‏لقطة شاشة 2022-01-06 في 10.08.40 ص

Republic of Iraq
Ministry of Higher Education

and Scientific Research
University of Baghdad
College of Science
Department of physics
Synthesis and study the

spectroscopic and structural
properties of gold NPS incorporate
in to photocatalysit materials via sol-
gel method
A thesis
Submitted to the Committee of College of Science,
University of Baghdad
In Partial Fulfillment of the Requirements for the Degree of
Master of Science in
Physics
By
Saja Hamdan Hassan
B. Sc. 2018
Supervised By
Assistant Professor Dr. Sarmed salih mehdi
Alawadi
2021 AD 1443 AH
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Chapter One Theoretical Part
Abstract
In this work, gold nanoparticles have been prepared by chemical

reduction method according to reductant type which has been used
sodium citrate, and many parameters which influence the properties of
preparing nanoparticles have been studied . One of the most important
parameter is the reduction period; from the results can be concluded that
preparing a small particle size , short reduction period needs not more
than 15 minutes.
Then the Titanium dioxide (TiO2) was synthesized by sol-gel technique ,

then it was mixed with gold nanoparticle (AuNPs).The resulting mixture
is incorporated into Polymer (Poly Vinyle Alcohol) PVA host to
synthesize a hard disk used as a purification disk to treat the pollutant
water .The pollutant solution has been exposed to different light sources
to complete the photocatalyst process. In this respect, sunlight, UV lamp,
green laser, blue laser, and combined UV lamp and green laser are used
as a photocatalysis source. Experimental work has been conducted to
adjust the right mixture and the right combination of light sources.
Results were recorded according and showed a significant reduction in
the purification time with less than half the standard period when the
conventional purification process is used, and we used the mixing
AuNP /TiO2 to test the effect of anti-bacterial by adding to Escherichia
coli (Gram-negative) bacteria and exposed to different types of rays (UV
lamb, green laser, and combined source between UV lamp and green
laser) for photocatalysis , from experiment results we conclude that
combined source between UV lamp and green laser is the best method
of anti-bacterial because it is working to prevent the growth of
bacterial aggregates.
Then many techniques have been done to test the samples and study their
optical properties and internal structure, such as Atomic force
microscopic , Scanning electron microscopic , Energy dispersion x-ray,
X-ray diffraction ,Fourier transfer Infrared ,ultraviolet visible
spectroscopic tests. Finally , many conclusions and suggested future
works are listed.
List of Terms
AFM Atomic force microscope
AuNP Gold nanoparticles
EDX Energy-dispersive X-ray spectroscopy
FTIR Fourior Transformation at Infrared region
FWHM Full Width Half Maximum
HAuCl4 Gold hydrochloric Acid
NP Nano Particles
PVA Poly Vinyle Alcohol
SEM Scanning electron microscope
SPR Surface Plasmon resonance
TiO2 Titanium dioxide
UV Ultra Violet
V Volume of the solvent
V1 Volume before dilution
V2 Total volume after dilution
W Weight
XRD X-ray diffraction
wavelength
abs wavelength of peak absorbance maximum
Contents :
Title Page
Chapter one: Introduction and Theoretical Part
1-1 Introduction
1-2 The Importance of Nanoscale
1-3 Nobel Metals Nanoparticles
1-4 Synthesis of Nanoparticles 5

1-4-1 Dispersion Methods (Top down method) 5
1-4-2 Reduction Methods (bottom up method) 6
1-4-2-1 Turkevich method 7
1-4-2-2 chemical reduction method 8
1-5 Chemistry of chemical reduction method 9
1-5-1 Reduction 10
1-6 Sol-gel method 10

1-6-1The gel formation 12
1-6-2 Aging 12
1-6-3Drying 12
1-6-4Calcination/sintering 12
1-6-5 Sol-gel parameters 13
1-7 The gold nanoparticales 14
1-7-1Properties of Au NPs 15
1-8 Surface Plasmon Resonance in Metal Nanostructures
18
(SPR)
1-8-1 Interaction of Light with Noble Metal Nanoparticles 20
1-9 General applications of Gold nanoparticles: 21
1-10 Titanium Dioxide (TiO2) 22
1-10-1 Crystal structure of (TiO2) 23

1-11Photocatalysis 24
1-11-1TiO2 as photocatalyst 26
1-11-2Mechanism of UV/TiO2 photocatalysis 27
1-11-3 photocatalyic degradation 28
1-11-4 Oxidation-Reduction Reactions 29
1-12Congo red: 31
1-13Antibacterial Activity 32
1-13-1Escherichia coli 33
1-11 Aim of the work 33
1-12 Literature survey 33
Chapter Two : Experimental part

2-1 Introdection 38
2-2 Chemical Materials 39
2-3 Samples Preparation 40
2-3-1 Preparation of dye solutions 40
2-3-2 Preparation of Gold Nanoparticles by using chemical 41
reduction method (Sodium Citrate Reduction Method)
2-3-3 Preparation of Titanium Nanoparticles by using sol 41
gel techniques
2-3-4 Preparation of of AuNP+TiO2 by using sol gel 42
techniques
2-3-5Preparation of AuNP,Au+TiO2, TiO2 films 43
2-3-6 Preparation of PVA polymer 43
Preparation of purification disk 43

2- Antibacterial Activity Test of Au NPs +TiO2 44
2-5Photocatalytic activity (UV.-laser. Camber) 45
2-6 The measuring devices 46
2-6-1X-Ray Diffraction (XRD)Analysis 46

2-6-2Fourier-Transform Infrared Spectroscopy 47
Atomic force microscopy 47
2-6-4 Scanning Electron Microscopy 48
2-6-5 Energy Dispersive X-ray Diffraction 49
2-6-6 Spectroscopic Measurements (UV-Visible) 50
Chapter 3: Results and Discussion
3-1 Introduction 53
3-2 Characteristics of Samples 53
3-3The X-ray Diffraction Measurement 54

3-4FTIR Spectra of TiO2 Films 55
3-4-1FTIR Spectra of Au/TiO2 Films 56
3-5 Atomic Force Microscopic (AFM) Measurement 57
3-5 The Scanning Electron Microscope measurement results 63
3-5-1The SEM results of Au nanoparticles 63

3-5-2 The SEM results of TiO2,Au/TiO2 nanoparticles 67
3-6The Energy-dispersive X-ray spectroscopy (EDX) results 69

of TiO2
3-7 Absorption and Fluorescence Spectra 70
3-7-1 Absorption spectra for Gold Nanoparticles which is 71
prepared by chemical reduction method
3-8Absorption spectra and energy gap for TiO2 andAu+TiO2 72

nanoparticles
3-9Antibacterial activity 75
3- The Purification of Water 77
3-11Conclusions 90
3-12Future works 91
3-9 References 92
Chapter One
1-1 Introductions:
A bulk material has constant physical properties regardless of its

size, but at the nanoscale level, these properties change. Bulk materials
larger than one micrometer have a smaller percentage of atoms at the
surface than the total number of atoms of the material. For the smaller
particles , the percentage of surface atoms increases, leading to changes
in the physical and chemical behavior of the materials. A nanoparticle has
a size range between 1 to 100 nm. The unexpected physical and chemical
behaviour of matter occurs at the nanometer scale, paving the way for
several scientific exploitations, making nanoparticles a significant area
of scientific research [1].
The conversion of normal materials particles to nanoparticles results in

unique properties . The decrease in the size of the particales leads to a
dramatic increase in the number of atoms at the surface compared to the
number of atoms in the center of the crystal [2]. Another phenomenon is
observed for metal nanoparticles where a color change is caused by the
decrease in the size of particles [3,4].
The main important thing in the nano dimension is the nanopartacales'

properties are far different from than bulk scale properties. Nanoparticles
are being used in different fields including electrical, biological textile ,
and chemistry in which the shape and size of colloidal metal particles
play a crucial role in the different applications , including the preparation
of magnetic, electronic devices wound healing , anti-microbial gene
expression , and in the preparation of biocomposites. Noble metal
colloids have optical, catalytical, electromagnetic properties , which are
dependent on the size and shape of the particles. The synthesis processes
9
for the preparation of colloidal nanoparticles with controlled morphology

are crucial [105] .
1-2 The Importance of Nanoscale
The Greek word "nano" (meaning dwarf) refers to a reduction of

size, or time, by 10-9 meters [5]. Materials can be placed into broad
categories according to their size Macroscopic matter , which is visible
with the naked eye, atoms and most molecules are microscopic matter
with dimensions < 1nm, and mesoscopic particles, such as bacteria and
cells that have dimensions on the order of micron(s), can be observed
with optical microscopes. Nanoscoping materials fill the gap between the
microscopic and the mesoscopic which is another class of matter . The
1.1, where the bacterium is huge in comparison, as it is clearly illustrated

in the figure below [6] :-
Figure 1-1 Comparison of small particles sizes [12]
10
The nanoscale is a magical point on the dimensional scale: Structures in

the nanoscale (called nanostructures) are considered at the borderline of
the smallest of human-made devices and the most significant molecules
living systems. Our ability to control and manipulate nanostructures will
make it possible to exploit new physical, biological and chemical
properties of systems that are intermediate in size , between single atoms,
molecules and bulk materials[7].
1-3 Nobel Metals Nanoparticles :-
Nobel Metals Nanoparticles is considered one of the most

important types of Nanoparticles due to their different types of
applications in all branches of life. Noble metal nanoparticles show
brilliant colors due to the surface plasmon resonance absorption. The
surface Plasmon resonance absorption examination is part of a large
ongoing research field to investigate properties on the nanometer
scale.[8,9] The color of metal nanoparticles is found to depend on the
shape and size of the nanoparticle and dielectric constant of the
surrounding medium, leading to many studies on their synthesis and
applications[9]. Since antiquity ,the striking effect of nanoparticales on
color has been known when tiny metal particles were used to color glass
in church windows. Silver particles stained the glass yellow, while gold
and copper particles made ruby glass [10]. However the nature of these
colloids remained unclear, until Faraday explained how metal particles
affect the color of church windows [9]. He demonstrated the preparation
of gold colloids by reducing an aqueous solution of gold chloride with
phosphorus,his samples displayed a stable, ruby-red color, and some of
them are still preserved today in the Faraday Museum in London.
Nowadays numerous additional procedures exist for the preparation of
noble metal colloids. Methods have long been known to generate
11
beautifully colored glass for Cathedrals by adding gold to generate

