SYNTHESIS AND CHARACTERISATION OF Mn DOPED TiO2

NANOPARTICLES FOR ANTIMICROBIAL APPLICATION

Dissertation submitted to the Department of Physics,

PSG College of Arts and Science (Autonomous), Affiliated to Bharathiar University,
in partial fulfillment of the requirements for the award of the Degree of

MASTER OF SCIENCE IN PHYSICS

Submitted by
SHANMUGHA PRIYA G
18MPH021

Under the guidance of

Dr. ELANGO.M M.Sc., M.Phil ., PGDCA., Ph.D.
ASSISTANT PROFESSOR IN PHYSICS

DEPARTMENT OF PHYSICS
PSG COLLEGE OF ARTS & SCIENCE
College with Potential for Excellence
(Status awarded by the UGC)
An Autonomous college - Affiliated to Bharathiar University
Re-Accredited with A Grade by NAAC (Third Cycle)
An ISO 9001:2008 certified institution
Coimbatore - 641014.
JUNE-2020

1
 DECLARATION

I,SHANMUGHA PRIYA G (18MPH021) hereby declare that the dissertation, entitled

“STRUCTURAL PROPERTIES OF Mn DOPED TiO2 NANOPARTICLES FOR
ANTIMICROBIAL APPLICATION” submitted to the PSG College of Arts & Science, in partial
fulfilment of the requirements for the award of the degree of Master of Science in Physics is a record of
original work done by me during the period 2019– 2020, under the guidance of Dr. ELANGO.M M.Sc.,
M.Phil., PGDCA., Ph.D. ASSISTANT PROFESSOR in Physics, Department of Physics at PSG College
of Arts & Science, Coimbatore-641 014.

Place: Coimbatore
Date:
Signature of the candidate

Name of student: SHANMUGHA PRIYA G

Roll No. : 18MPH021

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 CERTIFICATE
This is to certify that the dissertation entitled “STRUCTURAL PROPERTIES OF Mn DOPED TiO2
NANOPARTICLES FOR ANTIMICROBIAL APPLICATION” submitted to the Bharathiar
University, in partial fulfilment of the requirements for the award of the degree of MASTER OF
SCIENCE IN PHYSICS is a record of original work done by SHANMUGH PRIYA G (18MPH021)
during the period 2019-2020 of her study in the Department of Physics, PSG College of Arts and Science,
Coimbatore-641 014, under my supervision and guidance and the dissertation has not formed the basis for
the award of any Degree / Diploma / Fellowship / Associate ship or other similar title to any candidate of
any university.

Place: Coimbatore.
Date:

Head of the Department Faculty Guide

Submitted for the Viva Voce Examination held on 13-04-2015 in the Department of Physics, PSG
College of Arts and Science, Coimbatore-641014.

Internal Examiner External Examiner

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 ACKNOWLEDGEMENT
I avail this opportunity to thank my respected guide Dr. ELANGO.M M.Sc., M.Phil., PGDCA.,
PhD ., Department of Physics, PSG College of Arts and science, Coimbatore-641014 for his constant
encouragement, benevolence and the moral support throughout for carrying this project work.

I wish to thank Dr. V.VEERAVAZUTHI M.Sc., MS., M.Phil., PhD., Head of the Department of
physics.
I genuinely thank All the Faculty Members in the Department of Physics, PSG College of Arts and
Science, Coimbatore-641 014 for their kindness, moral support and constant help throughout my course
and also in the completion of my project I would like to express my thanks to respected VARUNA.J,
PhD scholar, Department of Physics, PSG College of Arts and science

I would also like to express my thanks to respected REVATHI.M, PhD scholar, Department of
Microbiology, PSG College of Arts and science

I would like to express my profound to Dr. T.KANNAIAN, M.Sc., Ph.D., secretary, PSG College of
arts and science, Coimbatore.

I extended my sincere thanks to Dr. D.BRINDA, M.Sc., Ph.D., Principal, PSG College of Arts and
Science, Coimbatore, for necessary facilities to do the project.

It is prestige to acknowledge the people whose constant guidance and motivating influence crowned
my efforts with successful completion.

SHANMUGHA PRIYA.G
(Reg.No:18MPH021)

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 TABLE OF CONTENTS

CHAPTER NO. TITLE PAGE NO.

1. INTRODUCTION
1.1 HISTORY OF NANOMATERIAL 06
1.2 HISTORY OF NANOTECHNOLOGY 06
1.3 NANOSCIENCE AND NANOTECHNOLOGY 08
1.4 NANOSCALE 08
1.5 STRUCTURAL CLASSIFICATION OF
NANOMATERIAL 09
1.6 CLASSIFICATION OF NANOSTRUCTURE 10
1.7 PROPERTIES OF NANOMATERIAL 11
1.8 SYNTHESIS OF NANOPARTICLE 14
1.9 APPLICATION 17
2. LITERATURE REVIEW 24
3. MATERIALS AND METHODS
3.1 MATERIAL INTRODUCTION 28
3.2 STRUCTURE OF TiO2 29
3.3 APPLICATION OF TiO2 NANOPARTICLES 31
3.4 INTRODUCTION ABOUT DOPANTS 32
3.5 METHODOLOGY 34
4. CHARACTERIZATION TECHNIQUE
4.1 INTRODUCTION 36
4.2 X-RAY DIFFRACTION (XRD) 36
4.3 ULTRAVIOLET VISIBLE SPECTROSCOPY (UV) 38
4.4 FOURIER TRANSFORM INFRARED SPECTROSCOPY 41
5. RESULTS AND DISCUSSION
5.1 X-RAY DIFFRACTION (XRD) ANALYSIS 43
5.2 ULTRAVIOLET VISIBLE INTEPRETATION 48
5.3 FOURIER TRANSFORM INFRARED SPECTROSCOPY
(FTIR) ANALYSIS 51
5.4 ANTIMICROBIAL ACTIVITY 52
6. CONCLUSION AND REFERENCES 54

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 CHAPTER-1
1. INTRODUCTION
1.1 HISTORY OF NANOMATERIAL
The history of nanotechnology can be traced back to when science began. Specifically, the first
known use of Nano Particle was made by artisans in the 9th century in Mesopotamia. The purpose
of using them was to generate a glittering effect on the surface of pots. The shiny effect on the
surface of ceramic was due to the presence of silver and copper NPs, dispersed homogeneously in
the glassy matrix. Even these days, pottery from the middle Ages and Renaissance often retains a
distinct gold- or copper-colour metallic glitter. This lustre contains Ag and Cu Nano Particle
dispersed homogeneously in the glassy matrix of the ceramic glaze.
The term Nano Particle was unaware for the artisans on those days. Several examples exist for
the use of nano composites by the ancient artefacts. One stunning example was the Lycurgus cup,
which was made by Romans from about AD 400; it was made of a glass that changes colour when
the light is passed on it. The glass was composed of Au–Ag alloyed Nano Particles, which are
distributed in such a way to make the glass look green in reflected light but, when light passes
through the cup, it reveals a brilliant red.
In the antiquities, Romans used Nano Particles to create steel swords with impressive strength,
shatter resistance, and exceptionally sharp edges between AD 300 and AD 1700. Another instance
of nano materials used by our ancestors was Maya Blue, a corrosion resistant azure pigment
discovered by pre-Columbian Mayan city of Chechen Itza in AD 800. The pigment is a complex
material containing clay with nano pores into which indigo dye was combined chemically to
create an environmentally stable pigment.

1.2 HISTORY OF NANOTECHNOLOGY

The word “nanotechnology” was introduced for the first time into a scientific world by
N.Taniguchi at the international conference on industrial production in Tokyo in 1974 in order to
describe the super thin processing of materials with nano meter accuracy and the creation of nano-
sized mechanisms. Ideas of nano technological strategy, which were put forward by Feynman,
were developed by E.Drexler in his book “Vehicles of creation: the arrival of the nanotechnology
era” published in 1986. In the second half of 1980s to the early 1990s a number of important
discoveries and inventions was made, which created an essential impact on the further
development of nanotechnology. Since then, a considerable intensification of nano technological

6
researches and designs is underway, the number of publications on nano technological subjects
increases sharply, practical application of nano technology expands.
In 1991 the first nano technological program of National Scientific Fund started to operate in the
USA. In 2001 the National Nano technological Initiative (NNI) of the USA was approved. The
principal idea of this program was formulated as follows: “National Nano technological Initiative
defines the strategy of interaction between federal departments of the USA for the purpose of
prioritizing nanotechnology development, which should become a basis for the economy and
national security of the USA in the first half of the 21st century”.
During 1996-98, prior to National Nano technological Initiative (NNI) approval, a special
committee of the American Centre for Global Technology Assessment monitored and analyzed
the development of nanotechnology in all countries and published the survey newsletters on the
basic trends of development and achievements for scientific, technical and administrative experts
in the USA. In 1999 the session of the Inter branch group on nano science, nano engineering and
nanotechnology (IWGN) took place, the result of which was the forecast on research in
nanotechnology for the next 10 years.
The same year the IWGN conclusions and recommendations were supported by the Presidential
Council on Science and Technology (PCAST), whereupon NNI was officially approved in 2000.
In a preamble to NNI the US president Clinton declared: “I earmark 500 million dollars in the
current fiscal year for the state nanotechnology initiative, which will enable us to create new
materials in the future (surpassing in characteristics the ones we have today thousands of times),
to download all data in the Congress Library on a tiny device, to diagnose cancer in a few affected
cells and to achieve other amazing results”. The initiative being offered is for at least twenty years
and promises to lead to important practical results”. As in the USA, considerable attention to
nanotechnology development is given in Japan.
In 2000 the Japanese Economic Association organized a special department on nanotechnology
under the auspices of the Industrial and Technical Committee, and in 2001 the Framework Plan of
nanotechnology research was developed. The main provisions of this plan were: to designate the
following as the basic directions of nano science "breakthrough": information technology,
biotechnology, power, environmental studies and materials technology; to provide for significant
capital investment to manufacturing based on nanotechnology; to intensify the research in the
areas above and to apply their results in manufacturing so that these became "drivers" of the future
nanotechnology revolution; to work out the national strategy of nanotechnology development,
and, first and foremost, to organize effective cooperation between industrial, state and scientific
departments and organizations in the research.

