Synthesis and Characterization of Bismuth Oxyiodide

A PROJECT REPORT
Submitted by
DIPTI OHOL

Under the guidance of

Dr.Sambhaji S. Warule
Department of physics
Assistant Professor
Nowrosjee Wadia College Pune- 411001

Project submitted in partial fulfilment for the award of the degree in

MSc Physics
Savitribai Phule Pune University.
2021-2022
 Modern education society’s
NOWROSJEE WADIA COLLEGE, PUNE
DEPARTMENT OF PHYSICS

CERTIFICATE

This is certifying that Dipti Ohol has satisfactorily completed

the project entitled “Synthesis and Characterization of Bismuth
Oxyiodide” towards partial fulfilment of MSc (physics) course
affiliated to
Savitribai Phule Pune University during the academic year 2021-2022.

Project Guide Head of Department

Dr.Sambhaji S.Warule Prof.(Dr.) F.I. Surve
 AKNOWLEDGEMENT

I have great pleasure in presenting this project report entitled

“Synthesis and Characterization of Bismuth Oxyiodide” for partial
fulfilment of the degree of MSc.
First and foremost, I would like to thank Almighty for giving me
strength, knowledge, ability and opportunity to undertake this research
and to preserve and complete it satisfactorily. I would like to express
my deep and sincere gratitude to my Guide Dr.Sambhaji S.Warule for
guiding me to accomplish this dissertation work. It was my privilege to
have guidance of him also indeed grateful to him for providing helpful
suggestions from time to time. Due to his constant encouragement and
inspiration I am able to present this dissertation.
Last but not the least, it would not have possible for me to complete
this report without support of my friends.

Dipti Ohol
 ABSTRACT
A nanostructured bismuth oxyiodide (BiOI) have been prepared
using controlled precipitation method. The resultant products were
characterized by X-ray diffraction (XRD), Scanning electron
microscopy (SEM), field emission scanning electron microscopy
(FESEM), UV-Visible spectroscopy and photocatalytic activity so as
to reveal their phase,morphological and structural properties. Organic
dyes,such as methyl orange(MO) and Coomassie brilliant blue
(CBB),were used to check the photocatalytic performance of the
composites when undergoing photodegradation in visible light. The
XRD patterns of as-synthesized pristine BiOI nanocomposite are at the
outset diffraction patterns appear very identical exhibiting a set of well
defined diffraction peaks,expect variation in intensity of the diffraction
peaks.The optical properties were investigated using UV-visible
spectroscopy.
Various synthesis methods have been reported to obtain different
morphologies of BiOI such as nanosheets,microspheres.
Furthermore,very recently few researchers have attempted BiOI
comopsites.However,studies on low tempreature synthesis of BiOI
nanostructures.A simple room temperature precipitation method is
employed to synthesize BiOI.
 INDEX

CHAPTER 1: Introduction to Nanotechnology

1.1 Introduction of Nano materials
1.2 Challenges in Nanotechnology
1.3 History of Nano materials
1.4 Classcification of Nanomaterials
1.5 Properties of Nanomaterials
1.6 Applications of Nanotechnology
1.7 Synthesis methods of Nanoparticles
1.8 Bismuth Oxyhalides
1.9 Bismuth Oxyiodide
CHAPTER 2: Synthesis and Characterization of BiOI
2.1 Synthesis of BiOI
2.2 Characterization Techniques
 X-Ray Diffraction
 Field Eimission Scanning Electron Microscope
 UV- visible Spectroscopy
 Photocatalytic Activity
CHAPTER 3: Results and Discussion
3.1 X-Ray Diffraction
3.2 Field Emission Scanning Electron Microscope
3.3 UV-visible Spectroscopy
3.4 Photocatalytic Activity
CHAPTER 4: References
 CHAPTER 1

INTRODUCTION TO NANO PARTICLES

Nanotechnology deals with small structures or small-sized materials. The

typical dimension spans from sub nanometer to several hundred
nanometers. A nanometer (nm) is one billionth of a meter. One nanometer is
approximately the length equivalent to 10 hydrogen or 5 silicon atoms
aligned in a line. Small features permit more functionality in a given space,
but nanotechnology is not only a simple continuation of miniaturization
from micron meter scale down to nanometer scale. Materials in the
micrometer scale mostly exhibit physical properties the same as that of bulk
form; however, materials in the nanometer scale may exhibit physical
properties distinctively different from that of bulk.

