“Synthesis and Characterization of Vanadium Oxide

Nanoparticles with Photo Luminescent Properties”

Submitted By:

Muhammad Yameen
Roll No. IU17S6LB005
M. Phil. Physics
Session 2017-2019

Supervised By:

DR. Gull Naz

DEPARTMENT OF PHYSICS
________________________________________________
_ The Islamia University of Bahawalpur Pakistan

1
 A thesis Entitled

Synthesis and characterization of Vanadium Oxide

Nanoparticles with Photo Luminescent Properties

Submitted to the Department of Physics,

The Islamia University of Bahawalpur

Supervised by

Dr. Gull Naz

Assistant Professor, Department of physics,

The Islamia University Bahawalpur

In the partial fulfillment of the requirement for the degree of Master of Philosophy
(M. Phil) in Physics
By
Muhammad Yameen
Roll No. IU17S6LB005
Session 2017-2019

Department of Physics,
The Islamia University of Bahawalpur Pakistan

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DEDICATED
To

MY Parents

WHO ENCOURAGED ME IN

EVERY WAY

& HAVE RAISED ME TO BE THE

PERSON I AM TODAY

DECLARATION
3
I certify that this research work entitled “Synthesis and Characterization of Vanadium

Oxide Naoparticles with Photo Luminescent Properties” is done by me. I also certify

that this thesis does not incorporated without acknowledgement any material previously

submitted for a degree in any university; and that to the best of my knowledge and belief

it does not contain any material previously published or written by another person where

due reference is not made in the text.

Muhammad Yameen

CERTIFICATE

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This is certifying that Muhammad Yameen has carried out the research work entitled
“Synthesis and Characterization of Nanoparticles with Photo Luminescent
Properties” presented in this dissertation under my supervision in the Department of
Physics, The Islamia University of Bahawalpur, Pakistan. This work is accepted in its
present form by the Department of Physics, The Islamia University of Bahawalpur as
satisfying the dissertation requirement for the degree of Master of Philosophy (M. Phil.)
in Physics.

Supervisor:

Dr. Gull Naz

Department of Physics,
The Islamia University of Bahawalpur,

Pakistan.

ACKNOWLEDGEMENTS

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 In the name of Allah, Most Merciful, the most beneficent and the most gracious
and countless darood-o-salaams to Holy Prophet Muhammad (Peace Be Upon Him).
Prior to anyone else, all gratitude and praises are due to the almighty Allah, who gave me
health and capacitance to achieve this goal. I am really grateful to Prof. Dr. Saeed
Ahmed Buzdar, Chairman of Physics Department, The Islamia University of
Bahawalpur, whose permanent guidance, appreciation and motivation, valuable
suggestions put me on the right track to complete my research work.

It is difficult to overstate my gratitude to my supervisor, Dr. Gull Naz (Assistant

Professor Deptt. of Physics); The Islamia University of Bahawalpur has been the ideal
supervisor. His sage advice, insightful criticism, sympathetic attitude, enthusiastic
supervision especially during experimental work and patient encouragement aided the
writing of this thesis.
A lot of thanks to Dean Faculty of Science Islamia University of Bahawalpur with
his permission I got access to Central laboratory of Science faculty where UV-Vis-spec
and FTIR-spec are tested. A lot of thanks to Dr. Maqsood and Dr. Sajida Noureen with
their help spectrofluorometric graphs and results are obtained.
I wish to express my sincere thanks to my respected teachers and all of my loving
and dear friends including senior research mates who helped me a lot in every way
especially their moral support was of great worth for me.

Last but not least, a very warm thank to my wonderful parents as well as my
brothers and sisters for their continuous encouragement, unconditional love, guidance,
and support, that they have always given me, helping me to succeed and instilling in me
the confidence, and value able suggestions for my studies and character.

Muhammad Yameen

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PREFACE

In “Synthesis and Characterization of Vanadium Oxide Nanoparticles with

Photoluminescent Properties” first principles calculations exhibit the effect of pressure
on electronic structure, magnetic behaviour and structural stability of quaternary
ScNiCrAl Heusler alloy. The ScNiCrAl alloy is found to be stable in ferromagnetic
phase. At pressure 8.0GPa, the half metallic behaviour of the alloy lost. At all pressures,
the band structures calculation exhibits that ScNiCrAl alloy shows indirect band gap. The
total magnetic moment calculation shows that the alloy follow Slater-Pauling rule as it
has 22 number of valence electrons. The FP-LAPW within the framework of DFT and
WIEN2K code is employed to predict possible outcomes. First chapter gives a brief
introduction to alloys, Heusler alloys and quaternary Heusler alloys. Second chapter of
the thesis describes the work already done in this field. In third chapter, methodology has
been given. Fourth chapter of the thesis helps to understand the electronic structure and
magnetic properties of quaternary ScNiCrAl Heusler alloy under pressure. At the end
there is an overall conclusion of the thesis. References to the literature are mentioned at
the end of thesis.

TABLE OF CONTENTS

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I DEDICATION iii
II DECLARATION iv
III CERTIFICATE v
IV ACKNOWLEDGEMENTS vi
V PREFACE vii
VI TABLE OF CONTENTS viii
VII LIST OF FIGURES xi
VIII LIST OF TABLES xii
IX ABSTRACT xiii

Chapter 1: INTRODUCTION (1-12)

1.1 Introduction to Nanoparticles 2
1.2 Properties of Nanoparticles 2
1.2.1 Surface Area to Volume Ratio 3
1.2.2 Color, Quantum Confinement and Band Gap 3
1.3 Classification 4
1.3.1 Dimensional Classification 4
1.3.2 Origin Based Classification 4
1.4 Synthetic Approach of Metal Oxide Nanoparticles 7
1.4.1 Bio/Green-synthesis of Nanomaterials 7
1.4.2 Laser Ablation Method 7
1.4.3 Slovo-Thermal Technique 7
1.4.4 Hydrothermal Synthesis 9
1.4.5 Sol-gel Method 9
1.4.6 Chemical Vapor Deposition (CVD) 9
1.4.7 Electrical Discharge Synthesis 9
1.5 Applications of Metal Oxide Nanoparticles 11
1.5.1 Biomedical Applications
1.5.2 Agriculture
1.5.3 Industry

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1.5.4 Agent in Chemical Reactions
1.5.5 Electronics
1.5.6 Sensors
1.6 Vanadium
1.6.1 Vanadium with Different Oxidation States
1.6.2 Vanadium Oxide Nanostructures
1.6.3 MIT States of Vanadium Oxides
1.6.4 Applications of Vanadium Oxides
1.6.5 Toxicity of Vanadium Oxide

Chapter 2: LITERATURE REVIEW (13-18)

Chapter 3:Materials and Methods (19-34)

3.1 Materials 20
3.1.1 Chemicals 20
3.1.2 Apparatus 22
3.2 Preparation of Sample 23
3.2.1 Composition 24
3.1.5 Synthesis of Samples 26
3.2 Characterization Techniques 27
3.2.1 UV-Visible Spectroscopic Studies 27
3.2.2 Photoluminescence 29
3.3 Fourier-Transform Infra-Red Spectroscopy 29
3.3.1 X-Rays Diffraction 29

Chapter 4: RESULTS AND DISCUSSIONS (35-50)

4.1 Computational Details 36
4.2 Results and Discussions 36
4.2.1 Crystal Structure and its Constancy under Pressure 36

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4.2.2 Electronic band structures 41
4.2.3 Magnetic Behaviour 44
Chapter 5: CONCLUSIONS (51-52)
Conclusion 57
References (53-56)

LIST OF FIGURES
Figures Page #
1.1 Crystal lattice of substitutional and interstitial alloys 5
1.2 Binary, ternary and quaternary alloys respectively shown in a, b and c figures 6
1.3 Crystal structure of Heusler alloys 8
1.4 Full X2YZ and half Heusler alloys XYZ with L21 and ClB type of structures 10
respectively.