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 Countries of Western Europe carry out research in nanotechnology within the framework of
national programs. In Germany research in nanotechnology is supported mainly by the Ministry
Of Education, Science, Research and Technology. In England nanotechnology development is
supervised by the Council of Physics and Technology Research and by the National Physical
Laboratory. In France the nanotechnology development strategy is defined by the National Centre
of Scientific Research.
More and more attention is given to nanotechnology development in China, South Korea, and
other emerging countries. Recently nanotechnology research began in the CIS countries, usually
within the framework of state scientific programs. Thus, the nanotechnology paradigm was
formed at the turn of the 1960s, while the 1980s and 1990s are the start of development of
nanotechnology in its own right.

1.3 NANO SCIENCE & NANOTECHNOLOGY

Nano science is the study and Nanotechnology is the exploitation of the strange properties of
materials smaller than 100 nm to create new useful subject. Nanotechnology is a known field of
research since last century. Since ‘‘nanotechnology” was presented by Nobel laureate Richard
P.Feynman during his well famous 1959 lecture ‘‘There’s Plenty of Room at the Bottom” (Feynman,
1960), there have been made various revolutionary developments in the field of nanotechnology.
Nanotechnology produced materials of various types at nano scale level. Depending on the overall
shape these materials can be 0D, 1D, 2D or 3D. The importance of these materials realized when
researchers found that size can influence the physiochemical properties of a substance e.g. the optical
properties.
Nanoparticles are not simple molecules itself and therefore composed of three layers i.e. (a) The
surface layer, which may be functionalized with a variety of small molecules, metal ions, surfactants
and polymers. (b) The shell layer, which is chemically different material from the core in all aspects,
and (c) The core, which is essentially the central portion of the nano particle and usually refers the
nano particle itself. Nanoscience is the study of the fundamental principles of molecules and
structures with at least one dimension roughly between 1 to 100 nano meters.

1.4 NANOSCALE
• Nanoscale properties and functions will be achieved through the control of matter at its building
blocks, atom-by-atom, molecule-by-molecule and nanostructure -by-nanostructure.
• At Nano scale the properties of the materials are different from their same bulk size counter parts.
These changes in properties may be due to quantum size effects.

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1.5 STRUCTURAL CLASSIFICATIONOF NANOMATERIALS

• The concept nano materials is thought to be most accurately defined as follows: “Nanomaterials
represent nano industry products in the form of materials containing structural nanoelements that
substantially improve or cause qualitatively new mechanical, chemical, physical, biological, and
other properties” .
• As follows from this definition, nanomaterials should not be necessarily nano crystalline
(consisting mainly of crystallites having a nano scale size in at least one dimension).
• The structural nano elements that radically change material properties can be represented by
fragments, pores, clusters, atom segregations, dislocation ensembles, phase transformation
products, dendrites, quasi crystals, and so on.
• Thus, nano materials can be conventionally divided into the following two groups: nano
crystalline and nano structured materials. We now consider the main types of nano materials in
more detail.

Nano fragmented materials are the materials containing dislocation fragments or sub grains whose size
is smaller than 100 nm. They mainly include the metals and alloys subjected to mega plastic (severe)
deformation.
Nano porous materials are the materials with a high volume density of nano pores smaller than 100 nm
located in the body of conventional grains or along their boundaries.
Nano dendrite materials contain the products of dendrite solidification in the form of nano dendrites or
degenerate dendrites (dendrite cells) appearing upon rapid solidification of a melt .
Nano dislocation materials are characterized by a high volume fraction of nano scale dislocation
ensembles or configurations of a certain type
Nano phase materials are the materials that contain phase transformation nano products.
Nano segregation materials contain grain boundary or other segregations of certain components that
have a nano size in at least one dimension.
Nano cluster (amorphous) materials According to modern concepts, multi component amorphous
metallic glasses have a nano cluster structure. The clusterization of amorphous alloys is more pronounced
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after local plastic flow. Therefore, the amorphous state of alloys produced by melt quenching should be
considered as a nano structured state.
Nano crystalline materials are the materials that mainly consist of nano crystallites.

1.6 CLASSIFICATION OF NANOSTUCTURE

Classification of nanostructure materials and systems especially depend on the dimension which lies
within the nano meter range, i.e. less than 100nm. The characteristic dimension is important for special
application.

• Zero-dimensional nanostructures- Quantum dots.

• One-dimensional nanostructures- Nanowires, Nanorods and Nanotubes.

• Two-dimensional nanostructures- Nanocoatings and Nanofilms.

• Three-dimensional nanostructures- Nanomaterial.

ZERO DIMENSIONS

The definition of nano particles differs depending upon the materials and application concerned.
Thus particles are smaller than 10-20nm, where the physical properties of solid materials themselves
would drastically change. These are the crystals made of metals, with size below 100nm free standing
or suspended in a fluid or embedded in another material. Generally the particle in 3 digit range of
nano meter in other words the particles from 1 to 100nm are generally called as nano particles. Nano-
particles can be

• Single crystalline or poly crystalline.

• Composed of single or multi-chemical elements.
• Exhibit various shapes and forms.
• Metallic, ceramic or polymeric.
• Exist individually or incorporated in a matrix.
• Amorphous or crystal

ONE DIMENSION

One dimension nano structures which are outside the nano scale. The nano wires with thickness below
100nm free standing or suspended in a fluid or embedded in another material. Several chemical strategies
are developed for 1D nano wires with different levels of control over the growth parameter

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One dimensional nanostructure can be,
• Amorphous or crystalline.

• Single crystalline or polycrystalline.

• Chemically pure or impure.

TWO DIMENSION

Two dimensional nanostructures exhibit plate-like shapes. This includes nano films, nano layers, and
nano coatings. The structural analysis of this coating will see grains (single crystal) of metal with
diameter in nano scale, joined by grain boundaries.

Two dimensional nanostructures can be,

• Made up of various chemical compositions.

• Used as a single layer or as multilayer structures.

• Deposited on a substrate.

• Integrated in a surrounding matrix material.

THREE DIMENSION
Three dimensional materials are thus characterized by having three arbitrarily dimensions above
100nm. Size is significantly larger than the grain sizes in which dimension of the materials are in all
directions.
Three dimensional nanostructures can be
• Dispersion of nano particles.
• Bundles of nano wires.
• Nano tubes.
• Multi nano layers

1.7 PROPERTIES OF NANOMATERIAL

Nano particles are important scientific tools that have been and are being explored in various
biotechnological, pharmacological and pure technological uses. They are a link between bulk materials
and atomic or molecular structures. While bulk materials have constant physical properties regardless of
its size, among nano particles the size often dictates the physical and chemical properties. Thus, the
properties of materials change as their size approaches the nano scale and as the percentage of atoms at
the surface of a material becomes significant. For bulk materials, those larger than one micrometer (or
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micron), the percentage of atoms at the surface is insignificant in relation to the number of atoms in the
bulk of the material.
• The properties of materials with nano meter dimensions are significantly different from those of
bulk materials.
• This is mainly due to the nano meter size of the materials which render them (i) large fraction of
surface atoms; (ii) high surface energy; (iii) spatial confinement; (iv) reduced imperfections,
which do not exist in the corresponding bulk materials. Due to their nano meter size, nano materials
are already known to have many novel properties.

ELECTRICAL PROPERTIES
• The electrical properties of nano materials vary between metallic to semiconducting materials. It
depends on the diameter of the nano materials. The very high electrical conductivity of nano
material is due to minimum defects in the structure.

THERMAL PROPERTIES
• The thermal conductivity of nano materials are very high, is due to the vibration of covalent
bonds. Its thermal conductivity is 10 times greater than the metal. The very high thermal
conductivity of nano material is also due to minimum defects in the structure.

MECHANICAL PROPERTIES
• Nano materials are very strong and withstand extreme strain. Most of the materials fracture on
bending because of the presence of more defects, but nano materials possesses only few defects in
the structure.

OPTICAL PROPERTIES
• One of the most fascinating and useful aspects of nano materials is their optical properties.
Applications based on optical properties of nano materials include optical detector, laser, sensor,
imaging, phosphor, solar cell, photo catalysis, photo electrochemistry and biomedicine. The
optical properties of nano materials depend on parameters such as feature size, shape, surface
characteristics, and other variables including doping and interaction with the surrounding
environment.
• Likewise, shape can have dramatic influence on optical properties of metal nanostructures.
However, when an isotropy is added to the nano particles, the optical properties of the nano
particles change dramatically.
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CATALYTIC PROPERTIES
• The evaluation of catalytic properties is classified mainly into following three kinds; they are
physical property, chemical property and testing method of catalytic activity.
• Particle morphology or microstructures are the physical properties; chemical properties are density
or quality of active site. Catalysis is a major field of nano science and technology.
• Catalyst provides an alternative pathway in which activation barrier of a reaction is lowered and
the reaction rate is increased. Catalysts are classified into three main categories namely,
heterogeneous, homogeneous and enzymatic but another type of catalyst has been known as quasi
homogeneous catalyst.
• Surface of the nano particles are unstable and get precipitate out of the solution. So substances
such as polymers, block copolymer surfactant and organic ligand are used to stabilize the metal
nano particles catalysis by nano particles in solution is known as quasi-homogeneous catalysis and
the catalyst as quasi homogeneous catalyst.
• Nano particles attract the researchers and large research activity has been going on to design nano
catalyst improving nano particle catalyst stability, activity, selectivity and mechanism.

STRUCTURAL PROPERTY
• For copper metallic clusters, the inter atomic spacing is observed to decrease with decreasing
cluster size. This effect can be explained by compressive strain induced by the internal pressure
arising from the shell radius of curvature in the nano particles.
• The same trend is observed in semiconductors and metal oxides. Metallic nano particles (gold) is
known to adopt polyhedral shape such as cube octahedral and these may be regarded as multiply
twinned crystalline particles in which the shapes can be understood in terms of the surface of
various crystallographic planes.

PHYSICAL AND CHEMICAL PROPERTIES

Physical & chemical properties of nano particle are due to three main reasons:
• The size of the nano particle is comparable to the Bohr’s radius of the excitons. This significantly
alters the optical, luminescent and redox properties of nano particle when compared to the bulk
material.

