4 Thermal Gravimetric Analysis 20
4.5 Particle Size Analysis 22
CHAPTER 5: CONCLUSION AND RECOMMENDATION 23

5.1 Conclusion 23

5.2 Recommendation 23

REFERENCES 24
APPENDICES 27

vii
LIST OF FIGURES

Figure 1.1 Connection of organic linkers and metal ions (or clusters) 1
leads to a three-dimensional framework.
Figure 3.1 Project Flow chart 10
Figure 3.2 Gantt Chart 11
Figure 3.3 Key Project Milestones 11
Figure 4.1 FTIR spectrum for MOF-2 synthesized at a) 80 oC, 24 hours, 17
b) 80 oC, 48 hours, c) 100 oC, 24 hours, d) 100 oC, 48 hours,
e) 120 oC 24 hours, and f) 120 oC 48 hours.
Figure 4.2. SEM images of MOF-2 synthesized at a) 80 oC, 24 hours, b) 80 19
o
C, 48 hours, c) 100 oC, 24 hours, d) 100 oC, 48 hours, e) 120
o
C 24 hours, and f) 120 oC 48 hours.
Figure 4.3 Figure 4.3. TGA curves of MOF-2 synthesized at a) 80 oC, 20
24 hours, b) 80 oC, 48 hours, c) 100 oC, 24 hours, d) 100 oC, 48
hours, e) 120 oC 24 hours, and f) 120 oC 48 hours.
Figure 4.4 Particle Size Distribution 22

LIST OF TABLES

Table 2.1 Different types of MOFs with surface area and pore volume 6
Table 2.2 Preparation of different MOFs 7
Table 2.3 Different characterization techniques used in research 7
Table 2.4 Preparation technology for MOF-2 9
Table 3.1 Chemical and material for experiment 12
Table 3.2 Apparatus for experiment 12
Table 3.3 Equipment for experiment 13
Table 3.4 Temperature and synthesis time 14
Table 4.1 Weight of the samples 16
Table 4.2 Bond and functional group of MOF-2 found in FTIR 18
spectrum
Table 4.3 Total weight loss (%) for MOF-2 in TGA 21
Table 4.4 Particle size of MOF-2 22

viii
 CHAPTER 1

INTRODUCTION

1.1 Background

Metal-Organic Frameworks (MOFs) are defined as compounds that consist of

metal ions or clusters coordinated to organic molecules to form one-, two-, or three-
dimensional structures that are composed of the tunable metal clusters and organic
linkers. Employing a simple cubic topology, Figure 1.1 shows the metal ions or
clusters (metal nodes) that serve as points connecting the structure meanwhile the
organic linkers serve as bridges connecting the metal nodes to form three-dimensional
framework.

Figure 1.1 Connection of organic linkers and metal ions (or clusters) leads to a three-
dimensional framework.

As a unique class of hybrid nanoporous materials, metal-organic frameworks

have attracted considerable interest in recent years (Chen et al., 2010). MOFs have an
exceptionally large surface areas and well-defined pores. Other than that, it display
high crystalline structure, strong bonding providing robustness, linking units that are
available for modification by organic synthesis (Jesse et al., 2004). Because of its
characteristics, they are considered as an excellent candidates for separation, storage,

1
catalysis, and other evolving applications. Typically, in MOF-2 case, they are obtained
either through experiment at room temperature with or without the presence of amine,
or through the transformation of MOF-1. In this research, the aim is to synthesis MOF-
2 at different temperature and heating time using conventional method known as
solvothermal method rather than at room temperature. The effect of different
temperature and time were analyzed using several characterizations analysis such as
Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy
(FTIR), Thermal Gravimetric Analysis (TGA), and Particle Size Analyzer (PSA) to
examine MOF’s surface morphology, thermal stability, functional group and particle
size respectively.