burgundy, red, or purple glass.[11] Faraday[12] attributed this color to
very finely divided colloidal gold, or gold nanoparticles. As the size or
shape of the nanoparticle changes, the observed color also changes. Gold
nanospheres have a characteristic red color, The color is due to the
collective oscillation of the electrons in the conduction band, known as
the surface plasmon oscillation.
1- Synthesis of Nanoparticles
Nanoparticles are commonly synthesized using two strategies: top-

down and bottom-up. In the top-down approach, the bulk materials are
gradually broken down in to Nano-sized materials , whereas in the
bottom-up approach, atoms or molecules are assembled into molecular
structures in the nanometer range.
Figure 1-2: Schematic illustration of the preparative methods of nanoparticles.[105]
12
1-4-1 Dispersion Methods ( Top-down method)
The principle behind the top-down approach is to take a bulk piece

of the material and then modify it into the wanted nanostructure. Cutting,
grinding and etching are typical fabrication techniques, which have been
developed to work on the nanoscale. However, top-down has proven
unsuccessful for several purposes. One of the problems with the top-
down approach is the imperfection of the surface structure. Such defects
in the surface structure can significantly impact on physical properties
and surface chemistry of the nanostructure due to the high surface to
volume ratio. Even though there are problems connected to using a
top-down approach, this is the method of choice when highly complex
structures are made [6]. The Top- down method typically starting from
bulk, involves laser ablation [7], spark discharge [13],..etc.
1-4-2 Reduction Methods (bottom -up method)
The bottom-up approach, or self-assembly, refers to the

constructing a structure atom -by-atom, molecule-by-molecule or cluster-
by-cluster. Colloidal dispersions used in the synthesis of nanoparticles
are a good example of a bottom-up approach. The size of the
nanostructures, which can be obtained with a bottom-up approach, spans
the full nanoscale. An advantage of the bottom-up approach is the
better possibilities to obtain nanostructures with less defects and more
homogeneous chemical compositions. [105] In our thesis synthesis of
gold nanoparticles are done using a bottom-up approach. Using a
bottom-up approach , provides the opportunity to produce gold
nanoparticles within the nanoscale. Bottom-up also gives the advantage
of producing stable gold nanoparticles compared to gold nanoparticles
produced with a top-down approach, because the nanoparticles are
13
placed in defined crystalline structures. The stability of the nanoparticles

is important when their properties are to be examined and exploited. The
bottom-up method starting from atoms, include chemical [14],
electrochemical [15], sono - chemical [16], thermal and photochemical
reduction [17].
Figure 1-3: The top-down approach vs. the bottom-up approach [18].
Figure (1-4) The different strategies & method to synthesis Nanoparticles[ 19]
14
1-4-2-1Turkevich method
One of the most well-known techniques for synthesising of AuNPs
is based on the reduction of HAuCl4 by citrate in water, was first
designed by Turkevich in 1951.
In this method, the HAuCl4 solution is boiled, and the trisodium citrate
dihydrate is then rapidly added into the boiling solution under vigorous
stirring. After a few minutes, the color of the solution changes from light
yellow to wine red. This method results in AuNPs measuring about 20
nm in diameter. In this technique, citrate ions play a double role , as both
stabilizing and reducing agents.[106]
1-4-2-2 chemical reduction method
The chemical reduction method can be considered one of the most

important and most popular preparation techniques for to preparing Au
colloids [20]. The citrate synthesis(the Turkevich method ) has its name
from the sodium citrate reduction of chloroauric acid to give colloidal
gold performed by John Turkevich et . al. in 1951 [19].
This synthesis was developed to control the process by adjusting the

reaction conditions to present improved results with higher
monodispersity and better size control. Through these investigations, we
know these solutions are sensitive to the changes in PH, the ionic strength
of the medium, and the presence of other organic materials [21].
This preparation is simple, but great care must be exercised to make

stable and reproducible colloid. Solution temperature, concentrations of
the metal salt and reducing agent, reaction time determine the size and
shape of the nanoparticles generated [22]. Spheres, rods, cubes, disks,
wires, tubes, branched, triangular prisms and tetrahedral nanoparticles
15
have been generated in gold, silver and platinum with various reduction
techniques and capping materials [23].
Generally, the preparation of AuNPs by the chemical reduction method

includes two main parts: (1) reduction by agents, for instance ,
borohydrides , aminoboranes , formaldehyde, hydrazine, hydroxylamine,
polyols, citric and oxalic acids, sugars, hydrogen peroxide, carbon mon-
oxide, sulfites, hydrogen, acetylene, and ono electronic reducing agents
including electron-rich transition-metal sandwich complexes;(2)
stabilization using agents, for instance trisodium citrate dihydrate, sulfur
ligands (in particular thiolates), phosphorus ligands, oxygen-based
ligands, nitrogen-based ligands (including heterocyclic compounds),
dendrimers, polymers and surfactants (in particular, cetyltrim
thylammonium bromide (CTAB).
1-5 Chemistry of chemical reduction method :-
The chemical reduction method can be considered as one of the

most important and most popular preparation techniques for preparing Au
colloids. It is obtained by the chemical reduction of gold salts by sodium
citrate [24]. This preparation is simple, but great care must be exercised
to make stable and reproducible colloid. The purity of water and reagents,
cleanliness of the glassware are critical parameters. Solution temperature,
concentrations of the metal salt and reducing agent, reaction time
influences particle size. Controlling the size and shape of metal
nanoparticles remains a challenge [25].
In this project, the synthesis of gold , nanoparticles are done using

a bottom-up approach , Using this approach allows producing gold
nanoparticles within the nanoscale.
16
Bottom-up also gives the advantage of producing stable gold

nanoparticles compared to gold nanoparticles produced with a top-down
approach , because the nanoparticles are placed in defined crystalline
structures. The stability of the nanoparticles is essential when their
properties are to be examined and exploited. The following sections will
describe how gold nanoparticles are formed and how the growth can be
controlled.
1-5-1Reduction :-
The synthesis of gold nanoparticles in this project will be based on

a chemical method. The starting point of the synthesis is the production
of a (HAuCl4) solution. When gold is dissolved in a suitable solvent, it
splits into a positive gold ion (Au+) and a negative (Cl ). To turn the gold
ions into solid gold, the ions have to be reduced by receiving an electron
from a donator. A flowchart illustrating the reduction of the gold ions by
adding of an electron can be seen in figure(1-3) . The flowcharts of the
equation illustrate the reduction of (Au+) in a solution. After the gold
germ has been formed , it starts to grow and continue the growth until the
equilibrium between the final nanoparticles and the (Au+)of the solution
is reached. [26]
Figure 1-3 AuNP synthesis using the Turkevich method [26] .
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1-6 Sol-gel method

Sol-gel is a simple method that produces ceramics and glasses with
better purity than high -temperature conventional process. Prepared
materials have high homogeneity, small particle size and high surface
area. In addition, this method is low- temperature treatment and low cost.
Sol-gel has produced various compositions in several forms, such as
powders, fibers and coating [27].
The sol-gel process has become an attractive and intensive area of
research to prepare highly homogeneous glasses, ceramics, and
composites. There are many reports that show the structures and
properties of gels depend on the initial stage of polymerization in the
conventional hydrolytic sol-gel transformation. It is known that two
reactions occur during the sol-gel transition: hydrolysis and condensation
[8].
The general formula for hydrolysis reaction is:
M (OR) n + H2 n-1 (1-1)
Where (n) is the number of alkoxide groups that depend on the central
atom (M). In the case of (Ti) metal, the hydrolysis reaction is achieved
according to the equation [28]:
2O Hydrolysis reaction (1-2)
Condensation reaction produces (Ti O Ti) bonds plus by products of
alcohol or water [37]:
(1-3)
2O (1-4)
By carefully controlling the synthesis conditions, these reactions may
lead to a variety of structures , and different final states for the materials.
The sol-gel process involves the formation of sol followed by gel
formation. Sol is a liquid suspension of solid particles in the range of
nanometer obtained by hydrolysis and condensation of the precursor
18
such as metal alkoxide. The condensation of sol particles produces a three

- dimensional gel network.
There are some advantages of the sol-gel method , such as high purity of
products , homogeneity , low-temperature treatment , and control of
particle size in the nanometer range.
The four steps in sol-gel preparation are as follows [27]:
1-6-1The gel formation
Hydrolysis and condensation are both nucleophillic displacement
reactions, the reactivity of metal alkoxides depends on the type and
concentration of precursor. Also the amount of water used effects the
reaction rate and gel characteristics. The ratio of water: metal alkoxide
must be suitable, gelation would not an occur if there is not excess of
water. Temperature and solvent are also important parameters.
1-6-2Aging
The aging step is between gel formation and solvent removal. The
cross-different structural linked network of gel was formed and extensive
condensation causes the gel to
.
1-6-3Drying
The aged sol is allowed to dry. This will removes most of the alcohol and
water trapped in the matrix.
1-6-4Calcination/sintering
Heat treatment is necessary to burn off any residues of organic in
the gel. High temperature leads to sintering and consequently decreases in
surface area. This process causes the gel material to crystallize and
convert into different structural forms.
19
1-6-5 Sol-gel parameters

