Study of Metal Doped Graphene Oxide

By
Hasaan Mahmood
CIIT/ FA19-BPH-092/LHR
Usman Jamil
CIIT/FA19-BPH-026/LHR
Supervisor:
Dr. Samia Aslam

BS Project Report
In
BS PHYSICS

COMSATS University Islamabad,

Lahore Campus- Pakistan

(Spring 2023)

I
 COMSATS University Islamabad

Study of Metal Doped Graphene Oxide

A Project Report Presented to

COMSATS University Islamabad, Lahore Campus

In partial fulfillment

Of the requirement for the degree of

BS (Physics)
By

Hasaan Mahmood
CIIT/ FA19-BPH-092/LHR
Usman Jamil
CIIT/FA19-BPH-026/LHR

(Spring 2023)

II
 Study of Metal Doped Graphene
Oxide

An Undergraduate project report submitted to the Department of Physics as

partial fulfillment of the requirement for the award of Degree of BS (Physics)

Name Registration Number

Hasaan Mahmood CIIT/ FA19-BPH-092/LHR

Usman Jamil CIIT/FA19-BPH-026/LHR

Supervisor: Dr. Samia Aslam

Designation, Department of Physics
Lahore Campus

COMSATS University Islamabad

(June, 2023)

III
 Project Report Approval

Study of Metal Doped Graphene Oxide

By

Hasaan Mahmood
CIIT/ FA19-BPH-092/LHR
Usman Jamil
CIIT/FA19-BPH-026/LHR
Has been approved

For the COMSATS University Islamabad, Lahore Campus

External Examiner:
Dr. Abdul Ghaffar
Assistant Prof., Department,
Institute

Supervisor:
Dr. Samia Aslam
Assistant Prof., Department of Physics, CUI, Lahore

Co-Supervisor:
Name of Co-Supervisor
Designation, Department of Physics, CUI,
Lahore

HoD:
Dr. Muhammad Asif
HoD (Department of Physics) CUI, Lahore

IV
 Declaration

I, Hasaan Mahmood, CIIT/FA19-BPH-092/LHR hereby declare that I have produced this

work, which is presented in this project report, during the scheduled period of study. I also
declare that I have not taken any material from any source except referred to wherever due. If
a violation of HEC rules on research project has occurred in this project report, I shall be
liable to punishable action under the plagiarism rules of the HEC.

I, Usman Jamil, CIIT/FA19-BPH-026/LHR hereby declare that I have produced this work,
which is presented in this project report, during the scheduled period of study. I also declare
that I have not taken any material from any source except referred to wherever due. If a
violation of HEC rules on research project has occurred in this project report, I shall be liable
to punishable action under the plagiarism rules of the HEC.

Date: Signature of the student:

Hasaan Mahmood
CIIT/FA19-BPH-092/LHR

Signature of the student:

Usman Jamil
CIIT/FA19-BPH-026/LHR

V
 Certificate

It is certified that Hasaan Mahmood, CIIT/FA19-BPH-092/LHR has carried out all the research work
related to this project report under my supervision at the Department of Physics, COMSATS University
Islamabad, Lahore Campus and the work fulfills the requirement for award of MS degree.
It is certified that Usman Jamil, CIIT/FA19-BPH-026/LHR has carried out all the research work related to
this project report under my supervision at the Department of Physics, COMSATS University Islamabad,
Lahore Campus and the work fulfills the requirement for award of MS degree.

Date:

Supervisor:

Dr. Samia Aslam

Designation
Department of Physics
CUI, Lahore.

Head of Department:

Dr. Muhammad Asif

Department of Physics
CUI, Lahore.

VI
 Dedicated to

Family, Teachers, Friends and Everyone who has assisted us in

our studies throughout our Life

VII
In The Name Of ALLAH, The Most Gracious, The Most Merciful

Abstract
In this work, The Ce nanoparticles are deposited on to GO powder, Nano composites have been
synthesized using wet chemical methods. Initially graphene oxide (GO) was prepared using modified
Hummer’s method. Then the Ce(NO3)3 was added using wet chemical method in already prepared GO
with varying concentrations of Ce(NO3)3 to obtain nano composites. Owing to the properties, Graphene is
a two-dimensional sp2-bonded carbon material that has a honeycomb crystal lattice structure with oxygen
atom. In this research, the effect of varying concentration of Ce precursor ((CeNO 3)3) on emission and
absorption properties of the nano composites was studied. A tuning effect on the emission and absorption
properties of GO has been investigated by adding varying concentration of Ce precursor (CeNO 3)3). The
absorption properties are studied using absorption spectroscopy technique. The emission properties are
studied using PL-Emission spectroscopy technique. It was observed that the varying concentration of Ce
precursor ((CeNO3)3) significantly tuned the emission and absorption properties of GO Nano composites.

ACKNOWLEDGEMENTS
2
All praises to Allah Almighty, who provided me with the strength to accomplish the final year project
(FYP). All respects for his Holy Prophet (PBUH), whose teachings are true source of knowledge &
guidance for whole mankind.

Before anybody else I thank my parents, who have always been source of moral support and driving force
behind whatever I do. I am indebted to my project advisor Dr. Samia Aslam for her encouragement,
inspiring guidance, remarkable suggestions, constructive criticism & friendly discussions which enabled
us to complete this report. Without her kind patronization, sincere coaching and continuous consultation, I
would not have been able to complete this task success fully.

Heartily, I am thankful to Dr. Samia Aslam for her constant and selfless support at every stage of project
work.

I am also grateful to Dr. Muhamad Asif HOD of physics department CUI Lahore. His encouraging
behavior as well as supporting attitude really opened new windows of knowledge for me. I offer my
deepest appreciation to him for providing me the lab/research facilities.

The ideas of report/thesis writing are usually attributable to all sources, which helped me a lot to compile
it. This is all due to the illuminated guidance of our teachers as they are the builders of my academic
carrier, all this could not have been done without their enlightened supervision and coaching.

I am also thankful to librarian of COMSTAS library.