1.2 Problem Statement

MOFs, and other well-known materials such as silica and activated carbon have
been widely applicable as adsorbents. As a new class of hybrid nanoporous material,
MOFs have attracted interest in its adsorption ability due to its extremely large surface
area and well defined pores. It has been claimed by a researcher that MOFs materials
can exceed the performance of activated carbon when removing toxic industrial
chemicals from air. MOFs unique characteristic of having uniform pores structure
compared to other materials has making it a more preferable candidate in adsorption.
It has also been investigated that the drawback of activated carbon in vacuum pressure
swing adsorption (VPSA) is low selectivity. Hence kinetic based materials like MOFs
are preferred. Furthermore, MOFs have the possibility to alter their structures and
functional properties by shifting the building blocks used in their construction. With
the ability to control pore dimension, shape of the channels, and chemical potential of
the surface, making it possible to build the adsorbent with the desired adsorption
properties (Mangano et al., 2013).

Compared to other MOFs, MOF-2 was usually synthesized at room

temperature with or without the presence of triethylamine (TEA) depending on what
type of zinc was used. At room temperature, they were left under continuous stirring,
2
however the time for stirring depends on the type of zinc used. There were only a few
studies reported for synthesis of MOF-2 using solvothermal method. Solvothermal
method is a conventional method that has been widely used in synthesizing MOFs.

One of the most difficult part in engineering MOFs is determining the correct
synthesis parameters such as temperature, heating time, pressure, metal source, organic
ligands and solvents that will yield the desired structure (Ordonez et al, 2014). So far,
to the best knowledge, there is no study that has been done on synthesis parameters of
MOF-2 using solvothermal method. Hence, this project will focus on the parameters
affecting the characterization of MOFs which are temperature and heating time.
Several characterization techniques were performed to analyze the characteristics of
MOFs that have been synthesized.

1.3 Objectives

The main objectives of this project are:

i. To synthesize metal organic frameworks material – MOF-2 using

solvothermal method.
ii. To study the effect of synthesis temperature and heating time on the
formation of metal organic frameworks material – MOF-2
iii. To characterize metal organic frameworks material – MOF-2 using
different analytical techniques.

3
1.4 Scope of Study

The project is focusing on synthesizing MOF-2 material which is Zn2 (BDC)2

where; Zn = zinc, BDC = benzenedicarboxylic acid, using solvothermal method. The
effect of the synthesis temperature and time on the characteristics of the MOF-2
produced were investigated using FTIR, TGA, SEM, and PSA. Most of the experiment
works were done in the Chemical Engineering laboratory and some of the
characterizations were done in Mechanical Engineering laboratory, UTP.

4
 CHAPTER 2

LITERATURE REVIEW

2.1 Porous materials

Porosity is the capability to hold a fluid. A solid can be regarded as porous if

the voids in its structure are large enough to accommodate guest molecules (Yilmaz et
al., 2012). In industry, the ability to bring molecules in and out of a porous material
has proven to be greatly beneficial. Uniform porosity which is found in MOF supports
the utilization of the pores as it allows more control of transport in and out of the
structure. Yilmaz et al. (2012) stated that each new MOF has the potential to offer
unique structural and chemical features that can be beneficial for an industrial
application.

One of the significance of porosity is in adsorption. MOFs, and other materials

such as silica and activated carbon have been widely known as adsorbents. Silica and
activated carbon are types of adsorbent broadly used in the purification and separation
of organic mixtures due to its high surface area and porosity (Unob et al., 2007). As a
new class of hybrid material, MOFs has also attracted interest in its adsorption ability
due to its characteristics of having extremely large surface area and well defined pores.
Glover (2015) published a paper detailing the importance of tuning MOFs adsorbent
surface chemistry to target specific adsorbate gases and he claimed that the outcome
is MOFs materials can exceed the performance of activated carbon when removing
toxic industrial chemicals from air. Cavenati et al, (2008) performed vacuum pressure
swing adsorption (VPSA) by applying equilibrium based adsorbent (activated carbon)
and kinetic based adsorbent (MOFs). The drawback of activated carbon is low
selectivity. Hence kinetic based materials are preferred

5
2.1.1 Metal Organic Frameworks (MOFs)

