INCORPORATION OF DOPED TiO2 INTO MOF OF Ti AND

BTC AND STUDY OF ITS PHOTOCATALYTIC EFFECT

A Thesis Submitted to Bahauddin Zakariya University

In Partial fulfillment of the requirements for the degree of
Master of Philosophy in Chemistry
By
Hafiz Muzammil Hussain
Roll No. MPH-C- 16-34
Session 2016-2018

Institute of Chemical Sciences

Bahauddin Zakariya University Multan, Pakistan
“To God belongs the east and the west where so ever you look
is the face of God”

Quran 2:115
 Dedicated to
My beloved

Parents especially my brothers

Who always guided and encouraged me.

 DECLARATION

I Hafiz Muzammil Hussain hereby declare that the research work described in this thesis was
carried out by me under the kind supervision of Dr. MUHAMMAD ATHAR, Associate
Professor at INSTITUTE OF CHEMICAL SCIENCES, BAHAUDDIN ZAKARIYA
UNIVERSITY, MULTAN for the degree of M.Phil in Chemistry.

I further declare that the work personified in the thesis is the result of my own research and that
it has been composed by me. Where suitable, I have made acknowledgement to the work of others.

Date: Hafiz Muzammil Hussain

 CERTIFICATE

CERTIFICATE

This is to certify that the thesis entitled “INCORPORATION OF DOPED TiO2 INTO MOF
OF Ti AND BTC AND STUDY OF ITS PHOTOCATALYTIC EFFECT” by Hafiz
Muzammil Hussain (MPH-C-16-34), submitted to the INSTITUTE OF CHEMICAL
SCIENCES BAHAUDDIN ZAKARIYA UNIVERSITY MULTAN for the Degree of Master
of Philosophy in Chemistry is a record of bonafide research work, carried out by him in the
Institute of Chemical Sciences BZU Multan under my supervision. I believe that the thesis fulfils
part of the requirements for the award of Master of Philosophy. The results embodied in the thesis
have not been submitted for the award of any other degree.

------------------------------------

(Supervisor)
Dr. Muhammad Athar
Associate Professor
Institute of Chemical Sciences
Bahauddin Zakariya University,
Multan, Pakistan
 ACKNOWLEDEMENT

All praises are for ALLAH ALMIGHTY, who is the most beneficial and merciful and respect for
His prophet HAZRAT MUHAMMAD (peace be upon him).

I express my deep gratitude to Dr. Muhammad Athar, my learned supervisor for his kind
guidance and encouragement throughout this work and providing all the opportunities needed in
my work.

I am obliged to Prof. Dr. Farzana (Director of Institute of Chemistry, Bahauddin Zakariya

University, Multan) for providing me the necessary facilities and help in carrying out my
dissertation work.

I am obliged to Mr. Fiaz (Student of Ph.D. at Institute of Chemistry, Bahauddin Zakariya

University, Multan) for helping me in characterization of my work.

I owe my special thanks to my parents whose prayer always paved success for me.

I may be failing in my duties if I do not thank all my batch mates for their constant encouragement.
I would more than ever like to thank my friends for their constant help throughout my work.

It would be injustice if I ignore the two persons which remain in touch with us more than others
are Mr. Muhammad Shafi (L.A) and Mr. Muhammad Ajmal (L.A). I am thankful to both for
special concern in this regard.

Hafiz Muzammil Hussain

CHAPTER 1 INTRODUCTION

1.1 General components of MOFs 2

1.2 Carboxylate as ditopic linkers 5

1.2.1 Four side connected ditopic carboxylate linkers as paddle-wheel clusters 6

1.2.2 Six side connected ditopic carboxylates as organic linkers (octahedral clusters) 6

1.3 Basic methods for synthesis of metal organic frameworks (MOF) 7

1.3.1 Solvothermal and non-solvothermal process 8

1.3.2 Microwave synthesis 8
1.3.3 Electrochemical synthesis 9
1.3.4 Mechanochemical method 9
1.3.5 Sonochemical synthesis 10
1.4 Characteristics of MOF 10
1.4.1 Porosity 11
1.5 Methodologies of incorporation of metal nanoparticles (MNPs) into pores of MOFs 11
1.5.1 Ship in bottle method 11
1.5.2 Bottle around ship method 12
1.5.3 One-step method 12
1.6 Photocatalysis 12
1.6.1 Mechanism of photocatalysis 13
1.6.2 Advance oxidation/reduction process and Photocatalytic reactions 14
1.6.3 Characteristics of good photocatalyst 16
1.7 Factors that affect the photocatalytic efficiency 16
1.7.1 Intensity of incident light 16
1.7.2 Concentration of substrate and its nature 16
1.7.3 Nature of photocatalyst 17
1.7.4 Concentration of photocatalyst 17
1.7.5 pH 17
1.7.6 Reaction temperature 18
1.8 Nanoparticles as photocatalyst 18
1.8.1 Doped nanoparticles as photocatalyst 18
1.8.2 Doping methods of TiO2 19
1.8.3 Ion-implantation method 19
1.8.4 Hydrothermal method 19
1.8.5 Sol-gel method 19
1.9 General characterization techniques 20

1.9.1 XRD Technique 20

1.9.2 Scanning electron microscopy 23

1.9.3 Transmission electron microscopy 24

19.4 UV/Visible spectroscopy 25

CHAPTER 2 EXPERIMENTAL

2.1 Chemical and reagents used 27

2.2 Instrumentation 28

2.3 Preparation of Titanium dioxide Nano particles 29

2.4 Synthesis of Silver oxide doped Titanium dioxide Nanoparticles 30

2.5 Synthesis of MOF of Benzene 1,3,5 Tricarboxylic Acid with Titanium Metal 30

2.6 Incorporation of TiO2 Nanoparticles in Ti(BTC) MOF 30

2.7 Incorporation of Ag2O/TiO2 Nanoparticles into Ti(BTC) MOF 31

2.8 Photo-catalytic degradation of Methylene Blue 31

2.8.1 Preparation of Dye Solution 31

2.8.2 In a typical procedure, photo-degradation studies of

methylene blue dye by synthesized samples 32

2.9 Photo-catalytic degradation of methyl orange 32

CHAPTER 3 RESULTS AND DISCUSSION

3.1 Powder XRD Analysis 33

3.1.1 Crystallite Sizes 36

3.2 Solid state UV/Vis Spectrophotometry 36

3.3 EDX and SEM 40

3.4 Photocatalytic degradation of Methylene Blue 43

3.4.1 Photo-catalytic Degradation of Methylene Blue by synthesized samples 43

3.5 Photo-catalytic degradation of Methyl Orange 47

3.5.1 Determination of ƛmax of Methyl Orange 47

3.5.2 Photo catalytic Degradation of Methyl Orange by synthesized samples 47

CHAPTER 4 REFRENCES 53

LIST OF FIGURES

Figure 1.1 General representation of MOF formation 2

Figure 1.2 Examples of different types of organic linkers 3
Figure 1.3 Secondary building units of different types of MOFs 4
Figure 1.4 Graphical illustration of the construction of some representative coordination

polymers/MOFs from SBUs and rigid linkers 5

Figure 1.5 Coplanar dicarboxylates linkers and square paddle-wheels like structure 6
Figure 1.6 Some representation of formation of extended IRMOF networks by replacing acetate

groups with benzene dicarboxylates 7

Figure 1.7 (a) Ship in bottle method; (b) bottle around ship method; (c) one-step method 12
Figure 1.8 Schematic representation of semiconductor photocatalytic mechanism 15
Figure 1.9 Schematic representation of oxidation of dye 15
Figure 1.10 Representation of doping TiO2 by sol-gel 20