There are many important parameters involved in the sol-gel
process: The nature of precursors, the molar ratios between the reactants,
and the nature of the solvent, temperature and catalyst nature or pH .
The existence of acid catalyst, weakly- crosslinked polymer is formed
and easily aggregates after drying yielding low porosity microporous
structure, due to fast three- dimensional growth of the network and a not
complete condensation of the system .
If the base catalyst is used, discrete highly branched clusters are formed
and lead to a mesoporous structure after gelation, due to the slow three-
dimensional growth of the network .
The increase in R-molar ratio value promote the hydrolysis reaction by
increasing the number of sites to be hydrolyzed, and since water is the by-
product of the condensation reaction, so it retards the condensation and
causes complete hydrolysis of monomers before significant condensation
occurs. The gelation process will last more time . Which would be
favorable for forming a highly cross-linked product. Conversely , a
reduction of R- value increases the chance of condensation of only
partially hydrolyzed molecules, producing a less cross-linked product .
The temperature of the reaction system is one of the most important

factors that influence the time required to transfer sol to gel. It was known
that the temperature of the reaction , until it reaches the gel point, ranges
from room temperature (RT) to 80ºC . In most cases, sol-gel synthesis is
carried out at room temperature, though both the sol and gel formation
rates are known to increase with increasing temperature by accelerating
the kinetics of hydrolysis-condensation reactions and thus reducing the
gelling time [37].
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1-7 The gold nanoparticles
Gold is one of the most noble metal nanoparticales and the most
extensively investigated one due to its unique tunable optical properties,
which can be applied in various applications such as sensing, detecting,
and imaging applications . In the research filed , developing new
protocols for preparing functionalized gold nanoparticles and using them
for biosensing is presently an active research area. The synthesis
techniques of gold nanoparticles have been continuously evolving,
leading to improvements in the control over their size and shape. In
addition to sensing, gold nanoparticles are an attractive candidate for
photothermal therapeutic, diagnostic, and drug delivery applications [107,
108].
Au NPs are being used in biomedical applications, cellular imaging,
molecular diagnosis, targeted therapy, and as contrast agents, photo
thermal agents, and radio sensitizers. Their usefulness is because of their
stability and unique optical, electronic, magnetic, oxidation resistance,
and structural properties, in addition to their structure, composite, and
shape [28]. Noble metal NPs such as Au NPs have been a source of great
interest to their unusual physical properties, especially because of their
sharp Plasmon absorption peak on the visible region. The resonance
frequencies depend on particle shape and size , and are stable for a long
period of months.
Also, exhibited absorbance, which provided powerful detection tools

and promise to enhance the effectiveness of different targeted cancer
treatments. Therefore it's a source of great application interest because
of its novel electrical, optical, and catalyst properties[ 29]. Produced
NPs are generally characterized by their size, shape and disparity.
Preliminary characterization of the synthesized NPs is carried out using
21
UV Vis spectroscopy. Absorption between 200 and 800 nm are

commonly used for different metal and metal oxide NPs. Noble metal
NPs, especially Ag and Au NPs exhibit unique optical properties as their
Surface Plasmon Resonance (SPR) ranges from 400 to 450 nm and 500
550 nm respectively [30]. The SPR property of Au NPs is strongly
associated with their size, shape, and dielectric environment. Thus Au
NPs can be tuned according to practical need. Using UV-Vis
spectrophotometer, Au nano sphere 10 nm has a strong absorption around
520 nm, but the SPR red shifts to 530 nm for the Nano spheres at 40 nm.
Because of the strongly enhanced SPR, Au NPs scatter light intensely at
the SPR frequency, making them excellent candidates for optical imaging
and labeling of biological systems[31,32]. As the dielectric constant of
the medium surrounding NPs attributed to the surface Plasmon oscillation
frequency, the environment change could be sensed by monitoring SPR
red shift[33,34].
Because of their chemical stability and optical properties, Au NPs have

been at the center of interest in Nano medicine. Those nanostructures are
unique in supporting collective oscillations of free electrons (surface
Plasmon's), which produce a series of novel functionalities, including
strong resonant absorption, scattering, dramatic field enhancement,
optical guidance and imaging beyond the diffraction limit, and
ultrasensitive bio sensing[35].
1-7-1Properties of Au NPs
Optical Properties of Gold Nanoparticles the field of Au NPs

research has received tremendous attention due to their unique optical
properties. The unique optical properties of Au NPs arise from their size
confinement effect [104]. The size confinement effect on the Au NPs
22
provides new electronic and optical properties. A distinct feature of Au

NPs is the strong vibrant color of their colloidal solution caused by the
surface Plasmon resonance (SPR) absorption [104]. For the last two
decades, many research groups have studied the optical characteristic
features of Au NPs with various sizes and shapes. It is worth noting that
Au NPs were used as a coloring agent for staining ch dating
back to the seventeenth century. The stained glasses with Au NPs are ruby
red in color. Colloidal Au NPs sample is ruby red in color and Mie
explained this phenomenon theoretically by solving Maxwell's equation
for the absorption and scattering of electromagnetic radiation by spherical
particles [104]. Since then, the developed theory has been widely used to
calculate the particle extinction spectra if the material dielectric function
is known and the particle size is smaller than that of the wavelength of the
light. The origin of the light absorption by Au NPs is the coherent
oscillation of the conduction band electrons induced by interacting with
the electromagnetic field. This effect is generally known as Surface
Plasmon Resonance(SPR) and this effect is absent in the individual atoms
and bulk form [104].
The properties of Au NPs are different from its bulk form because bulk
gold is yellow solid and inert in nature , but Au NPs are wine red
solution and are reported to be anti-oxidant. Inter particle interactions and
assembly of Au NPs networks play a key role in the determination of
properties of these NPs. Au NPs exhibit different sizes ranging from 1 nm
to 100 nm and they also exhibit different shapes such as spherical, sub-
octahedral, decahedral, icosahedral multiple twined, multiple twined,
irregular shape, tetrahedral, Nano triangles, Nano prisms, hexagonal
platelets and Nano rods [38].
23
Figure (1-4) Different shapes of Au NPs. 101]
Au NPs have been commonly used in the radiation medicine field

as a radiant enhancer and improvement in radiation therapy because of
their ability in treatment delivery. Also, Au NPs have different
applications in nanotechnology as a platform for labeling of proteins and
bio molecular detection. The Au NPs are non-toxic particles with large
surface area and can be modified with other molecules, and used in the
biomedical field [39]. Because of their small size , they comprise an
unusual physical, chemical and optical property ,making them very
important for diagnostic, biological and biomedical purposes. Widely
used nanoparticles are, AuNPs, quantum dots and super paramagnetic
nanoparticles. Among these nanoparticles, Au NPs are one of the most
useful nanoparticles in medical, chemical and biological sciences [40].
1-8 Surface Plasmon Resonance in Metal Nanostructures

(SPR)
The metallic NP consists of an immobile positively charged atom

core and negatively charged free conduction electrons. Surface plasmons
(SPs) are collective electronic excitations near the surfaces of metallic
structures [41]. As represented in figure (1-6) with a specific energy of
24
incident light the displacement of the negative charges due to the

intensity of the electric field gives rise to polarization charges at the NP
surface and thus the system acts like an oscillator (it is opposite to a
relaxation system in bulk metallic materials). When the system is in
resonance with the incident EM-waves the effect is called surface
Plasmon resonance (SPR). The SPR can be observed by measuring the
absorption spectra of NPs [42]. The energy at which the electrons begin
to oscillate is specific, and any wavelength of light of that energy will be
absorbed. This absorption results in a color change far from the original
gold color of the base metal [17].
The oscillation frequency is determined by four factors: the density of

electrons, the effective electron mass, the shape and size of the charge
distribution. It is possible to observe this resonance by measuring the
absorption spectrum of the metal nanoparticle, the intensity of the fields
depends on the shape, size, and composition of the metal particle [43].
Figure 1-6 show the collective oscillation of free electrons under the effect of an
electromagnetic wave [21]
Localized surface plasmon resonance (LSPR) occurs when light of the

appropriate wavelength interacts with a small metal nanoparticle
25
compared with the light's wavelength . A resonance occurs that results in

an increase in extinction coefficient of the NP at the resonance
w
NPcomposition, size and shape [44].This increased intensity decreases
rapidly with distance about metal, and becomes insignificant within a few
diameters of the nanoparticle [45]. The electromagnetic field of plasmons
on the nanoparticles account for different types of surface phenomena ,
these surface phenomena have been exploited in spectroscopic techniques
for the last 25 years. The most well-known Plasmon- enhanced
spectroscopic techniques are surface-enhanced infrared absorption
(SEIRA), surface -enhanced Raman scattering (SERS) and surface-
enhanced fluorescence (SEF).
1-8-1 Interaction of Light with Noble Metal Nanoparticles
The intensity of light that propagates through a medium containing

small particles is reduced by scattering and absorption. The extinction of
the light beam is given by [65]:
I ( z) I exp( n ext z)..........................................(1 5)

where I(z) is the intensity of the incoming beam after a distance z, n0 the
number of particles per unit volume and ext the extinction cross section
of a single particle. It holds:
ext abs sca ..........................(1 6)

Where and : are the absorption and scattering cross- sections
of a single particle, respectively. As a consequence of their reduced
dimensions , the optical properties of such particles are dominated by a
coherent collective oscillation of their conduction band electrons. As a
26
result, the absorption cross- section, which scales with their volume, can
reach values several orders of magnitude larger than common organic
dye molecules. Such collective oscillation is known as surface Plasmon
resonance [65]. In general, the term cross-section is used in physics to
quantify the probability of interactions between particular particles, A
larger extinction cross- section means a higher probability of light being
absorbed or scattered by an optical species [8].
Figure 1-7 Plot of the ratio between the extinction and physical cross- sections versus
the physical size of optical species.[105]
Two aspects are notable from Figure (1- 7) First, the sizes of the four
types of optical species are all smaller than the wavelength of visible
light. Second, only plasmonic nanocrystals have extinction cross- sections
larger than their physical cross-sections. With the ratio between the
extinction and physical cross sections being larger than 1, plasmonic
nanocrystals can strongly concentrate electromagnetic fields in the
vicinity of their physical boundary. This feature enables them to function
as an intermediary to enhance the interactions between other optical
species and far-field light [65]. The metal nanoparticles have a much
stronger interaction with light than the fluorophore [9].
27
1-9 General applications of Gold nanoparticles:
As described previously, the nanoparticles synthesized from gold

have created great interest, because of their surface Plasmon resonance
[46].The oscillation plasmon frequency for gold is in the visible region
with strong plasmon resonance. Gold nanoparticles resist oxidation and
have a longer shelf life than silver particles. Gold nanoparticles, though
more expensive, have superior stability, uniform surfaces and a high
affinity for organic groups providing the possibility of biocompatible
nanoparticles for bioanalysis[47].
Gold nanoparticles are one of the promising products in the

nanotechnology industry. They represent an important class of materials
in the development of novel devices that can be used in various physical,
biological, biomedical and pharmaceutical applications [48]. Therefore
there are objects of active research in various applications such as: photo-
thermal therapy[48], surface-enhanced Raman spectroscopy[49],
biochemical sensors[50], nanophotonics devices[51], biology[52], carrier
systems for drug delivery[53] , biosensing in vivo or in vitro
diagnostic[54], solar cells[55], optoelectronic device[56], diabetic healing
[57], coolingsystem[58], antibacterial against[59], cancer treatment[60],
catalysis[61], sensor[62], imaging, sensing, biology and medicine[63],
inkjet-printer[64]... etc.
1-10 Titanium Dioxide (TiO2)