As a new member of the porous solids family, the number of publications about
MOF has been increasing tremendously. There are hundreds of different MOFs that
varies in structure types, with chemical flexibility and compositional diversity reported
to date. MOFs can be defined as porous crystalline compounds forming 1, 2 or 3
dimensional structures with the use of metal ions. MOFs consist of metal ions and
organic molecules known as ligands. Based on Chemwiki (2014), ligands can be
described as ions or neutral molecules that bond to a central metal atom or ion. They
act as Lewis bases (electron pair donors), and the central atom acts as a Lewis acid
(electron pair acceptor). At least one donor atom with an electron pair is used to form
covalent bonds with the central atom. It was claimed that MOFs were born from
zeolites, a breakthrough supplement that works at the cellular level by trapping heavy
metals and toxins and safely removing them from the body. The high specific surface
area with Langmuir surface area reaching 10000 m2 /g and large pore volume up to 3
cm3 /g of MOFs led them as perfect candidates for catalysis, gas adsorption, separation
of gases and other applications. The pore size and surface area can be modified by
changing the synthetic conditions. In the future, it is believed that MOFs are able to
replace zeolites at every level due to its large surface area to volume. Table 2.1
represents different types of MOFs with their surface area and pore volume.

Table 2.1 Different types of MOFs with surface area and pore volume

MOF Surface area (𝒎𝟐 /𝒈) Pore volume (𝒄𝒎𝟑 /𝒈)

MOF – 177 3875 1.59
MOF – 5 2205 1.22
MOF – 1 1794 0.65
IRMOF – 3 1568 1.07
IRMOF – 62 1814 0.99
MOF – 199 1264 0.75
MOF – 74 632 0.39

6
 2.1.1.1 Synthesis Technology

In preparation of MOFs, there were different methods and operating conditions

that have been applied by the different researchers as shown in Table 2.2.

Table 2.2 Preparation of different MOFs

MOFs Technology Temperature Time Reference

Ni-MOF-74 Hydrothermal 100℃ 1 day Wu et al., (2013)
𝐂𝐮(𝐁𝐃𝐂)(𝐓𝐄𝐃)𝟎.𝟓 Solvothermal 120℃ 1 ½ day Lee et al., (2007)
𝐙𝐧(𝐁𝐃𝐂)(𝐓𝐄𝐃)𝟎.𝟓 Solvothermal 120℃ 2 days Lee et al., (2007)
𝐂𝐮(𝐁𝐃𝐂)(𝐓𝐄𝐃)𝟎.𝟓 Conventional 120℃ 1 ½ day Tan et al., (n.d.)
𝐍𝐢(𝐁𝐃𝐂)(𝐓𝐄𝐃)𝟎.𝟓 Conventional 120℃ 2 days Tan et al., (n.d.)
𝐂𝐨(𝐁𝐃𝐂)(𝐓𝐄𝐃)𝟎.𝟓 Conventional 120℃ 2 days Tan et al., (n.d.)
MOF-500 Conventional 100℃ 1 day Sudik et al., (2006)

2.1.1.2 Characterization techniques

Table 2.3 displays the different characterization techniques used on MOF in

past researches.

Table 2.3 Different characterization techniques used in research

Technique Reason Reference
FESEM (S4800, Hitachi) To evaluate morphologies of the Liu et al., (2014)
sample
XRD (D8 Advance, Bruker) To characterize crystal structure
FESEM (S4800, Hitachi) To characterize morphology and Huang et al., (2014)
thickness of the sample
XRD (D8 Advance, Bruker) To identify phase purity and
crystallinity
TGA (Perkin-Elmer) To evaluate the thermal stability
of the sample

7
 PXRD To confirm structural integrity of Chen et al., (2010)
the sample
High pressure adsorption To get pressure gas isotherm
analyzer (HPVA-100) graph

2.1.1.3 MOF-2

2.1.1.3.1 Synthesis method for MOF-2

MOFs were frequently synthesized using conventional solvothermal method

by heating a mixture of metal salt and organic linker in a solvent that typically contains
formamide to temperatures near or above the boiling point of the solvent (Getachew
et al., 2014). This method is widely used since it is commonly used to synthesize other
porous materials and often yield crystals suitable for XRD.

However, some researchers synthesized MOF-2 at room temperature. This was

done under stirring for few hours or up to days. The presence of amine is depends on
the metal salt used. Usually when zinc acetate dehydrate is used instead of zinc nitrate
hexahydrate, no amine is needed.