Name: Hasaan Mahmood

CIIT/FA19-BPH-092/LHR
Name: Usman Jamil
CIIT/FA19-BPH-026/LHR

3
Study of Metal Doped Graphene Oxide

4
Contents
Chapter # 01............................................................................................................................................................. 10
Introduction..............................................................................................................................................................10
1 Introduction to Nanotechnology..........................................................................................................................11
1.1 Classification of Nanoparticles.........................................................................................................................11
1.1.1 Organic nanoparticles................................................................................................................................12
1.1.2 Inorganic Nanoparticles.............................................................................................................................12
1.1.3 Carbon Based Nanoparticles.....................................................................................................................15
1.2 Semiconductors Nanoparticles.........................................................................................................................15
1.2.1 Semiconductor Nanostructure Classifications...........................................................................................16
1.3 Application of Semiconductor Nanomaterials..................................................................................................20
1.4 Graphene..........................................................................................................................................................20
1.5 Graphene Oxide...............................................................................................................................................21
1.5.1 Graphene Oxide Uses................................................................................................................................21
1.5.2 Characterization........................................................................................................................................22
1.5.3 Surface properties......................................................................................................................................22
1.5.4 Applications..............................................................................................................................................22
1.5.5 Related materials.......................................................................................................................................23
1.5.6 Hydrogen storage......................................................................................................................................24
1.6 Graphene and Solar panels...............................................................................................................................24
1.7 Composite Nanoparticles.................................................................................................................................25
1.8 Cerium Nitrate..................................................................................................................................................26
1.8.1 Structure of Ce(NO3)3................................................................................................................................27
1.8.2 Properties of Cerium Nitrate......................................................................................................................28
1.8.3 Uses of Cerium Nitrate..............................................................................................................................30
Chapter # 02.........................................................................................................................................................32
Material and Synthesis Method..........................................................................................................................32
2 Synthesis Methods of NSMs...............................................................................................................................33
2.1 Bottom-up Method...........................................................................................................................................34
2.1.1 Chemical Vapor Deposition (CVD)..........................................................................................................34
2.1.2 Sol-gel technique.......................................................................................................................................34
2.1.3 Electrochemical Deposition Technique.....................................................................................................35
2.1.4 Pyrolysis....................................................................................................................................................36
2.1.5 Solvothermal method.................................................................................................................................37
2.1.6 Hydrothermal method................................................................................................................................37
2.2 Top-down Method............................................................................................................................................38
2.2.1 Mechanical Milling...................................................................................................................................38
5
 2.2.2 Laser Ablation...........................................................................................................................................38
2.2.3 Sputtering..................................................................................................................................................39
2.2.4 Thermal Decomposition............................................................................................................................40
2.3 Synthesis Procedure.........................................................................................................................................41
2.4 Characterizations Technique............................................................................................................................45
2.4.1 Photoluminescence....................................................................................................................................45
2.4.2 UV-Visible absorption spectroscopy.........................................................................................................49
Chapter # 03.........................................................................................................................................................53
Result and Analysis..............................................................................................................................................53
3.1 UV-visible absorption spectroscopy study.......................................................................................................54
3.2 Photoluminescence (PL) Spectroscopy Study................................................................................................59
Chapter # 04.........................................................................................................................................................63
References.............................................................................................................................................................63

6
List of Figures

Figure 1.1: Classification of Nanoparticles

Figure 1.2: Organic Nanoparticles

Figure 1.3: Inorganic Nanoparticles

Figure 1.4: Metal Nanoparticles

Figure 1.5: Metal Oxides Nanoparticles

Figure 1.6: Various carbon-based nanomaterials were reported to induce cytotoxicity

Figure 1.7: Semiconductor Nanoparticles

Figure 1.8: Classifications of Semiconductor Nanostructures

Figure 1.9: Typical scanning electron microscope (SEM) and transmission electron microscope
(TEM) image of different types of 0D NSMs

Figure 1.10: Typical SEM image of different types of 1D NSMs

Figure 1.11: Typical SEM image of different types of 2D NSMs

Figure 1.12: Typical SEM and TEM image of different kinds of 3D NSMs

Figure 1.13: Single layer of carbon atoms

Figure 1.14: Structure of Graphene and GO

Figure 1.15: Graphene

Figure 1.16: Composite Particles

Figure 1.17: Cerium Nitrate

Figure 1.18: Silver Nitrate

Figure 2.1: Top-down & Bottom-up techniques

Figure 2.2: Chemical Vapor Deposition (CVD)

Figure 2.3: Sol-gel technique

Figure 2.4: Electrochemical Deposition Technique

Figure 2.5: Flame Spray Pyrolysis

7
Figure 2.6: Solvothermal method

Figure 2.7: Hydrothermal method

Figure 2.8: Mechanical Milling

Figure 2.9: Laser Ablation

Figure 2.10: Sputtering

Figure 2.11: Thermal Decomposition

Figure 2.12: A schematic of an emission experiment

Figure 2.13: Graph of Emission Spectrum

Figure 2.14: Schematic representation of UV spectroscopy. UV, Ultraviolet

Figure 2.15: A simplified schematic of the main components in a UV-Vis spectrophotometer

Figure 3.1: Absorption Spectra of the Sample 1

Figure 3.1: Absorption Spectra of the Sample 2
Figure 3.1: Absorption Spectra of the Sample 3
Figure 3.4: Tauc Plot of Sample 1
Figure 3.4: Tauc Plot of Sample 2
Figure 3.4: Tauc Plot of Sample 3
Figure 3.7: PL spectra of the Samples

8
List of Tables

Table 2.1: Detail of sample and Precursor

Table 3.1: Band gap values of the samples calculated from Plank's equation and Tauc plots

9
Chapter # 01

Introduction

10
1 Introduction to Nanotechnology
Nanotechnology can be explained as an innovation that is executed at Nano scale and
furthermore has applications in genuine world. Nanotechnology acquired a lot of consideration. At
the nuclear and sub-atomic level, it tends to be characterized as the reorganizing of matter. At
Nano scale the properties of matter vary from properties at a bigger scale. The essential parts of
nanotechnology are the nanoparticles. [1] Nanoparticles are the particles that reaches somewhere in
the range of 1 and 100 nanometers (1-100nm) in size and are they are comprised of metal, carbon,
natural matter or metal oxides. The nanoparticles are different in size, structure and shape. Deeply,
rounded, flat, tapered, circular, winding, and so on or can be unpredictable and differ from 1-100
nm in size. With surface varieties the surface can be an unpredictable or uniform. Some
nanoparticles are crystalline or amorphous with single or multi crystal solids either free or
agglomerated. Nanoparticles are currently utilized in everything like from avionic business,
cooking vessel and drug delivery. Nanotechnology is the key for a perfect and manageable future.
[1]

1.1 Classification of Nanoparticles

Nanomaterials are generally classified in:

1. Organic nanoparticles
2. Inorganic nanoparticles
3. Carbon based nanoparticles

Figure 1.1: Classification of Nanoparticles

11
1.1.1 Organic nanoparticles
Polymerases, polymer conjugates, micelles, vesicles and polymeric nanoparticles. These
nanoparticles are made up of carbon. Most of organic nanoparticles include different organic and
polymeric molecule. Which restrict the nanoparticle to control size below certain values. These
nanoparticles are biodegradable, harmless and some are like hollow tube which is use as capsule.
These distinctive characteristics make them useful in drug delivery. [2]

Figure 1.2: Organic Nanoparticles

1.1.2 Inorganic Nanoparticles

Inorganic nanoparticles are particles that are not made of carbon. Quantum dots, magnetic ceramics
and polystyrene are examples of inorganic nanoparticles. Inorganic nanoparticles are generally
classified into metal nanoparticles metal oxides. [2]

Figure 1.3: Inorganic Nanoparticles

12
1.1.2.1 Metal Nanoparticles
Metal based nanoparticles are nanoparticles that have been synthesized from metals using
either constructive or destructive methods to achieve a nanometric size. The most commonly used
metals for nanoparticle synthesis are cadmium (Cd), zinc (Zn), iron (Fe), aluminum (Al), copper
(Cu), lead (Pb), cobalt (Co), silver (Ag), and gold (Au). These nanoparticles have characteristics
such as a size range of 10-100nm, an amorphous or crystalline structure, cylindrical and spherical
shapes, sensitivity to environmental factors such as sunlight, air, and heat, and surface
characteristics such as surface charge density and a high surface area to volume ratio, among other.
[2]

Figure 1.4: Metal Nanoparticles

1.1.2.2 Metal Oxides Nanoparticles

These nanoparticles are primarily created to enhance or modify the properties of their
respective metal-based nanoparticles. Iron nanoparticles (Fe) rapidly oxidize to iron oxide (Fe2O3)
in the presence of oxygen at ambient temperature, increasing their reactivity when compared to
metal-based iron nanoparticles. Metal oxides based nanoparticles such as titanium oxide (TiO2),
aluminum oxide (Al2O3), iron oxide (Fe2O3), silicon dioxide (SiO2), zinc oxide (ZnO), and cerium
oxide (CeO2) are routinely manufacture.