Figure 1.11 Schematic diagram of a diffractometer system 21

Figure 1.12 Schematic diagram of transmission electron microscopy 25

Figure 1.13 Schematic diagram of UV/Visible spectrophotometer 26

Figure 3 XRD pattern of Ti(BTC) 33

Figure 3.1 XRD pattern of TiO2 34

Figure 3.2 XRD pattern of Ag2O/TiO2 34

Figure 3.3 TiO2@Ti(BTC) 35

Figure 3.4 XRD pattern of Ag2O/TiO2@Ti(BTC) 35

Figure 3.5 Solid state UV/Visible spectrum of TiO2 37

Figure 3.6 Solid state UV/Visible spectrum of TiO2@Ti(BTC) MOF 37

Figure 3.7 Solid state UV/Visible spectrum of Ti(BTC) MOF 38

Figure 3.8 Solid state UV/Visible spectrum of Ag2O/TiO2 nanoparticles 38

Figure 3.9 Solid state UV/Vis spectrum of Ag2O/TiO2@Ti(BTC) 39

Figure 3.10 UV/Vis spectra of all samples 39

Figure 3.11 EDX and SEM of TiO2 40

Figure 3.12 EDX and SEM of TiO2/Ag2O 41

Figure 3.13 EDX and SEM of Ti(BTC) MOF 41

Figure 3.14 EDX and SEM of TiO2/Ag2O@Ti(BTC) 42

Figure 3.15 EDX and SEM of TiO2@Ti(BTC) 42

Figure 3.16 Degradation of Methylene Blue by Ag2O/TiO2 44

Figure 3.17 Degradation of Methylene Blue by TiO2 44

Figure 3.18 Degradation of Methylene Blue by Ti(BTC) MOF 45

Figure 3.19 Degradation of Methylene Blue Methylene Blue by TiO2@Ti(BTC) 45

Figure 3.20 Degradation of Methylene Blue by Ag2O/TiO2@Ti(BTC) 46

Figure 3.21 Comparative study of Photo-Degradation by synthesized samples 46

Figure 3.22 Degradation of Methylene Orange by Ag2O/TiO2 nanoparticles 49

Figure 3.23 Degradation of Methyl Orange by Ti(BTC) MOF 49

Figure 3.24 Degradation of Methyl Orange by TiO2@Ti(BTC) 50

Figure 3.25 Degradation of Methyl Orange by Ag2O/TiO2@Ti(BTC) 50

Figure 3.26 Degradation of Methyl Orange by TiO2 51

Figure 3.27 Comparative study of Photo-Degradation by synthesized samples 51

LIST OF TABLES

Table 3.1 Crystallite Sizes of Samples 36

Table 3.2 Change in Absorbance of Methylene Blue by using different samples 43

Table 3.3 Change in Absorbance of Methyl Orange by using different samples 48

 Abstract

There are various types of photo-catalytic material have been synthesized and reported in the world
for various purposes at daily basis. Efficiency of photo-catalytic material is changing day by day
according to requirement of aims and objectives of work by researchers. Photo-catalytic material
works effectively in the presence of light. So, in case of purification of water, the photo-catalytic
material is the cheapest more reliable choice as compared all other purification methods. Added
photo-catalytic material become helpful in degradation of different kinds of contaminants which
may are be organic or inorganic nature. Doping of TiO2 by Ag2O increases the photo-catalytic
efficiency and increase the area of action in degradation of organic material in aqueous medium.
Incorporation Ag2O/TiO2 material into a MOF of Titanium metal and Benzene tricarboxylic acid.
The synthesis of MOF and incorporation of Ag2O/TiO2 is carried out by solvothermal process at
controlled temperature and pressure. The resultant material will be characterized by different
analytical techniques such as solid-state UV/Visible spectrophotometer, XRD pattern, elemental
analysis, SEM and TEM. Prepared Ag2O/TiO2@Ti(BTC) will show very good photo-catalytic
efficiency in photodegradation as compared to undoped TiO2 incorporated Ti(BTC) MOF e.g
TiO2@Ti(BTC). The synthetic photo-catalytic material Ag2O/TiO2@Ti(BTC) will have following
applications.

1. Photodegradation of azo dyes such methyl orange and methylene blue for purification of
industrial used water. This material can be used for elimination of organic pollutants from polluted
water.

2. This photo-catalytic material can be helpful in photodegrading of nitrophenol from industrial

used water in the presence of sun light.
Chapter 1

Introduction

A unique class of porous and multidimensional polymeric materials consisting of metal ions
centered by organic linkers is called metal organic framework. These frameworks are being studied
and discussed in coordination chemistry and material sciences by their physical and chemical
parameters. These heterogeneous materials are being synthesized and applied in different fields of
science from last two decades. The varying choice of metal and organic linkers leads to vast variety
of these materials in synthesis and in application [1]. With the passage of time, new researches in
this field are broadening the application of these materials into different processes like gas storage,
gas separation, separation of radioactive materials from water and specially in water splitting for
production of hydrogen fuel. Nuclear energy is one of the cheapest ways to overcome energy crisis
in country but leads to dangerous by products for human being and other living organisms on this
planet. So, there are some type of MOFs being used in extraction of such radioactive waste
materials from sea water. e.g. Zn-based MOFs as highly efficient U(VI) sorbent [2]. Due to high
surface area, porosity, pore volume and with tunable functionality leads to best use in catalysis and
storage of gases [3]. Demand of energy is increasing day by day which leads to huge amount of
CO2 production in atmosphere and causing pollution to our environment. But controllable porosity
and pore volume of MOFs leads to better capture and storage of CO2 molecules from atmosphere
and thus, play a very good role in cleaning of our environment as well. The efficiency of MOFs is
being increased day by day by selecting the suitable metal ions and clusters of organic linkers to
metals [4]. Due to striking features and applications of MOFs result into the new developments in
this field. There are variety number of methods of synthesis with vast area of applications such as
drug delivery and storage. The great number of publications are published in this regard. This
exclusive class of crystalline material has many virtues as thermal stability, ultra-high surface area,
low density, permanency in structure and easy approach of synthesis. This leading to importance
of MOFs in almost all fields of material sciences and coordination chemistry [5]. The various
shapes, different structural geometries of organic linkers and coordination number of metal ions
or clusters, give us a polymer with versatile topology and extended multidimensional polymeric
framework. But use of a single organic linker with inorganic metal ion is best known synthetic
process or strategy to produce a very high surface area in metal organic frameworks such as

1
HKUST-I (Hong Kong University of Science and Technology), MILs (Materials institute
Lavoisier) and ZIFs (Zeolitic imidazolate frameworks). The variety in the dimensions of metal
organic framework depend upon the binding mode of anionic organic linkers. Anionic organic
linker containing V-shape can only grow in one dimension but to increase the dimensionality,
neutral organic linkers are used which serve as a pillar. By altering anionic or neutral linkers the
extent of predicament in 3D framework are tuned. So, organic linkers exclusively functionalized
to meet desired applications of resultant metal organic framework (MOF) such as in gas separation,
gas storage, catalysis, magnetic properties, molecular identification and purification of water etc.
which were not possible with single linker system. Metal organic framework (MOF) with mixed
linkers show more versatility, tunability and more flexibility with desired topologies and porosities
[6]. Gas sorption is very attractive application of metal organic framework (MOF) now a days for
carriage and storage specially for hydrogen and methane fuel. But one of the problems is their
widespread storage for mobile applications. These materials must satisfy different criteria, such as
a high gravimetric measurements and volumetric uptake, facetious gas release and reproducible
cycling, in addition to being produced economically [7].