Table 2.4 represents the technologies that have been used to prepare
Zn2 (BDC)2. In this project, the effect of temperature and time on synthesis of MOF-2
were investigated.

8
 Table 2.4 Preparation technology for MOF-2

MOFs Technology Temperature Time Reference

Zn2 (BDC)2 - Room temperature 24 hours Getachew et al., (2014)
Zn2 (BDC)2 - Room temperature - Li et al., (1998)
Zn2 (BDC)2 Solvothermal 105℃ 24 hours Li et al., (2011)
CdMOF-2. Microwave 120℃ 48 hours Hu, M. (2011)

9
 CHAPTER 3

METHODOLOGY

3.1 Project Flowchart

Figure 3.1 shows the work flow of the project in final year project 2.

Experiment

 Perform laboratory work to

obtain samples

Data collection

 Send the samples to

characterization
 Collect and analyze the results

Assessment

 Prepare and submit progress

report, dissertation and
technical paper
 Viva

Final Report

 Prepare and submit hard bound

of project dissertation

Figure 3.1 Project Flow chart

10
3.2 Gantt Chart

Figure 3.2 Gantt Chart displays the period allocation for each work progress.

Figure 3.2 Gantt Chart

3.3 Key Project Milestones

Figure 3.3 represents the important dates for each work title.

Submission
of Submission
Submission
Start Project Submission Dissertation of Project
of progress Pre-SEDEX
laboratory work of Draft (soft bound) Viva Dissertation
report (1/12/15)
work continues Final Report and (18/12/15) (hard
(Monday, Technical bound)
(Week 1 - 7) (Week 8-12) (1/12/15)
9/11/2015) Paper (12/01/16)
(8&9/12/15)

Figure 3.3 Key Project Milestones

11
3.4 Material, Apparatus and Equipment

Table 3.1 shows the chemical and material used in the experiment.

Table 3.1 Chemical and material for experiment

No Material
1 Zinc(II) nitrate hexahydrate
2 H2 BDC
4 DMF
5 Ethanol
6 Acetone
7 Filter paper
8 Aluminium foil
9 Paraffin film

Table 3.2 represents apparatus used in the experiment.

Table 3.2 Apparatus for experiment

No Apparatus Quantity
1 Spatula 1
2 250mL beaker 1
3 120mL beaker 1
4 100mL beaker 1
5 100mL measuring cylinder 1
6 10mL measuring cylinder 1
7 Stirring rod 1
8 Filter funnel 1
9 Retort stand 1
10 Petri dish 1
11 Plastic dropper 1
12 Magnetic stirrer bar 1

12
 Table 3.3 displays equipment used in the experiment.

Table 3.3 Equipment for experiment

No Apparatus Quantity
1 Weighing balance 1
2 Magnetic hot plate stirrer 1
3 Ultrasonic device 1
4 Oven 1
5 Vacuum oven 1

3.5 Synthesis of MOF-2 material

3.5.1 Preparation of MOF-2 material

1) H2 BDC (0.83 g, 5.0 mmol), zinc(II) nitrate hexahydrate (1.31 g, 5 mmol),

and 50 mL of DMF were mixed in the 150 mL beaker.
2) The 150 mL beaker was wrapped with a layer of paraffin film, then the
mixture were stirred using magnetic hot plate stirrer to dissolve all solids.
3) The mixture were subjected to ultrasonic treatment at 50℃ for 3 hours until
clear solution is obtained.
4) The mixture were then be transferred to vessels and placed in oven to be
heated at certain temperature for certain time.
5) Step 1 to 4 was repeated several times with different temperature and
synthesis time according to Table 3.4.
6) The sample undergone centrifugation and then was filtered with filter
paper.
7) The sample was placed on petri dish to be completely dried under vacuum
oven at 100℃ overnight.

13
 Table 3.4 Temperature and synthesis time

Sample Temperature (℃) Synthesis time (hour)

1 60 24
2 48
3 80 24
4 48
5 100 24
6 48
7 120 24
8 48

3.5.2 Characterization of MOFs

3.5.2.1 Fourier Transform Infrared Spectroscopy (FTIR)

FTIR (model: 8400S, brand: Shimadzu) was used to identify functional group
and bonding in the sample.