13
Figure 1.5: Metal Oxides Nanoparticles

14
1.1.3 Carbon Based Nanoparticles
These nanomaterials are generally carbon-based and come in the shape of hollow spheres,
ellipsoids, or tubes. Fullerenes are spherical and ellipsoidal carbon nanoparticles, while nanotubes
are cylindrical carbon nanomaterials. Improved films and coatings, stronger and lighter materials,
and uses in electronics are all possibilities for these particles. [3]

Figure 1.6: Various carbon-based nanomaterials were reported to induce cytotoxicity

1.2 Semiconductors Nanoparticles

Semiconductor nanoparticles have properties like those of metals and non-metals. They are
found in the periodic table in groups II-VI, III-V or IV-VI. These particles have wide band gaps,
which on tuning show different properties. They are utilized in photo catalysis, electronics
contrivances, photo-optics and dihydrogen monoxide splitting applications.

Semiconductor NPs are known to possess a wealth of quantum phenomena and show unique
size-dependent material properties. These materials possess properties between metals and
nonmetals and therefore they have found various applications in the literature. With a change in the
particle size, dramatic modifications to their electronic and optical properties take place due to the
three-dimensional (3D) quantum confinement of electrons and holes when the size of the particle
approaches the Bohr radius of an exciton. Semiconductor NPs are known to possess wide band
gaps and have hence shown significant changes in their properties with bandgap tuning. Therefore,
they are finding applications in photocatalysis, photo-optics, and electronic devices. They have
15
immense potential in water-splitting applications, due to their suitable bandgap and band edge
positions.

Some examples of semiconductor nanoparticles are GaN, GaP, InP, InAs from group III-V,
ZnO, ZnS, CdS, CdSe, CdTe are II-VI semiconductors and silicon and germanium emanate from
group IV. [4]

Figure 1.7: Semiconductor Nanoparticles

1.2.1 Semiconductor Nanostructure Classifications

This classification is based on the number of dimensions of a material that are larger than
the Nano scale (100 nm). When the relative dimension is commensurable with the de Broglie
wavelength, electrons in Nano crystalline materials are restricted to regions preserving one, two, or
three dimensions (Figure 1). The de Broglie wavelength of a free electron in a semiconductor like
CdSe is roughly 10 nm. 2D nanostructures are semiconductor crystal nanostructures with a z
direction less than this crucial value (thin film, layer structure, and quantum well). Nanostructures
are characterized as 1D when both the x and z dimensions are less than this critical value (linear
chain structure, quantum wire), and 2D when the y dimension is less than this critical value. [3]

16
 Figure 1.8: Classifications of Semiconductor Nanostructures

1.2.1.1 Nanostructures with zero dimensions (0D)

As a result, all dimensions in zero-dimensional (0D) nanomaterials are quantified on the
Nano scale (no dimensions are more sizably voluminous than 100 nm). Nanoparticles are the most
frequent 0D nanomaterials. Nanomaterials with all exterior dimensions between 1 and 100 nm are
referred to as zero-dimensional nanomaterials (0D). Quantum dots, for example, are semiconductor
Nano crystals with dimensions of less than 10 nm that operate as potential wells and are used in
electronics to confine electrons and openings. Full spheres, such as anatase titanium dioxide;
dendrimers, which are highly symmetrical, branched macromolecules; hollow spheres produced,
for example, of carbon(fullerenes), sodium tungsten, or gold; palladium cubes; zinc rings. [3]

Figure 1.9: Typical scanning electron microscope (SEM) and transmission electron microscope
(TEM) image of different types of 0D NSMs, which is synthesized by several research groups. (A)
Quantum dots, (B) nanoparticles arrays, (C) core–shell nanoparticles

1.2.1.2 Nanostructures in one dimension (1D)

17
 One dimension is outside the Nano scale in one-dimensional nanomaterials (1D).
Nanotubes, nanorods, and nanowires all fall within this category. At the Nano scale, one-
dimensional (1D) nanomaterials have two exterior dimensions, with the third often occurring at the
micro scale. Nano fibers, nanotubes, nanowires, and nanorods are examples of this. Inorganic
materials such as carbon, titanium dioxide, silicon dioxide, zirconium dioxide, aluminum oxide,
titanium Nitride, or platinum, as well as a vast array of polymers such as nylon, polyurethane,
polyolefin, polyethylene terephthalate, polycarbonate, polyvinyl alcohol, polylactic acid,
polystyrene, polyamide, and others, have been used to create Nano fibers. They can be spun into a
yarn or formed into a web for filtration applications. Nanotubes have a unique hollow cylindrical
crystalline form with atoms arranged in a hexagonal pattern. [3]

Figure 1.10: Typical SEM image of different types of 1D NSMs, which is synthesized by several
research groups. (A) Nanowires, (B) Nano rods, (C) Nano tubes, (D) Nano belts, Nano ribbons, and
(F) hierarchical nanostructures

1.2.1.3 Nanostructures in two dimensions (2D)

Two dimensions are outside the Nano scale in two-dimensional nanomaterials (2D).
Grapheme, Nano films, Nano layers, and Nano coatings are all members of this class, which have
plate-like structures. Thin films, Nano coatings, and Nano plates are examples of 2D
nanomaterials, which have only one exterior dimension at the Nano scale. Thin films are made up
of ceramic or metal coatings that are only a few atomic layers thick. They're generally used in
physics and electronics, such as to make electrical components with insulating or conductive
surfaces or to change the optical reflectance of surfaces. Polymers and composites are only a few
of the materials that can be used to make Nano coatings. In that instance, the goal will be to
improve the hardness, abrasion resistance, or both. [3]
18
 Figure 1.11: Typical SEM image of different types of 2D NSMs, which is synthesized by our and
several research groups.(A) Junctions (continuous islands), (B) branched structures, (C) Nano plates,
(D) Nano sheets, Nano walls, and (F) Nano disks

1.2.1.4 Nanostructures in three dimensions (3D)

Materials that are not confined to the Nano scale in any dimension are called three-
dimensional nanomaterials (3D). Bulk powders, nanoparticle dispersions, nanowire and nanotube
bundles, and multi-Nano layers all fall into this category. 3D nanomaterials, the final dimensional
category of nanomaterials, have internal Nano scale features but no outward dimension at the Nano
scale. Nano composites and nanostructured materials are examples of this. Nano composites are
multiphase solid materials featuring at least one Nano scale exterior dimension in at least one
phase. Nano fillers spread in a bulk matrix are commonly referred to as Nano composites. 0D, 1D,
and 2D nanomaterials can be used to create these Nano fillers. Polymers, ceramics, and metals can
all be used as matrices. [3]

Figure 1.12: Typical SEM and TEM image of different kinds of 3D NSMs, which is synthesized by our
and several research groups. (A) Nano balls (dendritic structures), (B) Nano coils, (C) Nano cones, (D)
Nano pillars, and Nano flowers

19
1.3 Application of Semiconductor Nanomaterials
When compared to their traditional bulk equivalents and molecular materials,
semiconductor nanostructures exhibit intriguing physical and chemical properties as well as
practical capabilities. The most appealing aspects of these materials are their narrow and intense
emission spectra, continuous absorption bands, chemical and photo bleaching stability, process
ability, and surface usefulness. An enormous number of publications on the production of
semiconductor nanoparticles have accompanied the rise of "Nano chemistry." The spatial quantum
confinement effect, for example, causes dramatic changes in semiconductor nanomaterial optical
characteristics. The optical and surface properties of semiconductors are greatly influenced by their
high dispersion (high surface-to-volume ratio), which is caused by both physical and chemical
features of the semiconductor. As a result, semiconductor nanomaterials have been the subject of
intense research for the past two decade. [4]

