I I n t r o d u c t i on

I.1. Definition of Nanotechnology

Nanotechnology is enabling technology that deals with nano-meter sized
objects. It is expected that nanotechnology will be developed at several levels:
materials, devices and systems. The field of nanotechnology is one of most active
research areas in modern materials science. Nanoparticles exhibits new or
improved properties based on specific characteristics such as size, distribution and
morphology. There have been impressive developments in the field of
nanotechnology in the recent past years, with numerous methodologies developed
to synthesize nanoparticles of particular shape and size depending on specific
requirements and rapid growth of their novel applications [1]. The nanomaterials
level is the most advanced at present, both in scientific knowledge and in
commercial applications. A decade ago, nanoparticles were studied because of
their size-dependent physical and chemical properties [2]. Now they have entered a
commercial exploration period [3, 4].

Nanotechnology can be termed as the synthesis, characterization,

exploration and applications of nano-sized materials for the development of
science. It deals with the materials whose structures exhibit significantly novel and
improved physical, chemical, and biological properties, phenomena, and
functionality due to their nano scaled size. Because of their smaller size, they have
a larger surface area than macro-sized materials. The intrinsic properties of metal
nanoparticles are mainly determined by their size, shape, composition, crystallinity

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and morphology. Nanoparticles have distinct properties compared to the bulk form
of the same materials due to their smaller size, thus offering many new
developments in the fields of biosensors, biomedicine and biotechnology.
Nanotechnology is also being utilized in medicine for diagnosis, therapeutic drug
delivery and the development of treatments for many diseases and disorders. It is
an enormously powerful technology which holds a huge promise for the design and
medical application on early disease, treatment and prevention.

I.2. Background of Nanotechnology

The history of nanotechnology is quit long; nevertheless, major

developments within nanoscience have taken place during the last decades. The
idea of nanotechnology was first highlighted by noble laureate Richard Feynman,
in his famous lecture at the California Institute of Technology, 29th December,
1959, one of his research articles published in 1960 entitled, “There is plenty of
room at the bottom” discussed the idea of nanomaterials. He pointed out that if a
bit of information required only 100 atoms. Then all the books ever written could
be stored in a cube with sides 0.02 inch long. In 1970 Norio Taniguchi first defined
the term Nanotechnology. According to him “Nanotechnology mainly consists of
the processing of separation, deformation and consolidation of material by one
atom or by one molecule”. In 1980 another technologist, K. Eric Drexler, promoted
technological significance in nano scale and the main thing in nano dimension is
the properties of particles are far different than bulk scale properties.

I.3. Properties of Nanomaterials

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 Nanostructure materials are single phase or multiphase polycrystalline solids
with a typical average size a few nanometer (1=10 -9m). Basically, the range from
1-100nm is taken as nano range for convention as per National Nanotechnology
Initiative in the US and the size of hydrogen atom is considered as the lower limit
of nano whereas upper limit is arbitrary. Material is characterized by a large
number of interfaces in which the atomic arrangements are different from those of
crystal lattice. The basic classification of nanomaterials is done based on the
confinement, bulk structures show no confinements where as nano-wells and nano
wires can be obtained by 2D and 1D confinements respectively. The quantum
realm comes to the picture when there is a 3D confinement and leads to zero
dimension quantum structures, is quantum dot.

Living organisms are built of cells that are typically 10μm across. However,
the cell parts are much smaller and are in the sub-micron size domain. Even
smaller are the proteins with a typical size of just 5nm, which is comparable with
the dimensions of smallest manmade nanoparticles. This simple size comparison
gives an idea of using nanoparticles as very small probes that would allow us to
spy at the cellular machinery without introducing too much interference [5].
Understanding of biological processes on the nanoscale level is a strong driving
force behind development of nanotechnology [6].

I.4. Synthesis and Processing methods

The synthesis of nanomaterials can be well accomplished by two

approaches. Firstly, by “Bottom up” methods where small building blocks are
produced and assembled into larger structures. The main controlling parameter are
morphology, crystallinity, particle size and chemical composition by using
chemical synthesis, laser trapping, self assembly, colloidal aggregation techniques,

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secondly, “Top down” methods where larger objects are modified to give smaller
feature by film deposition and growth, nano imprint/ lithograph, etching
technology, mechanical polishing methods. These alterations in different
mechanical, thermal and other properties are due to increase in surface to volume
ratio of nanomaterials.

Fig.1. Schematic illustration of the

preparative methods of nanoparticles.

Synthesis of nanomaterials is most commonly done based on following three

strategies,

 Liquid- phase synthesis

 Gas- phase synthesis

 Vapour- phase synthesis

I.4.1. Liquid-phase synthesis

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 Liquid-phase transformations are possibly the most broadly used in order to
control morphology characteristics with certain “chemical” versatility and usually
follow a “bottom- up” approach. A number of specific methods have been
developed. Under liquid phase synthesis the technique used for synthesis are:

 Co-precipitation

 Sol-gel processing

 Micro-emulsions

 Hydrothermal/Solvo-thermal synthesis

 Microwave synthesis

 Sono-chemical synthesis

I.4.2. Co-precipitation method

This technique involves dissolving a salt precursor (chloride, nitrate, etc.) in

water (or other solvent) to precipitate the oxy-hydroxide from with the help of a
base. Very often, control of size and chemical homogeneity in the case of mixed-
metal oxides are difficult to achieve. However, the use of surfactants,
sonochemical methods, and high-gravity reactive precipitation appear as novel and
viable alternatives to optimize the resulting solid morphological characteristics.

I.4.3. Sol-gel processing

The method used to prepare metal oxides via hydrolysis of precursors,

usually alcoholic solution, resulting in the corresponding oxo-hydroxide.