4.1 The unit cell presentation the positions of atoms in Type-γ 39

configuration of quaternary ScNiCrAl Heusler alloy.

4.2 Total energy versus volume for different configurations of ScNiCrAl 40

alloy.
4.3 Lattice constant versus pressure for ScNiCrAl alloy. 42
4.4 Volume versus pressure for ScNiCrAl alloy. 43
4.5 Half metallicity gone for pressure ≥ 18.0GPa for ScNiCrAl alloy 45
4.6 Energy gap as a function of pressure. 46

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4.7 Representative band structures showing the effect of pressure (in spin 47
down) for ScNiCrAl alloy.
4.8 The reliance of valence band maxima (VBmax) and conduction band 48
minima (CBmin) on pressure for spin ↓state in ScNiCrAl alloy.
4.9 Total magnetic moment versus pressure for ScNiCrAl alloy 49

LIST OF TABLES

Tables Page #
4.1 The total energy (E), lattice constant (a), equilibrium volume (Vo) and 38
bulk modulus (B) of three types in ferromagnetic and paramagnetic
configurations of ScNiCrAl alloy.

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 Abstract

First principles approach based on Density Functional Theory is applied to probe

the structural, electronic and magnetic properties of Quaternary ScNiCrAl Heusler alloy
by implementing WIEN2K code. Full potential linearized augmented plane wave (FP-
LAPW) method is applied to carry out calculations under pressure for ScNiCrAl alloy.
The generalized gradient approximation (GGA) in the scheme of Perdew Burke
Ernzerhof (PBE) is employed to calculate exchange and correlation potentials. It should
be noted that the GGA is preferred over local spin density approximation (LSDA) due to
its accuracy. The total energy/cell of all three configuration ScNiCrAl alloy shows that
the alloy in Type-γ configuration exhibit the most stable state as compare to the Type-α
and in the Type-β configurations. The conducting behaviour for spin ↑ and
semiconducting gap for spin ↓ spectra reveals that the alloy is half metallic ferromagnet
at zero pressure. The Eg for ScNiCrAl alloy increases up to 0.43 eV with the increase in
pressure up to 6.0GPa. For pressure ≥ 8.0GPa, this alloy loses half metallic character. The
ScNiCrAl alloy follows the Slater-Pauling rule; MT = (NV – 18)μB as it has 22 valance
electrons.

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Chapter
1

13
 CHAPTER 1
INTRODUCTION
1.1 Introduction to Nanoparticles
Human civilization started with the stone, then advances pushes him to copper
and then to bronze after that to iron, a small era of polymers and now advanced materials
are studied having small size and enhanced properties [1]. It is the try of man to have
reduced size with efficient properties. Industries from past few decades are
manufacturing more small instruments and devices. Man has reduced the scale from
meter to 1/100th of mm by the invention of lenses. At the end of 20th century man has
found various methods of fabricating the material at the scale of 1/10th of micrometer [2].
It takes about 3 decades to develop a technology probing nanometer size objects. The
different groups of nanomaterials include fullerenes, ceramics, different metals mostly
transition metals and polymeric NPs.

In fact when we say a nanoparticle it doesn’t mean a single atom, atoms have
sizes at angstrom (10-10) scale where a nanoparticle can be in several nanometers (10-9) so,
a nanoparticle is a cluster of atoms and it is in all different from its bulk material.

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 At nanoscale the properties of materials are completely different from the
properties that a material have at bulk. However as we increase the number of atoms in
cluster a stage comes where all properties switch back to bulk, here bond energies
dominate. The reason behind this is that at nanoscale we shift from Classical Physics to
Quantum Physics. Some properties are given below that changes when we turn from bulk
to nanoscale or vice versa [3, 4].

1.2 Properties of Nanoparticles

NPs have some special properties that are not found in bulk of the same material.
Below a look of these properties

1.2.1 Surface Area to Volume Ratio (µ)

NPs are rich in surface to volume ratio that can be seen by the Figure 1. Higher
area leads to more influence with the interacting media. Generally, in NPs surface to
volume atoms ratio increases by increasing size of atom (r) and by decreasing the
physical size of the particle (s) and vice versa [5].

r
µ∝
s

This property has vide applications like in sensors, catalyst in reactions and a
mere change can be detected.

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1.1.2 Color, Quantum Confinement and Band Gap
At nanoscale, band gap can be changed by changing the quantum size of
nanoparticle, larger the size smaller the band gap and vice versa. Quantum confinement is
also another important parameter, confinement means to restrict the electron’s motion i.e.
discreteness. Color band gap and quantum confinement are related to each other [6].

1.2 Classification of Nanoparticles

Classification of nanoparticles is mainly of two types
1.2.1 Dimensional Classification
1. Zero-Dimensional having all dimensions in nanometer. They can be small
crystalline (cubic) or quantum dot or can be nanourchins when confinement is
enough. Opposite to band energies that are found in bulk materials, every crystal
diameter on nanoscale corresponds to a single discrete energy. Materials that exhibit
this type of discrete energies are referred to as “artificial atoms” or called as
‘quantum dots’.

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2. One-Dimensional having only two dimension in nanometer. They can be nanorods,
nanowires, nanotubes, nanowhiskers and nanofibers.

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3. Two-Dimensional having one dimension in nanometer. They can be nanosheets,
nanolayers and nanowires.

1.2.2 Origin Based Classification

Below are some classes for basis of NPs

1.2.2.1 Natural Nanoparticles
Milk is a nanocomposite. Volcanic eruptions, harsh fire disasters, viruses, and
proteins etc. are examples of some common natural NPs. Carbon nanotubes are also
found in ice cores of 10,000 years old [7].

1.2.2.2 Incidental Nanoparticles

These are the byproducts of some anthropogenic process like combustion of
Diesel/petroleum/natural gas, Welding fumes also contain metal oxide NPs [8].

1.2.2.3 Engineered Nanoparticles

Incidental NPs are complex in size distribution, shape and geometry. So we have
to engineer them by different techniques.

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 1. Carbon Based Nanoshapes.

Figure 1

These materials have a basic component carbon or carbon allotrope. They can
be spherical, ellipsoidal, nanotubes, nanotube rings, nanoonions, nanohorns
and nanofibers. The main focus of modern and latest tech is on carbon
nanotubes [9].

2. Metal Based Nanomaterials. Various metals are their salts are also used to
prepare nanomaterials. It can be gold NPs mainly used in high tech app, opto-
electronic, sensors, drug delivery, catalysis and nanowires. Silver NPs are widely
used as antibacterial applications. Iron oxide NPs (ferrites) have magnetic
applications. Copper titania and many transition metals have NPs and cover a
wide range of interdisciplinary applications. It’s necessary to mention here that
metallic NPs have shown a creditable results for the cure of cancer.