1.4 Graphene
Graphene is a material that is made of carbon atoms that are connected in a repeating
pattern of hexagons. Graphene is so thin; it's supposed to be two-dimensional. The direct-to-line to
the graph model, which makes it very useful functions, which will be the most powerful materials
in the world, as well as the simplest, the most senior and open. The graph has an infinite potential
for applications, we can say that in any line of business (for example, the electronics, medical,
aerospace, and more). [5]

Figure 1.13: Single layer of carbon atoms, which are the basis of many other materials. Graphite can
be used as a substance in a pencil, there arises a perfect graph. These materials are made from rolled
Graphene, and is used in a number of applications, starting from sports equipment to the life sciences

20
1.5 Graphene Oxide
Because of the expensive and relatively difficult to produce, considerable efforts are being
made to search for effective yet inexpensive ways to make and use the graph, the derivative, or
related to the materials. Graphene oxide (GO) is a material that is a monatomic layered material,
which are produced by the strong oxidation of graphite, which is cheap and plentiful. Graphene
oxide is an oxidized form of Graphene, imbued with the warmth of oxygen-containing groups. It is
intended to be easy to deal with, because it is spreading in the water (or other solvents) and can
also be used in order to make the graph. Graphene oxide is not a very good leader, but there are
processes in order to improve its mechanical properties. It is usually sold as a powder, is dispersed,
or the coated substrate. [5]

Figure 1.14: Structure of Graphene and GO

Graphene oxide is synthesized in the four main methods are: by Staudenmayer, Hoffmann,
Chest, and a Hammer. There are many variations of these two methods, with the continuous
research and improvement in order to achieve good results, and developments, as well as the
processes and procedures. The efficiency of the oxidation process is often estimated by the ratio
between the carbon monoxide (CO) to the graph of the oxygen. [5]

1.5.1 Graphene Oxide Uses

The Graphene oxide films can be obtained, we can say that of all of the substrates, and then
you become a leader. It is therefore particularly suitable for use in the production of transparent
conductive films, such as those used for flexible electronics, solar cells, chemical sensors, and
many others. The GO is also being studied as a substitute for tin oxide (ITO), and the batteries, and
touch screens. Graphene oxide has a large surface area so that it can be used as an electrode
material for batteries, capacitors, and solar cells. Graphene oxide is less expensive and easier to
produce than that of the graph and is therefore able to enter the mass-production and the time of
use.
21
 It is easy to mix different types of polymers and other materials, as well as improve the
properties of composite materials such as tensile strength, flexibility, electrical conductivity, and so
much more. Solid-shaped flakes of Graphene oxide attach to each other to form a thin, solid,
straight structure, which can be folded, wrinkled, and stretched. Such as Graphene-oxide structures,
which can be used in applications such as hydrogen storage, ion conductors, and the Nano filtration
membrane. Graphene oxide is in fluorescent lamps, which makes it particularly suitable for a
variety of medical applications. Bio-sensitivity, and to detect the presence of disease, drug carriers,
and anti-bacterial materials are just a few of the features that are available in the biomedical field.
[5]

1.5.2 Characterization
XRD, FTIR, flash drives, XPS, AFM, ASSURE, SEM/EDX, etc., are some of the
commonly used methods for the characterization of the GO samples. The experimental results of
the graphite /Graphene-oxide have been analyzed in great detail by the Ed. Because of the oxygen
distribution, the characteristics of the sheets and are polydisperse, the fractionation method can be
used to define a separate sheet of paper in the oxidation of the base. Also, the different areas of a
similar oxidation of the methods may have different characteristics due to the differences in the
treatment process, or quenching processes. [5]

1.5.3 Surface properties

You can also modify the surface of graphene oxide for the purpose of changing its
characteristics. Graphene oxide has unique finish, which gives it a very good surface-active
material, which stabilizes the different emulsion systems, Graphene oxide is left in the interface of
the emulsion system. [5]

1.5.4 Applications
1) Optical nonlinearity

The non-linear optical materials are of great importance for ultrafast photonics and
opto-electronics. Recently, the giant optical nonlinearity of graphene oxide (GO) has been
useful in a variety of applications. For example, navigate to the optical limitations that are
necessary in order to protect the sensitive equipment from laser damage. But the saturable
absorption can be used for pulse compression, the sleeping position and the q, the period of
time. In addition, the non-linear refraction (Kerr food, the effect is very essential, functionality,
including optical switching, signal recovery, and visual communication speed.

22
 One of the most interesting and unique features of the electrical and optical properties
can be dynamically improved by modifying the content of oxygen-containing groups with the
use of a chemical or physical reduction methods. The reception of the optical and raised in the
laser-induced reduction of the process due to the ever-increasing intensity of the laser radiation
are shown, and a variety of non-linear activity is detected in the four-step process, which may
serve as a promising solid-state material for non-functional units. It was demonstrated that
metal nanoparticles can significantly enhance the optical nonlinearity of Graphene oxide in the
incident as well. [5]

2) Coating

The optical transparent, multi-layer Graphene oxide films are resistant to dry
conditions. Under the influence of the water (or water vapor), the passing of the molecules
below a certain size. It consists of millions of pictures of stacks of barley and leaving the Nano-
scale images of the in-between. The closing of these Nano capillaries, by means of chemical
reduction of the iodo acid, it creates a film of the "reduced Graphene oxide" (r-GO), which is
completely independent of the gas, liquid, or harsh chemicals, with a thickness of 100 nm.
Glass, or copper plate covered with a single graph, the 'color' can be used as a container for
aggressive acids. The graphene-coated with plastic that can be used in pharmaceutical
packaging, in order to improve the shelf-life. [5]

1.5.5 Related materials

The dispersed Graphene oxide flakes can be managed through the dispersions (such as in
the production of a piece of paper) and compressed to produce an extremely strong piece of paper,
the graphene oxide.

Graphene oxide has been the use of DNA analysis in the app. In a large, flat surface area,
graphene oxide allows for the simultaneous induction of multiple DNA probes labeled with
different colors as to ensure the detection of multiple DNA targets by the same component. The
subsequent progress of the graphene oxide-based, DNA-based sensors can lead to a lot of cheap,
rapid, DNA-based analysis. Recently, as team of researchers from the University of L’Aquila
(Italy) and discovered a new wetting property of the graphene oxide, which was found in an ultra-
high vacuum up to 900 °C), which found a correlation between the chemical composition of the
surface of the surface free energy and its polar and the scattered subjects, giving reasons for the
wetting properties of graphene oxide and reduced graphene oxide. [5]

23
1.5.6 Hydrogen storage
Graphene oxide is also being studied for their use in hydrogen storage. Hydrogen molecules
can be stored between the functional groups based on the amount of oxygen available in each page.
With this, the hydrogen storage capacity can be further modified by modulating the inter-layer
distance between the bed sheets, as well as to make any changes and size. Research in the field of
metal in the decoration of the carbon precipitation, sorbents, in order to increase the energy of the
hydrogen, leading to the experiments of titanium and magnesium, which are anchored to the
hydroxyl groups, which make it possible to bind multiple hydrogen molecules. [5]

1.6 Graphene and Solar panels

The graph is composed of a single layer of carbon atoms that are connected by a repeating
pattern of hexagons. This is a 2-dimensional material with excellent properties, which means that it
can be referred to as a "miracle material". There is a very strong and almost completely transparent,
which is not entirely surprising, joints and flexibility. Graphene is made of carbon, which is good,
and it can be a relatively inexpensive material. The graph has a seemingly never-ending potential,
in order to improve the performance of existing products and inspire new ones.