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Condensation of molecules by giving off water leads to the formation of a network
of the metal hydroxide. Hydroxyl-species undergoes polymerization by
condensation and form a dense porous gel. Appropriate drying and calcinations
lead to ultrafine porous oxides.

I.4.4. Micro-emulsion technique

Microemulsion or direct/inverse micelles represent an approach based on the

formation of micro/nano reaction vessels under a ternary mixture containing water,
a surfactants and oil. Metal precusors on water will proceeds precipitation as oxo-
hydroxides within the aqueous droplets, typically leading to mono-dispersed
materials with size limited by the surfactant-hydroxide contact.

I.4.5. Solvothermal method

In this case, metal complexes are decomposed thermally either by

boiling in an inert atmosphere or using an autoclave with the help of pressure. A
suitable surfactant agent is usually added to the reaction media to control the
particle size growth and limit agglomeration.

I.4.6. Microwave synthesis

Microwave irradiation has received a considerable attention as a new

promising method for the one-pot synthesis of metallic nanostructures in solutions.
Microwave irradiation is an efficient heating method that has found a number of
applications in chemical

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synthesis because the technique is quite fast, simple and very energy efficient. The
main advantages of microwave-assisted reactions over conventional synthetic
methods are
 the kinetics of the reactions are increased by 1–2 orders of magnitude
 the initial heating process is rapid
 the microwaves induce the generation of localized high temperatures at
reaction sites, which enhances reaction rates
In addition, many experiments have shown that microwave heating can
lead to results that are different from those obtained by convectional heating.

I.4.7. Sono-chemical synthesis

Ultrasound is the part of the sonic spectrum which ranges from about 20
kHz to 10 MHz and can be roughly subdivided in three main regions: The range
from 20 kHz to around 1 MHz is used in sonochemistry. Sonochemistry is
typically based on acoustic cavitation phenomenon resulting from the continuous
formation, growth and implosive collapse of bubbles in the aqueous solution.
When solutions are exposed to strong ultrasound irradiation, sufficient sound
energy can drive the formation of novel nanostructures to occur under ultrasonic
irradiation.

Nanostructured materials can have significantly different properties,

depending on the chosen fabrication route. Each method offers some advantage
over the other while suffering limitation from the others too.

Out of plethora of size-dependant physical properties available to someone

who is interested in the practical side of nanomaterials, optical [7] and magnetic [8]
effects are the most used for biological applications.

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 The aim of this introduction is firstly to give reader a historic prospective of
nanomaterial application to biology and medicine, secondly to try to overview the
most recent developments in this field, and finally to discuss the hard road to
commercialisation. Hybrid bionanomaterials can also be applied to build novel
electronic, optoelectronics and memory devices (see for example) [9, 10].

I.5. Application of Nanomaterials

Once materials are prepared in the form of very small particles they change
significantly their physical and chemical properties. In fact in nano dimension,
percentage of surface molecule compare to bulk molecules is high and this
enhances the activity of the particle in nano dimension and therefore, the normal
properties of the particles like heat treatment, mass transfer, catalytic activity, etc.
are all increases. Compare to the organic nanoparticles, metal nanoparticles have
more industrial applications. Nanoparticles offer many new developments in the
field of biosensors, biomedicine and bio nanotechnology specifically in the
following areas of drug delivery, medical diagnostic and cancer treatment.
Nanostructured materials are becoming a part in human medical application,
including imaging or the delivery of therapeutic drugs to cell, tissue and organs.

Drug loaded nanoparticles interact with organ, tissue and are taken by cells.
Several studies have shown that the tissue, cell and even cell organelle distribution
drugs may be controlled and improved by their entrapment in colloidal nano
materials, mainly of the micellar structure, such as nano container. Magnetic
nanoparticles have been receiving considerable attention because of their wide
range of applications, such as the immobilization of the proteins and enzymes, bio
separation, immune assays, drug delivery and biosensors.

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 Ferromagnetic nanomaterials are of importance because of their reduced
sizes that can support only single magnetic domains. The recent synthesis of arrays
of 4mm diameter FePt nanoparticles with an extremely narrow size distribution has
promoted in a significant research effort in this area, due to their potential
technological application as recording media.

A list of some of the applications of nanomaterials to biology or medicine is given

below:

 Fluorescent biological labels [11-13]

 Drug and gene delivery [14, 15]
 Bio detection of pathogens [16]
 Detection of proteins [17]
 Probing of DNA structure [18]
 Tissue engineering [19, 20]
 Tumour destruction via heating (hyperthermia) [21]
 Separation and purification of biological molecules and cells [22]
 MRI contrast enhancement [23]
 Phagokinetic studies [24]
As mentioned above, the fact that nanoparticles exist in the same size
domain as proteins makes nanomaterials suitable for bio tagging or labelling.
However, size is just one of many characteristics of nanoparticles that itself is
rarely sufficient if one is to use nanoparticles as biological tags. In order to interact
with biological target, a biological or molecular coating or layer acting as a
bioinorganic interface should be attached to the nanoparticle. Examples of
biological coatings may include antibodies, biopolymers like collagen [25], or
monolayer of small molecules that make the nanoparticles biocompatible [26]. In
addition, as optical detection techniques are wide spread in biological research,

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nanoparticles should either fluoresce or change their optical properties. The
approaches used in constructing nano-biomaterials are schematically presented
below (see Figure 2.).

Fig.2. Approaches used in constructing nano-biomaterials.

Nano-particle usually forms the core of nano-biomaterial. It can be used as a

convenient surface for molecular assembly, and may be composed of inorganic or
polymeric materials. It can also be in the form of nano-vesicle surrounded by a
membrane or a layer. The shape is more often spherical but cylindrical, plate-like
and other shapes are possible. The size and size distribution might be important in
some cases, for example if penetration through a pore structure of a cellular
membrane is required.