1.2.2.4 Nanocomposites.
Different NPs are merged and doped to form a nanocomposite. Nanocomposites also
used in polymer and plastic industry.

NPs are also classified according to their morphology. By shape they can be
nanocore shells/ nanoshell cores, nanocubes, nanocubides, nanostars, nano branches and
clusters etc.

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1.3 Synthetic Approach of Metal Oxide Nanoparticles
Synthesis is important in studying nanoparticle’s size, shape, structure and mostly
all properties. Different techniques yield different results. Researchers have started from
passive nanostructures (1st generation), advances through Active nanostructures,
enhanced by systems of NPs and now a days molecular nanosystems that are used in
atomic design, different devices and emerging functions. There are a lot of synthesis
methods/techniques mainly top down or breaking process some of them are given below
[10, 11].

1.3.1 Bio/Green-synthesis of Nanomaterials

Different leaf extract and microbes like viruses, bacteria and fungus are also used
for the synthesis of NPs. Many reports have been published for microorganisms ability to
produce inorganic and complex nanostructures of silica, zinc oxide and magnetic NPs.
NPs are also synthesized by the extract of these microbes. Microbes extract contains
polysaccharides and proteins that can reduce metal ions and so to produce NPs [12, 13].
Tea waste of green tea is also used to synthesize and stabilize nanoparticles. Tea waste
contains polyphenols that are anti-oxidant agent and so reduce the metal ions and hence
produce NPs [14].

1.3.3 Laser Ablation Method

It’s a top down approach of making
NPs. Metallic NPs by this method are used in
recent studies usually where uncapped particles
are needed. We can say that laser ablation
method lacks of stability of NPs by any
surfactant. They are formed in water or in
organic solution where a metallic plate is
dipped in the solution and then laser falls on it
laser makes them plasma and by condensation of required metallic NPs are formed.

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1.3.4 Solvo-thermal Technique
During the last decade literature has
showed that more than 80% of researchers uses
this method for the preparation of nano-size
materials including films, powders, single
crystals and nanocrystals including various
morphologies [15].

1.3.5 Hydrothermal Synthesis

Hydrothermal fabrication needs solution and kept under high temperature and
high pressure mostly in Teflon lined autoclave. Wet methods are preferred because of
easily available and can be transformed into films and powders. It should be noted that
temperature of water solution should not exceed the super critical temperature of water
that is 374°C.

1.3.6 Sol-gel Method

Here, sol stands for colloidal suspension and gel is formed by the three
dimensional arrangement of that suspension when liquid in the solution evaporates its
density and viscosity increases. A temperature where gel is formed is called gel point.
Gel is a state where liquid and solid phases are mixed into each other. It is a wet chemical
process for synthesis of different NPs and also doped thin films. First of all in 1983 by
Greenberg VO2 films are fabricated. Basically in sol gel process we take a liquid in which
precursor is dissolved and then polymerization reaction results in oxide networks. Sol gel
method can be operated in normal temperature and pressure [16].

1.3.7 Chemical Vapor Deposition (CVD)

This is an industrial method for thin films on core shells or on substrates of
usually NPs. CVD is first time used for the deposition of vanadium in 1967, and then
increases its use. It has many techniques but most used are atmospheric pressure/aerosol
assisted chemical vapor deposition (APCVD/AACVD). The most recent technique is
electric field assisted chemical vapor deposition EACVD. Another method where in a

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vacuum chamber a pulsed laser is focused on the sample, mostly used for oxide film
growth called pulsed laser deposition PLD.OAD (Oblique Angle Deposition) method can
be used to set porosity and microstructure of thin deposited films named as sculptured
thin films (STFs) [17].

1.3.8 Electrical Discharge Synthesis

Apparatus consists of four parts an electrical
discharge generator, two electrodes (Anode and
Cathode), solution usually consists of metal salt or
nitrate with distilled water and ethyl alcohol, Glass
vessel and water cooling system. Concentration
should be in mili Mole and current should not
exceed from 60A, voltage is between 220-260V.
The colloidal solution of NPs is obtained, after
drying powder is formed [18].

1.4 Applications of Metal Oxide Nanoparticles

Metal oxide NPs have been vastly used and many industries are trying to use them
in their products. Some of them are listed below.

1.4.1 Biomedical Applications

Today’s applications include Bio-Detoxification, Anti-Malarial, Anti-Bacterial,
Anti-Cancer, bone cement, Dental instrumentation, Contact Lenses, tissue regeneration,
in vitro and in vivo Drug release and drug carrier. Gold NPs have vast applications in
Gene delivery, bio sensors and Bio imaging purposes. Silver NPs/ thin films are used in
clothes, food containers and in bandages for disinfectant, Toxicology, Nano ultra-
filtration of water Toxicology, Nano ultra-filtration of water and deodorizers [7, 19, 20].

1.4.2 Agriculture
In agriculture NPs are using as minimize the quantity of sprayed chemicals,
minimize nutrients losses, enhance yield through optimized water and nutrient
absorption, plant breeding, artificial clay, genetic engineering, plant protection products,
Controlled release of fertilizer, detection and removal of pesticides and insecticides and
Cleaning of soil contamination [21].

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1.4.3 Industry
Industry has a major part of any country’s economy. For the betterment of
industry NPs are playing good rule like in the formation of superglue and making it
stronger, making dyes more reliable also removal and degradation of dyes, Photo
degradation, less energy consumption devices, cosmetics and in solar cells [8, 22].

1.4.4 Chemical Reactions

Chemically NPs are extensively applied in possible energy transfer mechanism,
Photo luminescence, Photo catalysis, Nano-catalyst for organic reactions, detections of
chemicals& gasses and in electrode preparation for photo electrochemical analysis [23].

1.4.5 Electronics
NPs are being fabricated for transistors, Light Emitting Diodes, Forensics
(Fingerprints), Safety purposes, degradation of explosives, electronic field effect
transistors and plasmonics [24].

1.4.6 Sensors
Many transition metal NPs like gold have many applications in sensors making
like in calorimeter (the process of measuring state variables by changing the state of
sample. Nano based sensors can be optical (photo luminescent, photo absorber, surface
plasmon resonance or raman spectroscopy), mass sensitive, electrochemical nanogap
sensitive sensors and in biosensors or bioelectronics (Detection of chloramphanecol,
detection of pathogens in plants, detection of vitamin C) [25-28].

We can say now a days there is hardly a field where Nanomaterials are not used
itself or trying to use. In viewing these applications we can’t deny from the importance of
nanomaterials, their synthesis, their characteristics and their applications in different
fields.

1.6 Vanadium

Vanadium discovered in 1801 and named panchromium meaning all colors then
to erythronium meaning red emitter. In 1830 its name vanadium comes and is among the
transition metals with silvery white color when found in bulk. At nanoscale color changes

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with respect to the size of the nanoparticle as stated above in 1.1.2. Vanadium is a ductile
material having high discharge capacity means that vanadium based batteries have fast
charging and give more current when discharging. It has high energy density which
shows it can store more energy/charge in small volume with a broad band gap of ̴ 3.2 eV
[29]. Electronic configuration is as

1s2 2 s2 2p6 3s2 3p6 4s2 3d3 OR [Ar] 4s2 3d3

Vanadium is present in sea water as H2VO4 - ion. Vanadium is a part of living

bodies even found in human body also which take part in physiological processes. A
perfect diet should include 10-50 µg Vanadium daily. However it is beneficial up to a
certain specific level, higher amount of vanadium are toxic and may cause lung cancer
[11, 30].