TiO2 is a versatile , functional material due to its many usual
properties such as high refraction index, hydrophilicity [66],
biocompatibility [67], semiconductivity, corrosion resistance, low cost,
widely available, non-toxic and physicochemically stable substance [67-
72], high photo degradation efficiency, high photocatalytic activity, and
28
other advantages [68, 69-70]. Because its high refractive index, it is used
as an anti-reflection coating in silicon solar cells and many thin-film
optical devices.
Titanium dioxide is considered an n-type semiconductor due to the
presence of oxygen vacancies in the lattice. These vacancies are formed
upon the release of two electrons and molecular oxygen, leaving a
positive (+2) oxide ion vacancy [71].
1-10-1 Crystal structure of (TiO2)

TiO2 exists in both crystalline and amorphous forms and mainly
exists in three crystalline polymorphs, namely, anatase, rutile and
brookite [73]. All three types are expressed using the same chemical
formula (TiO2); however, their crystal structures are different. Titanium
dioxide absorbs light having an energy level higher than the band gap,
and causes electrons to jump to the conduction band to create positive
holes in the valence band. Despite the band gap value is 3.0 eV for the
rutile type and 3.2 eV for the anatase type, they both absorb only
ultraviolet rays. However, the rutile type can absorb the slightly closer
rays to visible light rays [74].
Anatase is the metastable state, anatase and rutile are tetragonal in
structure , while the brookite structure is orthorhombic [75].
The anatase phase is more active than the two other phases due to
coner share structure. It was widely used as a photocatalyst for various
organic compounds . The anatase type exhibits higher photocatalytic
activity, one of the reasons for this is the difference in the energy
structure between the two types.
In the rutile structure , each octahedron is in contact with 10 neighbour
octahedrons (two sharing edge oxygen pairs and eight sharing corner
oxygen atoms) , while in the anatase structure each octahedron is in
29
contact with eight neighbours (four sharing an edge and four sharing a
corner) [76].
Figure (1-7): Crystalline structures of titanium dioxide: (a) Anatase, (b) Rutile and (c)
Brookite [77]
1-11Photocatalysis
Photocatalysis is defined as (the acceleration of a photoreaction by
the presence of a catalyst). A catalyst does not change in itself or is
consumed in the chemical reaction [78].
The chlorophyll of plants is a type of photocatalyst. Photocatalysis
compared to photosynthesis, in which chlorophyll captures sunlight to
turn water and carbon dioxide into oxygen and glucose , as shown in the
figure (1-8). Photocatalysis creates a strong oxidation agent to breakdown
any organic material to carbon dioxide and water in the presence of
photocatalyst, light and water [78].
30
Figure (1-8): TiO2 Photocatalytic process compared to Photosynthesis of plants

[78]
The function of the photocatalyst can be divided into five major
categories as follows [78]:
1. Purifying water.
2. Preventing contamination.
3. Anti-bacteria.
4. Deodorizing.
5. Purifying the air.
The performance of the catalyst is judged from its activities,
selectivity and stability. Many physical and chemical variables
influence these properties .Thus, each catalyst should be characterized
by the properties before use to know that each catalyst can be
compatible with different reactions [27].
TiO2 is the most importance photocatalyst materials because it can
oxidize many organic compounds into harmless compounds such as
carbon dioxide and water by using ultraviolet light and near -visible-
light [79].
31
1-11-1TiO2 as photocatalyst
Titanium dioxide is an excellent photocatalyst with applications in

various fields. From figure (1-9), it can be seen that (ZnO and TiO2) have
the potential to produce hydroxyl radicals [78]. In other words, the redox
potential of the (VB) hole must be sufficiently positive to generate
hydroxyl radicals (OH.) and that of the (CB) electron must be sufficiently
negative to generate superoxide radicals (O2.-) [71]. (TiO2 and ZnO)
exhibit favorable band-gap positions compared to the other materials. (Ti)
in (TiO2) is capable of reversibly changing its oxidation state from (+4) to
(+3), and hence, (TiO2) is more favored compared to the other materials
for photocatalyst [80] and because the main advantages of TiO2 are its
high chemical stability, its nontoxicity, its relatively low cost and its
highly oxidizing power .
The following three factors pertaining to the band structure of titanium
dioxide have the most significant effect on photocatalytic reactions:
(1) Band -gap energy.
(2) Position of the lowest point in the conduction band.
(3) Position of the highest point in the valence band in photocatalytic
reactions, the band gap energy principally determines which light
wavelength is most effective, and the position of the highest point in the
valence band is the main determinant of oxidative decomposing power of
photocatalyst [74].
32
Figure (1-9): Band positions of various semiconductors and relevant redox couples
[80]
1-11-2Mechanism of UV/TiO2 photocatalysis
The mechanism of UV photocatalysis involves the generation of

valence band (VB) holes (h+ /VB) and conduction band (CB) electrons (e-
/ CB), when a semiconductor photocatalyst absorbs a photon of energy
greater than or equal to its band gap ( Eg). The holes mediate the
oxidation of organic compounds by forming hydroxyl radicals , and the
electrons mediate radiation and oxidation reactions by forming
superoxide radicals.
The mechanism of photocatalytic oxidation on the surface of (TiO2) is
explained as follows [81, 82]:
(1) Charge-carrier generation.
(2) Charge-carrier trapping.
(3) Charge-carrier recombination.
(4) Photocatalytic degradation.
33
1-11-3Photocatalytic degradation
Photo-induced holes have been proposed to directly oxidize
adsorbed molecules or react with surface hydroxyl groups to produce
(OH·) radicals. The (OH·) radicals are strong oxidizing species reacting
with almost any organic compounds. They can react with organic
compounds by hydrogen abstraction, electrophilic addition and electron
transfer [81].
Figure (1-10): Mechanism of UV/TiO2 Photocatalysis[112]
The rate of degradation was found to obey (pseudo) first- order kinetics
and hence the rate constant for degradation, (k), was obtained from the
first-order plot of kinetic analysis according to (Langmuir Hinshelwood)
equation [83]:
Ln(A0/A)=kt (1-7)
Where (A0) is the initial absorbance, (A) is the absorbance after a time (t)
of dye degradation under UV irradiation, and (k) is the pseudo first- order
decay rate constant in (min.-1).
1-11-4 Oxidation-Reduction Reactions
TiO2 is a semiconductive material that , during illumination acts as

a strong oxidizing agent lowering the activation energy for the
34
decomposition of organic and inorganic compounds. The illumination of

the surface of the TiO2 induces the separation of two types of carriers: an
electron (e ) and a hole (h+). To produce these two carriers, sufficient
energy must be supplied by a photon to promote an electron (e ) from the
valence band to the conduction band, leaving a hole (h+) behind in the
valence band. The recombination of holes and electrons is relatively slow
in TiO2 compared to electrically conducting materials, i.e., metals where
the recombination occurs immediately.
+
TiO2 +e (1-8)
The required energy that has to be supplied by the photons for the
promotion of the electrons depends on the band gap for the specific
material. The band gap is the difference in energy between the highest
permitted energy level for the electron in the valence band and the lowest
permitted energy level in the conduction band. The band gap is the
minimum energy of light required to make the material electrically
conductive [39]. The band gap energy, Eg of TiO2 (anatase) is
approximately 3.195 eV, which approximately corresponds to photons
with a wave length of 388 nm [37].
The photoinduced hole can oxidize a donor molecule (D) adsorbed on the
TiO2 surface.
D + h+ .
D+ (1-9)
The electron in the conduction band can reduce an acceptor molecule (A).
.
A+e A (1-10)
The strong oxidation power of the hole enables a one-electron oxidation
step with water to produce a hydroxyl radical (OH.).
H2O + h+ OH. + H+ (1-11)
Oxygen can act as an electron acceptor, and be reduced by the promoted
electron in the conduction band to form a superoxide ion (O2 ). The
35
superoxide ion is a highly reactive particle, able to oxidize organic

materials. The oxidation-reduction process is shown in Fig. (1-11)[37].
O+e (5)
Figure (1-11): Photopromotion of an electron, reduction of oxygen and oxidation of

water
Figure (1-12): Oxidation mechanism [37]
Figure (1-13): Reduction mechanism [37]
36
1-12Congo red:
Congo red is the sodium salt 3,3 -([1,1 -biphenyl]-4,4 -diyl)bis(4-
aminonaphthalene-1-sulfonic acid), its formula is (C32H22N6Na2O6S2) and
its molecular weight is (696.66 g/mole) and it is considered a secondary
diazo dye because it contains two azo groups (-N=N-) figure(1-14), and
is highly soluble in water resulting from a colloidal solution, but its
solubility is better in the organic solvents such as ethanol, and it absorbs
max=497nm [84,85] . It has a strong
affinity to cellulose fibers. However, Congo red in the cellulose industries
(cotton textile, wood pulp & paper) was used for a long time as a textile
dye , It is an anionic acid dye used as a laboratory aid in testing for free
hydrochloric acid in gastric contents, in the diagnosis of amyloidosis[86].
Figure(1-14): The structure of Congo red[87].
1-13Antibacterial Activity
The worldwide escalation of bacterial resistance to conventional

medical practices is a serious threaten to human health.
Microorganisms have been developing resistance to many antibiotics
due to the indiscriminate use of antimicrobial drugs, increasing clinical
problems in the treatment of infections [88].Different studies
demonstrate their excellent antimicrobial properties and their application
as drug delivery vehicles because of -their advantages such as controlled
37
release, improved solubility, specific site targeted delivery, reduced side