Figure 1.15: Graphene

Solar cells require materials that are electrically conductive and transmit light which is
coming from the advantages of the superconductivity, and the level of transparency. The graph is
really a very good leader, but there are a lot of good in the collecting of electrical power produced
by the solar panels. Therefore, the researcher is looking for the appropriate way to change the
graph for this particular purpose. Graphene oxide (GO), for example, is not a leader, but it is more
transparent and better-collector charge, which can be used with solar panels.

The conductive indium tin oxide (ITO) is the use of a non-conductive layer of the glass, the
transparent electrodes of the majority of the organic solar cell, in order to achieve these goals, but,
to ME, is a rare, fragile, and there are solar panels are expensive. In many studies, the focus is on
24
the graph of the changing PUBLIC-transparent OPV film. Others are looking for a way to make
use of the graph in order to improve the overall performance of the solar cell devices, the foremost
of OPV, but also in the active layer of the electrodes, interfacial layer, and the electron acceptors.
[6]

1.7 Composite Nanoparticles

Composite nanoparticles as core/shell nanoparticles or surface modified nanoparticles may be
considered as a special type of Nano composites. When these nanoparticles contain an inorganic
core and an organic shell one may speak about hybrid nanoparticles. Nanoparticles such as
graphene, carbon nanotubes, molybdenum disulphide and tungsten disulphide are being used as
reinforcing agents to fabricate mechanically strong biodegradable polymeric Nano composites for
bone tissue engineering applications. Composite nanoparticles are advanced materials having
recently gained increasing attention due to their scientific and technological importance. They find
a wide variety of applications such as catalysts with huge activity and specificity, metal
semiconductor junctions, optical sensors, and modifiers of polymeric films for packaging. From a
scientific point of view the composition and the atomic order of the aggregates, in addition to size,
are pivotal factors in determining their properties and functionalities, while the Nano scale regime
confers to them structural and electronic degrees of freedom which are inaccessible to bulk
materials. The first indispensable stage to develop novel nanotechnologies is the preparation of
tailored composite nanostructures. Virtually all the possible physicochemical phenomena have
been employed to reach this objective allowing setting up a huge number of protocols each one
with its specific advantages and disadvantages. The aspects of novel preparation methods are
addressed in two manuscripts.

25
 Figure 1.16: Composite Particles

1.8 Cerium Nitrate

Cerium nitrate is a chemical compound with the formula Ce(NO 3)3. It is composed of
cerium (Ce) cations and nitrate (NO3-) anions. Cerium is a rare earth metal belonging to the
lanthanide series of elements.

Cerium nitrate is commonly found in the form of a hydrate, Ce(NO 3)3·6H2O, which means
it has six water molecules associated with each formula unit. The hydrated form is a crystalline
solid that is often white or colorless.

Cerium nitrate is soluble in water, and its solutions are acidic due to the presence of nitric
acid from the dissociation of the nitrate ions. It is commonly used as a source of cerium in various
chemical reactions, as well as in the production of cerium oxide (CeO 2), which is used in catalysts,
glass polishing, and as a component in fuel cells.

Ce represents the chemical symbol for cerium, which is a rare earth metal. Cerium is part of
the lanthanide series of elements and is known for its relatively high reactivity and unique
properties. (NO3)3 represents the nitrate ion, which is composed of one nitrogen atom (N) bonded
to three oxygen atoms (O). The subscript 3 indicates that there are three nitrate ions in the
compound.

26
 When cerium nitrate is formed, the cerium cations (Ce3+) combine with the nitrate anions
(NO3-) to create an electrically neutral compound. The overall charge of cerium nitrate is neutral
because the +3 charge of the cerium cations is balanced out by the -1 charge of each nitrate anion.

Cerium nitrate can exist in different forms, including an anhydrous (without water) form
and hydrated forms with varying degrees of water molecules associated with each formula unit. For
example, Ce(NO3)3·6H2O represents the hexahydrate form of cerium nitrate, which contains six
water molecules per formula unit.

Moreover, cerium nitrate plays a role in different industries such as electronics, ceramics,
and optics. It is involved in the preparation of cerium-based materials like cerium-doped phosphors
used in fluorescent lighting. Additionally, it serves as a precursor for synthesizing other cerium
compounds. [7]

Figure 1.17: Cerium Nitrate

1.8.1 Structure of Ce(NO3)3

An illustration describing the structure of the cerium nitrate molecule is provided below. It can be
observed that cerium has an oxidation number of 3 in this compound. [7]

27
 Figure 1.18: Silver Nitrate

1.8.2 Properties of Cerium Nitrate

Some important physical and chemical properties of silver nitrate are listed in this
subsection.

1.8.2.1 Physical Properties

The physical properties of cerium nitrate:

1. Cerium nitrate usually exists as a white crystalline solid. It may also appear as a white
powder or granules.

2. It is odorless.

3. Cerium nitrate is soluble in water, meaning it can readily dissolve in water to form an
aqueous solution.

4. The density of cerium nitrate varies depending on its form and concentration. The density
of the anhydrous form is approximately 4.3 g/cm³.

5. The melting point of anhydrous cerium nitrate is around 45-50°C (113-122°F). However, it
can also exist as hydrates, and their melting points may differ.

6. Cerium nitrate is hygroscopic, meaning it has a tendency to absorb moisture from the air.

7. Cerium nitrate is relatively stable under normal conditions. However, it may decompose at
high temperatures, releasing toxic nitrogen dioxide gas (NO2) and oxygen gas (O2).

28
 8. Cerium nitrate crystallizes in the monoclinic crystal system.

9. When cerium nitrate is dissolved in water, it forms an acidic solution due to the presence of
nitrate ions.

It's important to note that these properties are general characteristics, and specific forms or
hydrates of cerium nitrate may have slightly different physical properties. [7]

1.8.2.2 Chemical Properties

Some of the chemical properties of cerium nitrate:

1. Cerium nitrate can undergo redox reactions, where cerium changes its oxidation state.
Cerium can exist in the +3 oxidation state in cerium nitrate. It can be further oxidized to
cerium (IV) in the presence of strong oxidizing agents.

2. Cerium nitrate is highly soluble in water. When dissolved in water, it dissociates into
cerium ions (Ce3+) and nitrate ions (NO3-). The solubility of cerium nitrate is influenced by
factors such as temperature and concentration.

3. When cerium nitrate is dissolved in water, it forms an acidic solution due to the presence of
nitrate ions. The nitrate ions can release hydrogen ions (H +) in solution, contributing to the
acidity.

4. Cerium compounds, including cerium nitrate, exhibit catalytic properties. Cerium (IV)
compounds, derived from cerium nitrate, are commonly used as catalysts in various
chemical reactions, including oxidation and reduction reactions.

5. Cerium nitrate can react with bases to form cerium hydroxide. The nitrate ions can be
replaced by hydroxide ions (OH-) from the base, resulting in the formation of cerium
hydroxide and the corresponding nitrate salt of the base.

6. Cerium nitrate can decompose upon heating to release nitrogen dioxide gas (NO 2), oxygen
gas (O2), and nitrogen monoxide (NO). This decomposition reaction occurs at elevated
temperatures.

7. Cerium nitrate can form complexes with various ligands. These complexes can exhibit
different properties and have applications in fields such as coordination chemistry and
catalysis.

It's important to note that the chemical properties of cerium nitrate may vary depending on the
specific conditions and the form of the compound. Additionally, the reactivity and behavior of
29
cerium nitrate may differ when interacting with other substances or under specific reaction
conditions. [7]

1.8.3 Uses of Cerium Nitrate

Cerium nitrate (Ce(NO3)3) has several important uses in various industries and applications.
Some of the common uses of cerium nitrate include:

1. Cerium nitrate is widely used as a catalyst in various chemical reactions. Cerium (IV)
compounds derived from cerium nitrate, such as cerium (IV) oxide (CeO 2), exhibit
excellent redox properties and are utilized as catalysts in oxidation and reduction reactions.
They find applications in automotive catalysts, petroleum refining, and industrial chemical
processes.