1.8 Vanadium with different Oxidation States

VxOx are among the most attractive materials with one reason of different
oxidation states. It can be VO, V2O3, V3O5, V3O7, V4O7, V4O9, V5O9, V5O11, V6O11, V6O13,
V7O13, V8O15, VO2 and V2O5 [31-33].

2.2 Vanadium oxide Nanostructures

Vanadates has more than 13 different phases.

2.3 MIT State of Vanadium Oxides

The VO2 shows MIT nearly at room temperature [34].

1.9 Applications of Vanadium Oxides

1. As an electrode in metal ion batteries [35, 36].
2. Gas sensors [33].
3. Antibacterial
4. Thermochromic Films
5. Optical switching [35].
6. Optical Data storage device [35].
7. Super capacitors, Pseudocapacitors, Hybrid capacitors [33].

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 8. Electrochromic layers [33].
9. Smart Windows
[16].

Toxicity of Vanadium for Living Organisms

Vanadium in bulk able to dye a apoptotic cell prompt tumor cells in the body [37].

Chapter 2
Literature Review
Various methods are introduced for storing energy here by Manoj and his
coworkers reemphasized the method of storing sunlight by smart windows. Smart
window can change its transparency and from opaque to translucent on applying voltage
and on removing voltage they come back to their previous state. Different materials

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layers are stacked onto each other making a sandwich. Electrochromic devices are
fabricated as two conducting electrodes for applying a potential and inside them
electrochromic (EC) layers and electrolyte having small sized cations usually of group 1 st.
EC materials which are used include transition metal oxides (like ZnO, NiO, TiO 2, WO3
and V2O5) and polymers. V2O5 changes its oxidation state and converts to V3O7 that have
EC properties. For their synthesis various methods are used but the sputtering method is
one to obtain nanorods with high reproducibility and adequate crystallinity. In this work
nebulizer spray pyrolysis (NSP) on the FTO substrate gives good film quality compared
to chemical vapor deposition.

The XRD characterization gives the presence of V 2O5 orthorhombic crystals in

large amount and a small amount of monoclinic crystals of V 3O7 are also present. The
size from scherrer’s equation, stokes & Wilson method, Lorentzian size and strain
broadenings are 37 nm and 0.04 % respectively. SEM images reveals morph is random
rods. AFM analysis gives surface topography which shows RMS roughness is 15.24 nm
an ideal value for rods. Surface skewness is -0.041 attributed to lakes on the rod surface.
XPS study showed vanadium has mixed oxidation states and 20 % has V +4 oxidation
states. This feature corresponds to characteristic of V3O7 (with oxidation of V+4) for
stability VO2 (Oxidation of V+4 ) and V2O5 (oxidation state V+5). UV-Vis-NIR
spectroscopy has resulted that the sample is transparent for NIR and translucent for
Visible and opaque to UV. From Tauc’s plot band gap is 2.52 eV that is intermediate
value lies between VO2 and V2O5 corresponding band gaps are 1.7 eV and 2.6 3 eV
respectively. Electrochemical and electrochromic analysis were performed by CV and
chronoamperemetry and chronocoulometry. Reference electrode, counter electrode and
working electrodes are used. CV resulted that many redox reactions are found from
multiple peaks attributed to V+4 and V+5.

The various coloration of sample on applying varying potential is due to band gap
variations. Here obtained nonorods have shown broaden redox peaks with enhanced
current density, improved intercalation and deintercalation all are due to enhanced
surface area. Reversibility was determined by chronocoulometry that is 91 % a small
drop is due to trapping of intercalated ions [33].

26
 Sodium vanadium fluorophosphate (Na3(VO)2(PO4)2F termed as NVFP)
nanosized particles are prepared from hydrothermal method at lower temperature.
Vanadium pentoxide V2O5 and H2C2O42H2O are stirred with water at 60° C, obtained
solution is then mixed with Na2SO4 and Na2HPO4 after that placed in Teflon lined
autoclave for low temperature range of 100 to 160° C for 12 h, obtained bluish solution is
then mixed with graphene and evaporated at 65° C to get the gel, and gel is dried at 500°
C. yellowish color is result of some amorphous vanadium oxide particles due to low
temperature. However higher temperature yields more crystalline results. Lower
temperature (100° C) sample has reversible capacity of 85.5 mAg-1 where moderate
temperature (120° C) sample has discharge capacity of 109.7 mAg -1. More high
temperature (160° C) have also low capacity of 87.6 mAg-1. Also by the presence of
graphene capacity increases. SEM and TEM images shows particle size is 100nm with
carbon coating of 4nm. Cycling performance is also enhanced by the presence of
graphene and capacity retention boosts upto 95.6% after 100 cycles, and 82% after 1200
cyles. We can say that these NPs can be used in Na-ion batteries as having low cost and
more reliable [36].

Vanadium oxide NPs are prepared from sol-gel method at the initial stage and
then doped with cobalt by addition of Co-acetate tetra-hydrate as reducing agent and
precursor the prepared solution is then hydrothermed at the temperature of 230°C for 24h
and finally dried at 80°C, dried powder is then annealed at 500°C in a furnace. By
comparing the sharp and narrow peaks of XRD with JCPD card’s the crystal is base
centered orthorhombic of Co3(VO4)2 and other is monoclinic with the formula of CoV 2O6.
The peaks are ascribed to water catalyst for oxidation having good magnetic properties.
To get the morphology of particles SEM images are taken out they are rods with diameter
of ranging from 10nm to 200nm and length is about 500nm, some of them are
agglomerated due to large surface area and to reduce energy. Vanadium has two V+3 and
V+4 oxidation states in the sample. For magnetizing properties hysteresis loop is drawn,
here by increasing the amount of Co in sample saturation decreases this is due to the
clustering of surface ions. These particles have strong potential against bacteria growth so
can be used in wound healing and treatment of infections [38].

27
 Spin coating technique is used for deposition of thin film on quartz that smooth,
crystalline and uniform. The speeds are kept at 1000rpm, 2000rpm, 3000rpm and
4000rpm with temperature of 350°C, 450°C and 450°C for the annealing purposes.
Various characterization techniques are used for the characterization of thin films. TEM,
FESEM and XRD are used to study the structure and width of film, electromagnetic
waves of visible and infrared ranges are tested and get their absorbance, reflectance and
transmittance. V+4 and V+5 are confirmed by XPS analysis. Nano thin film is harder than
microfilm found by indentation method. DSC verified that phase transition temperature
also decreases from 68 °C to 44 °C [39].

Vanadium has different oxidation states with changing morphology. Mostly

preferred VO2 has monoclinic, rhombohedral states and layered structure increases its use
in charge storage devices like Lithium Ion Batteries (LIB). V 2O5 is stable in structure
even at elevated temperatures with orthorhombic unit cell so V 2O5 is preferred to use in
LIBs. Energy efficient electrodes are made by using electrospinning fabrication of thin
films. In metal ion batteries vanadium electrodes are tested by changing the parameters of
elerospun. Vanadium has bad CV results in its pure form however doped with graphene
can result in enhanced retention of stability, cycle ability [35].