3.5.2.2 Scanning Electron Microscopy (SEM)

SEM (model: Pro X, brand: Phenom) was used to evaluate the surface
morphology of the sample material.

3.5.2.3 Thermal Gravimetric Analysis (TGA)

TGA (model: PYRIS 1, brand: Perkin Elmer) was used to check the thermal
stability of the sample.

14
3.5.2.4 Particle Size Analysis

Particle Size Analyzer (model: MS2000, brand: Mastersizer) was used to

measure the particle size of the sample.

15
 CHAPTER 4

RESULT AND DISCUSSION

4.1 Weight of the sample

The weight gain of the samples synthesized under different synthesis time and
temperature from the experiment were tabulated in Table 4.1. From Table 4.1, it is
observed that the highest weight gain was obtained at synthesis condition of 100℃ for
48 hours while at 60℃, either the solution was heated for 24 or 48 hours, there were
no crystal formed. It can be deduced that at temperature of 60℃ and below is not the
appropriate temperature to synthesize MOF-2. At lower temperature, the energy
supplied was not enough to optimize the formation of metal-ligand bond (Zn-BDC)
through condensation process meanwhile at elevated temperature of higher than the
boiling point of water, the chemical reaction involving water molecules and metal
clusters in MOF could lead to hydrolysis process where ligands were displaced. At
temperature more than the boiling point of water, water molecules started to dissociate
into H + and OH − that then displaced some ligand, which was BDC bond in the Zn-
BDC which resulted in lower weight gain at 120℃ compared to at 100℃ .

Table 4.1 Weight of the samples

Sample Temperature (℃) Synthesis time (hour) Weight (grams)

1 60 24
No crystal formed
2 48
3 80 24 0.2700
4 48 0.5277
5 100 24 0.6718
6 48 0.7569
7 120 24 0.6100
8 48 0.6832

16
4.2 Fourier Transform Infrared Spectroscopy

The infrared regions used in FTIR analysis is mid-IR; between 500 to 4000
cm−1 , which is the most widely used region to determine the structure of organic and
biochemical species. The samples were mixed with potassium bromide and turned into
pellet before being analyzed with FTIR. The graphs for FTIR analysis were obtained,
and the respective functional groups were determined based on the peak from the
graphs, using Appendix A and B as reference.

Figure 4.1 FTIR spectrum for MOF-2 synthesized at a) 80 oC, 24 hours, b) 80 oC,
48 hours, c) 100 oC, 24 hours, d) 100 oC, 48 hours, e) 120 oC 24 hours, and f) 120 oC
48 hours.

Based on Figure 4.1, all MOF-2 samples exhibited similar pattern where the
transmittance peak fell under the same wavelength range which led to same functional
groups and bonds. The functional groups and bonds found in the FTIR spectrum
confirmed the existence of the MOF-2 compound. The analyzed bonds included =C-
H bend, C-N stretch, C-H, C=C, N-H bend, and O-H. The bonds and functional groups
found in FTIR spectrum were listed in Table 4.2. The plots for each samples and their
respective functional groups and bonds analyzed can be found in appendix.

17
 Table 4.2: Bond and functional group of MOF-2 found in FTIR spectrum

Wavelength (𝐜𝐦−𝟏 ) Bond Functional group

1000-650 =C-H bend Alkenes

1250-1020 C-N stretch Aliphatic amine

1470-1340 C-H Alkanes

1680-1610 C=C Alkenes

1650-1580 N-H bend 1° amines

2400-2300 Not available Not available

3300-2500 O-H Hydrogen bonded alcohol,

phenols

18
4.3 Scanning Electron Microscopy

(a) (b) (c)

(d) (e) (f)

Figure 4.2. SEM images of MOF-2 synthesized at a) 80 oC, 24 hours, b) 80 oC, 48

hours, c) 100 oC, 24 hours, d) 100 oC, 48 hours, e) 120 oC 24 hours, and f) 120 oC 48
hours.