The size and size distribution are becoming extremely critical when
quantum-sized effects are used to control material properties. A tight control of the

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average particle size and a narrow distribution of sizes allow creating very efficient
fluorescent probes that emit narrow light in a very wide range of wavelengths. This
helps with creating biomarkers with many and well distinguished colours. The core
itself might have several layers and be multifunctional. For example, combining
magnetic and luminescent layers one can both detect and manipulate the particles.

The core particle is often protected by several monolayer of inert material,

for example silica. Organic molecules that are adsorbed or chemisorbed on the
surface of the particle are also used for this purpose. The same layer might act as a
biocompatible material. However, more often an additional layer of linker
molecules is required to proceed with further functionalisation. This linear linker
molecule has reactive groups at both ends. One group is aimed at attaching the
linker to the nanoparticle surface and the other is used to bind various moieties like
biocompatibles (dextran), antibodies, fluorophores etc., depending on the function
required by the application.

I.6. Historical Background of TiO2

The element Titanium was discovered in 1791 by William Gregor, in
England. Gregor spent much of his time studying mineralogy, which led him to his
discovery. This happened when he discovered a sample of a black sandy substance
in his neighbourhood. He studied this substance and after he was assured that it
was a mineral, he called it menachanite. Four years later a man named Martin H.
Klaproth, recognized that there was a new chemical element in this mineral, he
later named it Titanium after the Titans, which were humongous monsters that
ruled the world in Greek mythology. Martin H. Klaproth was not able to make
the pure element of titanium however, he was only able to produce TiO 2, or
Titanium Dioxide [27]

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I.7. Occurrence
Titanium dioxide occurs in nature as well-known minerals rutile, anatase and
brookite, and additionally as two high pressure forms, a monoclinic baddeleyite-
like form and an orthorhombic α-PbO2-like form, both found recently at the Ries
crater in Bavaria [28, 29]. The most common form is rutile, which is also the most
stable form. Anatase and brookite both convert to rutile upon heating [30]. Rutile,
anatase and brookite all contain six coordinated titanium. Titanium dioxide has
eight modifications - in addition to rutile, anatase and brookite there are three
metastable forms produced synthetically (monoclinic, tetragonal and
orthorhombic), and five high pressure forms.
(α-PbO2-like, baddeleyite-like and
cotunnite-like)
Fig.3. Structure of TiO2 [31]
The naturally occurring oxides can be mined
and serve as a source for commercial titanium.
The metal can also be mined from the other minerals such as ilmenite or
leucoxene ores, or one of the purest forms, rutile beach sand. These ores are the
principal raw materials used in the manufacture of titanium dioxide pigment. The
first step is to purify the ore, and is basically a refinement step. Either the sulphate
process, which uses sulphuric acid as an extraction agent or the chloride process,
which uses chlorine, may achieve this. After purification the powders may be
treated (coated) to enhance their performance as pigments [32, 33].
I.8. Properties of Titania
Physical and mechanical properties of sintered titania are summarised in
table.1, while optical properties are shown in table.2.

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 PROPERTY RANGE
Density 4 g/cm3
Porosit 0%
y of Rupture
Modulus 140 MPa
Compressive Strength 680 MPa
Poisson’s Ratio 0.27
Fracture Toughness 3.2 Mpa.m-1/2
Shear Modulus 90 GPa
Modulus of Elasticity 230 GPa
Microhardness (HV0.5) 880

Resistivity (25 0C) 1012

Resistivity (700 0C) 4 ohm.cm
ohm.cm
2.5x10
Dielectric Constant (1MHz) 85
Dissipation factor (1MHz) 5x10-4
Dielectric strength 4 kVmm-1
Thermal expansion (RT-1000 0C) 9x10-6

Thermal Conductivity (25 0C) 11.7 WmK-1

Table.1. Physical and mechanical properties of Titania [4]

Phase Refractive Index Density (g.cm-3) Crystal Structure

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Anatase 2.49 3.84 Tetragonal
Rutile 2.91 4.26 Tetragonal

Table.2. Optical properties of Titania [34]

I.9. Uses
Titanium dioxide (TiO 2) is a multifaceted compound. It's the stuff that makes
toothpaste white and paint opaque. TiO2 is also a potent photocatalyst that can
break down almost any organic compound when exposed to sunlight, and a
number of companies are seeking to capitalize on TiO 2 reactivity by developing a
wide range of environmentally beneficial products, including self-cleaning fabrics,
auto body finishes, and ceramic tiles. Also in development is a paving stone that
uses the catalytic properties of TiO2 to remove nitrogen oxide from the air,
breaking it down into more environmentally benign substances that can then be
washed away by rainfall. Other experiments with TiO2 involve removing the
ripening hormone ethylene from areas where perishable fruits, vegetables, and cut
flowers are stored; stripping organic pollutants such as trichloroethylene and
methyl-tert-butyl ether from water; and degrading toxins produced by blue- green
algae. It remains to be seen, however, whether the formation of undesirable
intermediate products during these processes outweighs the benefits offered by
TiO2's photocatalytic properties [35]. Titanium dioxide is a well-known
photocatalyst for water and air treatment as well as for catalytic production of
gases. The general scheme for the photocatalytic destruction of organics begins
with its excitation by supra band gap photons, and continues through redox
reactions where OH radicals, formed on the photocatalyst surface, play a major

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role. Titanium dioxide is non-toxic and therefore is used in cosmetic products
(sunscreens, lipsticks, body powder, soap, pearl essence pigments, tooth pastes)
and also in special pharmaceutics. Titanium dioxide is even used in food stuffs,
for instance in the wrapping of salami. Small amounts added to cigar tobacco are
the cause of the white ash cigar smokers so cherish [36].
I.9.1 Oxygen Sensors
Even in mildly reducing atmospheres Titania tends to lose oxygen and become
sub stoichiometric. In this form the material becomes a semiconductor and the
electrical resistivity of the material can be correlated to the oxygen content of the
atmosphere to which it is exposed. Hence titania can be used to sense the amount
of oxygen (or reducing species) present in an atmosphere [3].
I.9.2 Antimicrobial Coatings
The photocatalytic activity of titania results in thin coatings of the material
exhibiting self-cleaning and disinfecting properties under exposure to UV
radiation. These properties make the material a candidate for applications such as
medical devices, food preparation surfaces, air conditioning filters, and sanitary
ware surfaces [37].