CHALLENGES IN NANOTECHNOLOGY

Challenges include the building and demonstration of novel tools to study at

the nanometer level what is being manifested at the macro level. The small
size and complexity of nanoscale structures make the development of new
measurement technologies more challenging than ever. New measurement
techniques need to be developed at the nanometer scale and may require
new innovations in metrological technology. Measurements of physical
properties of nanomaterials require extremely sensitive instrumentation,
while the noise level must be kept very low. Although material properties
such as electrical conductivity, dielectric constant, tensile strength, are
independent of dimensions and weight of the material in question, in
practice, system properties are measured experimentally.
For example, electrical conductance, capacitance and tensile stress are
measured and used to calculate electrical conductivity, dielectric constant
and tensile strength. As the dimensions of materials shrink from centimeter
or millimeter scale to nanometer scale, the system properties would change
accordingly, and mostly decrease with the reducing dimensions of the
sample materials. Such a decrease can easily be as much as 6 orders of
magnitude as sample size reduces from centimeter to nanometer scale.

HISTORY OF NANOMATERIALS

History and development of nanomaterials Humans already exploited the

reinforcement of ceramic matrixes by including natural asbestos nanofibers
more than 4,500 years ago. The Ancient Egyptians were also using NMs
more than 4000 years ago based on a synthetic chemical process to
synthesize ≈5 nm diameter PbS
NPs for hair dye. Similarly, “Egyptian blue” was the first synthetic pigment
which was prepared and used by Egyptians using a sintered mixture
nanometer-sized glass and quartz around 3rd century BC. In ancient
geographical regions of the Roman Empire, including countries such as
Egypt, Mesopotamia, and Greece, the extensive use of Egyptian blue for
decorative purposes has been observed during archaeological explorations.
The synthesis of metallic NPs via chemical methods dates back to the 14th
and 13th century BC when Egyptians and Mesopotamians started making
glass using metals, which can be cited as the beginning of the metallic
nanoparticle era. These materials may be the earliest examples of synthetic
NMs in a practical application. From the late Bronze Age (1200–1000 BC),
red glass has been found in Frattesina di Rovigo (Italy) that is colored by
surface plasmon excitation of Cu NPs. Similarly, the Celtic red enamels
originating from the 400–100 BC period have been reported to contain Cu
NPs and cuprous oxide (cuprite Cu2O). Nevertheless, a Roman glass work
piece is the most famous example of ancient metallic NPs usage. Later, red
and yellow colored stained glass found in medieval period churches was
produced by incorporating colloidal Au and Ag NPs, respectively. During
the 9th century, Mesopotamians started using glazed ceramics for metallic
luster decorations. These decorations showed amazing optical properties
due to the existence of distinct Ag and/or Cu NPs isolated within the
outermost glaze layers. These decorations are an example of metal
nanoparticles that display iridescent bright green and blue colors under
particular reflection conditions. TEM analysis of these ceramics revealed a
double layer of Ag NPs (5–10 nm) in the outer layer and larger ones (5–20
nm) in the inner layer. The distance was observed to be constant at about
430 nm in between two layers, giving rise to interference effects. The
scattered light from the second layer leads to the phase shift due to the
scattering of light by the first layer. This incoming light wavelength
dependent phase shift leads to a different wavelength while scattering.
Later, the red glass was manufactured using this process all over the world.
In the mid-19th century, a similar technique was used to produce the
famous Satsuma glass in Japan. Today manufactured NMs can significantly
improve the characteristics of bulk materials, in terms of strength,
conductivity, durability, and lightness, and they can provide useful
properties (e.g., self-healing, self-cleaning, anti-freezing, and antibacterial)
and can function as reinforcing materials for construction or sensing
components for safety. Notwithstanding the other possible benefits, simply
taking advantage of the beneficial size and shape effects to improve the