• The surface of atoms constitutes a considerable fraction of the total number of atoms of the nano
particles. The natural size of the nano particle with the size of the nano particle.

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 • This determines the peculiarities of the kinetics of the chemical processes on the surface of the
nano particle.

1.8 SYNTHESIS OF NANOPARTICLES

The methods of synthesis of nano particles are well known for a long time as compared to the other
nanomaterials. For the synthesis of nano particles, the processing conditions need to be controlled in such
a manner that the resulting nano particles have the following characteristics:

1. Identical size of all particles,

2. Identical shape,
3. Identical chemical composition and crystal structure, and
4. Individually dispersed with no agglomeration
Two general ways are available to control the formation and growth of the nano particles. One is called
arrested precipitation and depends on either on exhaustion of one of the reactants or on the introduction of
the chemical that would block the reaction. Another method relies on the physical restriction of the
volume available for the growth of the individual nano particles by using templates.
The nano particles are prepared by the following methods:
1. Sol-Gel method

2. Precipitation method

3. Hydrothermal method

4. Chemical vapour deposition method

5. Co-precipitation method

1.8.1 CHEMICAL SYNTHESIS OF NANOSTRUCTURES

Nature fabricates complex nanostructures relying on simple criteria and a relatively small pool of
molecular building blocks. Robust chemical bonds join the basic components into covalent scaffolds.
Non-covalent interactions determine the three-dimensional arrangement and overall shape of the resulting
assemblies. The multitude of unique combinations possible for long sequences of chemically connected
building blocks provides access to huge libraries of nano-scaled molecules.

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1.8.2 SOL-GEL METHOD
As the name suggested Sol-Gel involves two types of materials or compounds, ‘SOL’ and ‘GEL’. First
of all Sol-Gel formation process is usually a low temperature process. This means less energy
consumption and pollution too. In the nuclear fuel synthesis it is a desired process. It is possible to
synthesize nano particles, nano rods, nano tubes etc. using Sol-Gel technique, Sols are solid particles in a
liquid. Gels are nothing but a continuous network of particles in liquid particles with pores filled with
liquid particles to form a network.
By drying the liquid, it is possible to obtain powders, thin films or monolithic solid. Sol-Gel method is
particularly useful to synthesize to ceramics or metal oxides although sulphides, boroids and nitrides also
are possible. Synthesis of Sol-Gel in general involves hydrolysis of precursors, condensation followed by
poly condensation to form particles, gelatin and drying process by various routes.

1.8.3 PRECIPITATION METHOD

Addition of the solutions with an appropriate concentration leads to precipitate. Deposited particles in
the bottom are filtered and calcites. However, to avoid agglomeration the capping agent (poly vinyl
alcohol) is added.

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PRECIPITATION THEORY
Many ionic reactions in aqueous solutions results in the phase. Study of these mechanisms will help us
to understand the chemical analysis of nano crystalline nucleation and growth process at the atomic level.
When the precipitation and dissolution reaction are reasonably rapid, equilibrium calculation can be
applied to describe the process. A typical precipitation theory is represented by,

A + B →AB (Solution) →AB (Solid)

Initially the precipitation starts with, the supersaturated solution. This super saturation can be reached
by various methods such as mixing solution containing reactants or by changing solubility by increasing
or decreasing temperature. So the precipitation takes place in two stages namely the nucleation and grain
growth. Co-precipitation is an important issue in chemical analysis, where it is often undesirable, but in some
cases it can exploited. In gravimetric analysis, which consists on precipitating the analyte and measuring its
mass to determine its concentration purity, co-precipitation is a problem because undesired impurities often
co-precipitate with the analyte, resulting in excess mass. This problem can often be mitigated by “digestion”
(waiting for the precipitate to equilibrate and form larger, purer particles) or by redissolving the sample and
precipitating it again. Thus the sample is washed several times and dried in order to volatize water, wash
liquid and other volatile impurities. Then the sample is calcinated.

1.8.4 HYDROTHERMAL METHOD

Hydrothermal synthesis includes the various techniques of crystallizing substances from high
temperature aqueous solution at high vapour pressures, also termed “hydrothermal method”.
Hydrothermal synthesis can be defined as a method of synthesis of single crystal that depends on the
solubility of minerals in hot water under high pressure. Possible advantages of the hydrothermal method
over other types of crystal growth include the ability to create crystalline phases which are not stable at
the melting point. Also, materials which have a high vapour pressure near their melting points can also be
grown by the hydrothermal method. The method is particularly suitable for the growth of large good-
quality of crystals while maintaining good control over their composition. Disadvantages of the method

16
include the need of expensive autoclaves, good quality of seed of a fair size and the impossibility of
observing the crystal as it grows.
1.8.5 CHEMICAL VAPOR DEPOSITION (CVD) AND CHEMICAL VAPOR
CONDENSATION (CVC)
Chemical Vapour Condensation (CVD) is a well-known process in which a solid is deposited on a
heated surface via a chemical reaction from the vapour or gas phase. CVC reaction requires activation
energy to proceed. This energy can be provided by several methods. In thermal CVD the reaction is
activated by a high temperature above 900°c. A typical apparatus comprises of gas supply system,
deposition chamber and an exhaust system. In laser CVD, pyrolysis occurs when laser thermal energy
heats an absorbing substrate. In photo-laser CVD, the chemical reaction is induced by ultra violet
radiation which has sufficient photon energy, to break the chemical bond in the reactant molecules,
another process called chemical vapour condensation (CVC) was developed in Germany in 1994. It
involves pyrolysis of vapours of metal organic precursors in a reduced pressure atmosphere. Particles of
ZrO₂,Y₂O3 and nano whiskers have been produced by CVC method.
1.8.6 CO-PRECIPITATION METHOD
In chemistry, co-precipitation (CPT) is carrying down by a precipitate of substances normally soluble
under the conditions employed. Analogously, in medicine, co-precipitation is specifically the
precipitation is specifically the precipitation of an unbound “Antigen along with an Antigen-Antibody
complex “.There are three main mechanisms of co-precipitation inclusion, occlusion and adsorption. An
inclusion occurs when the impurity occupies a lattice site in the crystal structure of the carrier, resulting in
a crystallographic defect; this can happen when the ionic radius and charge of the impurity are similar to
those of the carrier. An adsorbate is an impurity that is weekly bound (adsorbed) to the surface of the
precipitate. An occlusion occurs when an adsorbed impurity gets physically trapped inside the crystal as it
grows. Besides its applications in chemical analysis and in radiochemistry, co-precipitation is also
“Potentially important to many environment issues closely related water resources, including acid mine
drainage, radionuclide migration in fouled waste repositories, metal containment transport at industrial
and defence sites, metal concentrations in aquatic systems and waste water treatment technology”

1.9 APPLICATIONS

1.9.1 Carbon Based Structures

Carbon nano tubes are carbon based tubular structures. These structures are arranged in fashion like a
graphite sheet rolled up into a cylinder and capped at one or both ends by a bucky ball. These are
hexagonal networks of carbon atoms having diameter of 1nm and length from 1 to 100 nm. There are two
17
carbon based configuration that have received much attention recently: single-walled nano tubes
(SWNTs) and multiwalled nano tubes (MWNTs).

In addition to these types C 60 fullerenes is also a part of common configurations. These are hollow,
carbon-based, cage-like architectures (nano tubes and fullerenes), also known as bucky balls, which are
differ in the arrangement of their graphite cylinders. The size, geometry, and surface characteristics of
these macromolecules make them appealing for drug carrier usage and have remarkable physical
property. SWNTs and C60 fullerenes have internal diameters range of 1–2 nm. This dimension is
equivalent to about half the diameter of the average DNA helix, whereas MWNTs have diameters ranging
from several nano meters to tens of nano meters with 0.36 nm distance between layers of MWCNT,
depending on the number of walls in the structure. Size may vary in their length ranging from 1 μm to a
few micrometers As far as their architecture is concerned fullerenes and carbon nano tubes are typically
fabricated using laser ablation, chemical vapour deposition, electric arc discharge, or combustion
processes.

Characterization of these concentric forms is based on their strength and stability so that they can be
used as stable drug carriers. Cellular entry of nano tubes may be mediated by endocytosis or by insertion
through the cell membrane. Fullerenes have also shown drug targeting capability. Tissue-selective
targeting and intracellular targeting of mitochondria have been shown with use of fullerene structures.
Furthermore, experiments with fullerenes have also shown that they exhibit antioxidant and antimicrobial
behaviour.

1.9.2 Fullerenes

• They are also known as bucky balls, that are the carbon allotrope discovered in 1985 having
dimensions near around 7 Å in diameter and composed of 60 carbon atoms that are arranged in a
shape known as truncated icosahedrons
• Its shape is quite similar to soccer ball with 20 hexagons and 12 pentagons and is highly
symmetrical.
• There are various types of fullerenes such as Alkali doped fullerenes, endohedral fullerenes,
endohedral metallofullerenes, exohedral fullerenes and heterofullerenes. Alkali doped fullerenes
are the carbon allotropic structures that contains alkali metal atoms in between fullerenes
contributing valence electrons to neighbouring fullerenes .
• Similarly endohedral fullerenes have another atom enclosed inside the bucky ball. If they are
enclosed with metallic atom then they are called as metallofullerenes.

18
 • Owing to the very small size of C-60 fullerene, it is difficult to synthesize endohedral C-60
fullerenes. Therefore larger fullerenes (C 82 or C 84 ) fullerenes are used for synthesizing
endohedral fullerenes. Another type of fullerenes called as exohedral fullerenes or fullerene
derivatives or functionalized fullerenes which are synthesized by chemical reaction between the
fullerene and other chemical groups. Last class of fullerene compounds are heterofullerenes
where one or more carbon atoms are replaced by other atoms like nitrogen or boron.