1.1 General components of MOFs

To construct such type of materials, metal ions or cluster of metals are required with suitable
number of organic linkers. Metal ions are surrounded by these organic linkers in multiple
directions to give us a new and unique class of porous material which have a very broad and wide
applications in almost al fields of material sciences. There are many types of organic linkers for
metals in MOFs i.e. Monotopic, diatopic and multitopic organic linkers. A few examples of
organic linkers are given below;

Figure 1.1 General representation of MOF formation

2
Figure 1.2 Examples of different types of organic linkers

3
 Figure 1.3 Secondary building units of different types of MOFs

But generally, MOFs are synthesized with metal ions acting as nodes and organic linkers which
are donors that may contain oxygen atoms and nitrogen atoms. The synthesis of MOFs depends
upon the nature of organic linkers and oxidation state of metal ions along with suitable solvent and
pH [8].

4
1.2 Carboxylate as ditopic linkers

Carboxylic ditopic linkers have been studied for many years from the beginning of MOF. Because
of their accessibility and perceivable structures in formation of MOF by using secondary building
units (SBUs) through combination process. There are various types of structural features are being
studied through changing these carboxylate linkers with metals in single and cluster format. For
example, we can prepare a diamondoid structure by using ditopic linear linker with 4-connected
tetrahedral cluster and some others are examples are given below; [9]

Figure 1.4 Graphical illustration of the construction of some representative coordination

polymers/MOFs from SBUs and rigid linkers

5
1.2.1 Four side connected ditopic carboxylate linkers as paddle-wheel clusters
Formation of metal organic crystal structures depend upon the reaction conditions which are
applied on reactants (inorganic metal salts and organic linkers) during chemical reaction. For
example, zinc nitrate and benzene 1,4 dicarboxylic acid under solvothermal condition gives
crystalline MOF-5 [10] but on the other hand the reaction between zinc nitrate and benzene 1,4
dicarboxylic acid using DMF-toluene into triethylamine toluene solution, gives prism shaped
colorless crystals. This structure is 2-Dimensional due to presence of square planner paddle wheel
unite geometry as compared to MOF-5 which is purely 3-dimensional due to octahedral geometry
in unit structure [11]

Figure 1.5 Coplanar dicarboxylates linkers and square paddle-wheels like structure

1.2.2 Six side connected ditopic carboxylates as organic linkers (octahedral clusters)
When the ditopic carboxylate linker benzene 1,4 dicarboxylate is added instead of acetate linker
in formation of MOF-5, the 3-dimensional network with elegant and beautiful cubic structure of
MOF-5 is appeared. This newly formed MOF have uncommon and outstanding surface area,
stability and porosity. Surface area is measured was 2900m2/g. There is new approach to reticulate
the metals and organic linkers into extended form by using ditopic dicarboxylate linkers with
different lengths to produce variety of porous material with unique properties [12]. For example
when the benzene 1,4 dicarboxylate is added with zinc nitrate in solution of N,N diethyl formamide
leading to formation of new unique MOF-5 (IRMOF-1) with 90% yield. By changing the organic
linker in the place of benzene 1,4 dicarboxylate, such as biphenyl dicarboxylate, terphenyl
dicarboxylate and many other like these linkers lead to a new and different type of MOF-5. This
new 3-dimensional and unique porous material show various advantages upon the simple MOF-5

6
material. The pore size of this material can be extended and functionalized by using some
functional groups such as NH2, SO4, Br, C4H4 etc. pore size can also be varied by using organic
linkers with different lengths and in this way different types of properties are targeted [13].

Figure 1.6 Some representation of formation of extended IRMOF networks by replacing acetate
groups with benzene dicarboxylates

1.3 Basic methods for synthesis of metal organic frameworks (MOF)

There are several methods for preparation of metal organic frameworks in laboratory such as
solvothermal, microwave, electrochemical, mechanochemical and sonochemical. Water and other
organic solvents are used in these techniques. The pores of newly formed MOFs are filled by the
solvent molecules along with the unreacted initial reactants. This property is used in drug delivery
and storage. But purification of metal organic framework from by product and accommodated
particles in their pores is a difficult task. It becomes more difficult when it needs high temperature
for removal which results in collapsing of whole structure or removal of guest particles. Because

7
impurities cause decrease in catalytic activity. So, there are great number of methods for
purification and activation of impure MOFs and replacement of solvent with more volatile solvent
decreases the temperature treatment [14,15].

1.3.1 Solvothermal and non-solvothermal process

Solvothermal process is more general process just like hydrothermal process where water as a
solvent is used. But main difference between solvothermal and non-solvothermal processes is the
given temperature. In case of non-solvothermal process, the reaction temperature kept below the
boiling point of solvent used but the solvothermal process is carried out at boiling temperature or
above the boiling temperature and does not require any complex equipment. A good choice of
metal ion salt with suitable linkers at required temperature can give us a good yield of Metal
Organic Frameworks. But solvothermal process results in better yield of MOF with fine
crystallinity because of higher vapor pressure leading to large but regular crystalline material and
large surface area of MOFs. Therefore, this process requires better and special equipment’s such
as sealed container or autoclave and duration of reaction in container is very important factor for
production of this type of material. By varying reaction conditions, the product is changed to that
extent which gives different structures [16].

1.3.2 Microwave synthesis

There are two characteristics of microwave radiations, electrical and magnetic. The electrical
energy is responsible for providing energy in a reaction media. But energy of microwave is
0.037kcal/mol which would be insufficient for breaking of common organic bond and making of
new bonds. The interaction of microwaves with ions and molecules is responsible for production
of heat in the solution. The molecules and various ions show alignment with alternating
microwaves after interaction. When these low energy microwaves are passed through the prepared
electrolytic solution, the resistance generated that results increase of heating effect in a solution.
When the water is used as a solvent, heating effect is generated due to presence of hydrogen
bonding. This effect is observed efficiently in liquid state of water as compared to vapor state of
water because of low hydrogen bonding in gas phase and impossible for the solid materials. Several
types of MOFs have been synthesized by this method that reduces time duration, increases rate
reaction and percentage of yield of expected products. Therefore, solvent has special role in this

8
type of synthesis because solvent absorbs low energy microwaves efficiently and convert
electromagnetic kinetic energy into heat energy [17]. Several experiments have performed using
this technique to get desirable results in the synthesis of MOFs.

1.3.3 Electrochemical synthesis

It is also a special type of synthetic process used for preparation of MOFs in which metal ions are
not introduced into electrolytic solution in the form of salts. For the preparation of solution, metal
ions are mixed into a solution which contained dissolved organic linkers and anode is used for
depletion of negative ions and production of electrolyte into the solution by dissolution of anode.
In this way synthesis continue without any hurdle with large production of MOFs in a solution.
But there are some chances of deposition of the metal on cathode so, we use protic solvents to
avoid such type of problem in reaction and hydrogen gas is produced as a side product. If we use
some other solvents such as acrylonitrile, acrylates and maleates, this problem is solved due to the
consumption of hydrogen gas by these solvents. MOF (HKUST-1) was synthesized in 2005 by
this process for first time [18]. Copper sheet was used as a dissolving anode and dipped in a
solution containing 1,3,5-benzene tricarboxylic acid dissolved in methanol along with cathode
[19].

1.3.4 Mechanochemical method

This type of synthesis involves the reaction between two solids which are mixed manually by
using mechanical energy. This synthesis got special attention due to fast rate of reaction and high
yield of MOFs without using solvents. But there is no special theory which could explain in detail
the physiochemical processes occurring in this method. There are two types of models that explain
this type of synthesis, are hot-spot method and magma-plasma method. In the former method, two
reacting solid’s surfaces are exposed and brought in contact with high mechanical energy by using
the milling balls. It leads to sudden increase in temperature (>1000°C) at the point of contact for
short period of time (10-3 to 10-4 s). But in some cases, the further increase in temperature also done
by local treatment as per requirements of reaction at the point of contact. And in later case, focused
on contact spot created by colliding particles and the local temperature is increased up to 104 °C
because of formation of plasma and huge amount of released energy which also cause the release
of electrons. It just seems like that these processes are not approachable and successful in formation

9
of MOFs due to such high temperature which lead to destruction of organic linkers and overall
structure [20]. But such sudden burst of temperature and high milling pressure in between two
solid components initiate reaction rather than degradation of reacting species and products. The
presence of little amount of liquid give advantages to mechanical process such as high yield of
products with great percentage of crystallinity. This process enhances reactivity by continuous
milling process and give new surfaces. In 2001, the HKUST-1 (MOF) has been synthesized by
this method [21].