I.9.3. Applications
Applications for sintered titania are limited by its relatively poor mechanical
properties. It does however find a number of electrical uses in sensors and
electrocatalysis. By far its most widely used application is as a pigment, where it
is used in powder form, exploiting its optical properties [38].
I.9.4. Pigments
Titanium dioxide is the most widely used white pigment because of its
brightness and very high refractive index (n = 2.7), in which it is surpassed only

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by a few other materials. Approximately 4 million tons of pigmentary TiO 2 are
consumed annually worldwide. When deposited as a thin film, its refractive index
and colour make it an excellent reflective optical coating for dielectric mirrors and
some gemstones like "mystic fire topaz". TiO2 is also an effective opacifier in
powder form, where it is employed as a pigment to provide whiteness and opacity
to products such as paints, coatings, plastics, papers, inks, foods, medicines (i.e.
pills and tablets) as well as most tooth-pastes. Opacity is improved by optimal
sizing of the titanium dioxide particles. Titanium dioxide is often used to whiten
skimmed milk [39].
In cosmetic and skin care products, titanium dioxide is used as a pigment,
sunscreen and a thickener. It is also used as a tattoo pigment and instyptic pencils.
Titanium dioxide is produced in varying particle sizes, oil and water dispersable,
and with varying coatings for the cosmetic industry. This pigment is used
extensively in plastics and other applications for its UV resistant.
properties where it acts as a UV absorber dioxide, efficiently transforming
destructive UV light energy into heat. In ceramic glazes titanium acts as an
opacifier and seeds crystal formation. Titanium dioxide is found in almost every
sunscreen with a physical blocker because of its high refractive index, its strong
UV light absorbing capabilities and its resistance to discolouration under
ultraviolet light. This advantage enhances its stability and ability to protect the
skin from ultraviolet light. Sunscreens designed for infants or people with
sensitive skin are often based on titanium dioxide and/or zinc oxide, as these
mineral UV blockers are believed to cause less skin irritation than chemical UV
absorber ingredients. The titanium dioxide particles used in sunscreens have to be
coated with silica or alumina, because titanium dioxide creates radicals in the
photocatalytic reaction. These radicals are carcinogenic, and could damage the
skin [40].
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I.9.5. Photocatalyst
The photocatalytic properties of titanium dioxide were discovered by Akira
Fujishima in 1967 [9] and published in 1972 [41]. The process on the surface of
the titanium dioxide was called the Honda-Fujishima effect [42]. Titanium
dioxide, particularly in the anatase form, is a photocatalyst under
ultraviolet (UV) light. Recently it has been found that titanium dioxide, when
spiked with nitrogen ions or doped with metal oxide like tungsten trioxide, is also
a photocatalyst under either visible or UV light. It can also oxidize oxygen or
organic materials directly. Titanium dioxide is thus added to paints, cements,
windows, tiles, or other products for its sterilizing, deodorizing and anti-fouling
properties and is used as a hydrolysis catalyst. It is also used in the Graetzel cell, a
type of chemical solar cell. A substance that helps bring about a light catalyzed
reaction, such as chlorophyll in photosynthesis. Like photosynthesis, the reaction
continues throughout the day once begun [43]. Titanium dioxide has potential for
use in energy production: as a photocatalyst, it can
 Carry out hydrolysis; i.e., break water into hydrogen and oxygen. Were the
hydrogen collected, it could be used as a fuel. The efficiency of this process can
be greatly improved by doping the oxide with carbon [44].
 Titanium dioxide can also produce electricity when in nanoparticles form.
Research suggests that by using these nanoparticles to form the pixels of a screen,
they generate electricity when transparent and under the influence of light. If
subjected to electricity on the other hand, the
nanoparticles blacken, forming the basic characteristics of a LCD screen.
According to creator Zoran Radivojevic, Nokia has already built a functional
200*200-pixel monochromatic screen, which is energetically self-sufficient.

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In 1995 Fujishima and his group discovered the super hydrophilicity phenomenon
for titanium dioxide coated glass exposed to sun light [46]. This resulted in the
development of self-cleaning glass and anti-fogging coatings.TiO 2 incorporated
into outdoor building materials, such as paving stones in noxer blocks or paints,
can substantially reduce concentrations of airborne pollutants such as volatile

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organic compounds and nitrogen oxides. A photocatalytic cement that uses
titanium dioxide as a primary component, produced by Italcementi Group, was
included in Time's Top 50 Inventions of 2008 [47]. TiO 2 offers great potential as
an industrial technology for detoxification or remediation of waste water due to
several factors:-
 The process occurs under ambient conditions very slowly; direct UV light
exposure increases the rate of reaction.
 The formation of photocyclized intermediate products, unlike
direct photolysis techniques, is avoided.
 Oxidation of the substrates to CO2 is complete.
 The photocatalyst is inexpensive and has a high turn-over.