Hydrothermal synthesis are used to prepare Vanadium based oxide NPs with
different concentrations of NaOH and at various annealing temperatures of 200 °C to 500
°C. Finally prepared sample is characterized by XRD which gives vanadium structural
properties and phases. Vanadium particle size found to be from 38.62 nm to 78.63 nm
verified by TEM. Finally checked their conductivity, conductivity increases by
composites of graphene also by high PH value of solution during synthesis. Conductivity
increases by increase of temperature which shows its semiconducting behavior.
Annealing has strong effect on the stoichiometric calculations. Over these results
vanadium can be used in lithium ion batteries as an electrode or vanadium coated
electrode [40].

To find the concentration of vanadium atomic, mass spectrometer technique or

cloud point extraction method is used. Vanadium with graphene shows more retention
than pure graphene. All measurements were taken by atomic absorption spectrometer in

28
graphite furnace. Chemical solution of NH4VO3 is prepared as a stock solution. Water
samples are taken from university tap water, sea water, filtered water, hard water and rain
sample are tested for the concentration of vanadium. These show that graphene oxide can
be used to filter the unnecessary amount of vanadium form the water sample [41].

Vanadium oxide nanorods are reported for cost effective IR photo detector
applications that are synthesized by hydrothermal method. XRD results showed that the
structure is monoclinic and tetraclinic, further characterized by SEM and TEM which
confirmed the rod size to be 200-300nm. VO 2 show MIT at 68°C. Literature reported that
VOx are applied at actuators, smart windows, optical switches, sensors (gas), battery
electrodes and in Energy saving smart devices. Infrared photo emitter performance
depends upon band gap width, morphology and absorption coefficient [42].

Vanadiumoxide is used in smart windows for their Mott MIT at a temperature of

65.2°C due to change in crystalline structure from Monoclinic to Rhombohedral structure
having a hysteresis loop width temperature correspondence of 6.5°C. The synthesis is
done form hydrothermal analysis from source of V2O5 to VO2 with a reducing agent of
stearic acid without any more surfactant is used. XPS spectroscopy confirms the VO 2 in
the sample. XRD confirms the crystalline structure of synthesized material, FTIR
confirms the functional groups, SEM images displays a unique wire like shape of
Vanadium oxide, the size is found to 150nm with the tolerance of 30nm in diameter and
length is found in few micrometers, HRTEM gives interplaner spacing of 0.332nm and
0.484nm for the planes of miller indices (-111) and (100), Selected area electron
Diffraction resulted in VO2 nanowires and phase transition is revealed by DSC curves
[43].

For catalysis approach of vanadium NPs deposition, precipitation, co-precipitation

and impregnation like methods are not suitable it needs synergetic like effect among
compositions. However hydrothermal, solgel, ultra-sonication, microwave treatment etc
are best for catalysts because the prepared sample has porosity. Literature reported Mo-
V-O was prepared with hydrothermal treatment with pre ultra-sonication and resulted in
the presence of V play a key role in active sites and phase structure for best catalyst
approach. Similarly microwave treatment is also responsible for porosity and enhanced

29
interaction of dopant with vanadium. For light alkane conversions sol gel method is
reported. Mechanochemical treatment in the vanadium phosphate shows domain surface
orientation changes. In conclusion vanadium based catalysts are best be used for xidation
and hydrogenation of light alkanes. Catalytic performance is enhanced by the suitable
dopant and preparing method. Pretreatment microwave and ultrasonic waves are useful
for adsorption and desorption of reagent [44].

Vanadium shows thermo-chromic properties so it attracts the attention for being

used in smart applications like in smart windows. For these applications synthesis is a
key role because their characteristics depend strongly on microstructure and phase
composition. So gas vapor deposition method are best used like of chemical vapor
method and phase/physical vapor technique and also other methods like as solution
methods involving sol-gel method and simple chemical methods are used. Vanadium
oxide films are desired with high luminous transmittance, suitable transition temperature
and high modulation capability of solar energy. Multilayer construction of vanadium,
different elements doping, changing substrate selection, and structure modifications are
used to find good thermochromic applications. For the transition temperature to be at
room temperature (25°C) elemental doping (Metallic W) is a good technique. To increase
the modulation capability multi layers should be used this enhances the stability of thin
film in wet acidic conditions. Optical transmittance is enhanced by making porous films.
This make the films more optical. Also the brown or yellow color are not too much
interesting for their commercialization different doping can change their colors as well
[16].

Vanadium oxide shows transition from insulator to conductor which is shown by

IV graph that current goes to higher value and seems like an S shape, this property is
referred as MIT (MIT). This is used in electronics like as switching purpose. Here
transition in metal and insulator is found at 340k. so we say vanadium oxide has
temperature dependent electrical properties. For 0.1k change in temperature resistivity
changes 105Ωcm. It is referred to as Mott insulator or Mott MIT (MIT) [45].

Shammy Raj and his coworkers prepared vanadium oxide NPs and checked how
active these NPs in antibacterial approach and also their toxicity. NH 4VO3 is used as a

30
precursor in this preparation and we resulted a large size 300nm of V 2O5 by thermal
decomposition then characterizes by XRD (UK), and for morphology SEM (USA) and
resulted in the orthorhombic crystals. Annealed at 400°C which resulted in yellowish
color. After that CNH and XPS (USA) confirmed the complete formation of V2O5 from
NH4VO3 by getting percentage and ratio of elements present in the sample respectively.
EDAX images are also obtained. For size confirmation Dynamic light scattering zetasizer
is used. These NPs can be produced with different techniques however the challenge is
reproducibility.

Sample can remove bacteria from the waste water. To check their antibacterial
behavior bacteria is spread on agar coated glass made plates having V 2O5 with different
concentrations with a lid. After heating shifted to polystyrene glass plates covering a lid
incubated at 37°C for 12 hours. Intracellular ROS is produced by the 2,7 -
dichloroflorescindiacetate dye (DCFH2-DA). Bacterial incubation is done in dark and
then fluorescence microscope shines green light and resulted images are taken.

Bulk vanadium is toxic to human and animal and cause to apoptotic cell death and
ROS is produced in the body. Human HeLa cells are taken and then mixed with antibiotic
penicillin and another sample of human HeLa cells are mixed with V 2O5 at different
concentrations and then checked them [37].

In IPEI Tunis nanourchins of vanadium oxide are prepared by hydrothermal

treatment of aqueous solution of V2O5 treated at 180° C for 48 h. the resultant solution is
dried at 60°C for 4h and then characterized by XRD, FTIR, SEM, UV visible
spectroscopy, XPS, Impedance analysis, dielectric studies and conductivity study that
results interlayer stacking of molecules that are 16.37 Å (size of two molecules) which
shows two dimensional structure, presence of V=O and V-O-V bands, average diameter
of 20 µm and nanorod of urchins has average size of 25 µm, band gap found to be 3.65
eV, binding energy peaks confirm that in sample vanadium has two oxidation peaks that
are V+4 and V+5, shows semiconducting nature because impedance and temperature are
inversely related to each other as like in semiconductors, follow Jonscher’s law
repectively [46].