1.3.5 Sonochemical synthesis

The interactions of ultrasound waves with liquid layers generate the cavitation. The impact of
sound waves increases as the time of interaction increases. Vapors are also formed by this process
and pressure is released to normalize the boiling point which leads to increase the void formation
in liquid layers. The cavities begin to form in between the layers of liquid with finite size and
concentration. Pressure is higher in cavities and collapsed ultimately. There is difference in
between the temperature and pressure of bubbles formed and surrounding liquid [22]. The impact
of difference in temperature and pressure become a cause of disintegration of aggregated particles
which leads to the increment in surface area. The ultrasound waves are very important in this
chemical process due to great effect of formation of cavitation in liquid. The sonication leads to
several types of changes in chemical process such as bond rapture of some polymers, removal of
solvated material and adsorbed substances in liquid media. The choice of solvent is very important
in this regard. Volatile solvents are not suitable for this chemical process because of less formation
of bubbles inside liquid layers. In 2003, Zn3(BTC)2 MOF was prepared by using sonication process
which gave high yield of product [23].

1.4 Characteristics of MOF

Following are the characteristics of MOFs
Drug delivery
Gas storage
Water treatment
Catalysis
Gas separation

10
Porosity

1.4.1 Porosity
porosity is produced in the MOFs due to three-dimensional Coordinate bonding between linkers
and the inorganic metal ion. Porosity is tunable because of the variety in size and chain length of
the combining linkers. We can increase and decrease it accordingly. Porosity increases the surface
area of the MOFs and produce the pore channels in it. The nanoparticles can be introduced in these
pores by using some specific reaction methods. The incorporation of variety of nanoparticles
provide us different properties of MOFs. Photocatalytic properties of MOF can be enhanced by
incorporating some photocatalytic nanoparticles in it.

1.5 Methodologies of incorporation of metal nanoparticles (MNPs) into pores of MOFs

Generally, three main methods have been established for incorporation of nanoparticles into
MOFs.
1. Ship in bottle
2. bottle around ship
3. one-step synthesis

1.5.1 Ship in bottle method

This approach refers to encapsulation of small and active molecules or precursors of NPs into the
cavities of MOFs. Further treatment is also applied for getting the desirable structure and function
in MOFs. (figure a). there are also many other types of techniques which are used for introduction
the NPs precursors into MOF pores such as solid grinding, infiltration and vapor deposition
methods. But the Morphology, composition, location and structure of incorporated material
become a challenge to control precisely in this regard. Zehang et all compiled recent approaches
to control these challenges. The problem of aggregation of NPs on the surface of MOF can easily
be removed successfully by using double solvent method (DSM). This method create ease in “ship
in bottle” process by using hydrophobic and hydrophilic solvents and aqueous solution of
precursors of NPs can easily be introduced into cavities of MOFs. But volume of precursors should
be less than the pore volume of MOF [24].

11
1.5.2 Bottle around ship method
It is the two-step synthetic method. In the first step, NPs are prepared separately and stabilized by
using some surfactants and capping agents. This separately prepared material is added to 2nd
solution which contain the precursors of MOF. The nanoparticles will be surrounded by the
assembly of MOF material. This method is better than the “Ship in bottle” method because it leads
to elimination of the difficulties such as aggregation of NPs on surface of MOF. Other limiting
factors has also been resolved by this method such as control of size, structure and morphology of
the entrapped NPs as shown in figure 1.4 b

1.5.3 One-step method

This is very simple and straightforward strategy because it involves the direct mixing of two
separately prepared solutions of precursors of MOF and NPs. Growth is carried out and
incorporated MOF is obtained and a balanced ratio of reactants before mixing is required for better
incorporation.

Figure 1.7 (a) Ship in bottle method; (b) bottle around ship method; (c) one-step method [25]

1.6 Photocatalysis
Light is absorbed by a substance and that produce electron hole process that lead to generate some
free radicals. These radicals further carry out oxidation and reduction reactions. Photocatalysis is

12
giving us many solutions for problems that our society are facing now a days, specially in energy
crisis. Researchers are taking interest to locate a novel rout to prepare a such type of photocatalyst
that should be capable of converting the solar energy into chemical energy more efficiently [26].
Nanotechnology is becoming the best tool in synthesis of photocatalyst which enhances the
photocatalytic properties of materials. Nanotechnology is best tool to understand the mechanism,
work function of photocatalyst and elaborate the transformation of photocatalytic material at
surface level. The synthesis at the nanoscale helps us to understand the composition, mechanism
of action, factors affecting and novel use in heterogeneous catalysis. There are several methods to
prepare photocatalytic material at nanoscale and make them reproduceable, but some difficulties
are still existing. Photocatalyst should have a series of characteristics and properties depending
upon their applications in various fields such as particle size, energy band gap, surface area and
space between the electronic levels [27].

1.6.1 Mechanism of photocatalysis

Titania is a very good and most efficient known photocatalyst in semiconductor material.

TiO2 + hv(UV) → TiO2(eCB− + hVB+) (1)

TiO2(hVB+) + H2O → TiO2 + H+ + OH−• (2)

TiO2(hVB+) + OH−•→ TiO2 + OH• (3)

TiO2(eCB−) + O2 → TiO2 + O2•− (4)

O2•− + H+ → HO2• (5)

Dye + OH• → degradation products (6)

Dye + hVB+ → oxidation products (7)

Dye + eCB− → reduction products [28] (8)

13
1.6.2 Advance oxidation/reduction process and Photocatalytic reactions
Advance oxidation process is more efficient in use than conventional oxidation methods and is
very useful for the destruction of resistant synthetic organic species such as synthetic dyes. This
process uses the highly reactive specie OH radicals produced in photochemical reaction, by using
the solar energy. The most interesting feature of these radicals is to oxidize and degrade the various
organic substances with no selectivity. The reaction is initiated by absorption of light energy or
photons leading to excitation of electrons from filled valence band to empty conduction bands of
semiconductor material. Energy absorbed must be equal to band gap between these excitation
states leading to generation of electron hole process as given below;

Photoexcitation process: TiO2/semiconductor material + hυ → e− + h+

Oxygen ionosorption: (O2) adsorbed + e− → O2•−

Ionization of water: H2O → OH− + H+

Protonation of superoxides: O2•− + H+ → HOO• [29]

The hydroperoxyl radicals have scavenging properties

HOO• + e− → HO2−

HOO− + H+ → H2O2

Both the oxidation and reduction reactions are taking place at surface of photocatalyst and electron
hole recombination process is continued but there should be the presence of oxygen for scavenging
the electron. [30]

14
Figure 1.8 Schematic representation of semiconductor photocatalytic mechanism

Figure 1.9 Schematic representation of oxidation of dye [31]

15
1.6.3 Characteristics of good photocatalyst
1. It must be stable
2. It should be inert
3. It must be easily available and cheapest
4. Capability to absorb the maximum available light [32]

1.7 Factors that affect the photocatalytic efficiency

1. Intensity of light
2. Concentration of substrate
3. Nature of photocatalyst
4. Concentration of photocatalyst
5. pH of media
6. Reaction temperature

1.7.1 Intensity of incident light

Reaction proceeded by light energy is called photocatalytic reaction which highly depends upon
the intensity of absorption of light by photocatalytic material used in photocatalytic reaction. It has
been proved by calculated rate of degradation of various synthetic organic dyes with light intensity.
But there is only 5% incident light which is used in photosensitization and rest of light is reflected
or transmit through the material unfortunately. [33,34]