effects and enhanced cellular internalization. Additional advantages of
Nano antimicrobial formulations include its protective effect toward
antimicrobial drugs and ability to overcome resistance in conjugation
with antibiotics [89]. With significant developments in the understanding
of Nano systems, research efforts are being concentrated on integrating
them with biology. Resistance of bacteria to bactericides and antibiotics is
a subject of immense interest because of the development of resistant
strains. Some antimicrobial agent's act , as an irritant and hence novel
ways of formulating biocidal materials is an upcoming field of attraction.
It has been shown that antimicrobial formulations in the form of NPs act
as an effective bactericidal material against Gram positive and Gram
negative bacteria. In vitro antibacterial activities of Au NPs have been
reported [90]. Among all metal NPs, Au NPs have been considered a
highly useful platform for the efficient drug delivery-carrier system
because of their facile and well-studied synthesis, easy surface
fictionalization and biocompatibility and less toxicity [91].
1-13-1Escherichia coli
E. coli is a Gram-negative, facultatively anaerobic, rod shaped

bacterium of the genus Escherichia that is commonly found in the lower
intestine of warm blooded organisms (endotherms) [92]. Uropathogenic
E. coli (UPEC) strains possess several virulence determinants that allow
them to colonize the urinary tract, avoid host defences , and cause
damage to the uroepithelium [93]. Most E. coli strains are harmless, but
some serotypes can cause serious food poisoning in their hosts, and are
occasionally responsible for product recalls due to food contamination
[94], the harmless strains are part of the normal flora of the gut , and can
38
benefit their hosts by producing vitamin K2 and preventing colonization

of the intestine with pathogenic bacteria [95].
1-11 Aim of the work
The work aims to synthesis the Au NPs and study the structures
and spectroscopic properties of Au NPs doped photo catalyst materials ,
such asTiO2 NP Analysis of result to identify the prepared samples in
suitable photocatalyst applications such as antibacterial activity and
Water Purification .
1-12 Literature survey
The solution of liquid gold has been first mentioned by Egyptian

and Chinese authors around 5th century BC. In fact , Ancients believed in
their metaphysical and healing powers[96].
Colloidal gold has been used since Ancient Roman times to colour glass
of intense shades of red, or mauve, depending on the concentration of
the metal. A fine example is the famous Lycurgus Cup in the British
Museum, dated 4th century AD[97]. Au colloids have been used in
medicine for all the middle ages believing in their curative properties for
various diseases [98].
Faraday was the first scientist to publish a scientific paper on gold

colloidal suspension and light-material interaction, published in 1857.
(The Bakerian Lecture). He was the first researcher to realize that the red
color of gold is due to gold nanoparticles in the solution, and he was the
first to use phosphorous as a reducing agent to reduce gold chloride to
gold nanospheres. [99] Many synthetic methods for colloidal metal
particles were developed in the early 20th century, both physical or
chemical, until the fundamental work of Turkevitch in 1951[100] .
39
In (2011), K Mani Rahulann et al. The spectral and nonlinear optical

properties of Au-doped TiO2 nanoparticles prepared by sol-gel are
investigated HRTEM studies reveal that the particles are 8 13 nm in
size, which is also confirmed by phase analysis using XRD The
nonlinear optical response of these samples using 5 ns laser pulses at 532
nm wavelength shows the existence of an effective three-photon
absorption behavior in the observed nonlinearity. It is found that the
optical limiting performances of these nanoparticles are greatly enhanced
with an increased volume ratio of Au. Increasing the concentration of the
Au dopant lowers the limiting threshold and enhances the optical limiting
performance.
In (2014), A. Ayati et al.gold nanoparticles (Au-NPs) have received great

attention due to their effectiveness in degrading and mineralizing organic
compounds progress in the field of photocatalytic oxidation of various

water pollutants such as toxic organic compounds by Au-NPs/TiO2 under
solar, visible, and UV irradiation. , are discussed. The support type,
loading amount, and particle size of deposited Au-NPs are the most
important Au/TiO2 catalytic activity parameter . Our study showed in
particular that the modification of TiO2, including semiconductor
coupling can increase the photoactivity of Au/TiO2. In contrast, doping
large gold NPs can mask or block the TiO2 active sites, reducing
photocatalytic activity. The optimized loading amount of Au-NP varied
for each experimental condition.
In the same year (2014), Muhammad Hussain et al. Au/TiO2

composites were synthesized . The obtained Au/TiO2 structures are
multifunctional An aqueous solution by Au/TiO2 structure was found to
be more efficient than that of pure TiO2 microspheres. The improved
40
photocatalytic activity of the Au/TiO2 structures is attributed to the stable

structure large surface area, and increase in charge separation due to the
strong electronic interaction between Au NPs and TiO2 microspheres
Au TiO2 structures provide a new platform for applications in
photocatalysis and the design of enzymeless biosensors.
In (2018),Hind Fadhel, Dr. Falah. It is found that Au NPs affected the

antibacterial activity. The inhibition zone increased with laser energy, Au
NPs were more effective against gram positive bacterial strains than the
gram negative bacteria.
In the same year (2018), Riyad H. Al Anbari et al. showed that

Prepared TiO2
crystallites were successfully synthesized by a conventional sol-gel
process . It was found that the structural and optical properties of TiO2
TiO2
showed excellent antibacterial activity against Staphylococcus aurousand
Pseudomonas aeruginosa .
In(2019) , Rafael Hernández1 et al.showed that synthesized Au TiO2

nanopowders, nanopowders Finally, it is possible to conclude that Au
atoms that are partially oxidized are filling oxygen vacancies of the TiO2
crystal structure in those powders consequently, this fact is producing a
compression in the anatase lattice, when thesame calcination temperature
450c was used to produce the powder.
In(2020) , Suresh Sagadevan et al. demonstrated the antimicrobial and

photocatalytic activity of Au/TiO2 nanohybrids formed by the two-step
synthesis involving the hydrothermal and seed growth method. The
41
physical characterization of the fabricated Au/TiO2 nanohybrids

exhibited an absorbance authenticating the successful doping, while the
diffraction pattern revealed superimposition of the anatase phase of TiO2
NPs with the crystal phase of AuNPs in the formation of Au/TiO2
nanohybrids. The susceptibility testing from antimicrobial studies
indicated that the nanohybrids exhibited significant inhibition of bacterial
and candidal growth in a synergistic manner that
detained candidal growth at all dosages. Also, the photocatalytic activity
of nanohybrids in degrading the MB dye in an aqueous solution was
studied.
42
Chapter Two Experimental part
Chapter Two
43
Introduction
This chapter describes the experimental procedure used to prepare

the gold nanoparticles using the chemical reduction method , study its
structural and spectroscopic properties of prepared nanoparticles , and
prepare photocatalyst materials (TiO2) using the sol-gel technique.
Study the structural and spectroscopy properties of AuNps doped

photocatalyst material (TiO2) . The measuring devices used to study the
structure of prepared gold nanoparticles, Au/TiO2 NP such as AFM, FE-
SEM, FTIR, X-ray diffraction ,and the absorption and fluorescence
spectra are described . Finally this chapter includes the UV-laser
camber design that is polluted with some natural dyes and the studies the
anti-bacterial effect of Au+TiO2 NP on some types of practical bacterial
applications in present work . Figure (2-1) clarifies the main practical
steps.
Figure( 2-1): Flow chart of practical steps in the present work
44
2-2 Chemical Materials
The precursors, solvents ,and other chemicals used in this work are
listed in the table (2-1).
Table (2-1): Specifications of the starting chemical materials
material Chemical formula vendor Purity
Gold hydrochloric HAuCl4 Philip Harris 99.9%

acid 393.83 (g/mol) chemical
companyBDH)
Sodium citrate Na3C6H5O7 Sigma-Aldrich 98%
258.06 (g/mol)
Polymer (Poly CH2CCH3COOCH3 fluka

Vinyle Alcohol) 100.07(g/mol) (Switzerland)
PVA
Ethyl alcohol C2H5OH - 99.9%
46.07 (g/mol)
Distilled water H2O - -
18 (g/mol)
Titanium Ti[OCH(CH3)2]4 - 99%

Isopropoxide (TIP) 284.215
nitrate acid HNO3
Congo red dye C32H22N6Na2O6S2 Aldrich -
45
2-3 Samples Preparation
2-3-1 Preparation of dye solutions
The dye solutions were prepared by dissolving the required amount

of the dye into the solvent; the weight of the dye was measured using a
mattler balance of 0.1mg sensitivity. The weight of the dye W (in g) was
calculated using the following equation
W=Mw -1)
where Mw is molecular weight of the dye (g/mole), V is the volume of

the solvent (ml), C is the molar concentration (mole/litter).
To prepare the diluted solutions, the following equation was used:
C1 V1 =C2 V2 -2)
where C1 is the high concentration [M], V1 is the volume before dilution

(l), C2 is a low concentration [M], and V2 is the total volume after
dilution (l).
2-3-2 Preparation of Gold Nanoparticles using chemical

reduction method
At first, a solution of ~5.0 x 10-3M HAuCl4 had been prepared by

dissolving the precursor of gold in water. (0.1699 g HAuCl4 in 100mL
deionizedH2O) and dilluted it. On another hand , 5% sodium citrate
solution was prepared (0.25g in 50mLof H2O). Then started to work as
the procedure below to synthesis gold nanoparticles by heating the diluted
solution of HAuCl4 until it begins to boil , then added 1mL of 0.5%
sodium citrate solution drop by drop , as soon as boiling commences.
The heating process had been continued until a color change was evident
46
(pale purple). After 5 minutes from the boiling point , the solution was
removed from the heater and continued to stir until it was cooled to room
temperature. All the above procedures have been repeated by variation
the reduction period from 4 minutes to 15 minutes ,that shown in figures
(2-2a)and (2-2b).
Figure 2-2a The HAuCl4 solution Figure2-2bThe.goldnanoparticles Which

is prepared by chemical
which is used in preparation of gold reduction method
2-3-3 Preparation Titanium Nanoparticles using sol gel

technique
Tio2 has been prepared by sol-gel technique as follow prepared by
two solutions :
The first solution consists of 1.25:1.25 ml of Titanium Isoprppoxide

(TIP) (is the main donor material) and Isopropanol , The second solution
consists of 50 ml distilled water with a PH = 3 (by adding a some drops
47
of HNO3), then added the first solution to the second solution and mixed
on the stirrer, until the color of the solution changed to white that is a
first indication to the creation of Tio2 NP .
2-3-4 Preparation of AuNP+TiO2 using sol- gel techniques:

Tio2 has been prepared by sol-gel technique as follow prepared by
two solutions :
The first solution consists of 1.25:1.25 ml of Titanium Isoprppoxide

(TIP) (is the main donor material) and Isopropanol , The second solution
consists of 50 ml distilled water with a PH = 3 (by adding a proper
amount of HNO3), then we added the first solution to the second solution
and mixed on the stirrer, until the color of the solution changed to white
that is a first indication to the creation of Tio2 NP then 2.5 ml of AuNP

was added, still on mixing in the stirrer 2 hours , as shows in the figure
(2-3).
distilled water
(Tip) + Isopropanol
with a PH = 3
mixing on the stirrer for
2h
AuNP TiO2
mixing in the stirrer 2 hour
AuNP+ TiO2 mixture
Figure (2-3): Schematic diagram showing the preparation of Au+ TiO2 nanoparticles
via sol-gel method
48
2-3-5Preparation of AuNP, AuNp +TiO2, TiO2films
Gold Nanoparticles were prepared with different reduction times

(4, 5, 6, 8, 10, 12, and 15) minutes in the same way mentioned
previously , Then the AuNp +TiO2 films were prepared by gratifying
centring method by putting a drop of gold or TiO2 colloidal on to
microscopic slide glass to get a film after a period of drying , in the
same way preparation , AuNp +TiO2, TiO2 films, then we use this films
in structure testing such as AFM and FE-SEM.
2-3-6 Preparation Polymer (Poly Vinyle Alcohol) PVA polymer
In order to prepare the PVA solution ,a 50 ml of distilled water

was heated to70 c° at this point 3.5gm from PVA powder was added to
the heated water step by step until the solution reached complete
dissolving after 1hour . Finally 5 PVA solution has been obtained
Preparation of purification disk
As mentioned before in section 2-3-4 Au+TiO2was prepared ,

then added 2.5ml of the mixture to 7.5 PVA . The final solution was
pured in a circular dish and let dry at a temperature of 70 c° to form a
hard disk used in the purification process.
Figure 2-4 the Purification disk
49
2- Antibacterial Activity Test of Au NPs +Tio2
A mixture of (Au NP /TiO2) was added to the Escherichia coli ( gram

negative ) bacteria as shown in figure (2-5)
Figure (2-5) A mixture (Au/TiO2 NP) added to the E. coli bacteria.
And then exposing the mixture (gold with titanium dioxide and E. coli
bacteria) to radiation (green laser ) for one hour it is important to motion
that the distance between the source and the ray is 15 cm ,Then activated
in a bacterial medium N_ Agar, The same process had been done by using
a UV lamp .
The same procedure was repeated to the mixture of AuNP+TiO2 +Ecoli

bacteria using a combing source UV lamp and green laser at the same
time to study its effect on E.coli bacteria activity, that shown in figure (2-
6).
50
Figure (2-6): Schematic diagram showing Antibacterial Activity Test.
2-5Photocatalytic activity (UV.-laser. Camber)
This camber (UV.-laser. Camber) has been designed as shown in

figure (2-7) , which consists of a black opaque box(height 60cm and
width 30 cm) and a UV lamp fitted at the top of the box inner side. A
laser source is inserted from the top of the box through a hole to provide
the irradiation source. The sample is placed as shown at the bottom of the
box.
51
Figure (2-7): UV.-laser. Camber
2-6 The measuring devices:
2-6-1X-Ray Diffraction (XRD)Analysis

In order to study the structural properties of the prepared samples,
the x-ray diffraction patterns were recorded by a Shimadzu 6000 X-Ray
diffract meter system. This system measures the diffraction intensity as a
function of Bragg's angle. The r with a
wavelength of 1.5406Å, current of 30mA and voltage of 40 kV.
-60
degrees with a speed of 4 deg /min. The inter-planer distance (dhkl) for
different planes was determined by using Bragg's law [102]:
n d sin -3)
Where n is the reflection order, is Bragg's angle, and is the
wavelength of X-ray radiation 1.54056Å.
52
The data obtained from the XRD measurements can be used to calculate
the crystallite size (C.S.) of the prepared samples according to Debye-
Scherer's formula [102]:
D= -4 )
Where is the wavelength of x-ray radiation 1.540 -

width at half-maximum of the peak on the XRD pattern, is the
diffraction angle, and 0.9 is a
2-6-2Fourier-Transform Infrared Spectroscopy

In order to recognize the bonding modes of the prepared
compounds, the FTIR measurements were done by FTIR spectrometer
(SHIMADZU FTIR-8400S) on KBr pellets containing the prepared
samples as shown in figure (2-8) . These measurements were performed
in the spectral range from 400 to 4000 cm .
Figure (2-8): Fourier-Transform Infrared Spectrometer.
Atomic force microscopy

In order to study the surface roughness and topography of the
prepared samples AFM was used. The atomic force microscope is one of
the types of scanning probe microscopes , where a topographic image of
53
the sample surface can be achieved based on the interactions between the
tip and the surface of the sample. It is characterized by imaging almost any
surface type, including polymers, ceramics, composites, glass, and
biological samples. AFM provides several advantages compared to
traditional microscopy techniques. AFMs probe the sample and perform
measurements in three dimensions on the surface of the sample, and hence
can present a three-dimensional image of the sample surface . This
provides a significant advantage over any microscope available
previously , as shows in the figure (2-9).
Figure (2-9): Atomic force microscope.
2-6-4 Scanning Electron Microscopy

The structural and morphological analysis of any thin film can be
performed using scanning electron microscopy (SEM). Scanning Electron
Microscope (SEM) uses a focused beam of high energy electrons to
generate various signals at the surface of the solid samples. The signals
that derive from the electron sample interactions reveal information about
54
the sample, including The texture of the sample, chemical composition,

crystalline structure, and orientation of materials that make up the
sample: secondary electrons and backscattered electrons are usually used
for imaging samples: Secondary electrons are most valuable to show
morphology and topography on samples, and backscattered electrons are
most valuable to demonstrate in composition in poly phase samples (i.e.,
for rapid phase discrimination), the electronic beam produces feature x-
ray of each element in the metal . Scanning electron microscopy analysis
is considered nondestructive , meaning that the x-rays generated by
electron interactions do not lead to volume loss of the sample , so it is
possible to analyses the same materials repeatedly .
2-6-5 Energy Dispersive X-ray Diffraction
Energy-dispersive x-ray spectroscopy (EDX) is an analytical

technique used for the compositional analysis of elements contained in
the materials. It is a technique used in conjunction with SEM to
determine the elemental composition of the final sample. Due to the
interactive between the primary electron beam and the sample
investigation ; the resalting signals include secondary electrons , Auger
electrons and characteristic x-rays. The characteristic X-ray is a
fingerprint of the element from which it is emitted. The emitted X-ray is
sensed and collected by the EDX detector. The EDX detector also
separates the characteristic X-rays of the different elements into different
energy spectra. The nomenclature of the emitted X-rays is dependent on
the inner shell on which the hole is located and the outer shell from which
the electron transit to fill the hole. The wavelengths of electrons depend
on the energy difference between the two shells involved in the electronic
transition. In other words, the elemental composition is directly
55
determined by measuring the energy of the emitted X-rays, the electron

beam is scanned pixel by pixel across a selected area of interest.
Specified in a general way, the brighter the color appears , the higher the
concentration of the specific element.
2-6-6 Spectroscopic Measurements (UV-Visible)
The prepared samples' transmission and absorption spectra were

recorded using a computer-controlled UV-visible spectrophotometer
(model K-MAC Spectra Academy SV-2100), as shown in figure (2-10) .
This measurement process could be precisely controlled by suitable
software installed on a personal computer. The light source can also be
replaced by a laser source to measure the irradiance of the sample. In this
case, the test quartz cell should have four transparent sides.
The following equation can calculate the energy bandgap (Eg) [102]:
=A( )n 2-5)
where is the absorption coefficient, A is a constant, and n is a given
value depending on the optical transition's nature , n may have values
1/2,2,3/2 and 3 corresponding to direct allowed , indirect allowed , direct
forbidden and indirect forbidden transitions respectively , with r=1/2.
When the momentum not conserved, the transition must be attended by a
photon, this case is an indirect transition, When the electron momentum
is conserved, the transition is direct .
56
Figure (2-10): (a)The computer-controlled spectrophotometer (K-MAC Spectra

Academy SV-2100) used for(b) the UV-visible spectroscopic measurements, the
internal design, and(c) the operating software front on PC.
57
Chapter Three Results and Discussion
Chapter Three
58
3-1 Introduction
In this chapter, the characterizations of the prepared samples were
determined by different parametric tests, such as X-ray diffraction (XRD)
patterns, Fourier-transform infrared spectroscopy (FTIR), scanning
electron microscopy (SEM), Energy-Dispersive X-ray (EDX)
Spectroscopy ,UV-Visible spectroscopy and Atomic Force Microscopic
(AFM). The spectroscopic studies for AuNPs are prepared by chemical
reduction method and study the absorption and fluorescence spectra. Also
, Preparation of Titanium dioxide by sol-gel technique and adding it to
gold colloidal and using it in applications as an anti-bacterial and water
purification.
3-2 Characteristics of gold nanoparticales :-

Figure (3-1) shows the image of the colloidal of gold nanoparticles
was prepared by hot chemical reduction method at different reduction
periods4, 5, 6, ,8,10,12 and 15 minutes.
Figure (3-1):Show the Gold Nanoparticles which is prepared by chemical

reduction method by variation the reduction time
From the image, it is clear that the prepared AuNp has a red color.
It is clear from the image that the color of colloidal is red which is the
59
main indicator of gold nanoparticle creations so it agrees with the global

results.[105]
3-3The X-ray Diffraction Measurement:-
X-ray diffraction is essential in the determination of the crystal

structure and the crystalline. The XRD patterns for TiO2 nanoparticles of
different sizes exhibited strong diffraction peaks indicating TiO2 in the
anatase phase, as shown figure (3-2).
Figure(3-2) X-ray diffraction spectrum of Au+TiO2NP prepared using chemical

reduction method and sol-gel techniques.
48.1°,56.8,63.1°, 70.1° and 75° were corresponding to (101),(103), (004),