31
 Faheem with his coworker prepared NPs of vanadium oxide by using autoclave at
the temperature of 200° C from V2O5 and Distilled water, after that Nitric Acid (HNO3) is
added drop by drop in the solution that extracts heat from the solution. The shade of the
solution changes from mealy to brown then to reddish brown and finally to yellowish.
Prepared product is dried at 80°C and then characterized by XRD, HRTEM, FESEM,
EDS, SAED, UV Visible and Near IR spectroscopy. The shape is found orthorhombic as
the highest peak is at (010). EDS results that the sample contains only vanadium and
oxygen in the sample, and the ratio is confirmed that sample has V2O5. FESEM gives
morphology of synthesized sample that are very long nanobelts of size millimeter
because rods can be seen even at the scale of millimeter from SEM and diameter is found
to be 40 nm to 60 nm. All FESEM characteristics are confirmed by TEM also. These long
rods are best suitable for use in supercapacitors. The Raman spectroscopy confirms the
structure is orthorhombic. The bandgap is 2.3 eV which have optical, optoelectronic and
electrical properties. For field emission properties an electrode used of stainless steel is
used as cathode and interplaner spacing is fixed at 200 µm and a graph between current
density and electric field is plotted. The field enhancement factor of superlong vanadium
oxide nanorod is greater than the AlN, SiC, Si, VO2, WO3, ZnO and ZnS. Electrical
properties are also confirmed by Placing in TEM at STEM hoder and found enhanced
conductivity. MSM model gives these calculations Electron mobility, conductivity and
carrier concentration [47].

For the synthesis of vanadium NPs Aqueous Zinc Acetate is chosen and mixed
with NH4VO3 in a beaker drop by drop, both are taken as 0.1 M. Synthesis temperature is
kept at 80° C, dried at 60° C and annealed at 600° C in a muffle furnace. XRD peaks for
as prepared sample confirms Zn3V2O7(OH)2.2H2O which shows presence of water,
annealed sample matched with JCPD’s card and confirmed the nature of ZnV 2O6. Narrow
FWHM shows highly crystalline structure. The morphology of as prepared and annealed
one is same that is nanosheets and is shown by FESEM. Hydrogen absorption
measurements are also done by placing 0.5 g of sample in stainless steel container, In
about 8minutes 90% of hydrogen is absorbed in sample.

32
 For electrochemical test electrode from ZnV2O6, carbon, ethanol and Nickel are
pasted and after drying is used. Capacitance of the given sample is calculated by the
given formula

I
C=
m∗ΔV
∆t

In this equation

C = Capacitance of synthesizes material (Cathode)

I = Discharge Current that is in amperes

m = mass of sample from which cathode is formed

ΔV
= sweep rate of voltage with units of V/s
∆t

Here ZnV2O6 has 380F/g capacitance and its current density (J) is 0.5A/g.
enhanced capacitance is attributed to double layer capacitor that is formed inside the
capacitor. PL that is shifted to blue region is attributed to defects and vacancies present in
the crystal due to Zinc [48].

Sodium vanadium oxide nanobelts/rods are synthesized by hydrothermal method

having diameter in nanometer range and length in micrometer range. By calcination size
of material is reduced. It has moral gas sensing properties for the detection of acetone and
alcohol at the temperature of 260°C. The prepared Na27V84O224 is more sensitive towards
ethanol than nanorods of V2O5. XRD results are matched with JCPD cards and structural
properties are found from SEM and TEM that shows its nanobelt structure. Several
nanorings are also observed. For gas sensing application sample is characterized by BET
to calculate the surface area which is found to be 18.7m 2/g and 20.2m2/g for as
synthesized and annealed sample respectively. Increment in the area is referred to
breakage of rods due to heat. Resultant nanorods are checked for gas sensing and found
sensing S=3.45 for 100 ppm of ethanol at temperature of 260° C. The presence of Na + ion
in the structure and low electronegativity are the causes of enhanced sensing of gas. DFT

33
(Density Functional Theory) simulation has also been used for the sensing performance
of sodium and vanadium oxide composites [49].

Microsheets of VOPO4 are obtained by the exfoliation of VOPO4.2H2O that are

obtained by ultrasonification of bulk layers which are attached to each other by hydrogen
bonding. H-bonding are easily broken by the strong ultrasound energy and obtained
graphene like sheet are also porous that is shown by the SEM images. XRD peaks shows
the VOPO4 thin sheet has the tetragonal structure. Exfoliated thin sheets have shown no
intra-layer change in structure. Thickness of the sheet is checked by TEM, HR-TEM and
AFM that is 4.07nm which is about 4-6 atoms stacking size. Providing large area with
lower weight stores more charge. So obtained 2D film has high electrochemical effects
like high redox potential. Raman spectra ar 1347 cm-1 shows small D highly crystalline
and fine quality graphene. Thin film has large conductivity in temperature region of 150-
300 K. Obtained film has the greater cycle ability over charging-discharging and
bending-extending deformation. Thin sheet is spread on gold substrate to make electrode
and then between two electrodes electrolyte is placed having separation between them. It
makes double layer super capacitor. Electrolyte gel is prepared from distilled water, PVA
powder and LiCl when stirred at 95° C. CV analysis for galvanic charge-discharge ranges
from 0 V to 1.2 V at electrochemical station, shows redox current peak at 1.1 V for
oxidation and 0.9 V for reduction. A slight internal resistance drop is also observed of
0.098 V [50].

Now a days scientists are attempting to store charges in Electrochemical Double

Layer Capacitor (EDLC) because of more cycle life, excellent power and fast reaction at
the electrode surface with electrolyte. Electrolyte with high surface area and conducting
materials like graphene is suitable, non-aqueous, less electron flow and high ionic flow
are excellent as they have high capacity. Electrode material has also an importance for
high capacitance and more cycle-ability. For these properties electrode is porous so have
the ability of storing ions inside them. Electrodes from graphene, onion like carbons,
nanotubes and aerogels improving energy in EDLCs. Opposite to EDLC pseudocapacitor
have redox reaction (Faradaic process) at the surface of electrode. They are classified in
two types as polymers (conducting electricity) and transition metal oxides. Ruthenium

34
(Ru) is most widely used material in pseudocapacitor due to high specific capacitance of
1358 F g-1 and high conductivity. Ru changes oxidation sates from 2 to 4.

An improvement to EDLC and pseudocapacitor is hybrid capacitor where both

phenomena’s are used, faradaic electrode is joined with capacitive electrode. Hybrid
capacitors provide high energy density, higher power capability and higher capacitance.
Besides these benefits it has a drawback of cycle-ability of faradaic electrode. To
overcome this carbon based materials are doped. Poor performance of electrodes is due to
the lower conductivity. So Mn and graphene made electrode has high capacitance, good
cycle-ability. Graphene/RuO2 mixed structure electrode also have enhanced capacitance.
Then TiO2 and SnO2 with graphene are tested and showed good performance in hybrid
capacitors. In this work V2O5 has layers morphology. By separating the layers of about 3
nm width have specific capacitance of 1308 F g -1 was obtained. It showed high
capacitance over low weight, this is attributed to high surface area. Carbon paper and
carbon foam have high porosity and large surface area allowing electronic conductivity
[51].