As shown in Figure 4.2, the MOFs that have been synthesized using different
temperature and time display different SEM images. The images showed the growth
of MOF-2 was not uniform and there was polydispersity in shape and size. The shape
was seen to be rectangular with slanting structure for all samples.

These SEM results did not produce similar shape to the one synthesized at
room temperature as reported by Getachew et al. (2014) or the one synthesized using
solvothermal method by Li et al. (2011). However, Figure 4.2 d) resembled SEM
image for MOF-2 reported by Aiyappa et al. (2013).

19
4.4 Thermal Gravimetric Analysis

In TGA, nitrogen gas was used with the temperature rate of 5℃/min. Usually
in TGA curves for MOF-2, there were three steps of weight loses observed. The first
step of weight loss represents the loss of water molecules, the second weight lost is
corresponding to the volatilization of the discrete DMF molecules in the framework,
while the last step refers to the decomposition of the MOF-2 framework.

Figure 4.3. TGA curves of MOF-2 synthesized at a) 80 oC, 24 hours, b) 80 oC, 48

hours, c) 100 oC, 24 hours, d) 100 oC, 48 hours, e) 120 oC 24 hours, and f) 120 oC 48
hours.

The first step of weight loss were not visible in the TGA plots because all water
molecules present in the samples have been eliminated in vacuum oven, except for
Figure 4.3 a), since during the experiment, the pump with the vacuum oven was not
functioning. Figure 4.3 a) displayed similar TGA plots as reported by Li, et al. (2011)
and Getachew, et al (2014) that have dried the samples naturally. Overall, all the
curves have similar pattern to each other.

The first step of weight loss for Figure 4.3 a) was observed around 60℃
(4.07wt%), the second step was below 200℃ (18.28wt%), and the third step of weight

20
loss was above 400℃ (45.36wt%). Figure 4.3 b) first step of weight loss was seen
around 160 ℃ (13.75wt%) and the second step of weight loss at above 400℃
(48.96wt%). The TGA data represented in Figure 4.3 c) has weight losses at 140℃
(10.02wt%), and same as previous data, above 400℃ (56.74wt%). MOF-2 synthesized
at 100℃ for 48 hours shown in Figure 4.3 d) exhibited similar graph style as in Figure
4.3 c) where the first step of weight loss observed around 130℃ (11.08wt%), and final
weight loss above 400℃ (55.56wt%). For Figure 4.3 e), first weight loss at 130℃
(13.83wt%) and second weight loss at 440℃ (52.06wt%) meanwhile Figure 4.3 f) has
weight loss at 140℃ (13.51wt%) and at 420℃ (43.01wt%).

Table 4.2 tabulated the total weight loss for each samples in TGA where the
highest weight loss was at 80℃ 24 hours.

Table 4.3 Total weight loss (%) for MOF-2 in TGA

Sample Temperature Synthesis time Total weight loss

(°C ) (hour) (%)
a) 80 24 73.95
b) 48 70.72
c) 100 24 68.33
d) 48 70.12
e) 120 24 68.98
f) 48 61.03

21
4.5 Particle Size Analysis

The particle size of MOF-2 at different synthesis parameters was tested at

refractive index of 1.500.

Figure 4.4 Particle Size Distribution

Figure 4.4 presented the particle size distribution of MOF-2. It could be seen
that each samples has distinct particle size distribution with the average specific
surface area of 0.288 𝑚2 /g, surface weighted mean of 20.865𝜇𝑚 and volume weighted
mean of 49.684 𝜇𝑚. Table 4.4 showed the particle size diameter for each sample.

Table 4.4 Particle size of MOF-2

Sample Temperature Synthesis time Particle size,

(°C ) (hour) diameter (𝝁𝒎)
a) 80 24 55.862
b) 48 39.187
c) 100 24 60.470
d) 48 57.589
e) 120 24 36.436
f) 48 56.867

22
 CHAPTER 5

CONCLUSION AND RECOMMENDATION

5.1 Conclusion

According to the study, it can be concluded that the temperature of 60℃ and
lower is not suitable to synthesize MOF-2 as it will not produce any crystal. Meanwhile
100℃ was found to be the optimum temperature with the highest weight gain. For the
characterization, FTIR spectrum found that all the MOF-2 samples contained =C-H
bend, C-N stretch, C-H, C=C, N-H bend, and O-H bonds. SEM images showed
polydispersity in shape and size for each samples. TGA graphs observed the step of
weight losses for the samples at below 100℃, above 100℃, and above 400℃ while the
particle size distribution exhibited different particle size for each samples.