1.7.2 Concentration of substrate and its nature

It is necessary condition for organic molecule to be degraded or oxidized is, should have to adsorb
on surface of photocatalyst which is further depends upon the nature of substituent attached on
aromatic compounds [35]. For example, nitrophenol oxidize faster due its higher adsorption on
photocatalytic material than simple phenol, monochloro aromatic oxidizes faster than di, tri and
tetra chloro aromatic compounds. It is observed that, the aromatic compounds containing electron
withdrawing groups such as nitro and benzoic, adsorb more efficiently in dark than in light as
compared to those which contain electron donating groups. [36] The concentration of organic
substrate is also responsible for rate of reaction such as high concentration leads to more occupied

16
places on the surface of material and slow rate of reaction is resultant are called catalyst
deactivation. [37]

1.7.3 Nature of photocatalyst

There’s close relationship between surface of organic reagent and coverage of surface of
photocatalytic material because the hitting photons are responsible for rate of photocatalytic
reaction. [38] The particle and agglomerate size is very influential factors that controls the
performance of photocatalytic oxidation process which is surface phenomena. For example, there
are various methods for preparation of TiO2 nanoparticle with different morphology to gain
desirable application and physical properties such as its activity and stability in photochemical
reaction. [39] The surface property is very influential in desirable photocatalytic application such
as small Nanoparticles have greater tendency and higher activity in photolytic degradation of
organic compounds. [40]

1.7.4 Concentration of photocatalyst

There is direct correlation between the rate of reaction and concentration of photocatalytic
material, the rate of photodegradation increases as amount of catalyst increases in the reaction
media [41]. But optimum amount of photocatalytic material should be determined to avoid the
excess use of material that causes the reduction, scattering of light and less penetration in reaction
media solution. [42]

1.7.5 pH
The pH is very important factor that govern in all type of reactions taking place. It also controls
the particle surface activity and charge density on it. By using the acidic and basic alkaline media,
the protonation and deprotonation is carried out respectively on the surface of Titania
nanoparticles. [43]
According to following equations

TiOH + H+ → TiOH2+

TiOH + OH− → TiO− + H2O

17
Above equation shows that the Titania bear positive charge in acidic medium but negative in
alkaline medium. The catalyst shows better efficiency in less acidic medium. It is also being
studied the adsorption of organic reagent on surface of catalyst is controlled by the changing the
extent of pH. It is also reported that photo removal of organic reagent is enhanced by changing the
pH of solution so, optimized pH in which rate is maximum and economical is determined
experimentally. [44]

1.7.6 Reaction temperature

Rate of Reaction is also under control of reaction temperature. There are experimental evidences
of relation between the temperature and photocatalytic degradation of organic material. As we
know that by increasing temperature, increases the desorption of organic material on surface of
photocatalytic catalyst lead to decrease the photodegradation of organic reagents in solution and it
is good agreement with Arrhenius equation. [45]

1.8 Nanoparticles as photocatalyst

Nanosized photocatalysts are such type of semiconductor particles which are a few nanometers in
size. The studies showed unique properties of nanosized material as compare to its bulk form.
Particles that have the diameter range between 1 to 10nm possess such kind of properties that fall
into transition between molecular and bulk phase. The band gap increases as the particle size
decreases which is indicated by the absorption of high wavelength shift to shorter wavelength and
give high redox potential.

1.8.1 Doped nanoparticles as photocatalyst

Greater enhancement of the photoactivity is achieved by doping the nanosized particles with
suitable metal ion or metal oxide. The work of choi et al. provide a comprehensive study of 21
different metal ions dopants on nanosized TiO2 nanoparticles. The dopant ion or metal oxide
occupied into the lattices or interstitial sites of resultant material. The photoactivity is influenced
by the d-electronic configuration of the dopant to the energy levels of photocatalytic material. This
phenomenon creates the electron trap and increases the lifetime of generated charge carrier. Hence
redox potential is influenced.

18
1.8.2 Doping methods of TiO2
A new type of energy level produced in band gap of the TiO2 when the metal nanoparticles are
dispersed in the matrix of TiO2, the visible light absorption is increased and hence activity is
increased. There is advantage of doping the TiO2 with transition metals because these metals
increase the photo-catalytic activity of TiO2 by reducing the rate of recombination of electron-hole
process while irradiation There are various types of methods have been proposed to dope or
incorporate the impurity into TiO2. Following are sol-gel, ion implantation, chemical vapors
deposition, plasma and ion-assisted sputtering considered the best methods for doping the TiO2.

1.8.3 Ion-implantation method

Electronic and photo-catalytic properties are transformed and modified by bombarding the TiO2
with metal ion with high energy of collision. In this method high energy (150 to 200keV) is used
to penetrate the metal ions deep into core bulk of TiO2 particles. The resultant material is calcined
under high temperature (450°C to 475°C). Cr or V metal ions are preferably used as doping agents
in this method. This prepared doped material has very good efficiency and effectively work in
decomposition the NO into its components N2 and O2. This method can also be used in doping of
other transition metals such as V,Cr,Mn,Ni and Fe [46].

1.8.4 Hydrothermal method

By using the hydrothermal method Ag2O/TiO2 doped material are obtained which has very good
photo-catalytic property under visible and ultraviolet light. This material is prepared by dissolving
the titanium tetra butoxide in n-octanol solvent at 230°C. this solution is reacted with aqueous
solution of AgNO3 and NaOH and heated in autoclave. The resultant powder material is dried and
calcined at 560°C. this powder doped material has good efficiency in dye degradation under visible
and ultraviolet light in aqueous media. [47].

1.8.5 Sol-gel method

it is a versatile method and for preparation of Nanosized particles. This procedure requires simple
instruments in laboratory for preparation of Nanosized material. During the incorporation, the
gelatin stage is appeared which allows the direct interaction of active doping agent to TiO2 and

19
resultant material shows catalytic or photo-catalytic property. The typical representation of doping
the TiO2 is given below.

Figure 1.10 Representation of doping TiO2 by sol-gel

1.9 General characterization techniques

1.9.1 XRD Technique

X-ray diffraction (XRD) is most power full characterizing techniques which is used to analyze the
crystalline materials. It gives the complete information about phases, structures, crystals,
crystalline defects, crystal orientations and structural parameters such as average grain size. In this
technique, the monochromatic beam of x-rays is directed upon the targeted sample and diffraction

20
pattern is appeared on screen which are further converted into the form of peaks with their
intensities. This diffraction pattern is very useful and considered as fingerprint for each material
which is analyzed in fields of pharmaceutical industry, micro-electronics, geological applications
and forensic sciences.

x-rays are produced in cathode tube and filtered to produce the mono-chromatic light. These x-
rays are bombarded on the target samples and by constructive interference of mono-chromatic
beam, they are scattered to specific angles due to presence of lattices in crystalline material.
following figure is explaining the process occurring in technique.

Figure 1.11 Schematic diagram of a diffractometer system.

By satisfying the Bragg’s law, the incident rays form constructive interference after scattering by
specific angles as.

21
 Bragg’s law = nλ2dsinθ

n = integer

λ = wavelength of x-rays

d = inter planer spacing

θ = diffraction angle

This law explains the relationship of wavelength x-rays to the diffraction pattern and interplanar
spacing in crystalline target material. x-ray diffractometer has such type of geometry that the
sample is rotated in the path of x-ray beam at angle of 2θ. By scanning of targeted material through
2θ angles, the sample which is in powdered form have random orientation lead to all possible
diffraction pattern which are further converted into peaks with intensities. These peaks tell
information about the d-spacing which help in identification of unknown material or compound
because each compound or material have its unique pattern or d-spacing which is also called its
fingerprint. Further the patterns are also matched with reference as well. There are only three basic
components present x-ray diffractometer (1) x-ray tube (2) sample holder (3) x-ray detector as
shown above diagram. This technique is widely used for identification or analyzing the unknown
material in nature or synthesized in laboratory. Identification of unknown material is very critical
work in studies of biology, environmental sciences, engineering and material sciences. The
applications of this technique in identifications of identification and evaluation of fine-grained
material such as characterization of mixed layer clay or simple clay. There is also a various
problems and difficulties arise during the determination of unit cell and cell dimensions.