Supercapacitor or ultracapacitor are the replacement of metal ion batteries due to

fast delivery rate, high power density and more cycle ability. Energy densiy can be
calculated by

1 2
E= C V
2

where E= energy density, C = capacitance of capacitor, V = applied voltage.

Graphene based nanosized capacitors with double layered are prepared but they have low
capacity to store a charge however when they are doped with metal their capacitance is
enhanced. For this purpose vanadium is commonly used, having high porosity. Bulk V2O5
has 11 W h kg-1 and paper like same material shows 45 W h kg -1 due to porous surface.
Vanadium oxide nanosheets are prepared by freeze-drying method (in this method
sample is frozen by dropping liquid nitrogen on the sample directly and then dried by
cryodesiccator to obtain high surface area at the time of evaporation of water) that have 4
nm width and shows high capacitance, less diffusion, excellent stability and high energy
density. These properties show electrochemical behavior so an electrode is prepared from
35
the sample for CV system and tested, also checked by galvanic charge and discharge with
various current densities and get the supporting results. Jixin Zhu reported a new method
for the preparation V2O5 nanosheets through bulk. Bulk vanadium pentoxide is stirred
with H2O2 in the presence of H2O [52].

For obtaining Different shapes NPs (nanoarchitecture) electrochemical method is

suitable for the deposition, because it needs electronic conductivity instead of carbon
conductivity which enhances its stability. Electronic conduction and large surface area of
nanosheet are main causes of formation of high power electrodes. Nanosheets spacing is
altered and more Na+ ions can be intercalated here. Electrostatically attracted electrons
and Na+ ions provide short and long range transfer of charges, hence increases charge
diffusion with minimal loss of charge and current. In literature V 2O5 dual layer nanosheet
cathode (cathode) is tailored which operates on redox potential 3V and provides capacity
more than 250 mAh/g, energy density varies but averagely 760 Wh/kg, having C/8
cycling rate and power goes to 1200W/Kg. This ensures fast charging. So these sheets are
more stable and more eleastic and can be long term maintained for sodium ion batteries.
Insertion and extraction of Na+ is done by Helium filled dry glovebox, Synchrotron is
used for XRD measurements and for SAXS/WAXS measurements, XPS,XAS and
electron microscopy is also used for characterization [53].

This literature reported various techniques of synthesis yield varying results about
shapes of NPs (morphologies). Synthetic techniques are chemical vapour deposition,
electrode deposition (anodic) and most favourable is hydrothermal synthesis. All these
methods gives different structures including vanadium based nano clusters, tubes and
urchins (all in nanometer scale). The dependence on structure can be on solute,
Temperature, pH, foreign species of organic and inorganic, surfactants and on the
valency of vanadium (Vanadium shows +2, +3, +4 and +5 valencies). These vanadium
based nanoshapes shows better and developed electrochemical properties, best cycling
performance, enhanced capacity of charge storage and more energy density that’s why it
is used in batteries (Usually in Li-ion battery) as electrodes. For the manufacture of Li-
ion battries nanourchins are suitable. Nanourchin has nanorods on its surface and they
have reliable properties of more cycleability and high specific charge capacity. These

36
rods have same crystalline structure as of V2O5. The presence of impurity in structure and
defects causes a significant increase in specific capacity of nanorods. These all effects are
observed only under high reducing conditions [54].

This method includes CTAB as surfactant or capping agent. By changing reaction

conditions or varying the precursors we can control or change the shape and structure of
NPs. Vanadium pentoxide is used for this purposes that reported with different valencies
and different structures and the size of NPs can be about 45nm to 160nm. VPSEM and
TEM shows that the shpe is like a nanorod, XRD confirms that the crystal structure of
these rods is orthorhombic, XPS results in blue shift than the bulk V 2O5 that shows
increase in band gap and hence it is due to C type impurity, It is confirmed by this
experiment that the V2O5 show better catalytic activity [55].

Chapter 3

Materials and methods

3.1 Materials

3.1.1 Chemicals
1. CTAB ( CH3(CH2)15N(Br)(CH3)3)
2. Ammonium Chloride (NH4Cl)
3. Sodium meta vanadate (Na2VO3)
4. Deionized water (H2O)

5. Acetone (washing purpose)

All chemicals are purchased from Sigma-Aldrich, and used as purchased

without any further purification.

3.1.2 Apparatus

Following apparatus is used in synthesis

37
 1. Beakers, Glass vials with hard lid, (Pyrex)

2. High precision electronic balance, Oven, Centrifuge machine, Thermometer,

3. Spatula, Magnetic hot plate, Magnetic stirrer,

3.2 Preparation of sample

3.2.1 composition

Serial No. Sample Mass(g) of Mass(g) of Mass (g) of

Code Na2VO3 CATB NH4Cl

1 VO1 0.5 2.5 5.0

2 VO2 0.5 2.5 6.0

3 VO3 0.5 2.5 7.0

3.2.2 Synthesis of Samples

At start, 0.5 g of sodium meta vanadate (Na2VO3) stirred with 400 ml of deionized

water at room temperature until dissolved completely. At same time, in another

beaker 2.5 g of CTAB and 100ml of deionized water stirred at room temperature.

When both solutions become homogeneous then CTAB solution is poured into the

vanadate solution and temperature is increased to 90 °C gradually during the stirring.

Three samples are prepared by this procedure for VO1, VO2 and VO3.

For VO1:

The color of solution changes from whitish to transparent and then again fuggy

when 5 g of NH4Cl mixed in the solution. During the synthesis pH maintained

38
 between 6 and 8. The solution kept at this temperature for an hour and 30minutes to

the complete reaction, 50% water evaporated and final transparent yellowish solution

is used for UV-Vis spectroscopy and spectrofluorometric analysis. After that the

solution is kept in oven at 100 °C for six hours, obtained powder is then characterized

further for FTIR and XRD.

For VO2 and VO3:

Same method is adopted for these samples as stated for preparation of VO1

sample except the quantity of NH4Cl. Mass (g) of NH 4Cl is 6.0 g for VO2 and 7.0 g for

VO3 is used.

3.3 Characterization techniques

3.3.1 UV-Visible Spectroscopic studies

It is simplest techniques used for studying optical properties of nanoparticles.

Molecules having unbound electrons can absorb UV or Visible light. Spectral properties

of particles not smaller than 2 nm are studied via UV-Vis-Spec by absorbance intensity,

because the metals with sizes smaller than 2 nm have confined electrons i.e. their

electrons remain in their discrete shells, so they don’t show surface plasmon resonance.

Intensity of light emitted from the source is measured by the detector (photomultiplier

tube or charge coupled device) and again measured after passing same light from the

sample. Difference between emitted light from and source and transmitted light form

sample gives absorbance, finally absorbance verses wavelength is plotted for optical

properties.

39
3.3.2 Photoluminescence

PL is nondestructive and noncontact method to probe the properties of sample.

Optical properties, crystal defects, quality of crystal, efficiency for the transportation,
trapping, migration, production of electron-hole pair and their recombination depend
upon PL. When photon (electromagnetic wave) falls on electron having energy

E = hf

where E = energy of photon, h = Plank’s constant, f = frequency of light

It can be absorbed by electron if E is equal to any higher band gap, in result electron
goes to upper state leaving behind a hole. This process is named as excitation. The PL is
the result of recombination of electron hole pair either directly or indirectly (shown in
Figure 3.).