Applications

• Diagnostics Endohedral metallofullerenes can be used for diagnostic purposes as radio contrast
media in magnetic resonance imaging and other imaging procedures.
• Animal studies with C-60 fullerene conjugated with thyroglobulin have produced a C-60 specific
immunological response. This can be used to design methods of estimation of fullerene levels in
the body when used for therapeutic or diagnostic purposes.
• Drug transport Fullerenes are being investigated for drug transport of antiviral drugs, antibiotics
and anticancer agents.
• Free radical scavengers Due to presence of high number of conjugated double bonds in the core
structure fullerenes can also be used as free radical scavengers. They also provide protection to
the mitochondria against injury induced by free radicals, owing to this property they can be used
in cancer therapy.
• Photosensitizers Fullerenes especially exohedral fullerenes can be used as photosensitizers in
photodynamic therapy against various types of malignancies.
• These fullerenes potentially generate reactive oxygen species when stimulated by light and kills
the target cells. This method is now also being investigated for antimicrobial property as these
cause cell membrane disruption especially in Gram positive bacteria and mycobacterium.
• Stimulate host immune response and production of antibodies Fullerenes are efficient in
stimulating host immune response and production of fullerene specific antibodies.

1.9.3 Quantum Dots

Quantum dots (QDs) are nano crystals of semiconducting materials measuring around 2–10 nm,
consisting of a semiconductor inorganic core (CdSe), an aqueous organic coated shell (e.g., ZnS) to
improve optical properties, and can be made to fluorescence when stimulated by light.
19
• Quantum dots bear a cap which enables them in improving their solubility in aqueous buffers.
They are neither atomic nor bulk semiconductors.
• Their properties originate from their physical size, which ranges from 2 to 10 nm in radius. Owing
to the to their narrow emission, bright fluorescence, high photo stability and broad UV excitation
Quantum dots have been adopted for tracking of intracellular process for longer time, for in vitro
bio imaging and for real time monitoring .
• As far as the its applications are concerned Quantum dots covers medical areas as a diagnostic as
well as therapeutic tool for in vitro and in vivo detection and analysis of bio molecules,
immunoassays, DNA hybridization, diagnostic tools (magnetic resonance imaging, MRI), time
graded fluorescence imaging of tissue, development of non-viral vectors for gene therapy,
labelling of cells, as therapeutic tools for cancer treatment and transport vehicles for DNA,
protein, drugs or cells.
• In addition they can be also tagged with bio molecules and used as highly sensitive probes.
• In addition quantum dot probes provide real time imaging of the sentinel node with Near Infra
Red (NIR) fluorescence system which is having the potential to produce reduced background
noise and deeper penetration of rays into the biological sample.

1.9.4 Nano shells

• Nano shells are the new modified forms of targeted therapy, having core of silica and a metallic
outer layer.
• These thin coated core particles of different material have gained considerable attention now
days. The properties of nano shells can be altered by simply tuning the core to shell ratio.
• With the recent advancement in new techniques it is now possible to synthesize these
nanostructures in desired shape, size and morphology.
• Nano shells are synthesized to create novel structures with different morphologies, since not
possible to synthesize all the materials in desired morphologies.
• For obtaining desirable morphology core particles of different morphologies such as rods, wires,
tubes, rings, cubes, etc. can be coated with thin shell in core shell structures.
• These shells are inexpensive as precious materials can be deposited on inexpensive cores.
• Therefore while synthesizing nano shells expensive material is required in lesser amount than
usual.
• Targeting of nano shells can be achieved by using immunological methods. Nanoshells occupies
variety of applications in diverse areas such as providing chemical stability to colloids, enhancing

20
 luminescence properties, engineering band structures, biosensors, drug delivery, etc. Synthesis of
nano shells can be useful for creating.

Applications
• Cancer therapy: Nano shells are tuned to absorb infra red rays when exposed from a source
outside the body and get heated and cause destruction of the tissue.
• This has been studied in both in vitro and in vivo experiments on various cell lines.
• Diagnostic purposes: They are useful for diagnostic purposes in whole blood immunoassays e.g.
coupling of gold nano shells to antibodies to detect immune globulins in plasma and whole blood.
• Hydro gel mediated delivery: Nano shells can be easily embedded in hydro gel polymer
containing the drug. Such type of delivery system can be used for targeting tumour cells.
• Micro metastasis and diabetes: Nano shells are currently studied for micro metastasis of tumours
and also for treatment of diabetes.

1.9.5 Nano bubbles

• Nano bubbles (NBs) are nano scaled bubble like structures that are generated in the interface of
hydrophobic surfaces in liquids.
• These nano bubbles remain stable at room temperature and when heated to physiological
temperature within the body coalesce to form micro bubbles.
• The mechanism of NB formation is based on the nucleation of gas at the hydrophobic surface
from a supersaturated solution, leading to trap atmospheric gases. However the formation of NBs
is thermodynamically forbidden, but the life time of NBs is reached event to the orders of hours.
• There are four types of nano bubbles: bulk, interfacial, plasmonic and oscillating nano bubbles.
• Cancer therapeutic drugs can be incorporated into these nano scaled bubbles like structures.
• Nano bubbles potentially exhibit advantages in targeting the tumour tissue and delivering the drug
selectively under the influence of ultrasound exposure. This may enhance the intracellular uptake
of the drug by the tumour cells. Additionally these nano bubbles can be easily visualized in
tumour by means of various ultrasound methods.
Applications

Delivery of drugs NBs can be potentially utilized in delivery of drugs like doxorubicin in vitro and
in vivo .

• These NBs reach the tumour and get accumulated which is followed by formation of micro
bubbles by coalescing of nano bubbles.
21
 • Disruption of the micro bubbles occurs when the site is focused with high intensity focused
ultrasound, which ultimately causes release of the drug.
• This may results in accumulation of higher levels of drug in the target cells and reduced toxicity
and increased efficacy. This method needs further exploration for its utility in treatment of various
malignancies.
• Gene therapy Liposomal nano bubbles and micro bubbles are also being studied for effective non
viral vectors for gene therapy. Nano bubbles combined with ultrasound exposure have shown
improved transfer of gene in both in vitro and in vivo studies.
1.9.6 Paramagnetic Nano particles

Magnetic drug targeting is conceptualized with an objective to target magnetic drug carrier particles at a
specific site in the body using an externally applied magnetic field.

• Magnetic nano particles are a class of particulate materials of less than 100 nm size that can be
manipulated under the magnetic field.
• These particles are composed magnetic elements such as cobalt, nickel, iron and their respective
oxides such as magnetite, maghemite, cobalt, ferrite and chromium dioxide.
• The classification of these particles is based on their magnetic susceptibility which is defined as
ratio of induced magnetization to the applied field. Paramagnetic nano particles have a greater
magnetic susceptibility than conventional contrast agents.
• They are investigated for both diagnostic and therapeutic purposes. For diagnostic purpose
paramagnetic iron oxide nano particles are used as contrast agents in magnetic resonance imaging.
• Targeting with paramagnetic nano particles enables identification of specific organs and tissues.

1.9.7 Nanosomes

• Nanosomes are currently being used for medical applications such as targeting, diagnosis and
therapy.
• Brain targeting: These nanosomes are being developed for treatment of various tumours (CNS
tumours) e.g. silica coated iron oxide nano particles coated with polyethylene glycol used to
access specific areas of brain involved with tumour.
• Tumour targeting: Nanosomal delivery with magnetic resonance imaging and laser assist in
targeting the nano particle specifically to the tumour cells and destroy the cells loaded with
these nano particles by the heat generated by iron oxide particles by absorbing the infra red
light.

22
 • ROS production: Their stable integration with photo catalyst produces reactive oxygen
species when stimulated by light and destroy the target tissue.
• These nano form exhibit advantages over conventional drugs in being much safer without the
adverse effects of cancer chemotherapy drugs and also the absence of development of drug
resistance.

Nanotechnology finds applications in fields such as Agriculture, Automotive, Chemical Industries,

Construction, Cosmetics, Defence, Electronics ,Energy/Power, Environment ,Food and drink
packing ,Healthcare, Marine Materials, Oil and gas, Safety, Security etc...

23
 CHAPTER-2

2. LITERATURE REVIEW

Literature survey is the comprehensive and extensive examination of several research works done by
many researchers on the selected field and briefing of their findings. Literature survey excludes the
chance of repetitions in research works and help for the comparison.

Sabriye Pişkin et al., (2013) reported that nano sized materials are attracting a great deal in biological
and pharmaceutical applications. Especially, metal oxide nanoparticles are known to possess antibacterial
properties. TiO2 nanoparticles, have become a new generation of advanced materials due to their optical,
dielectric, and photo-catalytic characteristics from size quantization. These properties have been applied
in removing bacteria and harmful organic materials from water and air. In this work, we investigated
antimicrobial activity of synthesized TiO2 nanoparticles by ultrasound method. The TiO2 nanoparticles
were characterized by X-ray diffraction, nano sizer and atomic force microscopy analyses. The
antibacterial effect of these obtained nanoparticles was examined on E. coli (ATCC 8739), Staph.aureus
(ATCC 6538), P.aeruginosa (ATCC 9027), C.albicans (ATCC 36232) and B.subtilis (ATCC 6633). The
synthesized TiO2 nanoparticles were found to be effective against these bacteria’s. Based on this study,
we may conclude that the synthesized by ultrasound method TiO2 nanoparticles can be a good inorganic
antimicrobial agents.