In the recent years, scaling optical and electronic properties of nano-

materials, which become strongly size dependant focused attention on the
preparation of nanoparticle semi-conductors [48]. TiO2 is the promising material
as semi- conductor having high photochemical stability and low cost. Well-
dispersed titania nanoparticles with very fine sizes are promising in many
applications such as pigments, adsorbents and catalytic supports [49]. In almost all
of these cases, when the particle size is reduced greatly, especially to several
nanometer scales, due to the large surface-to-volume ratio, some novel optical
properties can be expected [50]. It is not surprising; therefore, that much research
has been focused upon the reduction of particle size. It was usually found that
different routes often produce different results [51]. So it is necessary for us to
investigate in detail the methods which may have important effect upon the
particle size.

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 In the present work, we have synthesized TiO 2 nanoparticles via two
different routes (sol-gel route and hydrothermal method) and tried to analyze the
two on the basis of their crystallinity, crystallite size, band gap and structural
properties. X-ray diffraction (XRD) is used to calculate crystallite size. and
Scanning electron micrograph (SEM) images are shown to clearly see the particle
size and grain size respectively.

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II Review of Literature

Hengbo Yin et al. [2001] studied the synthesis of phase- pure nano-
particulate anatase and rutile TiO2 using TiCl4 aqueous solutions. Here phase- pure
anatase TiO2 nanocrystallites ranging from 2 to 10 nm in size were synthesized
directly from a TiCl4 aqueous solution using citric acid as an additive. Citric acid
was found to play a decisive role in stabilizing the TiCl 4 aqueous solution, leading
to the selective formation to the anatase TiO 2 nanocrystallites in hydrothermal
autoclaving. On the other hand, hydrothermal autoclaving of the rutile TiO 2
embryos prepared by room temperature peptization of the TiCl 4 aqueous solution
give rod-like rutile TiO2 nanocrystallites under neutral conditions. The presence of
KCl or NaCl enhanced the crystal growth of the rutile embryos in the hydrothermal
process [52].
In this study they have concluded that Nano-particulate rutile TiO 2
nanocrystallites with rod-like shapes were prepared by hydrothermal treatment at
high temperature of the rutile embryos prepared by hydrolysis of TiCl 4 aqueous
solution at low temperature. Water as a neutral reaction medium was beneficial to
the formation of the well-particulate rutile nanocrystallites. The presence of NaCl
and KCl in the hydrothermal processing of rutile embryos enhanced the crystal
growth via coalescence of the embryos.

Chie- I Wu et al. [2008] studied that Nano-sized titanium dioxide TiO2 powder
was successfully prepared from its precursor titanium (IV) isopropoxide
(TTIP) by a system comprising of

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supercritical fluids microemulsion and supercritical-drying method, in which TTIP
reacted in reversed micelles formed by surfactant Zonyl FSJ employing a
supercritical carbon dioxide system. The milky white product, collected from the
bottom of the pressure cell turned into sol– gel after sitting in the air for 5 days.
Amorphous TiO2 particles with particles size 2–7 nm can be obtained from the sol–
gel by the supercritical-drying method. The amorphous TiO 2 particles were
converted to anatase phase by calcining at 500 0C [53].

Yadong Yao et al. [2009] reported that Titanium dioxide (TiO2) porous ceramic
pellets with three dimension nano-structure were prepared using nano TiO 2
powder. The TiO2 porous ceramic pellets were composed of TiO 2 nanoparticles
with 14–16 nm in diameter and had porosity of 74.85%. The mean pore size of the
TiO2 porous ceramic pellets was 20.73 nm and the main pore size ranged from 3 to
16 nm. The mass loss of the TiO2 ceramic pellets was less than 5% after 20 d
immersion in water. The antibacterial properties of the TiO 2 pellets were studied.
The sterilization rate of Colibacillus (hospital polluted water with bacterium) can
reach 99% after 3 h photocatalytic process and these TiO 2 pellets are easy to be re-
activated and cyclically be used [54].

Zhang et al. [2005] studied that TiO2 nanoparticles were introduced into High-
impact polystyrene (HIPS) in the form of master batch where TiO 2 was pre-
dispersed in HIPS by melt compounding [27]. Energy dispersive X-ray
spectrometer (EDS) composition distribution maps indicate that TiO2
nanoparticles are dispersed randomly in the nanocomposites comprising low TiO2
content (≤2wt.%), while the dispersion is inferior at high TiO 2 content. The
variation in the dispersion behavior influences the mechanical properties of
nanocomposites. Significantly, the surface of nanocomposites shows a strong

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absorption of UV light in the wavelength range of 250∼400 nm, an increase in the
TiO2 content of nanocomposites raises the absorbance in the region. HIPS/TiO 2
nanocomposites have a satisfactory antibacterial effect on Escherichia coli (E. coli)
and Staphylococcus aureus (S. aureus) [55].

Xu Wei-guo et al. [2004] studied that TiO2 nanometer thin film with
photocatalytic antibacterial activity were prepared by the sol gel method on fused
quartz and soda lime glass precoated with a SiO 2 layer. The thin films were
characterized by X-ray photoelectron spectroscopy, scanning electron microscopy
and X-ray diffraction. The results show that sodium and calcium diffusion into
nascent TiO2 film is effectively retarded by the SiO2 layer precoated on the soda
lime glass. The antibacterial activity of the films was determined. The crystalline
of TiO2 nanometer thin film has an important effects on the antibacterial activity of
the film [56].