(200), (211), (204), (116) and (215) crystal planes which are in
accordance with that of the standard spectrum [71]. Average crystallite
size of the composite estimated using equation (2-4).
60
Figure(3-3) The X-ray diffraction spectrum of Au+TiO2NP [109]
The reflections in the diffraction pattern can be indexed to the face-

centered cubic Au (JCPDS card No. 002-1095). The diffraction peaks at
2 values of41°and 64.61 and 77.91 can be indexed to the (200) and
(220) planes of the Au nanoparticles, respectively, indicating the
successful decoration/ formation of metallic Au NPs on the surface of
TiO2microspheres.This result was agreed with S.Zeng and K.Tye [109] .
3-4FTIR Spectra of TiO2

FTIR spectra, in the range 400 to 4000 cm-1, were recorded using the
spectrometer FTIR for the prepared sample as shown in Figure(3-4) The
structure al of TiO2 was clearly observed in this spectra for prepared
sample. The band assigned to Ti-O stretching vibration was observed at
around 503 and 586 422 -O-Ti
bonds in the TiO2 lattice. The peaks at around 3444.87 and 1631
are due to the stretching and bending vibration of the OH group in water
molecules [114, 115].
61
Figure (3-4) The FTIR spectrum for TiO2
3-4-1FTIR Spectra of Au/TiO2
The FTIR spectrum shown in figure (3-5) is recorded for Au/ TiO2
water molecules. The structural characteristics of TiO2 are also observed

through the absorption bands at around 478.35
On the other side, the intensity of bands at 3417.86cm-1 and 1627.92
cm-1 shift towards higher wavenumbers after Au adding, indicating the
formation of Au TiO2 composite [19]. The insertion of Au into the host
lattice of TiO2 should result in the downward shift of the peak.
62
Figure (3-5) The FTIR spectra for Au/TiO2
3-5 Atomic Force Microscopic (AFM) Measurement:-

Gold Nanoparticles grain size determination was carried out with
AFM test. The solution of gold nanoparticles was coated using spin
coating technique or gravity cintering technique and then tested by AFM.
The results show that the average Grain size was variated inside the
nanoscale (1-100nm). The results of AFM test for AuNP 4min sample
was produced with average roughness of 4.828 nm, and a root mean
square value of .266nm, as shown in figure (3-6).
63
Figure (3-6):shows the AFM result for AuNP 4min
The results of AFM test for AuNP 5min sample was produced with
average roughness of 9.312nm and root mean square value of 15.7nm, as
shown in figure (3-7).
average roughness of 7.441 nm and root mean square value of 10.99nm,
as shown in figure (3-8).
64
65
Figure (3-11): shows the AFM resalt AuNP12min
66
Figure (3-12): shows the AFM resalt AuNP15min
Table (3-1) Reduction time and Grains size (nm)
Reduction time (minute) Grains size (nm)

4 47.57
5 75.07
6 64.79
8 75.25
The results in a table (3-1) show that when the reduction time increases,
the grain size increases.
67
The results of AFM test for TiO2 sample was produced with average
roughness of 4.328 nm and a root mean square value of 9.041nm, as
shown in figure (3-13).
Figure (3-13): shows the AFM resalt Tio2 NP
The results of AFM test for AuNP+TiO2 sample was produced with
Figure (3-14) shows the AFM resalt Au+Tio2 NP

68
Table (3-2) Material and Grains size (nm)
material Grains size (nm)

TiO2
Au+TiO2
The results in a table (3-2) show that when the reduction time increases,
the grain size increases.
3-6 The Scanning Electron Microscope measurement
3-6-1The SEM results of Au nanoparticles :

The SEM results for gold nanoparticles which are prepared by the
chemical reduction method by changing the reduction time from the
boiling point. By carefully searching the SEM images, it is possible to
observe that the gold nanoparticles are spherical with a semi-uniform
distribution and by having a more focused magnification power it is
possible to see that the particle size reaches from 13.5 nm to 26.8 nm. it is
possible to see that the size of the particle is 13.5nm to 22.33 nm with
uniform particles distributed inside the gold clusters that for the case of
4minutes as a reduction time, at the case 5min the size of the particle is
18.3nm to 21.5 nm , at the case 6min the size of the particle is 20.58nm to
21.8 nm, at the case 8min the size of the particle is 22.1nm to 23.6 nm, at
the case 10min the size of the particle is 22.4nm to 23.8 nm, at the case
12min the size of the particle is 23.1nm to 25.5 nm, Finally and at the
case15min the size of the particle is 24.2 to 26.8 nm .
A cursory glance at the images shows that the gold nanoparticles tend to
aggregate in the form spherical with a semi-uniform distribution and that
the particle diffusion within this pool is uniform and the particle size is
approximately constant within the 20-30 nm range.
69
Figure(3-15) show the SEM image with magnification force = 50 kx of AuNP which
had been prepared using 4 minutes as a reduction period
had been prepared using 5minutes as a reduction period
70
71
had been prepared using12 minutes as a reduction period
72
had been prepared using 15minutes as a reduction period
All these result's will be listed in table 3-3

Table (3-3) The Reduction time and AuNP particle size
Time (minute) The range of Particle size (nm)
4min
5min
6min
8min 22.1-23.6
10min 22.4-23.8
12min 23.1 -25.5
15min 24.2-26.8
The results in table (3-3) show that when the reduction time increases, the
particle size increases.
73
3-6-2 The SEM results of TiO2, Au/TiO2 nanoparticles :
Now the SEM results for TiO2 nanoparticles were prepared by

sol-gel techniques to be shown and discussed . By looking carefully at
the SEM images it is possible to observe that TiO2 are spherical with a
semi-uniform distribution . By having a more focused magnification
power, it is possible to see that the particle size reaches from 23.8 nm to
26.3 nm, shown in figure(3-22).
Figure(3-22) show the SEM image with magnification force = 50 kx of TiO2NP which
had been prepared using the sol- gel technique
While the SEM results for Au+TiO2 nanoparticles were prepared by

sol-gel techniques be shown and discussed . By looking carefully at the
SEM images , it is possible to observe that the gold nanoparticales are
spherical with a semi-uniform distribution . By having a more focused
74
magnification power , it is possible to see that the particle size reaches

form 30.8 nm to 47.3 nm, shown in figure (3-23).
Figure(3-23) The SEM picture for Au/TiO2NP prepared by chemical reduction method and sol-gel
techniques.
All these result's will be listed in table 3-4

Table (3-4) The material and AuNP / TiO2particle size
material The range of Particle size (nm)
TiO2 23.8-26.3
Au/TiO2 30.8-47.3
The results in table (3-4) show that when the reduction time increases, the
particle size increases.
3-7 The Energy-dispersive X-ray spectroscopy (EDX) results

of TiO2 :-
Figure(3-24) shows the EDX results for Au+TiO2NP, mixture . From the
EDX spectrum, the existence of gold with 26.88% percentage was
75
clearly seen and presence of Ti with 0.53% percentage. An amount of

72.59 for oxygen and 0.53 % for Titanium as it has been shown in figure
(3-24) & table (3-5).
Figure (3-24)shows the EDX result of Au+TiO2NP which had been prepared by
chemical reduction method and sol gel method
Table (3-5) Percentages of each element as recorded by the EDX
Element Line Int W% A%
O ka 132.3 72.59 96.85
Ti ka 1.6 0.53 0.24
Au ka 1.3 26.88 2.91
3-8 Absorption and Fluorescence Spectra
The absorption and fluorescence spectra are recorded for all

prepared samples as a function of , varied parameter to reach the
optimum conditions for preparing gold nanoparticles and to study the
mixing with Tio2.
76
3-8-1 Absorption spectra of Gold Nanoparticles which is

prepared by chemical reduction method :-
Figure 3-25 shows the effect of varying the reduction period on
surface Plasmon spectra of AuNP. From the first sight to these curves
,the maximum peak absorption was variated between 518 - 52 nm.
Through careful consideration to figure 3-25 one can notice that the
behavior is somewhat unregularly from 4-5-6 minutes as a reduction
time except in the case of the 8-10 -12and 15-minutes there is a apparent
behaviour of increasing absorption intensity with increasing the reduction
period and the maximum peak intensity was a bout 522nm.This increase
in absorption intensity may be due to increasing the concentration of
AuNP in colloidal with increasing the reduction period and this behaviour
agrees with Beer Lamberts law. All these behaviours are illustrated in
figure 3-25and in table 3-6.
77
Figure(3-25) The total absorption spectra of AuNP prepared by the hot reduction
method
Table (3-6)The values of the peak position of AuNP which had been prepared by
variation the reduction periods
Time day Peak position/Time of redaction (minute)

reduction
time
Initially
1day
7day
day
30day
3-8-2 Absorption spectra and energy gap for TiO2

&Au+TiO2 nanoparticles :-
The UV-visible absorption spectrum of TiO2 sample ,prepared by

sol gel technique in a range of 300-600nm, is illustrated in figure (3-
26).
78
Figure (3-26): shows the absorption spectrum for TiO2 nanoparticles prepared by
sol- gel techniques , the maximum peak absorbance occurred at 369.5 nm.
The maximum peak absorbance occurred at 369.5 nm.
Figure 3-27 gives an approximation of the energy for this direct allowed
band gap which is determined and equal to 3ev .
Figure (3-27): shows energy band gap for TiO2 NP
79
The UV-visible absorption spectrum of Au+ TiO2 sample in the range of

300-600nm is illustrated in figure (3-28).
Figure (3-28): shows the absorption spectrum for Au +Tio2 nanoparticles prepared by
hot chemical reduction method and sol- gel techniques
While the maximum peak absorbance occurred at 465.8 nm.
Figure 3-29 gives an approximation of the energy for this direct allowed
band gap which is determined and equal to 2.9ev .
Figure (3-29): shows the absorption spectrum for Au +TiO2 nanoparticles prepared by
hot chemical reduction method and sol- gel techniques .