Kimitoshi Sato et al., (2009) reported Aggregation and dispersion behaviour of nano meter and sub
micro meter scale TiO2 particles in aqueous suspension were investigated using three kinds of mechanical
dispersion methods: ultrasonic irradiation, milling with 5-mm-diameter balls, and milling with 50 lm
beads. Poly acrylic acids with molecular weights ranging from 1200 to 30,000 g/mol were used as a
dispersant, and the molecular weight for each dispersion condition was optimized. Viscosities and
aggregate sizes of the sub micrometer powder suspensions were not appreciably changed in the ultrasonic
irradiation and 5-mm-ball milling trials. In contrast, in the trials in which nano particle suspension was
used, ultrasonic irradiation produced better results than 5-mm-ball milling. Use of ultra sonication
enabled dispersion of aggregates to primary particle sizes, which was determined based on the specific
surface area of the starting TiO2 powders, even for relatively high solid content suspensions of up to 15
vol%. Fifty micrometer- bead milling was also able to disperse aggregates to the same sizes as the
ultrasonic irradiation method, but 50-lmbead milling can be used only in relatively low solid content
suspensions. It was concluded that the ultrasonic dispersion method was a useful way to prepare
concentrated and highly dispersed nano particle suspensions.
24
V.Parthasarathy et al., (2009) have synthesised TiO₂ nanoparticles and reported about the research
work which attempted synthesis and characterization of titanium dioxide nano particle and their
application on woven and knitted fabrics (100% cotton & 45/55% polyester/cotton) for antibacterial
activity. The titanium dioxide (TiO₂) nano particles were prepared with urea as a reacting medium. These
nano particles have an average size of 9 nm, which was confirmed by Transmission Electron Microscope
(TEM). 1% of the nano TiO₂ were applied on both woven and knitted fabrics. The presence of nano
particles on the fabric surface was confirmed by Scanning Electron Microscope (SEM). The nano TiO₂
impregnated woven and knitted (100% cotton & 45/55% polyester/cotton) fabrics showed excellent
antibacterial activity against two representative bacteria, Staphylococcus aureus (Gram positive) and
Klebsiella Pneumoniae (Gram Negative).The antibacterial property of untreated fabrics showed no
reductions whereas the titanium dioxide nano particles treated 100% cotton woven shows 85% and 64%
reduction, 45/55% polyester/cotton woven shows 93% and 78% reductions, 100% cotton knitted fabrics
showed 75% and 58%, and 45/55% polyester/cotton knitted fabrics showed 79% and 74% reductions
against Staphylococcus aureus and Klebsiella Pneumoniae bacteria, respectively. Mechanical properties
such as tensile strength, elongation, crease recovery, air permeability of nano TiO₂ treated fabrics did not
change considerably than the untreated fabrics.

Vilas.S.Desai et al., (2009) reported the process of Heterogeneous Photo catalysis (HP) using
titanium dioxide photo catalysts is a field of immense research potential for researchers worldwide.
TiO2 as a photo catalyst has been widely applied for air and water remediation. This study reports
the synthesis of a visible light responsive nano sized TiO2 photo catalyst by a modified sol-gel
process. The synthesized TiO 2 photo catalyst exhibits photo catalytic activity against some common
pathogenic microorganisms such as Escherichia coli, Pseudomonas aeruginosa, Klebsiella
pneumonia and Staphylococcus aureus under visible light illumination. TiO 2 is known to exhibit
photo catalytic activity under UV light irradiation, the results obtained in this study using solar
irradiation are very promising and enables the use of cheaply available solar energy for the process
of photo catalysis.

Claudius Kormann et al., (1988) have reported the syntheses of transparent colloidal solutions of
extremely small titanium dioxide particles (d < 3 nm) in water, ethanol, 2-propanol, and acetonitrile are
presented. Quantum-size effects are observed during particle growth and at the final stages of synthesis.
They are quantitatively interpreted by using a quantum mechanical model developed by Brus. The
particles prepared in aqueous solution possess the anatase structure and consist of about 200 TiO2,
molecules at their final growth stage. The colloidal particles can be isolated from solution as white
25
powders that are soluble in water and ethanol with no apparent change in their properties. In organic
solvents the quantum-size TiO2 particles appear to form with rutile structure. Excess negative charge on
the particles resulting either from deprotonated surface hydroxyl groups or from photo generated or
externally injected charge carriers causes a blue shift in the electronic absorption spectrum, which is
explained by an electrostatic model. Electrons can be trapped in the solid as a Ti 3+ species, which has a
characteristic visible absorption spectrum. As much as 10% of the available Ti4+ ions can be reduced
photo chemically in the solid with a quantum yield of 3%. Molecular oxygen reoxidizes the Ti3+ centres,
leading to detectable amounts of surface-bound peroxides. The photo catalytic activity of the small TiO2
particles is demonstrated.

S.Mahshida et al., (July 2007) synthesised titanium dioxide nanoparticles by hydrolysis. Titanium
dioxide nanoparticles have been prepared by hydrolysis of titanium isopropoxide. Aqueous solution with
various pH and peptizing the resultant suspension has been applied for preparation of the TiO₂ nano
powder with narrow size distribution. The influence of pH on the particle size and morphology of
prepared powder has been evaluated. Synthesized powder is characterized by X-ray diffraction, scanning
electron microscopy (SEM) and transmission electron microscopy (TEM). Experimental results have
shown that the as-prepared powders have entirely consisted with anatase crystalline phase. Only powder
acquired from an acidic solution has fine particle size with spherical morphology. The anatase to rutile
transformation occurred at temperatures lower than 600 °c.

Gupta Shipra Mital, et al., has reported the climate change and the consumption of non-renewable
resources are considered as the greatest problems facing mankind. Because of this, photo catalysis
research has been rapidly extending. TiO2 nanoparticles have photo catalytic applications including the
decomposition of organic compounds and production of H2 as a fuel using solar energy. This article
reviews the structure and electronic properties of TiO2, compares TiO2 with other common
semiconductors used for photolytic applications and clarifies the advantages of using TiO2 nanoparticles.
TiO2 is considered close to an ideal semi conduct as for photo catalysis, but possesses certain limitations
such as poor absorption of visible radiations and rapid recombination of photo generated electrons/hole
pairs. In this review articles, various methods used to enhance the photo catalytic characteristics of TiO2
including dye sensitization, doping, coupling and capping are discussed. Environmental and energy
applications of TiO2, including photo catalytic treatment of wastewater, pesticide degradation and water
splitting to produce hydrogen have been summarized.

Hongbo Shi Hongbo Shi et al., (2013) have synthesised Titanium dioxide (TiO₂) nano particles and
stated that TiO2 nano particles possess different physicochemical properties compared to their fine
particle (FP) analogy, which might alter their bioactivity. Most of the literature has focused on the
26
respiratory system, showing the importance of inhalation as the primary route for TiO2 nano particles
exposure in the workplace. TiO2 nano particles may translocate to systemic organs from the lung and
gastrointestinal tract (GIT) although the rate of translocation appears low. Oral exposure mainly occurs
through food products containing TiO2 Nano particles-additives. Most dermal exposure studies, whether
in vivo or in vitro, report that TiO2 nano particles do not penetrate the stratum corneum (SC). In the field
of nano medicine, intravenous injection can deliver TiO2 nano particulate carriers directly into the human
body. Upon intravenous exposure, TiO2 nano particles can induce pathological lesions of the liver, spleen,
kidneys, and brain. We have also shown here that most of these effects may be due to the use of very high
doses of TiO2 nano particles. There is also an enormous lack of epidemiological data regarding TiO2 nano
particles in spite of its increased production and use. However, long-term inhalation studies in rats have
reported lung tumours.

27
 CHAPTER-3

3. MATERIALS AND METHODS

3.1 MATERIAL INTRODUCTION

Nano particle research presents wide scope for the development of novel solutions in the field of
healthcare, cosmetics, optics and electronics. Altering their molecular and atomic states results in
unexpected outcomes, which may not be possible by using the materials in their original states. This
article deals with the properties and applications of titanium oxide nanoparticles.
Titanium oxide (TiO2) is available in the form of nano crystals or nano dots having a high surface area.
They exhibit magnetic properties. Titanium belongs to Block D, Period 4 while oxygen belongs to Block
P, Period 2 of the periodic table. Titanium oxide is also known as flamenco, rutile, titanium dioxide and
dioxotitanium. Titanium oxide nanoparticles are known for their ability to inhibit bacterial growth and
prevent further formation of cell structures.
Titanium dioxide, also known as titanium (IV) oxide or Titania, is usually occurring oxide of titanium,
chemical formula TiO2. When used as a Pigment, it is called titanium white, Pigment White 6 or
CI77891. Generally it is sourced from Ilmenite, rutile and anatase. It has wide range of applications, from
paint to sunscreen to food colouring, it has E number E171.
Titanium was once considered a rare metal, but now-a-days it is one of the most important metals in the
industry. The element was first discovered by Gregor in England in 1970, the mythological first sons of
the earth, the titans, in 1975. Chemically, Titanium is one of the transition elements in group IV and
period IV of Mendeleev’s periodic table. It has the atomic number 22 and atomic weight 47.9. Being a
transition element, titanium has an incompletely filled d shell in it is electronic structure.
Titania (TiO2) is a cheap and innocuous inorganic material extensively employed in industrial and
commercial applications such as pigment in the paint industry, as sun blocking material in cosmetics, as a
binder in medical fields. For instance, more than 4 million tonnes of the white pigment are annually
consumed by the paint industry worldwide, being the pigment most widely used because of its brightness,
high refractive index and low-cost.
Titanium dioxide is classified as a wide band-gap semiconductor, the anatase form have a band gap of
3.2 eV. Much of the bio-toxicity of TiO2 is attributed to photo effects wherein the material is illuminated
with ultraviolet light. Band gap illumination produces an electron–hole pair excited state is a much
stronger oxidant and reductant than is the ground state. Under standard conditions the excited electron has
a reduction potential of about 0.0 V while the hole has an oxidizing power of about 3.2 V.

28
3.2 STRUCTURE OF TiO2
TiO2 is a wide band gap semiconductor that presents photo activity upon near UV or Higher irradiation,
absorbing photons and transforming them into chemical redox energy. Although TiO2 is inert and do not
promote chemical reactions without irradiation, the handling of very finely divided TiO2 particles requires
taking safety measures.
Titania (TiO2) has three crystalline structures namely
▪ Anatase
▪ Rutile
▪ Brookite

• Rutile structure is thermodynamically stable while other two are in metastable state.
• Rutile contains two TiO2 molecules per unit cell, where a=4.59Å c=2.95Å
• Anatase contains four TiO2 molecules per unit cell where a=3.78Å c=9.51Å

PHASE CRYSTAL SYSTEM

Rutile Tetragonal
Anatase Tetragonal
Brookite Orthorhombic

29
 Molecular Formula Tio2

Molecular Mass 79.866g/mol

Appearance White solid

Density I 4.23 g/cm3 (rutile)

Density II 3.78 g/cm3(anatase)

Melting point 18430ᵒC

Boiling point 2972ᵒ C

Solubility in water Insoluble

CHEMICAL PROPERTIES
The following tables list the chemical properties of titanium oxide.