Vilas S. Desai et al. [2009] studied that the process of heterogeneous

photocatalysis (HP) using TiO2 photocatalysts. This study reports the synthesis of
a visible light responsive nanosized TiO2 photocatalyst by a modified sol-gel
process. The synthesized TiO2 photocatalyst exhibits photocatalytic activity against
some common pathogenic microorganisms such as Escherichia coli, Pseudomonas
aeruginosa, Klebsiella pneumonia and Staphylococcus aureus under visible light
illumination. TiO2 is known to exhibit photocatalytic activity under UV light
irradiation, the results obtained in the study using solar irradiation are very
promising and enables the use of cheaply available solar energy for the process of
photocatalysis [57].
In this study they have concluded that TiO2 synthesized by sol-gel method exhibits
bactericidal activity when irradiated with sunlight against the common human

23
pathogens tested. This opens up newer avenues for the development of solar
assisted alternative technologies for disinfection of water bodies contaminated with
pathogenic organisms.

Guifen Fu et al. [2005] studied a sol-gel chemistry approach was used to fabricate
nanoparticles of TiO2 in its anatase form. The particle size is shown to be sensitive
to the use of HClO4 or HNO3 as acid catalyst. The gold-capped TiO2
nanocomposites were processed by the reduction of gold on the surface of the TiO 2
nanoparticles via a chemical reduction or a photoreduction method. Different
percentages of vanadium-doped TiO2 nanoparticles, which extended the TiO2
absorption wavelength from the ultraviolet to the visible region, were successfully
prepared. The TiO2 nanocomposite coatings have been applied on glass slide
substrates. The antibacterial activity of TiO2 nanocomposites was investigated
qualitatively and quantitatively. Two types of bacteria, Escherichia coli (DH 5R)
and Bacillus megaterium (QM B1551), were used during the experiments. Good
inhibition results were observed and demonstrated visually. The quantitative
examination of bacterial activity for E. coli was estimated by the survival ratio as
calculated from the number of viable cells, which form colonies on the nutrient
agar plates [58].

Huijun Zhang et al. [2006] studied the antibacterial properties of nanometer TiO 2
thin films, nanometer Fe3+-TiO2 films have been prepared on glass by RF
magnetron co-sputtering method. The influence of Fe element and calcination
temperature on the films structure was investigated. The principle of substitution
impurity to improve the activity was discussed. The bactericidal activity for the
bacteria cells was estimated by relative number of bacteria survived calculated
from the number of viable cells which from colonies on the nutrient agar plates.

24
The crystallite size of the anatase phase increases with increasing calcinations
temperature. The nanometer Fe3+ -
TiO2 thin films exhibited a high antibacterial activity, which was enhanced with the
increase of temperature of thermal treatment and formation of anatase crystalline
structure [59].

Iram B. Ditta et al. [2008] studied that TiO2-coated surfaces are increasingly
studied for their ability to inactivate microorganisms. The activity of glass coated
with thin films of TiO2, CuO and hybrid CuO/ TiO2 prepared by atmospheric
Chemical Vapour Deposition and TiO2 prepared by a sol–gel process was
investigated using the inactivation of bacteriophage T4 as a model for inactivation
of viruses. The chemical oxidising activity was also determined by measuring
stearic acid oxidation. The results showed that the rate of inactivation of
bacteriophage T4 increased with increasing chemical oxidising activity with the
maximum rate obtained on highly active sol– gel preparations. However, these
were delicate and easily damaged unlike the Ap-CVD coatings. Inactivation rates
were highest on CuO and CuO/TiO2 which had the lowest chemical oxidising
activities. The inactivation of T4 was higher than that of Escherichia coli on low
activity surfaces. The combination of photocatalysis and toxicity of copper acted
synergistically to inactivate bacteriophage T4 and retained some self-cleaning
activity. The presence of phosphate ions slowed inactivation but NaCl had no
effect. The results show that TiO2/CuO coated surfaces are highly antiviral and
may have applications in the food and health care industries [60].

S.Q Sun et al. [2008] studied a liquid phase deposition (LPD) method that has
been devised for the deposition of Ag–TiO 2 thin films on ceramic tiles with glazed
surface at a low temperature. The Ag–TiO 2 thin films obtained were well-adhered,

25
homogenous and coloured by interference of reflected light. From these analyses, it
was found that silver ions were trapped in TiO2 matrix and their reduction could be
achieved at 600 ºC annealing temperature. The antibacterial activity against S.
aureus and E. coli has been studied applying the so called antibacterial-drop test.
The Ag–TiO2 thin films exhibited a high antibacterial activity. The releasing rate
of silver ions from
the Ag–TiO2 film was 0⋅118 μg/ml during 192 hrs. The antibacterial effect of Ag–
TiO2 thin film
before and after aging in a weathering chamber for 48 h was compared and the
results show that
the antibacterial activity is not compromised after weathering [61].

Huanjun Zhang et al. [2009] studied the antimicrobial properties of Ag-based

materials have been actively investigated recently. In such materials, control of the
size of the Ag particles is critical to their bactericidal performance. Anovel one-pot
sol-gel scheme is described here. It incorporates room temperature ionic liquids
(RTILs) to synthesize Ag/TiO2 nanocomposite powders. The presence of RTILs is
indispensable to the control of the size of the Ag particles. Highly dispersed,
metallic Ag nanoclusters are formed on the TiO 2 nanoparticles surface after
calcination of the gel. The average cluster size of Ag can be controlled to be below
5 nm with high Ag loading (7.4 wt%). Antibacterial tests using 7.4wt% Ag/TiO 2
on 105 CFU/ml Escherichia coli (E. coli) strains incubated on Luria-Bertani
(LB)/agar plates show that bacterial growth was inhibited by 98.8% at an Ag
concentration of 1.2 μg/ml. Complete inhibition was achieved at 2.4 μg (Ag)/ml.
At this concentration, a 3.9wt% Ag/TiO2 sample, with a smaller Ag cluster size
(<3 nm), completely inhibited bacterial growth in a more populated E. coli
community (∼3 × 106 CFU/m;). In fact, 1.6 μg/ml Ag suppressed bacterial growth

26
by 99.9% with 3.9wt% Ag/TiO2. Both the small Ag cluster size and the unique
structure of TiO2 nanoparticles supporting highly dispersed Ag clusters are
identified to be the sources of a superior bactericidal performance of the RTILs
derived Ag/TiO2 [62].