There are following limitations about this technique

1. For identification of unknown material, it must be in single phase and homogeneous.

2. There are various complications during the indexing and determination of cell dimensions.

22
3. Material should be grinded just like fine powder.

4. Detection limit become very less in case of mixed material.

5. There must be reference file in case of identification of inorganic material.

6. The worsen complications arise when peak overlay encountered during analysis.

7. More experienced worker can use this technique for identification of unknown material [48].

1.9.2 Scanning electron microscopy

Scanning electron microscopy is very useful technique used to collect the information about the
external texture or morphology of unknown material or compound. In this technique, the high
beam of electrons is bombarded on bulk surface of material. then various type of signals is
produced due to electron-sample interactions. These signals give a complete information about the
external morphology (texture) of a sample, orientation of material, chemical composition that
make up the sample and crystalline structure. Electron with very high kinetic energy create
electron-sample interactions in which energy of beam is dissipated and variety of signals are
produced. These signals are produced due to two types of electrons, the secondary electrons which
produces the SEM image while back scattered electrons which are called primary electrons that
provide the information about crystalline structure. The secondary electrons are more useful and
valuable due to SEM image processing that shows the external morphology of material.

Following are essential components in SEM instrumentation

1. Electron source
2. Electron lenses
3. Sample stage
4. Detector for all signal of interest
5. Display or output devices

Strength
1. Easy to handle and usage
2. Require minimum sample preparation

23
3. Data processing or acquisition is very fast and approximately less than 5 minutes
4. Not too much experience is required to operate instrumentation and software

Limitation
1. Sample should be in solid state and must be in microscope chamber
2. Sample should be able to bear low pressure as in vacuum
3. The lighter elements such as hydrogen helium can not be detected by SEM
4. Horizontal dimensions are limited to 10cm while vertical dimensions are limited to 40mm
5. Most of instruments cannot detect the elements whose atomic number is less than 11

1.9.3 Transmission electron microscopy

It is an imaging technique in which a high beam of electron is focused onto targeted material or
specimen leading to broad version on photographic film. It is very useful tool for material sciences.
The beam of electron is thrown upon a very thin layer of sample then the interaction of atoms
presents in sample and beam of electron provide various and value able information specially about
structural feature such as dislocation and grain boundaries about prepared sample. This technique
is very useful in determining growth of layer, chemical composition and the defects in
semiconductors. Transmission electron microscopy is operated exactly on the principal which is
basis for light microscope. Due to very small wavelength of falling electrons as compared to light,
the results are very clear and have better optimal resolution. So, it reveals finest information about
structure.

24
 Figure 1.12 Schematic diagram of transmission electron microscopy

19.4 UV/Visible spectroscopy

It is an analytical technique that allows the interaction of ultra violet-visible radiation with material
and give value able information about it. The interacting radiation have enough energy that
produce electronic transition or excitement from lower to higher level and give information types
of bonding present in material specially. Electrons that have promoted to higher energy levels,
come back to their original level or orbital which result in release of light or some other radiation.
Wavelength of absorbed light tells about the type of bonding by measuring energy gap between
energy levels formed in a molecule.

Beer-lambert law

Absorption of light is proportional to path length of light through sample and the concentration of
sample molecules.

25
 A = εcl

A = absorbance

ε = molar absorptivity

c = concentration of sample molecules

l = path length of sample tube through which light pass through

Going through interpretation of uv spectra, it is observed that there are very few peaks in spectra
as compared to I.R spectra that produce confusion in understanding the about information about
compound. But uv spectra give clear but limited information about a compound or sample. Most
absorption of organic compounds is due to the presence of 𝜋 electrons and chromophore also have
such type of electrons in it. Following is the schematic diagram about uv visible
spectrophotometer.

Figure 1.13 schematic diagram of uv/visible spectrophotometer [49]

26
Chapter 2

Experimental

2.1. Chemicals and reagents used

Sr Chemicals Formula Molecular Purity Supplier

# weight
(g/mole)
1 Sulfuric acid H2SO4 98 98% Sigma
Aldrich
2 Hydrochloric HCl 36.5 37% Sigma
acid Aldrich
3 Titanium TiCl4 189.88 99.9% Sigma
tetrachloride Aldrich
4 1,3,5 Benzene C9H6O6 210 98% Sigma
tricarboxylic Aldrich
acid
5 Sodium NaOH 40 80% Sigma
hydroxide Aldrich
6 Methanol CH3OH 32 97% Sigma
Aldrich
8 Acetone CH3COCH3 58 98% Sigma
Aldrich
9 Dimethyl C3H7NO 73.09 97% Sigma
formamide Aldrich
10 Ethanol C2H5OH 46 99% Sigma
Aldrich
11 Silver nitrate AgNO3 169.87 99% Sigma
Aldrich

27
 13 Aqueous NH3OH 34 30% Sigma
Ammonia Aldrich

2.2 Instrumentation

1. Centrifuge Machine

For removal of precipitates from solution, centrifuge machine was used through centrifugation
process provided by YESCOM, model Number YJ 03-O43-4000

2. Oven

The temperature which required for reaction was provided by Memmert oven model No. DINCN
60525IP-20.

3. Diffractometer
To perform the powder X-ray diffraction analysis of the prepared samples, Philips X’ pert PRO
3040/60 diffractometer having Cu-Kα radiation source was used.

4. Spectrophotometer
The spectrum of absorption for degradation of samples of the dye was taken with UV-Vis
Spectrophotometer of Shimadza of model UV-1800.

5. Photo reactor
Photo catalytic degradation of dye was performed using photo reactor having UV lamp as source
of UV radiations. The ultraviolet lamp is inserted inside the photo reactor in such a way that it can
be easily changed in order to provide other sources of light as the requirement of the analysis. The
photo reactor is made up of wooden box. The dimensions of the reactor are 3.5 feet in length, 3
feet width and height are 3.5 feet. Inner side of photo reactor is covered with aluminum foil to
reflect radiations to sample Photo catalytic degradation of dye was performed using photo reactor
having UV lamp as source of UV radiations.

28
6. Hot Plate Stirrer
Proper heating and for the mixing of samples properly Scilogex hotplate-stirrer was used.

7. Weighing Balance
For synthetic purpose, all the chemicals were precisely weighed by using Analytical Balance.

8. Sonicator
For proper mixing and for composite formation, the sonication was performed in high intensity
ultrasonic bath by using high quality sonicator of MIISONIX model XL-2020.

2.3 Preparation of Titanium dioxide Nano particles

Starting material used in this preparation was TiCl4. 10% solution of H2SO4 was prepared by
dilution of concentrated H2SO4 stock solution. 10% solution of sulfuric Acid was taken in round
bottom flask and fitted in ice bath and temperature was set at 0°C. 1mL pure TiCl4 was added in
this solution slowly dropwise and stirred the solution vigorously. Due to hydrolysis of TiCl4, white
fumes of HCl were produced in flask. By continuous stirring of solution, a greyish colored solution
was formed, which was heated to about 60°C till solution became clear. The solution was kept at
this temperature while complete removal of hydrochloric acid from solution. Then solution was
kept at room temperature for one and half hour. The solution was still acidic, and pH was very
low. Later, NH3 was added dropwise in concentrated form to this solution until pH became 7 and
white colored precipitates were obtained. White precipitates were separated out by using centrifuge
machine and then washed the precipitates by using deionized water until no other ions left in
solution. White coloured precipitates were cooled at room temperature and then gelled for 12
hours. Chloride identification test was carried out to check presence of chloride ions in precipitates.
The test showed that there were no chloride ions in them. So, these precipitates were dried and
calcinated at 600°C temperature. Off white colored anatase nanoparticles were prepared by this
method [50].