Chemical Symbol TiO2

CAS No 1317-80-2
Group Titanium 4
Oxygen 16
Electronic Configuration Titanium [Ar] 3d² 4s²
Oxygen [He] 2s² 2p4
Chemical compositions
Titanium 59.93
Oxygen 40.55

PHYSICAL PROPERTIES

Density 42.23g/cm³

Molar Mass 79.9378g/mol

30
THERMAL PROPERTIES
The thermal properties of Titanium oxide nanoparticles are as below

Melting Point 1,843°C

Boiling Point 2,9720 C

3.3. APPLICATION OF TiO2 NANOMATERIALS

The existing and promising applications of TiO2 nanomaterials include paint, toothpaste, UV
protection, photocatalysis, photovoltaics, sensing, and electrochromics as well as photochromics. TiO2
nanomaterials normally have electronic band gaps larger than 3.0 eV and high absorption in the UV
region. TiO2 nanomaterials are very stable, nontoxic, and cheap.
Their optical and biologically benign properties allow them to be suitable for UV protection
applications. A surface is defined as superhydrophilic or superhydrophobic if the water-surface contact
angle is larger than 130°or less than 5°, respectively. TiO2 nanomateirals can be imparted with
antifogging functions on various glass products, i.e., mirrors and eyeglasses, having superhydrophilic or
superhydrophobic surfaces.
For example, Feng et al. found that reversible superhydrophilicity and superhydrophobicity could be
switched back and forth for TiO2 nanorod films. When the TiO2 nanorod films were irradiated with UV
light, the photogenerated hole reacted with lattice oxygen to form surface oxygen vacancies. Water
molecules kinetically coordinated to these oxygen vacancies, and the spherical water droplet filled the
grooves along the nanorods and spread out on the film with a contact angle of about 0°, resulting in
superhydrophilic TiO2 films. After the hydroxy group adsorption, the surface transformed into an
energetically metastable state. When the films were placed in the dark, the adsorbed hydroxy groups were
gradually replaced by atmospheric oxygen, and the surface evolved back to its original state. The surface
wettability converted from superhydrophilic to superhydrophobic. Stain-proofing, self-cleaning properties
can also be bestowed on many different types of surfaces due to the superhydrophilic or
superhydrophobic surfaces.
TiO2 nanomaterials have also been used as sensors for various gases and humidity due to the electrical
or optical properties which change upon adsorption. One of the most important research areas for future
clean energy applications is to look for efficient materials for the production of electricity and/or
hydrogen. When sensitized with organic dyes or inorganic narrow band gap semiconductors, TiO2 can
31
absorb light into the visible light region and convert solar energy into electrical energy for solar cell
applications.
For example, an overall solar to current conversion efficiency of 10.6% has been reached by the group
led by Gratzel with DSSC technology.TiO2 nanomaterials have been widely studied for water splitting
and hydrogen production due to their suitable electronic band structure given the redox potential of water.
Another application of TiO2 nanomaterials when sensitized with dyes or metal nanoparticles is to build
photochromic devices. Of course, one of the many applications of TiO2 nanomaterials is the photo
catalytic decomposition of various pollutants.

3.4 INTRODUCTION ABOUT DOPANTS

To increase the UV-Visible light absorption of TiO2 addition of Transition metals can improve the
photo catalytic activity by decreasing the energy band gap or preventing (e-,h+) pair combination by (e-
,h+) trapping.

3.4.1 MANGANESE
In steels, manganese improves the rolling and forgiving qualities as well as strength, toughness,
stiffness, hardness and hardens ability. In aluminium and antimony, manganese addition forms highly
ferromagnetic compounds, especially in the presence of small amounts of copper.

Manganese is the fifth most abundant metal in the Earth’s crust. Its minerals are widely distributed, with
pyrolusite (manganese dioxide) and rhodochrosite (manganese carbonate) being the most common. The
main mining areas for manganese are in China, Africa, Australia and Gabon. The metal is obtained by
reducing the oxide with sodium, magnesium or aluminum, or by the electrolysis of manganese sulfate.
Manganese nodules have been found on the floor of the oceans. These nodules contain about 24%
manganese, along with smaller amounts of many other elements.

32
CHEMICAL DATA

Symbol Mn

Type Transition metal

Appearance A hard brittle, silvery white

Atomic weight 51

Relative atomic mass 54.938

Density 7.3g/cm³

Melting point 1246°c

Boiling point 2061°c

APPLICATIONS
1. Manganese is too brittle to be of much use as a pure metal. It is mainly used in alloys, such as steel.
Steel contains about 1% manganese, to increase the strength and also improve workability and resistance
to wear. Manganese steel contains about 13% manganese. This is extremely strong and is used for railway
tracks, safes, rifle barrels and prison bars.
2. Drinks cans are made of an alloy of aluminum with 1.5% manganese, to improve resistance to
corrosion. With aluminum, antimony and copper it forms highly magnetic alloys.
3. Manganese (IV) oxide is used as a catalyst, a rubber additive and to decolorize glass that is coloured
green by iron impurities. Manganese sulfate is used to make a fungicide. Manganese (II) oxide is a
powerful oxidizing agent and is used in quantitative analysis. It is also used to make fertilizers and
ceramics.

33
3.5METHODOLGY

3.5.1 SYNTHESIS OF TiO₂ BY CO-PRECIPITATION METHOD

MATERIALS USED
Titanium Tetraisopropoxide (TTIP), Ammonium Hydroxide, manganese acetate, deionised water.
SYNTHESIS OF TiO₂ NANOPARTICLES
TiO2 nano powders were prepared via co-precipitation method using the precursor Titanium
Tetraisopropoxide (TTIP), Manganese acetate as dopant, Ammonium Hydroxide as precipitating agent
and deionised water as solvent. 0.5N or 0.125M of TTIP was added to 100 ml of deionised water. The
solution is stirred for an hour and then 0.1052g of manganese acetate was added. The solution mixture is
stirred for about 3 hour using magnetic stirrer during which Ammonium Hydroxide was added slowly to
maintain pH. Then the sample centrifuged and washed for three times in order to remove impurities. The
sample is dried in oven at 60°C for 1 hour. The oven dried TiO2 was calcined to 500°C for 3 hours. The
same procedure is repeated for Mn doped TiO2 for different pH. The synthesised nano particles were
confirmed using characterisation techniques.

TTIP (0.5N) +Deionised

water (100 ml)
+Manganese Acetate
(0.5%)
Stirred for 1 hour

Adding Ammonia solution

drop by drop till desired
pH is reached

Stir for 3 1/2hours

Centrifuge (3000 rpm

for 10 mins)

Calcination (4000c for 3

hours)

34
PREPERATION OF FUNGAL MEDIUM
3.6g of potato dextrose broth and 3g of agar is stirred into 150 ml of water and the mixture is
autoclaved. The Petri dish is kept in UV for some time.1ml of ethanol is mixed with 3ml of medium. The
media is kept in UV for 30 minutes and Aspergillus is spread over it and wells are made. 0.05g of doped
TiO2 nano particles are stirred into 4ml of deionised water and ultrasonificated for 10 minutes with
irradiation time of 2 minutes. 6 micro litre of sample is poured into the well using micropipette and kept
at room temperature for three days.

35
 CHAPTER 4
4. CHARACTERIZATION TECHNIQUE
4.1 INTRODUCTION
Instrumentation helps us understand the specific properties of the substances, to be studied in a rapid
manner accurately as well as reliable to understand measured values. The grown nano particles are
subjected to various studies. Structural, Optical and compositional studies on the nano particles (which
are grown) could be made precisely using sophisticated techniques such as X-ray Diffraction (XRD),
Fourier Transform- Infrared Spectroscopy (FT-IR) and Ultra-Violet (UV) spectroscopy.

4.2 X-Ray Diffraction (XRD)

Von Laue in 1912 discovers the x-ray diffraction method. This provided a wealth of valuable
information to science and industries. This x-ray diffraction studies gives known about the arrangement
and the spacing of an atom in crystalline materials. The X-ray is electro-magnetic radiation of wavelength
about 1Angstrom, which is about the same size as an atom. They occur in that portion of the
electromagnetic spectrum between gamma-ray and ultraviolet. The x-ray diffraction is one of the most
important characterization tools used in solid state chemistry and material science. We can determine the
size and the shape of the unit cell for any compound very easily using the diffraction of x-rays.

4.2.1 PRINCIPLE
X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase identification
of crystalline material and can provide information on unit cell dimensions. It is a versatile, non-
destructive technique that reveals detailed information about the chemical composition and
crystallographic structure of natural and manufactured materials. By varying the angle theta, the Bragg's
Law conditions are satisfied by different d-spacing in polycrystalline materials.
nλ = 2dsinθ
Where,
n is an integer referring to the order of reflection.
λ is wavelength of the radiation.
d is the spacing between the crystal lattice planes responsible for a particular diffracted beam.
θ is the angle that incident beam makes with lattice Planes.
These diffracted X-rays are then detected and processed and counted. By scanning the sample through a
range of 2θangles, all possible diffraction directions of the lattice should be attained due to the random
orientation of the powdered material. Conversion of the diffraction peaks to d-spacing allows

36
identification of the mineral because each mineral has separate d-spacing. Typically, this is achieved by
comparison of d-spacing with a standard reference patterns.
When a beam of X-rays directed at a crystal interacts with the electrons of the atoms in the crystal. The
electrons oscillate under the impact and become a new source of electromagnetic radiation. The waves
emitted by the electrons have the same frequency ass the incident rays and the emission is in all the
directions. There are millions of atoms in the crystal; the emission in a particular direction is the
combined effect of the oscillations of electrons of all the atoms. The emission will be in phase and
reinforce one another only in certain specific directions, there is destructive interference of the emissions
from different sources.

Figure 4.2.1 Bragg’s reflection from a crystal

A Detector records and processes this X-ray signal and converts the signal to a count rate which is then
output to a device such as a printer or computer monitor. The geometry of X-ray diffractometer is such
that the sample rotates in the path of the collimated X-ray beam at an angle θ while the X-ray detector is
mounted on an arm to collect the diffracted X-rays and rotates at an angle of 2θ. The instrument used to
maintain the angle and rotate the sample is termed a goniometer

Figure 4.2.2 Experimental setup of X-Ray diffraction.