2. Cerium nitrate is employed in the production of glass, particularly in the manufacture of

glasses with high refractive indices. By incorporating cerium compounds, such as cerium
(IV) oxide, into the glass composition, it can improve its optical properties, UV absorption,
and resistance to discoloration caused by sunlight. This makes it valuable in the production
of sunglasses, camera lenses, and other optical devices.

3. Cerium nitrate is utilized as a key component in glass polishing powders and abrasives.
Cerium oxide slurries, prepared from cerium nitrate, are applied to glass surfaces during
polishing processes to achieve a smooth and scratch-free finish. It is commonly used for the
polishing of optical lenses, flat glass, and precision glass products.

4. Cerium nitrate finds application in the ceramic industry as a dopant or additive to enhance
the properties of ceramics. Cerium compounds can improve the mechanical strength,
electrical conductivity, and thermal stability of ceramics. They are used in the production of
ceramic capacitors, solid oxide fuel cells, and other ceramic-based electronic components.

5. Cerium nitrate is employed in analytical chemistry as a reagent and standard for various
chemical analyses. It can be used for the determination of metals, such as uranium, through
precipitation reactions and complex formation. Cerium nitrate solutions can also be used in
redox titrations, where the cerium ions act as a titrant to determine the concentration of
other substances.

6. Cerium compounds, including cerium nitrate, have shown potential as flame retardants.
They can be incorporated into polymers and textiles to enhance their fire resistance and
reduce flammability.

30
Cerium nitrate is utilized in research laboratories and academic institutions for various
experimental purposes. Its unique chemical properties and versatile applications make it valuable
for studying catalysis, redox chemistry, materials science, and other fields of research. [7]

31
 Chapter # 02

Material and Synthesis

Method

32
2 Synthesis Methods of NSMs
Nanomaterials with regulated size, shape, dimensionality, and structure are synthesized using a
variety of methods. The two most common ways for fabricating nanomaterials are the "Top Down"
and "Bottom Up" approaches. Depending on the operation, reaction state, and protocols used, these
approaches are classified into several methodologies. [8]

 Top-down Techniques

Physical processes are used in this procedure, which involves the reduction of bulk materials
into Nano sized particles. It's also referred to as the destructive method. Milling with a machine.
Top-down procedures include nanolithography, laser ablation, sputtering, and thermal breakdown.
[8]

 Bottom-up Techniques

Bottom up, also known as constructive method, is a chemical strategy to building materials from
atoms to clusters to nanoparticles. The procedure that are used in this technique are Sol-gel,
spinning, chemical vapor deposition, pyrolysis, and biosynthesis are some of the techniques used.
[8]

Figure 2.2: Top-down & Bottom-up techniques

33
2.1 Bottom-up Method

2.1.1 Chemical Vapor Deposition (CVD)

It is a chemical process in which gaseous molecules on the surface of the substrate change into
solid material in the form of 0-D, 1-D, 2-D, and 3-D NSMs. CVD involves exposing the base
material to one or more vaporize sources, which react and breakdown on the substrate surface to
generate the desired deposit. The procedure is carried out in a low-pressure chamber that is sealed
off from the outside world. Medical gadgets, photovoltaic devices, automotive components, some
integrated circuits, and silicon wafers all benefit from CVD. [9]

Figure 2.2: Chemical Vapor Deposition (CVD)

2.1.2 Sol-gel technique

It is a wet chemical approach for gelation-based nanoparticle synthesis. Techniques of
precipitation and hydrothermal treatment, It is one of the simplest and most cost-effective methods
for producing metal oxides and oxide composites. Sol is a colloidal solution in which solid
particles (of various diameters) are disseminated in liquid and Gel is a solid molecule immersed in
a solvent. [8]

34
 Figure 2.3: Sol-gel technique

2.1.3 Electrochemical Deposition Technique

Electric current is utilized to deposit metallic coating (a composite layer nanostructure-
containing substance) onto a desired base material in the electrochemical deposition method (called
substrate). This approach uses a two- or three-electrode electrochemical setup. The anode
(sheet/rod coating metal) and cathode (the Meta to be coated) are put in liquid electrolyte
electrodes, which are coupled to the dc power supply, which applies a specific voltage between the
source and the work piece. Under the influence of the field, the source ionizes, and ions begin to
move towards the work piece. Ions begin to deposit on the work piece’s surface. As a result, a thin
coating is formed over time. [10]

35
 Figure 2.4: Electrochemical Deposition Technique

2.1.4 Pyrolysis
Pyrolysis is a process for producing nanoparticles that is extensively utilized. Pyrolysis is
the process of burning a precursor with flame. The precursor could be a liquid or a gas that is
injected into the furnace under high pressure through a small hole and burns. The nanoparticles are
then recovered by separating the products using air classification. Some furnaces, on the other
hand, use laser and plasma to generate high temperatures for easy evaporation. Pyrolysis is
advantageous since it is a low-cost, high-yielding and efficient process. [8]

Figure 2.5: Flame Spray Pyrolysis

36
2.1.5 Solvothermal method
This method of nanomaterial synthesis is quite similar to the hydrothermal approach, in
which the process is carried out in a metal autoclave, also known as a pressure vessel. The primary
difference is that in the solvothermal process, we employ organic solvents (e.g., methanol, ethanol,
ammonia, etc.) instead of water 1191. This process is commonly used to make metal oxide
nanostructures, semiconductors, ceramics, and polymers. [11]

Figure 2.6: Solvothermal method

2.1.6 Hydrothermal method

Single crystals (nanoparticles) are generated in a hydrothermal reactor (also known as an
autoclave) under high temperature aqueous solution and high vapor pressure levels in the
hydrothermal process. It's commonly utilized for producing high-quality nanomaterials while
preserving control over their content and form. [12]

37
 Figure 2.7: Hydrothermal method

2.2 Top-down Method

2.2.1 Mechanical Milling

Mechanical milling involves in reducing the size of components and post-annealing them in
an inert atmosphere using a high-energy mill. Nano composites can also be made by mechanical
milling. Mechanical milling is a sort of extreme plastic deformation that produces particle shape,
fracture produces particle size reduction, and cold-welding produces particle size growth. [12]

Figure 2.8: Mechanical Milling

2.2.2 Laser Ablation

Laser ablation is a green and simple approach to create metal nanoparticles without the use
of a surfactant or chemicals. The physical properties of the metal and the surrounding medium are
used to guide the laser ablation process. A laser beam interacts with a metal plate in this method,
38
causing heat to be generated and metal to be photo ionized. After that, the nanoparticle will be
discharged into the liquid and dispersed. [8]

Figure 2.9: Laser Ablation

2.2.3 Sputtering
The process of depositing a thin covering of nanoparticles and subsequently annealing them is
known as sputtering. A sputtering process involves exposing atoms or clusters of selected materials
to a highly focused and accelerated beam of inert gas such as helium or argon (7). The form and
size of nanoparticles are influenced by layer thickness, annealing temperature and time, substrate
type, and other parameters. [12]

Figure 2.10: Sputtering

39
2.2.4 Thermal Decomposition
Thermal breakdown is a process in which chemical in a substance break due to endothermic
chemical disintegration caused by heat. The temperature at which an element chemically
decomposes is referred to as decomposition temperature. Monodispersed nanoparticles can be
produced through thermal breakdown. [12]

Figure 2.11: Thermal Decomposition

40
 2.3 Synthesis Procedure

 Dissolve 0.05g of already prepared GO powder in 25ml distilled water.