29
2.4 Synthesis of Silver oxide doped Titanium dioxide Nanoparticles

The titanium butoxide [Ti(OC4H9)4] solution in ethanol solvent was prepared and another solution
of NaOH was also prepared. These two stock solutions were prepared in advance. 0.2M Titanium
butoxide in ethanol and 1M aqueous solution of NaOH were used as stock solution. 10mL titanium
butoxide from stock solution was mixed with 10mL solution of NaOH aqueous from stock solution
in separate beaker. 25mg of AgNO3 was mixed with above prepared mixed solution. Then this
solution of Ti(OC4H9)4, NaOH and AgNO3 was stirred for 1hour on magnetic stirrer. After that
this solution was transferred into autoclave which was stainless steel and Teflon lined. The solution
was heated in autoclave at 200°C for 24 hours. The resultant material was collected in precipitate
form and washed with deionized water. The free Ag+ ion test was performed by washing
precipitates with 0.1M HCl solution and then washed with deionized water until pH became
neutral. The precipitates were dried in air and at 100°C for 6 hours.

2.5 Synthesis of Ti(BTC) MOF

Synthesis of MOF was carried out by reflux synthesis method. TiCl4 and benzene 1,3,5
tricarboxylic acid was used as a reactant in this synthesis. A solution was prepared by dissolving
2mL TiCl4 into 20mL of methanol and 20mL of Dimethyl formamide in round bottom two neck
flask fitted at condenser. The solution was stirred vigorously and heated to reflux. Another solution
was prepared by dissolving 0.8g of benzene 1,3,5 tricarboxylic acid into 20mL methanol. This
solution was added to first solution dropwise by using dropping funnel. 1 drop per minute time
was set to drop a solution into flask. After complete mixing of these two solutions, a white
gelatinous viscous material was formed. Stirring with heating continues for 12 hours with reflux
condenser. White gelatinous material was filter out using centrifuge machine and washed it with
different solvents such as methanol, ethanol, acetone, dimethyl formamide and deionized water.
This gelatinous material was dried in oven at 80°C for 48 hours. On drying, crystalline material
was obtained with off white color.

2.6 Preparation of TiO2@Ti(BTC) MOF

1mL pure TiCl4 was added to a solution containing 50mL methanol and 50mL dimethyl formamide
in a two neck round bottom flask 0.09g TiO2 Nano particles were added to this solution for

30
incorporation purpose and sonicated it for 30 minutes. Flask was fitted to reflux condenser with
stirring and heating vigorously and continuously. 0.8g Benzene1,3,5 tricarboxylic acid was
dissolved in 25mL methanol and added to above solution dropwise at the rate of 1 drop per minute.
The solution was heated and stirred strongly and continuously for 12 hours on heating plate under
reflux constantly. Dense white colored precipitates were formed in round bottom flask which were
filter out by using centrifuge machine and washed with different types of solvents e.g. methanol,
dimethyl formamide and deionized water. After filtration, material was dried in oven at 80°C for
48 hours. Light yellowish crystalline material of Ti(BTC) MOF incorporated with TiO2
nanoparticles was formed by this process.

2.7 Preparation of Ag2O/TiO2@Ti(BTC) MOF

Ag2O/TiO2 nanocomposite was incorporated into Ti(BTC) MOF by following the same procedure
as mentioned previously. The only difference was that instead of using TiO2 nanoparticles, 0.05g
Ag2O/TiO2 nanocomposite was used under same procedure. [51]

2.8 Photo-catalytic degradation of Methylene Blue

2.8.1 Preparation of Dye Solution

• Concentrated standard solution was prepared by adding 0.035g of methylene blue dye into
1-liter deionized water.
• Now 100mL was taken from this concentrated standard solution of dye and diluted by
adding 900mL more deionized water.
• Covered dye solution with Al foil and placed in dark for one hour.
• For dye degradation given catalyst (0.001g) was mixed in above solution (100mL).
• The mixture was irradiated by UV light using UV spectrophotometer with continuous
stirrer.
• Absorbance was checked after every 10 minutes interval.

31
2.8.2 In a typical procedure, photo-degradation studies of methylene blue dye by synthesized
samples
0.2 g of photocatalytic material was added in 50mL of methylene blue solution. The solution was
kept under constant stirring for one hour in photo reactor in dark. Then absorbance was determined
for the solution of lambda max of methylene blue. Then the solution was shifted toward UV light
and 5mL solution was withdrawn from each solution for measurement of photo-catalytic effect on
methylene blue dye by using UV/Vis spectrophotometer at 10 minutes regular intervals.

2.9 Photo-catalytic degradation of methyl orange

For determination of photo-catalytic activity on methyl orange, same procedure was followed
which has mentioned for photo-degradation of methylene blue.

32
Chapter 3

Results and Discussion

3.1 Powder XRD Analysis

Purity of sample and identification of phase and associated parametric quantities are analyzed by
powder XRD technique. Scherer’s formula is used to calculate the crystallite size and lattice strain
when the FWHM (full width at half maximum) and 2theta values were already known.

Figure 3 PXRD pattern of Ti(BTC)

33
 Figure 3.1 PXRD pattern of TiO2

Figure 3.2 PXRD pattern of Ag2O/TiO2

34
 Figure 3.3 PXRD pattern of TiO2@Ti(BTC)

Figure 3.4 PXRD pattern of Ag2O/TiO2@Ti(BTC)

35
Figure 3.1 is the PXRD graph of Ti(BTC)

Figure 3.2 is the PXRD graph of TiO2 nanoparticles in anatase form. These all peaks are calculated
and matched with the reference pattern (00-001-0562).

Figure 3.3 is PXRD graph of Ag2O/TiO2 material in which peaks with 2θ values 26.60˚, 68.59˚,
65.34˚ and 54.79˚ are matching with reference code (00-012-0793) which confirm the presence of
Ag2O in TiO2 anatase nanoparticles. The peaks with 2θ values 48.37˚, 25.26˚, 75.37˚ and 83.21˚
are well matched with reference pattern (00-001-0562) which represent the presence of TiO2

Figure 3.4 shows the PXRD pattern of TiO2@Ti(BTC). Peaks with hkl values 101, 200, 111 and
311 are well matched with reference code (00-001-0562).

Figure 3.5 shows the PXRD graph of Ag2O/TiO2@Ti(BTC). The peaks with hkl values 200, 311
at 37.9˚ and 65.34˚ 2θ are matching with reference code (00-012-0793) that confirm the presence
of Ag2O particles. Peaks with hkl values 101, 200 at 25.28˚ and 48.37˚ 2θ are matching with
reference pattern (00-001-0562) which confirm the presence TiO2 nanoparticles in MOF.

3.1.1 Crystallite Sizes

Table 3.1 Crystallite Sizes of Samples

Ti(BTC) Ag2O/TiO2 TiO2 TiO2@Ti(BTC) Ag2O/TiO2@Ti(BTC)

40.6nm 7.8nm 8.7nm 37.96nm 43.5nm

3.2 Solid state UV/Vis Spectrophotometry

Solid state UV/Vis spectrophotometer is used for examining the absorbance of all prepared
samples. The following graphs are drawn from data taken out by UV/Vis spectrophotometer.