appearance of materials is still a major application of NPs. Moreover, the
commercial use of NMs is often limited to the bulk use of passive NMs
embedded in an inert (polymer or cement) matrix, forming a
nanocomposite. In 2003, Samsung introduced an antibacterial technology
with the trade name Silver Nano™ in their washing machines, air
conditioners, refrigerators, air purifiers and vacuum cleaners, which use
ionic Ag NPs. NPs and NSMs are extensively used in auto production: as
fillers in tires to improve adhesion to the road, fillers in the car body to
improve the stiffness, and as transparent layers used for heated, mist and
ice-free, window panes. By the end of 2003, Mercedes-Benz brought a NP-
based clear coat into series production for both metallic and nonmetallic
paint finishes. The coating increases the scratch resistance and enhances the
gloss. Liquid magnets, so-called ferrofluids, are ultrastable suspensions of
small magnetic NPs with superparamagnetic properties. Upon applying a
magnetic field, the liquid will macroscopically magnetize, which leads to
the alignment of NPs along the magnetic field direction. Recent research
has focused on creating enhanced Earthbased astronomical telescopes with
adaptive optics and magnetic mirrors with the shape-shifting capability
made up of ferrofluids. TiO2 NPs are commercially used in solar cells with
dye-sensitization ability.
CLASSIFICATION OF NANOMATERIALS
Nanomaterials have extremely small size which having at least one
dimension 100 nm or less. Nanomaterials can be nanoscale in one
dimension (eg. surface films), two dimensions (eg. strands or fibres), or
three dimensions (eg. particles). They can exist in single, fused, aggregated
or agglomerated forms with spherical, tubular, and irregular shapes.
Common types of nanomaterials include nanotubes, dendrimers, quantum
dots and fullerenes. Nanomaterials have applications in the field of nano
technology, and displays different physical chemical characteristics
from normal chemicals (i.e., silver nano, carbon nanotube, fullerene,
photocatalyst, carbon nano, silica). According to Siegel, Nanostructured
materials are classified as Zero dimensional, one dimensional, two
dimensional, three dimensional nanostructures.
Classification of Nanomaterials (a) 0D spheres and clusters; (b) 1D
nanofibers, nanowires, and nanorods; (c) 2D nanofilms, nanoplates, and
networks; (d) 3D nanomaterials. Nanomaterials are materials which are
characterized by an
ultra fine grain size (< 50 nm) or by a dimensionality limited to 50 nm.
Nanomaterials can be created with various modulation dimensionalities
as defined by Richard W. Siegel:zero(atomic clusters, filaments and
cluster assemblies), one (multilayers), two (ultrafine-grained overlayers
or buried layers), and three (nanophase materials consisting of
equiaxed nanometer sized grains) .
PROPERTIES OF NANOMATERIALS.
1) Mechanical properties-Mechanical properties of materials depends
upon the composition and bonds between the atoms, viz. covalent, ionic,
mettallic, etc. when the size of materials is reduced to nanoscale, materials
tends to single crystals. It is possible to determine various mechanical
properties like elastic, hardness, ductility, etc. of different nanostructures.
Techniques like bending measurement, velocity of sound measurement,
identification etc. can be used. in case of mettalic nanocrystalline materials
that elastic modulii reduce dramatically.
2) Thermal properties- Thermal properties of Nanomaterials have only
shown a slower progress. This is partially due to the difficulties of
experimental 12 measuring and controlling the thermal transport in
nanoscale dimensions. Thermal properties of Nanomaterials, recent
advances in experiments have shown that certain Nanomaterials have
extraordinarily thermal properties compared to their macroscopic
counterparts. For example, silicon nanowire has a much smaller thermal
conductivities compared to bulk silicon because of tubular structures of
carbon. In Nanomaterials there is huge fraction of surface atoms and also
large surface energy. Also the lattice constants are reduced due to decrease
in dimensions. So the Nanomaterials have lower melting point or phase
transition temperature. The self-purification is an intrinsic thermodynamic
property of Nanomaterials. Due to a reduction in size, there is an increase in
perfection. Atomic force microscope (AFM) has been introduced to