3.3.3 Fourier-Transform Infra-Red Spectroscopy

Fourier transform is mathematical algorithm which converts the data into

spectrum obtained by IR-electromagnetic radiation absorptions. It indicates the various

bands, functional groups, compound identification and structural analysis. We have

40
operated the FTIR in the range of mid IR frequency ranging from 4000 cm -1 to 1000 cm-1.

Total energy when electromagnetic is absorbed is the sum of all energies as

E toal = E vibrational + E electronic+ E translational + E vibrational

E vibration = When energy is absorbed by band it vibrates about its mean position.

E electronic = It is due to transition associated with electrons

E translational = displacement of molecule/functional group

E rotational = vibration arises by the absorption of microwave region of electromagnetic

radiation [56].

3.3.4 X-Rays Diffraction

Crystallographic phase, lattice constants, presence of unknown materials, defects

and chemical composition are characterized by XRD difractogram obtained by XRD

machine nondestructively. Every crystal has its own unique and specific difractogram

that is used for the identification of crystals.

Principle used here is Bragg’s diffraction law. That is

2dsinθ = n λ

Where d is crystallographic adjacent plane spacing, θ is Bragg diffraction/scattering

angle, n is Bragg order of diffraction and λ is wavelength of x-rays used.

The machine is operated at 2θ ranging between 20° to 80°, with wavelength of

Cukα (λ = 1.5406 Å) at room temperature. When filament current is 30 mA electrons are

41
emitted from the surface of cathode and move toward anode made of copper due to high

potential of 40 kV, here x-rays are produced. Ni filter

For measurement of particle size from XRD Scherrer equation is used

kλ
d=
β cosθ
Where
d = grain size
k = scherrer constant = 0.89
λ = wavelength used in XRD
β = FWHM = full length at half maxima of highest intense peak
θ = respective angle of highest intense peak (Diffraction angle)

Chapter 4

Results and discussions

4.1 UV-Visible Spectroscopy

The UV-Vis absorption spectra of all three samples (VO1, VO2 and VO3) are
shown in Figure 4.1 A, B and C. All three samples show the same absorption peaks i.e.
at 300 nm. It leads to that a slight change in quantity of NH 4Cl in the sample preparation
has no effect on UV- Visible absorption of nanoparticles. UV-Visible Spectroscopy has a
connection to electronic structure. As the band gap of vanadium oxide is of the order of 3
eV, the vanadate NPs absorb UV light while transparent for visible region of
electromagnetic spectrum. The 84.9% transparency has been calculated in this case. A
small absorption in visible region is due to band edge touching the visible region and also
due to some scattering of light from nanostructures.

The energy gap of all the samples has been calculated by using the formula

E = 1240/λ ---------------------------------------------- (4.1)

42
For sample A:

E = 4.1333 eV

For sample B:

E = 4.1333 eV

4.2 Photoluminescence Analysis

The PL graph of samples is shown in Figure 4.2. It is in accordance with the UV

analysis as the vanadate NP shows excitation peak at 300 nm wavelength whose

43
corresponding energy is 4.13 eV. The prepared samples are pure because no shoulder
peak is observed, nor change in band gap.

Two emission peaks are the result of indirect de-excitation one is at 600 nm and
other is at 900 nm. Higher excitation peak leads to production of excitons. Exciton’s life
time depends upon the intensity of emission peak because recombination results in
emission of photon. PL intensity tells the electron-hole recombination rate, recombination
and intensity are directly proportional to each other, and the recombination rate is
inversely proportional to PL.

Spectrofluorometric peak at 600 nm is attributed to the color of sample. This shows

emission of orange color from the sample. Visible emission has optical applications.

A small peak representing emission at 900 nm with corresponding energy 1.37 eV is

in Near-Infrared region of electromagnetic spectrum. So vanadium oxide NP’s can be
used as Infrared radiation emitters in many applications like in therapy (Gentle healing,
stimulate the physical body and mind, fat loss, expansion of capillaries, boost immune
system, relieving of pain), heating (cooking, room heating, welding of plastics, hardening
of paints) and in wireless communications (short range).

44
Figure 4 Spectrofluorometric plot of wavelength (nm) and intensity of emitted radiation (a.u.) for 3 samples of
vanadium oxide NPs 1. 5g of NH4Cl 2. 6g of NH4Cl 3. 7g of NH4Cl.

4.3 FTIR Spectroscopy

FTIR reveals about bond stretching and squeezing at the time of sample
formation, to check this pure CTAB and VO2 sample are tested via FTIR
spectroscopy. Pure CTAB has a peak between 3300 and 3500 cm -1 which is NH2
vibration and disappeared in VO2. Methylene –CH2- has two vibrations
symmetric and asymmetric with corresponding wavenumber of 2853 cm -1 and
2920 cm-1 remain unchanged. Vibrational peak at 1750 cm-1 shifted to 1745 cm-1
showing increase in weak bonding like van der waals forces at the surface of
nanoparticle with surfactant. Wavenumber 1652 cm-1 which is absent in pure
CTAB emerged in VO2 showing H-bonding. CH2- bonding at 1470 showed no
change. V-O bonding of various groups emerge at 1393 cm -1. C-N stretching
resembled to 1146 cm-1. The peak at 956 cm-1 shifted to 966 cm-1 and becomes

45
more intense showed the conversion of CH 2 bonding to V=O bonding [57],
similarly 730 cm-1 changes to 738 cm-1 resembling change of CH2 rocking to V-O-
V vibrations. Smaller wavenumber peak in CTAB at 651 is B-Br stretching which
disappeared in VO2. Two higher wave number peaks at 3814 cm-1 and 3733 cm-1
are not assigned as they needs NMR data for further explanation [58].

46
4.4 XRD Results
XRD difractograms of all prepared samples (VO1, VO2 and VO3) are
shown in Figure 4.4 A, B, C, and D, where D is the standard XRD of V 2O5 with
rhombohedral crystal structure. The obtained peaks are matched with standard
ICDD Reference Code 00-001-0359. So XRD confirms the presence of V 2O5
with orthorhombic crystal structure having lattice constants as a = 11.48Å, b =
4.36Å, c = 3.55Å. The corresponding (hkl) values of the observed peaks that are
best matching with 2θ = 20.258, 21.712, 26.27, 31.2, 32.412, 41.395, 47.547,
51.66, 59.179 and 72.033, are (010), (110), (101), (400), (011), (111), (020),
(411), (221), (421) and (231), respectively.

The best peaks matching is observed in Sample VO2 in comparison to

samples VO1 and VO3. This fact leads that the moderate concentration of NH 4Cl
resulted in good agreement to ICDD card (00-001-0359) with rhombohedral
crystalline shape, while by increasing or decreasing the amount of NH4Cl leads to
other phases like monoclinic and tetragonal of VO2 that are present as in sample
VO1 and VO3.

Particle size is calculated by using scherrer’s formula which is 31.54 nm

28.9 nm and 45.5 nm for the samples VO1, VO2 and VO3. Here the particle size
of sample with moderate amount of NH4Cl is shortest showing increase in particle
size by the increasing or decreasing the mass (g) of NH4Cl.

47
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