36
 Figure 3.5 Solid state UV/Visible spectrum of TiO2

Figure 3.6 Solid state UV/Visible spectrum of TiO2@Ti(BTC) MOF

37
 Figure 3.7 Solid state UV/Visible spectrum of Ti(BTC) MOF

Figure 3.8 Solid state UV/Visible spectrum of Ag2O/TiO2 Nanoparticles

38
Figure 3.9 Solid state UV/Visible spectrum of Ag2O/TiO2@Ti(BTC)

Figure 3.10 Solid state UV/Visible spectrum of all prepared samples

39
The figure 3.5 shows the absorbance spectrum of TiO2 anatase nanoparticles are showing the
maximum absorbance at 200nm. But overall absorbance range of this compound is from 200nm
to 350nm as depicted. But when this figure is compared with the figure 3.8, the absorbance range
has increased from 200 to 900nm. This increase in overall absorbance range is due to the presence
of Ag2O nanoparticles into the TiO2 lattices. The maximum absorbance values extend from 200nm
to 230nm because of doping of Ag2O into TiO2 lattices. The maximum absorbances at 230.7nm,
280.78nm and 380.6nm. it can be concluded that doping TiO2 with Ag2O also extend the
absorbance range of TiO2 nanoparticles

The figure 3.6 shows the absorbance spectrum of TiO2@Ti(BTC) MOF material. The maximum
absorbance is at 210.22nm and 310.45nm. And figure 3.7 is showing the absorbance values at
200nm and at 300nm. By comparing these graphs, it can be concluded that the incorporation of
TiO2 into Ti(MOF) extend the absorbance range of simple Ti(MOF).

3.3 SEM and EDX Analysis

Figure 3.11 SEM and EDX Analysis of TiO2 nanoparticles

40
Figure 3.12 SEM and EDX Analysis of TiO2/Ag2O nanoparticles

Figure 3.13 SEM and EDX Analysis of Ti(BTC) MOF

41
Figure 3.14 SEM and EDX Analysis of TiO2/Ag2O@Ti(BTC)

Figure 3.15 SEM and EDX Analysis of TiO2@Ti(BTC)

42
3.4 Photocatalytic degradation of Methylene Blue

To determine the photo-catalytic effect of synthesized materials on methylene blue dye, the
UV/Vis spectrophotometer was used. This type of process gives the absorbance data only, not any
intermediate products formed during photo-catalysis. So, by measuring the maximum absorbance
of light spectrum, the photo-degradation is evaluated. Distilled water was taken as a reference.

3.4.1 Photo-Degradation of Methylene Blue by synthesized samples

A dilute methylene solution is prepared in distilled water and divided into 5 different solutions
each having 100mL volume of methylene solution and equal amounts (0.2g) of synthesized
material. following data is observed and calculated.

Table 3.2 Photodegradation of Methylene Blue by using prepared samples

Sr# Time Ag2O/TiO2 TiO2 Ti(BTC) TiO2@Ti(BTC) Ag2O/TiO2@Ti(BTC)

1 0 0.341 0.520 0.465 0.540 0.553

2 10 0.219 0.465 0.323 0.533 0.442

3 20 0.200 0.363 0.293 0.525 0.411

4 30 0.172 0.322 0.266 0.478 0.372

5 40 0.150 0.221 0.231 0.434 0.251

6 50 0.135 0.214 0.209 0.388 0.131

7 60 0.060 0.180 0.206 0.310 0.030

43
Figure 3.16 Photo-Degradation of Methylene Blue by Ag2O/TiO2

Figure 3.17 Photo-Degradation of Methylene Blue by TiO2

44
 Figure 3.18 Photo-Degradation of Methylene Blue by Ti(BTC) MOF

Figure 3.19 Photo-Degradation of Methylene Blue Methylene Blue by TiO2@Ti(BTC)

45
Figure 3.20 Photo-Degradation of Methylene Blue by Ag2O/TiO2@Ti(BTC)

Figure 3.21 Comparative study of Photo-Degradation by synthesized samples

46
Figure 3.16 is showing declined absorbance of light in the form of graph of Methylene Blue which
is due to Ag2O/TiO2 nanoparticles

Figure 3.17 is showing the declined in absorbance graph of Methylene blue because of presence
of TiO2.

Figure 3.18 is showing decrease in absorbance graph of Methylene Blue because of presence of
Ti(BTC)

Figure 3.19 shows the decrease in absorbance of methylene blue because of the photo-catalytic
material TiO2@Ti(BTC)

Figure 3.20 shows the declined absorbance graph of Methylene Blue due to presence of
Ag2O/TiO2@Ti(BTC)

Figure 3.21 shows the comparative study of photo-degradation of methylene blue in the presence
of TiO2, TiO2/Ag2O, Ti(BTC), Ag2O/TiO2@Ti(BTC) and TiO2@Ti(BTC) samples

3.5 Photo-catalytic degradation of Methyl Orange

Photo-catalytic degradation was observed by added photo-catalytic material through uv/vis

spectrophotometer. The pure deionized water used as reference in this process.

3.5.1 Determination of ƛmax of Methyl Orange

Very dilute solution of Methyl Orange is prepared by using distilled water in standard form. This
standard solution is kept in dark to avoid from interaction from direct light which causes
degradation of solution. Maximum absorbance was checked by using spectrophotometer
instrument. λmax is measured very carefully to carry out further photocatalytic study of prepared
samples.

3.5.2 Photo catalytic Degradation of Methyl Orange by synthesized samples

47
A dilute solution of Methyl Orange was prepared and divided into 5 equal parts having 100mL
volume of Methyl Orange solution and equal amounts (0.2g) of synthesized materials. Following
data is observed due to photocatalysis.

Table 3.3 Photo-Degradation of different prepared samples

Sr# Time Ag2O/TiO2 Ti(BTC)MOF TiO2@Ti(BTC) Ag2O/TiO2@Ti(BTC) TiO2

1 0 0.451 0.631 0.531 0.751 0.565

2 10 0.391 0.471 0.40 0.442 0.423

3 20 0.284 0.414 0.355 0.411 0.393

4 30 0.224 0.355 0.250 0.321 0.364

5 40 0.181 0.290 0.189 0.230 0.231

6 50 0.131 0.222 0.120 0.211 0.211

7 60 0.105 0.153 0.1 0.03 0.207

Change in absorbance is due to change in concentration caused by action of photo-catalyst added into dye
solution. Catalyst is reducing in nature which reduce the dye molecules in solution and convert the
molecules into cationic form. In this way, the colour become faint and dye start to degrade to maximum
extent and is indicated by low absorbance of light as shown in table of values.

48
Figure 3.22 Photo-Degradation of Methylene Orange by Ag2O/TiO2 nanoparticles

Figure 3.23 Photo-Degradation of Methyl Orange by Ti(BTC) MOF

49
 Figure 3.24 Photo-Degradation of Methyl Orange by TiO2@Ti(BTC)

Figure 3.25 Photo-Degradation of Methyl Orange by Ag2O/TiO2@Ti-BTC

50
 Figure 3.26 Photo-Degradation of Methyl Orange by TiO2

Figure 3.27 Comparative study of Photo-Degradation by synthesized samples

51
Figure 3.22 is showing declined absorbance graph of Methyl Orange which is due to Ag2O/TiO2
nanoparticles

Figure 3.23 shows the decreased absorbance graph of Methyl Orange due to presence of Ti(BTC)
MOF

Figure 3.24 shows the reduction in absorbance due presence of TiO2@Ti(BTC) photo-catalytic
material.

Figure 3.25 is showing absorbance graph of Methyl orange due to presence of Ag2O/TiO2@
Ti(BTC)

Figure 3.26 shows the declined absorbance graph of Methyl Orange due to presence of TiO2.

Figure 3.27 shows the decrease in concentration of Methyl orange in solution due to different
photocatalytic added material. Ag2O/TiO2@Ti(BTC)MOF showing good results in photocatalytic
activity as compared to simple Ti(BTC) MOF.

52
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