37
 The geometry of an X-ray diffractometre is such that the sample rotates in the path of the collimated X-
ray beam at an angle θ while the X-ray detector is mounted on an arm to collect the diffracted X-rays and
rotates at an angle 2θ. The instrument used to maintain the angle and rotate the sample is termed a
goniometer. For typical powder patterns, data is collected at 2θ from ~5◦ to ~70◦ angles that are present in
the X-ray scan.

4.2.3 APPLICATIONS
X-ray powder diffraction is most widely used for the identification of unknown crystalline materials.
Determination of unknown solids is critical to studies in geology, environmental science, material
science, engineering and biology. Other applications include
➢ Characterization of crystalline materials.

➢ Identification of fine-grained minerals such as clays and mixed layer clays that are difficult to
determine optically.

➢ Determination of unit cell dimensions and measurement of sample purity.

4.3 ULTRAVIOLET- VISIBLE SPECTROSCOPY

Ultraviolet–visible spectroscopy or ultraviolet-visible spectrophotometry (UV-Vis or UV/Vis) refers
to absorption spectroscopy or reflectance spectroscopy in the ultraviolet-visible spectral region. This
means it uses light in the visible and adjacent (near-UV and near-infrared [NIR]) ranges. The absorption
or reflectance in the visible range directly affects the perceived colour of the chemicals involved. In this
region of the electromagnetic spectrum, molecules undergo electronic transitions. This technique is
complementary to fluorescence spectroscopy, in that fluorescence deals with transitions from the excited
state to the ground state, while absorption measures transitions from the ground state to the excited state.
The Ultraviolet spectroscopy is useful as an analytical tool for two reasons. First it can be used to
identify some functional group in molecules and secondly, it can be used for determining the current
strength of the substance is extremely useful. Ultraviolet spectroscopy is used mostly in chemical and
biochemical laboratories for variety purposes. When the visible or ultraviolet light is absorbed by the
substances, the electron in the ground state gets excited from ground to higher energy state.

4.3.1 PRINCIPLE
The Principle of ultraviolet-visible absorption is that the Molecules containing π-electrons or non-
bonding electrons (n-electrons) can absorb the energy in the form of ultraviolet or visible light to excite
these electrons to higher anti-bonding molecular orbitals. The more easily excited the electrons (i.e. lower
energy gap between the HOMO and the LUMO), the longer the wavelength of light it can absorb.
38
4.2.3 BEER-LAMBERT’S LAW
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 radiation with thickness of the absorbing solution is proportional to the incident radiation as
well as the concentration of the solution.
The expression of Beer-Lambert law is-
A = log (I0/I) = ε. C. L
Where,
A = absorbance
I0= intensity of light incident upon sample cell
I = intensity of light leaving sample cell
C = molar concentration of solute
L = length of sample cell (cm.)
ε = molar absorptivity
From the Beer-Lambert law it is clear that 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.

4.3.4 WORKING
The functioning of this instrument is relatively straightforward. A beam of light from a visible and/or
UV light source (coloured red) is separated into its component wavelengths by a prism or diffraction
grating. Each monochromatic (single wavelength) beam in turn is split into two equal intensity beams by
a half-mirrored device. One beam, the sample beam (coloured magenta), passes through a small
transparent container (cuvette) containing a solution of the compound being studied in a transparent
solvent. The other beam, the reference (coloured blue), passes through an identical cuvette containing
only the solvent.

39
 Figure 4.3 Working mechanism of UV Spectroscopy

The intensities of these light beams are then measured by electronic detectors and compared. The
intensity of the reference beam, which should have suffered little or no light absorption, is defined as I0.
The intensity of the sample beam is defined as I. Over a short period of time, the spectrometer
automatically scans all the component wavelengths in the manner described. The ultraviolet (UV) region
scanned is normally from 200 to 400 nm, and the visible portion is from 400 to 800 nm.

4.3.5 APPLICATIONS
1. Quantitative Analysis
➢ The change in absorbance for a given concentration change is greater, leading to greater
sensitivity and accuracy in measurement

➢ The relative effect of other substances or impurities is smaller

➢ The rate of change of absorbance with wavelength is smaller, and the measurement is not so
severely affected by small errors in the wavelength setting.

2. Qualitative Analysis
➢ It is used to study the transition of electron.
➢ To determine chemical structure of complex molecules

40
4.4 FOURIER TRANSFORMS INFRARED SPECTROSCOPY (FTIR):

When IR radiation is passed through a sample, some radiation is absorbed by the sample and some
passes through (is transmitted). The resulting signal at the detector is a spectrum representing a molecular
‘fingerprint’ of the sample. The usefulness of infrared spectroscopy arises because different chemical
structures (molecules) produce different spectral fingerprints. The FTIR uses interferometry to record
information about a material placed in the IR beam. The Fourier Transform results in spectra that analysts
can use to identify or quantify the material.

• An FTIR spectrum arises from interferograms being ‘decoded’ into recognizable spectra.
• Patterns in spectra help identify the sample, since molecules exhibit specific IR fingerprints

Fig: 4.4.1 FTIR Instrumentation

IR can be categorized into three wavelength regions: near IR (400-10cm-1), mid IR (4000-400cm-1) and
far IR (14000-4000cm-1).The IR vibrations are corresponding to distinct energies. The absorption of IR
radiation by molecules takes place only at certain wavelengths and frequencies. When IR radiations fall
on chemical bonds, they absorb only those radiations with frequencies that match with their vibrational
modes.
The spectrum with IR versus frequency is useful to identify the functional groups and bonds in the
material. The characteristic band produced by impurities helps to quantify the impurity concentration
within the material. The analysis of the obtained interferrogram is not an easy process, thus it is achieved
through a mathematical tool, Fourier transformation. In genera this transformation is carried out within
the computer and we get a final desired spectrum, which can be easily
analyzed.
INSTUMENTATION
Fig.4.5.1 represents the block diagram of FTIR spectrometer. A glowing blackbody source is used to
emit IR Radiations. The beam passes through an aperture, which controls the amount of energy falls on

41
the sample, the encoding of spectrum occurs in the interferometer. The output is known as
interferogram.There is a sample compartment which contains the sample holder where the sample is kept.
The IR radiations are transmitted through the Sample and specific energies of IR radiations will be
absorbed depending upon the sample material. The final interferrogram signal passes to the detector for
digitalisation of signal. The digitalised output of the detector reaches the computer, where the Fourier
transformation occurs. The final output of FTIR spectroscopy is obtained there and will be available to
the users for further interpretation.

APPLICATIONS

1. Useful to find various functional groups present in the material. Functional Groups give their own
characteristic peaks in the IR absorption spectra at specific or within the narrow frequency ranges.
2. Compound identification: It is useful to identify the organic compounds, since each compound has
a unique IR spectrum.

42
 CHAPTER-5
RESULTS AND DISCUSSION

5.1 XRD ANALYSIS

In order to determine the size and study the structural properties of the different pH synthesized particles of
TiO₂, the powder X-ray diffraction (XRD) analysis was performed. The graphs 5.1.1, 5.1.2 and 5.1.3 show
the XRD spectrum for TiO2 doped with Mn at 5% concentration with pH 6, pH 8 and pH 10 respectively.
The TiO₂ nano particles were examined via XRD analysis and the spectrum was shown. The diffraction peaks
indexed as [1 0 1], [1 0 3], [1 0 5], [1 1 6] are the fundamental reflections of the prepared samples. These
peaks are in good agreement with the standard JCPDS Card (JCPDS file no 894921) in anatase phase. The
sharpness of the peaks reveals that the prepared samples are crystalline state. The peak broadening in the
spectrum confirms that the sample is indeed nanostructure. The crystallite size analysis has been done and the
average crystallite size is found by using the Debye Scherrer approximation formula.

5.1.1 DATA ANALYSIS FOR XRD DATA:

TiO2 Mn DOPED pH-6:

Fig: 5.1.1 TiO2 Mn doped pH 6

43
TABLE 5.1.1: TiO2 Mn DOPED PH-6:

2θ θ F.W.H.M GRAIN MILLER STRAIN DISLOCATION

(deg) (deg) (rad) SIZE INDICES DENSITY
(nm) (10)14
g/cm3
25.39189 12.695945 0.87926 1.616462 101 0.975718 0.382709
37.9792 18.9896 1.64575 0.89099 112 1.195606 1.259672
48.08733 24.043665 1.05696 1.43645 200 0.592278 0.484638
54.67099 27.335495 1.95789 0.79720 211 0.946896 1.573487
62.85473 31.427365 1.65952 0.97914 204 0.678953 1.043051
75.37529 37.687645 1.50381 1.16511 215 0.486643 0.736655

TABLE 5.1.2: LATTICE PARAMETERS:

Lattice Parameters Anatase

a(Å) 3.7812
c(Å) 9.34062

TiO2 Mn DOPED PH-8:

Fig: 5.1.2 TiO2 Mn doped pH 8

44
TABLE 5.1.3: TiO2 Mn DOPED PH-8:

2θ θ F.W.H.M GRAIN MILLER STRAIN DISLOCATION

(deg) (deg) (rad) SIZE INDICES DENSITY
(nm) (10)14
g/cm3
25.41 12.705 1 1.421341 101 1.10889 0.49499
38.06908 19.03454 1.78641 0.821053 112 1.29449 1.483396
48.11132 24.05566 1.00474 1.511251 200 0.56269 0.437851
54.73827 27.369135 1.77546 0.879382 211 0.85743 1.293137
62.95477 31.477385 1.42138 1.143803 204 0.58038 0.764359
69.83768 34.91884 2.12371 0.796237 116 0.76053 1.577302
75.51211 37.756055 1.78762 0.981040 215 0.57706 1.039026

TABLE 5.1.4: LATTICE PARAMETERS:

Lattice Parameters Anatase

a(Å) 3.7794

c(Å) 9.3212

TiO2 Mn DOPED PH-10:

Fig: 5.1.3 TiO2 Mn doped pH 10

45
TABLE 5.1.5: TiO2 Mn DOPED PH-10:

2θ Θ F.W.H.M GRAIN MILLER STRAIN DISLOCATION

SIZE INDICES DENSITY
(nm) (10) 4
g/cm3
25.36287 12.68144 0.84328 1.68534 101 0.93689 0.352069
38.00243 19.00121 1.88826 0.776611 112 1.37088 1.658031
48.05732 24.02866 1.0624 1.42893 200 0.59574 0.489754
54.73656 27.36828 1.77082 0.88168 211 0.85522 1.286407
62.9729 31.48645 1.75027 0.92896 204 0.71442 1.158785
69.72755 34.863775 1.97575 0.85529 116 0.70899 1.367007
75.42725 37.713625 1.47336 1.18961 215 0.47634 0.706629

TABLE 5.1.6: LATTICE PARAMETERS:

Lattice Parameters Anatase

a(Å) 3.7834
c(Å) 9.3822

The diffraction peaks are positioned at (1 0 1), (1 1 2), (2 0 0), (2 1 1), (2 0 4), (2 1 5)
corresponding to crystal planes as shown in the graphs 5.1.1, 5.1.2 and 5.1.3. These peaks are in good
agreement with the standard result of anatase phase (JCPDS file no 894921) of TiO₂. The sharpness of the
peaks revealed that the grown samples were highly crystalline state. The marked peak broadening in the
sample confirms that the sample is indeed nanostructure. The particle size analysis has been done and the
average particle size is found using the method indicated below. The results confirm that Mn is doped
into TiO2 nanostructure.