5.2 Recommendation

In future work, this project can be further improved by running more synthesis’
parameters of temperature and time so that the parameters can be studied in more
details. Other than that, the characteristics of the MOFs can be analyzed using various
techniques such as X-ray Diffraction (XRD), Atomic Force Microscopy (AFM) and
Field Emission Scanning Electron Microscopy (FESEM). Furthermore, the
application of the MOFs in separation, drug delivery, catalysis and storage should be
analyzed as well.

23
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 APPENDICES

Appendix A IR absorption table 27

Appendix B IR absorption table 28
Appendix C FTIR data for MOF-2 at 80℃, 24 hours 28
Appendix D FTIR data for MOF-2 at 100℃, 24 hours 29
Appendix E FTIR data for MOF-2 at 120℃, 24 hours 29
Appendix F FTIR data for MOF-2 at 80℃, 48 hours 30
Appendix G FTIR data for MOF-2 at 100℃, 48 hours 30
Appendix H FTIR data for MOF-2 at 120℃, 48 hours 31
Appendix I TGA data for MOF-2 at 80℃, 24 hours 31
Appendix J TGA data for MOF-2 at 100℃, 24 hours 32
Appendix K TGA data for MOF-2 at 120℃, 24 hours 32
Appendix L TGA data for MOF-2 at 80℃, 48 hours 33
Appendix M TGA data for MOF-2 at 100℃, 48 hours 33
Appendix N TGA data for MOF-2 at 120℃, 48 hours 34

27
Appendix A IR absorption table

28
 Appendix B IR absorption table

Peak Bond Functional group

750.26 =C-H bend Alkenes
1101.28 C-N stretch Aliphatic amine
1386.72 C-H Alkanes
1623.95 C=C Alkenes
N-H bend 1° amines
3288.40 O-H Hydrogen bonded
alcohol, phenols

Appendix C FTIR data for MOF-2 at 80℃, 24 hours

29
 Peak Bond Functional group
752.19 =C-H bend Alkenes
1384.79 C-H Alkanes
1583.45 C=C Aromatic rings
3172.68 O-H stretch Carboxylic acid

.Appendix D FTIR data for MOF-2 at 100℃, 24 hours

Peak Bond Functional group

748.33 =C-H bend Alkenes
1380.94 C-H Alkanes
1583.45 C=C Aromatic rings
3184.26 O-H stretch Carboxylic acid

Appendix E FTIR data for MOF-2 at 120℃, 24 hours

30
 Peak Bond Functional group
743.42 =C-H bend Alkenes
1361.09 C-H Alkanes
1557.29 C=C Aromatic rings
3110.28 O-H stretch Carboxylic acid

Appendix F FTIR data for MOF-2 at 80℃, 48 hours

Peak Bond Functional group

746.40 =C-H bend Alkenes
1382.87 C-H Alkanes
1579.59 C=C Aromatic rings
3224.76 O-H stretch Carboxylic acid

Appendix G FTIR data for MOF-2 at 100℃, 48 hours

31
 Peak Bond Functional group
744.47 =C-H bend Alkenes
1366.45 C-H Alkanes
1574.52 C=C Aromatic rings
3169.33 O-H stretch Carboxylic acid

Appendix H FTIR data for MOF-2 at 120℃, 48 hours

Appendix I TGA data for MOF-2 at 80℃, 24 hours

32
Appendix J TGA data for MOF-2 at 100℃, 24 hours

Appendix K TGA data for MOF-2 at 120℃, 24 hours

33
Appendix L TGA data for MOF-2 at 80℃, 48 hours

Appendix M TGA data for MOF-2 at 100℃, 48 hours

34
Appendix N TGA data for MOF-2 at 120℃, 48 hours

35