Materials & Methods

Preparation of TiO2 Nanoparticles

3.1. Materials

Chemical reagents such as high pure Titanium (IV) iso-propoxide (TTIP)

were purchased from Alfa aeser. Absolute ethanol was obtained from Merck and
all the other chemicals used in this work were of analytical grade. Unless otherwise
mentioned, double distilled water was used for the preparation of aqueous
solutions and washings.
3.2. Synthesis of TiO2 by sol gel method:

27
 All the reagents used were of analytical grade and no further purification was
done before use. The sol-gel synthesized TiO2 was obtained from Titanium (IV)
iso-propoxide (TTIP) was dissolved in absolute ethanol and distilled water was
added to the solution in terms of a molar ratio of Ti: H 2O = 1:4. Nitric acid was
used to adjust the pH and for restrain the hydrolysis process of the solution. The
solution was vigorously stirred for 30 min in order to form sols. After aging for 24
hrs, the sols were transformed into gels. In order to obtain nanoparticles, the gels
were dried under 120oC for 2 hr to evaporate water and organic material to the
maximum extent. Then the dry gel was sintered at 450 oC for 2 hrs were
subsequently carried out to obtain desired TiO2 nanocrystalline.

3.3. Synthesis of TiO2 nanoparticles by hydrothermal method:

Analytical grade titanium tetrachloride was adopted as the source material
and sodium hydroxide as mineralizer. An aqueous solution of titanium was
obtained by mixing one molar stoichiometric ratio of TTIP in 50 ml of distilled
water. The solution 2-3 mol of NaOH with stirring at several minutes, resulting in
a white colloidal sol. The final volume was adjusted to 90 ml using distilled water.
Therefore, 90ml sol was transferred to a 100 ml Teflon lined auto clave vessel. The
sealed vessel was heated to 240 oC for 12 hrs and the resultant precipitate was dried
at 450 oC for 2 hrs to obtain TiO2 nanoparticles.
3.4. Characterization Studies
The XRD pattern of TiO2 was obtained using a X-ray diffractometer Schimadzu
model: XRD 6000 with CuKα radiation in the range of 20-70 (λ=0.154nm). The
surface morphologies of TiO2 samples were studied using the Hitachi S-4500
Scanning Electron Microscope (SEM). UV-Vis absorption spectra TiO 2 were

28
recorded using a Varian Cary 5E spectrophotometer at room temperature in the
range of 200- 700nm.The photoluminescence (PL) spectra of TiO2 were recorded
by the Perkin-Elmer lambda 900 spectrophotometer with a Xe lamp as the
excitation light source.

IV Results & Discussion

4.1. HRSEM Investigation of TiO2 Nanoparticles

The scanning electron microscope (SEM) uses a focused beam of high-

energy electrons to generate a variety of signals at the surface of solid
specimens. The signals that derive from electron- sample interactions reveal
information about the sample including external morphology, chemical
composition, and crystalline structure and orientation of materials making up the
sample. In most applications, data are collected over a selected area of the surface
of the sample, and a 2-dimensional image is generated that displays spatial
variations in these properties. Areas ranging from approximately 1 cm to 5
microns in width can be imaged in a scanning mode using conventional SEM
techniques (magnification ranging from 20X to approximately 30,000X,
spatial resolution of 50 to 100 nm). The SEM is also capable of performing

29
analyses of selected point locations on the sample; this approach is especially
useful in qualitatively or semi-quantitatively determining chemical
compositions (using EDS), crystalline structure.
SEM images of the nanoparticles prepared via both the routes are shown in
Fig. 4, Fig. 5 shows the SEM image of sol-gel derived nanoparticles. Clear
nanostructures can be seen having grain size of ~ 30 nm. The crystallite size as
observed from TEM in this case is ~ 8 nm. This shows that one grain in sol-gel
derived nanoparticles is approximately equal to three crystallites. So it is clear that
the nanoparticles seen by SEM image consist of a number of crystallites which are
seen by TEM image. SEM image of nanoparticles prepared by hydrothermal
method is shown in
Fig.5. Grain size in this case is ~ 100 nm. Crystallite size as seen from TEM image
is ~ 19 nm in this case. This shows that one grain in hydrothermal derived
nanoparticles consists of approximately five crystallites. XRD results are
confirmed by the combined study of these SEM images.

30
Fig.4 (a) SEM micrographs of TiO2 nanoparticles synthesized via sol-gel route

Fig.5(b) SEM micrographs of TiO2 nanoparticles synthesized via

hydrothermal method.

4.1. HRTEM Analysis of TiO2 nanoparticles

HRTEM image of a prepared TiO 2 with different methods such as, Sol-

31
Gel and hydtrothermal were shown in Figure. 6 (a) and (b). As shown in Figure
6a and b the diameter and length of the NPs were found to be ∼100 nm and
∼200nm, respectively. The phase and crystal structure of the TiO 2 NPs were
confirmed by electron diffraction pattern.The corresponding electron
diffraction pattern (Figure 6) displays the poly-crystalline nature and could be
indexed to the mixed anatase and rutile TiO 2 phase nanostructures. Fig. 6b
shows the TEM image of TiO 2 NPs obtained by a hydrothermal method. These
nanoparticles products have an intact morphology with an average diameter of
200nm. As observed from the corresponding diffraction patterns (Fig. 6b), TiO 2
NPs possess highly crystallized anatase structure without any impurity phase.
which is in good agreement with the obtained XRD pattern .