46
TiO2 Pure PH-9:

Fig 5.1.4 TiO2 Pure

TABLE 5.1.7: TiO2 PURE:

2θ θ F.W.H.M GRAIN MILLER STRAIN DISLOCATION

(deg) (deg) (rad) SIZE INDICES DENSITY
(nm) (10)14
g/cm3
25.123 12.561 0.29046 5.1113 101 0.07087 0.05391
27.263 13.631 0.28918 5.1306 101 0.07025 0.05323
53.578 26.789 0.08821 18.4030 105 0.01968 0.01968

TABLE 5.1.7: LATTICE PARAMETERS:

Lattice parameters Anatase

a(Å) 3.85768
c(Å) 9.72498

5.1.2 PARTICLE SIZE ANALYSIS

Average crystallite size has been calculated from the recorded XRD pattern using well known Debye
Scherrer Equation,

47
Where,
λ = 1.5406Å
β = F.W.H.M (radians)
θ = position corresponding to peak (radians)

5.1.3 UNIT CELL DETERMINATION

For tetragonal structure, the inter planar spacing between the two closest parallel planes with the Miller
indices given by d is given by

Using above formula we calculated the values of lattice parameters a, c.

5.2 UV-VISIBLE INTERPRETATION

The spectral data recorded showed the strong cut off at 410.57 nm; where the absorbance value is
minimum. The data is corroborated in the % Reflectance mode.
When dopants and defects are introduced, additional extrinsic electronic levels can be located in the
energy band gap of the TiO2. UV-Visible spectra of pure and doped TiO2 are shown in Fig. 5.2.1, 5.2.2,
5.2.3 and 5.2.4. It can be seen that with the pH of the solution increasing the absorption and transmission
energy increases i.e. for pH of 6, 8 and 10 the energy gap is 4.0336 eV, 4.0600 eV and 4.1002 eV
respectively. Thus the absorption edge gradually shifted to the higher energy region in the spectra.

48
 Figure 5.2.1 Pure TiO2 pH – 9
The mechanism of the origin of the visible spectra is associated with the electronic transitions from the
valence band to dopant level or from the dopant level to the conduction band can effectively red shift the
band edge absorption threshold. Thus pH variation ensures fine tuning of band gap.

Figure 5.2.3 TiO2 Mn doped pH -8

49
 Figure 5.2.3 TiO2 Mn doped pH -8

Figure 5.2.3 TiO2 Mn doped pH -10

It is observed that no accountable change has been observed for Mn doped TiO2 with pH 6, pH 8and pH
10. However, a negligible quantity of shift is seen. Since the average absorption edge gradually shifted to
the higher energy region in the spectra, this negligible quantity of variation doesn’t show accountable
effects on the antimicrobial activity. The energy gap of the particles were found using Planck’s quantum
formula
𝑬=𝒉𝝂
Where,
E - Energy gap in eV
h - Planck’s constant in eV
ν = 𝒄𝝀
ν - Frequency of light
50
c - Velocity of light
λ - Wavelength of light
Therefore, it was observed that the absorption peak of Mn2+ doped TiO2 were in the UV region. Optical
properties of the doped and pure TiO2 nano particles were analyzed using UV visible of absorption
spectroscopy under dispersing the molecules using ethanol as solvent at room temperature.

5.3 FTIR ANALYSIS OF TiO2 :

The FTIR analysis shows the prepared TiO2 nanoparticles doped with Manganese Acetate at different
pH contains stetching bonds corresponding to Manganese Acetate dopants and TiO2 nanoparticles.

Fig 5.3.1 TiO2 Mn doped pH 6

Fig 5.3.1 TiO2 Mn doped pH 8

51
 Fig 5.3.1 TiO2 Mn doped pH 10

The fig 5.3.1, 5.3.2 and 5.3.3 shows the FTIR spectrum corresponding to different pH. The transmittance
peak at 3443.50 cm-1, 3423.8 cm-1, 3433.65 cm-1 corresponds to O-H stretching mode of hydroxyl group
due to moisture absorption by nanoparticles. The transmittance peak at 1634.47 cm-1, 1627.92 cm-1,
1641.36 cm-1corresponds to C=O stretching mode of Manganese Acetate present as a dopant. The
transmittance peak at 594.52 cm-1,541.99 cm-1,432.05cm-1, 660.19cm-1, 545.28 cm-1, 426.26cm-1, 587.14
cm-1, 537.89 cm-1 ,454.17 cm-1corresponds to TiO2 nanoparticles.

5.4 ANTIMICROBIAL ACTIVITY

5.4.1ANTIFUNGAL ACTIVITY
The results of antifungal activity against Aspergillus shows a good variation with variation in pH of Mn
doped TiO2 nanoparticles, fig 5.4.1, 5.4.2 and 5.4.3 shows antifungal activity of pH 6, pH 8 and pH 10 of
Mn doped TiO2 nanoparticles.
The antifungal activity is done using ultra sonification method of dispersion of metal oxide nanoparticles
without ultra sonication the activity was feeble as indicated by figure 5.4.4 for pH 10 Mn doped TiO2
nanoparticles (there is no zone of inhibition found in this case).

52
5.4.2 ANTIBACTERIAL ACTIVITY

The synthesised TiO2 nanoparticles showed only very feeble antibacterial activity which doesn’t vary
with the pH of the dopant.

53
 CHAPTER 6
6.1 CONCLUSION

• TiO2 nano particles were prepared using wet chemical precipitation method.
• The TiO2 matrix was impured with Mn2+ ions at of 5wt %. The prepared doped nano particles with
different pH were subjected to analytical techniques for material confirmation.
• From the XRD analysis, it was inferred that the prepared TiO2 nanoparticles are in anatase phase.
From which we also attributed that the particles were in nano dimensional state.
• The UV visible spectra shows a strong blue shift in band edge absorption further confirms the nano
dimensional state of the material prepared.
• The functional groups are analyzed using FTIR spectroscopy and the absorption peaks in the
region 400 – 800 cm-1 confirms the formation of TiO2 nano particle. The peaks in the region 1600
cm-1 indicates the doping in the nanomaterials.
• The Antimicrobial activity shows no effect on antibacterial activity with variation in pH while
there is a considerable difference in the antifungal activity with increase of pH which is attributed
to the increase in basicity of nano material doped with 5% transition metal Mn.
• Hence from the present work, we can conclude that increasing the pH of TiO2 nanoparticles doped
with transition metals like Mn increases the antifungal activity against Aspergillus which is
recommended for indoor pollution control using TiO2 nano particles.

6.2 REFRENCE

1. Xiaobo Chen and Samuel S. Mao -Titanium Dioxide Nano materials: Synthesis, Properties,
Modifications and Applications (Rev. 2007) (2902-2926).
2. K V Raman, R Gopalan and P S Raghavan, Molecular Spectroscopy,(2004)(106-119).
3. S O Pillai, Solid State Physics, 8th edition, (2018) (749-775).
4. Wilson, Kamali Kannangara, Geoff Smith, Michelle Simmons, Bukhard Raguse, Nanotechnology-
Basic science and Engineering technologies().
5. L. Zhang, D. Pornpattananangkul, C.-M.J. Hu, and C.-M. Huan, “Development of Nano particles for
Antimicrobial Drug Delivery.” Current Medicinal Chemistry, vol.17, (2010) (585-594).
6. L. Raki, J. Beudoin, R. Alizadeh, J. Makar, T. Sato, Cement and concrete nano science
and nano technology ,(2010) (918–942).
7. H. Nalwa, Encyclopedia of Nano science and Nano technology, first ed., American
Scientific Publishers, Valencia, CA, (2004).
54
8. V. Pokropivny, V. Skorokhod, Classification of nanostructures by dimensionality and
Concept of surface forms engineering in nano material science, Mater. Sci. Eng. (2007) (990–993).
9. Y. Huang, L. Kavan, I. Exnar, and M. J. Gratzel, ‘‘Rocking Chair Lithium
Battery Based on Nano crystalline TiO2 (Anatase),’’ J. Electrochem. Soc., (1995).
10. M.horie, K.Fujita. “Toxicity of metal oxides nano particles.” Advanced in Molecular
Toxicology.(2011)(145-178).
11. C.Jayaseelan, A.A. Rahuman, S.M. Roopan, A.V. Kirthi, J. Venkatesan, S.Kim, M.Iyappan, C. Siva.
“Biological approach to synthesize TiO2 nano particles using Aeromonas hydrophila and its antibacterial
activity.” Spectro chemical Acta Part A: Molecular and Bio molecular Spectroscopy, vol. 107, Apr. 2013,
(82–89).
12. Robertson TA, Sanchez WY, Roberts MS: Are commercially available
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INTERNET
1. www.rsc.org
2. www.sciencedirect.com
3. www.edinst.com
4. www.researchgate.net

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