80
3-9Antibacterial effect
The antibacterial effect of Au /TiO2 NPs was tested on E.coli

bacteria by exposing it to different irradiation source such as (UV lamp,
green laser, UVlamb with a green laser ,and combined source green laser
and UVlamp). Figure (3-30) reveals the zone of inhibition of Au NPs on
bacteria strains, in which that Au /TiO2 NPs exhibited a higher effect on
E. coli. When growing the mixture consisting of gold, titanium dioxide,
and E. coli(Gram-positive) inside nutrient agar and waiting for 24 hours,
it proved highly effective as an anti-bacterial .
Figure (3-30): Au /TiO2 NPs with bacteria E.coli .
After 24 hours of culture, we note that the effectiveness of the

added Au NP / TiO2 mixture does not lead to the growth of bacteria in the
dish that was exposed to ultraviolet radiation, and compared to the dishes
before treatment, we note the activity of the material against bacteria. The
81
same way of processing but used green laser and combined source
between UV lamp and green laser. When using a green laser, notice the
growth of few groups of bacteria ,but when used a combined source
between UV lamp and the green laser does not lead to the growth of
bacteria in the dish .We note the activity of the material against
bacteria.That lead us to important conclusion that the TiO2 and Au must
be effect us to an important conclusion that the TiO2 and Au must be
affected together to get a high anti-bacterial effect because using a
combined source leads to complete absorption inside Au/TiO2 mixture .
UV will be absorbed from TiO2 and green laser will be absorbed from
AuNP .Guide to the health of our conclusion , when green laser had been
used as a single exposure irradiation source, no anti bicameral effect was
observed.
Figure (3-31): Au /TiO2 NPs with bacteria E.coli .
3- The Purification of Water
The water Purification is the second application in thesis , after

preparing the purification disc , Now will discuss the purification process,
82
as mentioned before that AuNP/TiO2 in PVA disk had been immersed

inside dilluted Cong red dye solution and it has exposed to different light
rays such as sun light ,UV lamp , green laser , blue laser and combined
source between UV lamp and green laser for all using source its
absorption spectra had been examined with a time intervals
(30,60,90,120,150,and 180)minutes except at the case of combined
source the absorption spectrum had been examined with a time internals
(10,20,30,40,50,60and 70) minutes, the pollutant water has been
purificated after 180 minutes at the case of sunlight and UV source while
it had been purificated after 70 minutes at the case of combine
source, that the main result in work where as the purification period has
been reduced from 180 to 70 minutes at the case of combined source if it
compared with single photocatalyst source such as sunlight and UV
source of noteworthy at the case of using laser a lonely such as green or
blue laser the pollutant solution didn't purificate .
An explanation of the purification method carried out in this work is that

the increase in the intensity of the incident light (through a combined
source ) led to the acceleration of the purification process of the Congo
red dye. The increase in the light intensity increases the number of
incident photons on the photocatalyst's valence band. It promotes more
electrons to the conduction band, which increases the number of released
hydroxyl radicals. Then, the reaction rates will be increased. In addition
to that using a combined source leads to jointly participation of TiO2 &
AuNP in purification process because of UV source has a resonance
absorption band gap with TiO2NP &green laser has a resonance band gap
with AuNP .Absorption spectra of Congo red dye with different light
source are shown in Figures (3-34,3-35, 3-36, 3-37,3-38,3-39,3-40,3-
41,3-42,3-43,3-44,3-45,3-46, 3-47 ,and 3-48).
83
Figure3- 2Degradation mechanism of Congo red
The mechanism of Vis photocatalysis involves the generation of

valence band (VB) holes (h+ /VB) and conduction band (CB) electrons
(e-/ CB) when a semiconductor photocatalyst absorbs a photon of energy
greater than or equal to its band
oxidation of organic compounds by forming hydroxyl radicals , and the
84
electrons mediate reduction and oxidation by forming superoxide

radicals[113].
Figure(3-33)Mechanism of UV+Vis/Au+TiO2 photocatalysis[113]
Figure ( 4) The peaks of absorbance with wave length for Combined source between UV lamp and green
laser
85
Figure (3-35) The peak of absorbance intensity for Combined source between UV lamp and green laser
Figure (3-36) The dye during the purification stage of Combined source between UV lamp and green
laser
86
Table (3-7)The absorbance and intensity peaks of Combined source between UV

lamp and green laser
Time (min) Absorbance Intensity
0 0.3 1
10 0.125 0.41
20 0.11 0.36
30 0.08 0.26
40 0.07 0.23
50 0.06 0.2
60 0.04 0.13
70 0.01 0.03
Figure (3-37) The peaks absorbance with wave length of the sunlight source
87
Figure (3-38) The peak of absorbance Intensity for the sunlight
Figure (3-39) The dye during the purification stage of the sun light source
88
Table (3-8)The absorbance and intensity peaks of the sunlight source

0 0.3 1
30
0.124 0.41
60
0.118 0.39
90
0.11 0.36
120
0.1 0.33
150
0.074 0.24
180
0.05 0.16
Figure (3-40) The peaks absorbance with wave length of UV lamp source
89
Figure (3-41) The peak of absorbance intensity for UVlamp source
Figure (3-42) The dye during the purification stage of the UVlamp source
90
Table (3-9)The absorbance and intensity peaks of the UVlamp source
0 0.3 1
30
0.25 0.83
60
0.24 0.8
90
0.23 0.76
120
0.22 0.73
135
0.19 0.63
180
0.15 0.5
Figure (3-43) The peak absorbance with wave length of the blue laser source
91
Figure (3-44) The peak of absorbance intensity for the blue laser source
Figure (3-45) The dye during the purification stage blue laser source
92
Table (3- )The absorbance and intensity peaks of blue laser source

0 0.3 1
30
0.295 0.98
60
0.24 0.8
90
0.22 0.73
120
0.21 0.7
150
0.19 0.63
180
0.17 0.56
Figure (3-46) The peaks absorbance with wave length of the green laser source
93
Figure (3-47) The peak absorbance intensity of the green laser source
Figure (3-48) The dye during the purification stage of the green Laser Source
94
Table (3- )The absorbance and intensity peaks of the green laser source
0 0.3 1
30
0.29 0.96
60
0.25 0.83
90
0.21 0.7
120
0.15 0.5
150
0.14 0.46
180
0.06 0.2
95
3-11 Conclusions
Some points from this work can be concluded :
1- In the case of preparing gold nanoparticles by the chemical

reduction method , a short reduction period will be needed to
obtain a smallest particle size.
2- A hard disk used in the purification process consists of
AuNP/TiO2 , and PVA could not be used more than just once in
the purification process .
3- That combined source between UV and green laser showed a
significant reduction in the purification time with less than half the
standard period when the conventional purification process is
used.
4- Using AuNP/TiO2 mixing to study the antibacterial effect ,we
conclude that combined source between UV and green laser as
irradiation source is the best method to achieve the highest
percentage of antibacterial effect . Because they are working to
prevent the growth of bacterial aggregates .
96
3-12Recommendations for Future Works
The following works are suggested for future studies:
1-Synthesis another photocatalyst material such as ZnO mixed with gold

nanoparticles , and using it in applications as an anti-bacterial and water
purification.
2-Using another method to prepare nanoparticles such as AgNP mixing

it with TiO2 or ZnO, and studying its photocatalyst activity .
3-Using a purification disk with other dyes .
4- Using another method, such as the sputtering pulse laser deposition

PLD, to synthesis of TiO2.
97
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Republic of Iraq

Ministry of Higher Education

Synthesis and study the

In this work, gold nanoparticles have been prepared by chemical

Then the Titanium dioxide (TiO2) was synthesized by sol-gel technique ,

1-4 Synthesis of Nanoparticles 5

1-5 Chemistry of chemical reduction method 9

1-6 Sol-gel method 10

1-10-1 Crystal structure of (TiO2) 23

Chapter Two : Experimental part

Preparation of purification disk 43

2-5Photocatalytic activity (UV.-laser. Camber) 45

2-6 The measuring devices 46

2-6-1X-Ray Diffraction (XRD)Analysis 46

3-3The X-ray Diffraction Measurement 54

3-5-1The SEM results of Au nanoparticles 63

3-6The Energy-dispersive X-ray spectroscopy (EDX) results 69

3-8Absorption spectra and energy gap for TiO2 andAu+TiO2 72

A bulk material has constant physical properties regardless of its

The conversion of normal materials particles to nanoparticles results in

The main important thing in the nano dimension is the nanopartacales'

for the preparation of colloidal nanoparticles with controlled morphology

1-2 The Importance of Nanoscale

The Greek word "nano" (meaning dwarf) refers to a reduction of

1.1, where the bacterium is huge in comparison, as it is clearly illustrated

Figure 1-1 Comparison of small particles sizes [12]

The nanoscale is a magical point on the dimensional scale: Structures in

1-3 Nobel Metals Nanoparticles :-

Nobel Metals Nanoparticles is considered one of the most

beautifully colored glass for Cathedrals by adding gold to generate

Nanoparticles are commonly synthesized using two strategies: top-

Figure 1-2: Schematic illustration of the preparative methods of nanoparticles.[105]

1-4-1 Dispersion Methods ( Top-down method)

The principle behind the top-down approach is to take a bulk piece

1-4-2 Reduction Methods (bottom -up method)

The bottom-up approach, or self-assembly, refers to the

placed in defined crystalline structures. The stability of the nanoparticles

1-4-2-2 chemical reduction method

The chemical reduction method can be considered one of the most

This synthesis was developed to control the process by adjusting the

This preparation is simple, but great care must be exercised to make

Generally, the preparation of AuNPs by the chemical reduction method

1-5 Chemistry of chemical reduction method :-

The chemical reduction method can be considered as one of the

In this project, the synthesis of gold , nanoparticles are done using

Bottom-up also gives the advantage of producing stable gold

The synthesis of gold nanoparticles in this project will be based on

Figure 1-3 AuNP synthesis using the Turkevich method [26] .

1-6 Sol-gel method

such as metal alkoxide. The condensation of sol particles produces a three

1-6-5 Sol-gel parameters

The temperature of the reaction system is one of the most important

1-7 The gold nanoparticles

Also, exhibited absorbance, which provided powerful detection tools

UV Vis spectroscopy. Absorption between 200 and 800 nm are

Because of their chemical stability and optical properties, Au NPs have

Optical Properties of Gold Nanoparticles the field of Au NPs

provides new electronic and optical properties. A distinct feature of Au