(b)
(a)
Fig.6. HRTEM image of TiO 2 NPs synthesized via Sol-Gel route (a) and
Hydtrothermal (b).
4.2. X-RAY Diffraction method
X-ray diffraction is a versatile, non-destructive analytical method for
identification and quantitative determination of various crystalline forms, known as
‘phases’ of compound present in powder and solid samples. Diffraction occurs as
waves interact with a regular structure whose repeat distance is about the same as

32
the wavelength. The phenomenon is common in the natural world, and occurs across
a broad range of scales. For example, light can be diffracted by a grating having
scribed lines spaced on the order of a few thousand angstroms, about the wavelength
of light. It happens that X-rays have wavelengths on the order of a few angstroms,
the same as typical inter-atomic distances in crystalline solids. That means X-rays
can be diffracted from minerals which, by definition, are crystalline and have
regularly repeating atomic structures. When certain geometric requirements are met,
X-rays scattered from a crystalline solid can constructively interfere, producing a
diffracted beam. In 1912, W. L. Bragg recognized a predictable relationship among
several factors are,
1. The distance between similar atomic planes in a mineral (the interatomic spacing)
which we call the d-spacing and measure in angstroms.
2. The angle of diffraction which we call the theta angle and measure in degrees. For
practical reasons the diffractometer measures an angle twice that of the theta angle.
Not surprisingly, we call the measured angle '2-theta'.
3. The wavelength of the incident X-radiation, symbolized by the Greek letter
lambda and, in our case, equal to 1.54 angstroms.
nλ= 2dsinθ ,
where,
λ- wavelength of X-ray d-interplaner spacing,

33
 θ-diffraction angle n-0,1,2,3….
Fig.7. Scematic diagram of Bragg’s diffraction
Here, XRD was done by the X-ray diffraction of the as milled powder
samples were performed using the diffractometer. X-Ray diffraction patterns
were recorded from 20˚ to 90˚ with a PANalytical system diffractometer
(Model: DY-1656) using Cu Kα (λ=1.542Ao) with an accelerating voltage of 40
KV. Data were collected with a counting rate of 1˚/min. The Kα doublets were
well resolved. From XRD, the crystallite size can be found out by using the
scherrer’s
formula

Where,

P – crystallite size
λ – wavelength(1.54A0),
β - Full maxima half
width,

34
 2000

1500
Intens ity (a.u.)

1000

500

0
10 20 30 40 50 60 70 80
2 theta(degree)

pattern of

35
TiO2 nanoparticles synthesized via hydrothermal method.
IV.3. UV-visible Spectral Characterization Studies
The optical absorbance coefficient α of a semiconductor close to the band edge
can be expressed by the following equation:

When α is the the absorption coefficient, Eg is the absorption band gap, A is

constant, n depends on the nature of the transitions, n may have values ½, 2,
3/2 and 3 corresponding to allowed direct, allowed indirect, forbidden
direct and forbidden indirect transitions respectively. In this case n=1/2 for
direct allowed transition [63]. The absorption spectra of TiO 2 nanoparticles are
shown in Fig.10. The absorption band edges were estimated around 351 and 362
nm (about 3.54 and 3.43eV). The band gap energy can be determined by
extrapolation to the zero coefficients, which is calculated from the above

equation. The intercept of the tangent to the plot αh versus

hfig.10) gives a good approximation of the band gap energy for this
direct band gap materials.

0.5

0.4
Absorbance (arb. unit)

Sol-Gel method

0.3
Hydtrothermal matheod

0.2

0.1

0.0 36
300 400 500 600 700 800
Wavelength (nm)
Fig.10. UV-vis absorption spectra of TiO 2 nanoparticles via different method.

4.4. Photo- Luminescence spectra

Photoluminescence (PL) spectra of the nanoparticles obtained by both the
processes are shown in Fig.10. The first peak in PL spectra between 320-400 nm
corresponds to the direct recombination between electrons in the conduction
band and holes in the valence band [64]. TiO 2 nanoparticles prepared via sol-gel
method show high luminescence than hydrothermal derived nanoparticles. This
could be due to the chemical instability caused during the fabrication process. As
can be seen from the PL spectrum of sol-gel derived nanoparticles, the intensity
peak is observed at 354 nm. If we calculate the band gap value from this
wavelength, it comes out to be 3.5 eV. The PL intensity peak in case of
hydrothermal derived nanoparticles is observed at 359 nm. From this value, band
gap comes out to be 3.45 eV.

Fig.11.

37
Photoluminescence of TiO2 nanoparticles obtained via different method.
V Summary & Conclusion

TiO 2 nanoparticles were prepared via sol-gel and hydrothermal methods.

SEM images of the nanoparticles prepared via both the routes are shown in Fig.
4and 5 shows the SEM image of sol-gel derived nanoparticles. Clear
nanostructures can be seen having grain size of ~ 30 nm.
XRD of these samples reveals that the required phase is present with a little
amount of impurities. The Kα doublets were well resolved. From XRD, the
crystallite size can be found out by using the scherrer’s formula.
The absorption spectra (UV-Vis) of TiO 2 nanoparticles are shown in Fig.7. The
absorption band edges were estimated around 351 and 362 nm.
Photoluminescence (PL) spectra of the nanoparticles obtained by both the
processes are shown in Fig. 11. The first peak in PL spectra between 320-400 nm
corresponds to the direct recombination between electrons in the conduction
band and holes in the valence band . TiO 2 nanoparticles prepared via sol-gel
method show high luminescence than hydrothermal derived nanoparticles. This
could be due to the chemical instability caused during the fabrication process. As
can be seen from the PL spectrum of sol-gel derived nanoparticles, the intensity
peak is observed at 354 nm. If we calculate the band gap value from this
wavelength, it comes out to be 3.5 eV.

38
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