 Dissolve 0.41g of cerium nitrate pressure in the same beaker.
 Let the solution stirrer for 1-hour at room temperature.
 Wash the sample several times DI water and centrifugation.
 The powder will be dried at 100°C to remove moisture from the sample.
 Similar procedure will be adopted for B and C sample using 0.84g and 1.21g concentration
of Ce-Nitrate.

Table 2.1: Detail of sample and Precursor

Distilled Graphene Weight of

Sample Water Oxide CeNO3 Stir Sample Sample
(ml) (g) (g) (hour) Type Color

A 25 0.05 0.41 1 Powder Black

B 25 0.05 0.84 1 Powder Black

C 25 0.05 1.21 1 Powder Black

2.3.1 FLOW CHART

41
SAMPLE 1

SAMPLE 2

42
SAMPLE 3

43
44
2.4 Characterizations Technique

2.4.1 Photoluminescence
Photoluminescence is the emission of light which is caused by the irradiation of a substance
with other light. The term embraces both fluorescence and phosphorescence, which differ in the
time after irradiation over which the luminescence occurs. The radiated light is often visible, but
can also be in the ultraviolet or infrared spectral region. Photo-excitation causes electrons within a
material to move into permissible excited states. When these electrons return to their equilibrium
states, the excess energy is released and may include the emission of light (a radiative process) or
may not (a nonradiative process). The energy of the emitted light (photoluminescence) relates to
the difference in energy levels between the two electron states involved in the transition between
the excited state and the equilibrium state. The quantity of the emitted light is related to the relative
contribution of the radiative process. [13]

Forms of Photoluminescence
 Fluorescence: When the chemical substrate undergoes internal energy transitions before
relaxing to its ground state by emitting photons, some of the absorbed energy is dissipated
so that the emitted light photons are of lower energy than those absorbed. One of such most

familiar phenomenon is fluorescence, which has a short lifetime (10- 8 to 10-4s). [13]
 Phosphorescence: Phosphorescence is a radiational transition, in which the absorbed energy
undergoes intersystem crossing into a state with a different spin multiplicity. The lifetime of

phosphorescence is usually from 10-4 - 10-2 s, much longer than that of Fluorescence.
Therefore, phosphorescence is even rarer than fluorescence, since a molecule in the triplet
state has a good chance of undergoing intersystem crossing to ground state before
phosphorescence can occur. [13]

45
Instrumentation
A schematic of an emission experiment is given below. An excitation wavelength is
selected by one monochromator, and luminescence is observed through a second monochromator,
usually positioned at 90° to the incident light to minimize the intensity of scattered light reaching
the detector. If the excitation wavelength is fixed and the emitted radiation is scanned, an emission
spectrum is produced. [14]

Figure 2.12: A schematic of an emission experiment

46
Excitation versus Emission Spectra
Photoluminescence spectra are recorded by measuring the intensity of emitted radiation as a
function of either the excitation wavelength or the emission wavelength. An excitation spectrum
is obtained by monitoring emission at a fixed wavelength while varying the excitation wavelength.
When corrected for variations in the source’s intensity and the detector’s response, a sample’s
excitation spectrum is nearly identical to its absorbance spectrum. The excitation spectrum
provides a convenient means for selecting the best excitation wavelength for a quantitative or
qualitative analysis. [14]

In an emission spectrum a fixed wavelength is used to excite the sample and the intensity
of emitted radiation is monitored as function of wavelength. Although a molecule has only a single
excitation spectrum, it has two emission spectra, one for fluorescence and one for
phosphorescence. Figure shows the UV absorption spectrum and the UV fluorescence emission
spectrum for tyrosine. [14]

Figure 2.13: Graph of Emission Spectrum

Applications
Apart from the detection of light emission patterns, photoluminescence spectroscopy is of great
significance in other fields of analysis, especially semiconductors.

 Band Gap Determination

Band gap is the energy difference between states in the conduction and valence
bands, of the radiative transition in semiconductors. The spectral distribution of PL from a
semiconductor can be analyzed to nondestructively determine the electronic band gap. This

47
 provides a means to quantify the elemental composition of compound semiconductor and is
vitally important material parameter influencing solar cell device efficiency. [15]

 Impurity Levels and Defect Detection

Radiative transitions in semiconductors involve localized defect levels. The

photoluminescence energy associated with these levels can be used to identify specific
defects, and the amount of photoluminescence can be used to determine their concentration.
The PL spectrum at low sample temperatures often reveals spectral peaks associated with
impurities contained within the host material. Fourier transform photoluminescence micro
spectroscopy, which is of high sensitivity, provides the potential to identify extremely low
concentrations of intentional and unintentional impurities that can strongly affect material
quality and device performance. [15]

 Recombination Mechanisms

The return to equilibrium, known as “recombination”, can involve both radiative and
nonradiative processes. The quantity of PL emitted from a material is directly related to the
relative amount of radiative and nonradiative recombination rates. Nonradiative rates are
typically associated with impurities and the amount of photoluminescence and its
dependence on the level of photo-excitation and temperature are directly related to the
dominant recombination process. Thus, analysis of photoluminescence can qualitatively
monitor changes in material quality as a function of growth and processing conditions and
help understand the underlying physics of the recombination mechanism. [15]

 Surface and Structure and Excited States

The widely used conventional methods such as XRD, IR and Raman spectroscopy
are very often not sensitive enough for supported oxide catalysts with low metal oxide
concentrations. Photoluminescence, however, is very sensitive to surface effects or
adsorbed species of semiconductor particles and thus can be used as a probe of electron-
hole surface processes. [15]

48
Limitations of Photoluminescence Spectroscopy
Very low concentrations of optical centers can be detected using photoluminescence, but it
is not generally a quantitative technique. The main scientific limitation of photoluminescence is
that many optical centers may have multiple excited states, which are not populated at low
temperature.

The disappearance of luminescence signal is another limitation of photoluminescence

spectroscopy. For example, in the characterization of photoluminescence centers of silicon no
sharp-line photoluminescence was observed when they had captured self-interstitials. [15]

2.4.2 UV-Visible absorption spectroscopy

Ultraviolet (UV) visible spectroscopy is used to characterize various kinds of organic,
inorganic, and biological materials. This technique counts the amount of light that enters a sample.
It serves as a tool for locating, describing, and researching nanoparticles as well as a diagram of
UV-visible spectroscopy. It explains how UV-visible spectroscopy is represented schematically.
Absorption spectroscopy is used to investigate the connection between absorbance spectra and
particle size distributions of quantum-sized Nano crystals. UV spectroscopy has been discovered to
be one of the best methods for analyzing the size, shape, and surface property of metal
nanoparticles in the form of colloidal dispersion systems. Figure 2.12 depicts the operation of UV-
visible spectroscopy. [16]

Figure 2.14: Schematic representation of UV spectroscopy. UV, Ultraviolet

49
UV spectroscopy is a type of absorption spectroscopy in which the molecule absorbs light in the
UV region (200-400 nm). The electrons are excited from their ground state to a higher energy state
as a result of the UV radiations being absorbed. The energy difference between the ground state
and the higher energy states and the energy of the UV light that is absorbed are equal. E = hv is the
formula for energy, where h is Planck's constant (h = 6.626 x 10 -34 J s), v is the frequency of the
radiation, and J represents the energy (SI units of J). The most preferred transition, in general, is
from the highest occupied to the lowest unoccupied molecular orbital. Such electron transfer
processes can occur in both inorganic and organic molecules (- * (pi to pi star transition)) as well
as transition metal ions (d-d transitions and ligand-to-metal or metal-to-ligand charge transfer
transitions). The UV (190-400 nm) and visible (400-800 nm) areas of electromagnetic radiation are
used in this absorption spectroscopy, which operates in the range 190 to 800 nm. It is also
sometimes referred to as electronic spectroscopy since the absorption of UV or visible radiation by
a molecule causes a transition between the molecule's electronic energy states.

UV spectroscopy obeys the Beer-Lambert law, which states that when a beam of
monochromatic light is passed through a solution of an absorbing substance, the rate of decrease of
intensity of the radiation with thickness of the absorbing solution is proportional to the incident
radiation as well as the concentration of the solution.

The expression of the Beer-Lambert law is:

A = log (I0/I) =ECL
where A is the absorbance, I0 is the intensity of light incident upon the sample cell, I is the
intensity of light leaving the sample cell, C is the molar concentration of the solute, L is the length
of the sample cell (cm), and E is the molar absorptivity.

From the Beer-Lambert law it is clear that the greater the number of molecules capable of
absorbing light of a given wavelength, the greater the extent of light absorption. This is the basic
principle of UV spectroscopy. [17]

How does a UV-Visible spectrophotometer work?

While there are many different types of UV-Visible spectrophotometers, let us look at the major
components shown in Figure 1 to acquire a better grasp of how they work.[10]

50
 Figure 2.15: A simplified schematic of the main components in a UV-Vis spectrophotometer

Applications
Some common applications of UV–VIS spectroscopy are briefly listed here:

 The absorption of a reactant or product at constant wavelength provides a means of monitoring

the progress of a chemical reaction. Clinical studies using indirect measurement of reaction is
characterized by enzymes can also be carried out.
 DNA or Deoxyribonucleic acids are involved in protein synthesis in living cells and preserve
genetic information. Changes in pH or heating can lead to denaturation with the resultant
increase in absorption at 260 nm. Monitoring absorption at this wavelength is useful for
denaturation monitoring.
 Appearance of additional peaks due to presence of impurities can help establish purity of
standard materials
 Absence or presence of functional groups results in absence of presence of their characteristic
absorption bands
 Identification and quantitative determination of polynuclear aromatic compounds
 Non – absorbing molecules can be estimated by combination with derivative forming
molecules that produce new spices with absorption characteristics in the UV – VIS region
 Quantitative estimation of ionic solutions of transition metals or complex forming ligands
 Versatility of UV-VIS spectroscopy has been adapted to detection in HPLC technique. It is the
most popular detection mode in HPLC for organic molecules.

The scope of applications of UV – VIS spectroscopy is fast expanding and new applications
are daily reported. The simplicity, accuracy and cost effectiveness contribute to its popularity in

51
areas such as pharmaceuticals, life sciences, foods, environmental studies, forensics and
mineralogy Today it is difficult to imagine a laboratory that is not equipped with a UV- Visible
spectrophotometer. [17]

52
 Chapter # 03

Result and Analysis

53
3.1 UV-visible absorption spectroscopy study

CeO2-GO-1

300.27 nm (n-transition C-O bond)

Absorbance(a.u)

399 nm -CeO2

300 350 400 450 500 550 600 650 700 750 800 850
Wavelength (nm)

Figure 3.1: Absorption Spectra of the Sample 1

54
 CeO2-GO-2
265 nm (n-transition C-O bond)
Absorbance(a.u)

CeO2

A b s orb a n c e (a .u )
406 nm -CeO 2

400 450 500 550

Wavelength (nm)

300 450 600 750

Wavelength(nm)

Figure 3.2: Absorption Spectra of the Sample 2

55
 Figure 3.3: Absorption Spectra of the Sample 3

The UV-visible absorption spectroscopy of the samples was recorded using PERKEN
ELMER lambda-750 UV-visible NIR spectrophotometer. The absorption spectra of the samples
are shown in Figure (3.1-3.6). However, with the increase of wave number, the intensity of UV–
Vis absorption decreases rapidly, and then tends to level-off. The direct band gap energy (Eg) for
the ceria nanostructure was determined by fitting the absorption data to the direct transition
equation. The direct band gaps of the nanostructures were determined by extrapolating the linear
region of the tauc plots (figure 3.4-3.6) calculated using famous Tauc equation given below.
1
(αhν ) = A (hν−E g ) ……………… (1)
n

Where α is the absorption coefficient, A is a constant, h is plank constant Eg is the band gap of the
bulk material, n is a constant whereas the value of n=1/2 for a direct band gap transition. The band

56
 hc
gap of CeO2 and GO was also separately calculated using Plank’s equation E g=
λ
.The
wavelength was obtained by extrapolating the linear region of the absorption region or the center of
the sharp absorption peak. However, with the increase of wave number, the intensity of UV–Vis
absorption decreases rapidly, and then tends to level-off. The direct band gap energy (Eg) for the
ceria nanostructure was determined by fitting the absorption data to the direct transition equation
[18]. It was observed that the band gap of CeO 2 nanostructures varied between 2.6-3.4 eV
calculated from both above mentioned methods and well matched with the reported literature [19].
The band gap of the CeO 2 did not show prominent variation after the formation of the
nanocomposite. The band gaps of GO calculated from both methods was also well matched with
the literature [20]. The values of the band gaps are listed in Table 3.1.

Figure 3.4: Tauc Plot of Sample 1

57
Figure 3.5: Tauc Plot of Sample 2

Figure 3.6: Tauc Plot of Sample 3

58
 Table 3.1: Band gap values of the samples calculated from Plank's equation and Tauc plots

Band gap Band gap Band gap

calculated calculated calculated
from Plank’s from Plank’s from Tauc
No. Sample Name equation equation plots
eV eV eV
CeO2 GO CeO2-GO

1 CeO2-GO-1 3.10 4.13 3.37

2 CeO2-GO-2 3.05 4.68 4.25

3 CeO2-GO-3 3.25 4.51 4.07

3.2 Photoluminescence (PL) Spectroscopy Study

The photoluminescence (PL) spectra of CeO2 with graphene oxide can be influenced by the
interaction between these two materials and the defect states introduced by graphene oxide.
However, it is important to note that the specific PL spectra of CeO2 with graphene oxide can vary
depending on the synthesis method, the graphene oxide concentration, and other experimental
conditions.

In general, the PL spectra of pure CeO2 typically exhibit a broad band centered around 440-
470 nm, which is attributed to the transition between the 5d band of cerium ions and the oxygen
vacancies in the CeO2 lattice [21]. This emission is known as the oxygen vacancy-related band.
CeO2 also shows a relatively weak emission peak at around 540-560 nm, known as the green band,
which is associated with transitions between the 5d band and the valence band.

When CeO2 is combined with graphene oxide, the PL spectra can be modified due to the
interaction between the two materials. The presence of graphene oxide can introduce additional
defect states or energy transfer processes, which may affect the emission properties of CeO 2. The
interaction between CeO2 and graphene oxide can lead to changes in the intensity and position of
the PL peaks.

It is worth mentioning that the PL spectra of CeO 2 with graphene oxide can also be
influenced by other factors such as the size and morphology of the CeO 2 nanoparticles, the degree
of graphene oxide reduction, and the presence of other dopants or impurities [22]. Therefore, the
59
specific PL characteristics of CeO2 with graphene oxide would need to be determined
experimentally for a given synthesis approach and experimental conditions.

2000
CeO2-GO-1
CeO2-GO-2
Photoluminiscence Intensity (a.u)

CeO2-GO-3
1500

1000

500

0
400 500 600 700 800 900 1000
Wavelength(nm)

Figure 3.7: PL spectra of the Samples

60
Chapter # 04

References

61
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