measure the thermal transport of nanostructures with nanometer-scale high
spatial resolution, providing a promising way to probe the thermal
properties.
3) Electrical properties- The effects of size on electrical conductivity of
nanostructures and Nanomaterials are complex, since they are based on
distinct mechanisms. These mechanisms can be generally grouped into four
categories: surface scattering including grain boundary scattering, quantized
conduction including ballistic conduction, Coulomb charging and tunneling,
and widening and discrete of band gap, and 13 change of microstructures. In
addition, increased perfection, such as reduced impurity, structural defects
and dislocations, would affect the electrical conductivity of nanostructures
and Nanomaterials. Conventional and rechargeable batteries are used in
almost all applications that require electric power. The energy density
(storage capacity) of these batteries is quite low requiring frequent
recharging. Nanocrystalline materials are good candidates for separator
plates in batteries because they can hold considerably more energy than
conventional ones. Nickel-metal hydride batteries made of nanocrystalline
nickel and metal hydrides are envisioned to require far less frequent
recharging and to last much longer.
4) Optical properties- Nanocrystalline systems have attracted much
interest for their novel optical properties, which differ remarkably from bulk
crystals. Key contributory factors include quantum confinement of electrical
carriers within nanoparticles, efficient energy and charge transfer over
nanoscale distances and in many systems a highly enhanced role of
interfaces. The linear and nonlinear optical properties of such materials can
be finely tailored by controlling the crystal dimensions, and the chemistry of
their surfaces, fabrication technology becomes a key factor for the
applications.
5) Chemical Properties- One of the important factors for the chemical
applications of Nanomaterials is the increment of their surface area which
increases the chemical activity of the material. Due to their enhanced
chemical activity, nanostructures materials can be used as catalysts to react
with such noxious and toxic gases as carbon monoxide and nitrogen oxide
in automobile catalytic converters and power generation equipment to
prevent environmental pollution arising from burning gasoline and coal.
APPLICATIONS OF NANOTECHNOLOGY:
Nano science in food processing: In food processing Nano science is used
for improving food ingredients packaging, flavoring and coloring and safety
monitoring. Major food processing companies are using Nano science in
testing the chemical reactions and for enhancing preservatives.
Nano science in medicine: In the field of medical sciences Nano science is
used to detect the cancerous bacteria in the human body at early stages.
Blood thinner used to regulate the blood level and the body also uses
nanostructure particles.
Nano science and automobiles: In automobile engineering Nano science
plays important role in making brakes of the vehicle more efficient and soft
and for improving the liquids of the disc brakes in the world of automobile
industry, Nano science is also used for making engines stronger and
reliable. Protective nano-paint for cars are made that resist water and dirt,
resistant to chipping and scratches, brighter colors, enhanced gloss to cars
all these advancement came into being when Nano science stepped into
field.
Influence of Nano science in our lives: Nano science has a great impact in
our lives and lifestyles Nano science when merged with nanotechnology
provided us with the Neuro-electrical machines and other health care
devices, which has reduced the death rate in the world. Nano science has
given us the better way to live and provided us with the exigent and flawless
products. Later on we would be definite seeing the more improved products
of Nano science because it has given us the new eye to see and realize the
world.
Nanotechnology in energy: Nanotechnology will play important role in the
field of energy. There is considerable amount of research going on to tap
hydrogen fuel by spitting water (H2O) using sunlight in presence of
Nanomaterials (photo catalyst). Hydrogen fuel is essential for an energy
source so it can be stored with the help of carbon nano-tubes which are now
easily available.
SYNTHESIS METHODS OF NANOPARTICLES:

Physical Methods:
1. Physical vapor deposition With Consolidation
2. Laser Vaporization
3. Laser Pyrolysis
4. Chemical vapour deposition Electric arc Deposition
5. Direct Precipitation Method
Chemical Methods:
1. Colloids and Colloids in Solution
2. Stober method
3. Microwave irradiation method
4. Sol-Gel Method
5. Hydrothermal Method
6. Biological Methods
7. Synthesis using microorganisms
8. Synthesis using plant extracts
9. Synthesis using DNA

BISMUTH OXYHALIDES
Development of two-dimensional (2D) layered nanomaterials of bismuth
oxyhalides (BiOCl, BiOBr, and BiOI) has attracted considerable interest
due to the renewable energy conversion. A new class of 2D layer
semiconductor materials and tunable morphologies enhance the
photocatalytic reactions. The dominant {001} facet engineering structures
and bandgap controlling can be achieved by changing the stoichiometry
ratios of the precursor solution. Synthesis of polymer composite thin films
and fabrication methods involve free-standing flexible films, which are used
as a dip photocatalyst for degradation of pollutants. 2D nanomaterials and
surface-interaction engineering modification with noble metal nanoparticles
establish hybrid nanostructures. The hybrid nanostructures enhanced the
light absorption property through the plasmonic effect-induced “hot
electrons” that improve the conductivity of the materials and are used in
photodetector and surface-enhanced Raman scattering applications. The
bandgap of the 2D layer nanomaterial was controlled by modulating the
thickness and concentration of the precursor element. 2D layer structures of
bismuth oxyhalides are a promising avenue for featured diverse
technologies and wide applications in electronics, optoelectronics,
photodetectors, and photovoltaics.

Recently, a new class of photocatalysts comprising ternary semiconductors

such as bismuth oxyhalides (BiOX, X = Cl, Br and I) and metal-free
catalysts including g-carbon nitride has emerged.
Specifically, slabs of [X–Bi–O–Bi–X] are combined van der Waals forces
to form a tetragonal matlockite crystal structure, as depicted in Fig. A
decahedral asymmetric structure is formed when four oxygen atoms and
four halogen atoms surround each central bismuth ion in [X–Bi–O–Bi–X].
The outstanding properties (optical, electronic, and structural) of these
layered materials are generated from the synergistic effect of strong
covalent bonding and van der Waals interaction among the atomic layers
BiOX materials were used as storage and ferroelectric materials, catalysts,
and pigments. However, recently, they have found new applications in
various fields including photocatalytic purification of wastewater and gases,
oxidation of alcohols, water splitting, and organic synthesis. Extensive
works have been reported on the use of BiOX for the photocatalytic
degradation of organic dyes in wastewater, but no significant studies have
been reported on their PEC properties. The high charge transfer ratio owing
to their indirect band gaps together with their crystallinity makes these
materials potential candidates for the production of H2. Besides, enhanced
charge separation can be obtained along the (001) plane of BiOX an
induced perpendicular internal electric field has been abundantly used for
photocatalytic applications, but only shows activity in the UV (ultraviolet)
region. In contrast, BiOX materials have the advantage of a wide bandgap
range, varying from 3.3 eV (BiOCl) to 1.8 eV (BiOI), allowing visible light
photocatalysis. Since Zhang's group reported the fabrication of 3D-
microspheres of BiOX on 2D-nanoplates solvothermal synthesis for the
degradation of methyl orange, researchers have focused on the
photocatalytic activity of BiOX materials.
BISMUTH OXYIODIDE
Bismuth oxyiodide (BiOI) is a p-type semiconductor which is commonly
applied as a photocatalyst for photocatalytic reaction during the last decade .
Since it has the bandgap energy ~1.8 eV, this material has good absorption
in the visible spectral range. It is interesting to note that this oxyhalide
semiconductor also has an environmentally benign character . The wider
application of BiOI can extend for a photoanode used in
photoelectrochemical devices . Several ways are common to synthesize
BiOI, either including the solvent usage or solvent-less process.Generally,
hydrothermal and solvothermal methods are used to produce BiOI powder
for photocatalytic application .However, successive ionic layer adsorption
and reaction, as well as chemical-based deposition have been employed to
deposit BiOI films for photovoltaic study .Nevertheless, as an alternative,
the BiOI film’s preparation for solar cell application also can be carried out
via the doctor blade method which will be discussed in this report. Some
key aspects of semiconductor materials’ properties are noted to be a crucial
matter for the device performance as different parameters in synthesis can
result in different physical properties of materials. The morphology, size,
crystallinity, and optical properties are needed to be considered, since those
characteristics can be affected by the procedure of materials preparation, the
concentration of precursors , surfactant selection, and solvent selection. The
post-treatment after the material synthesis process, like calcination, also can
change the material properties. It seems to be similar to the BiOI structure,
since it consists of [Bi2O2] 2+ slabs that allow for stoichiometric changing
due to the calcination for producing the derivate of BiOI . Moreover, the pH
adjustment during the synthesis process is an important factor which affects
BiOI structure. BiOI and its derivation have been reported mostly for
photocatalytic application due to their effectivity in the separation of
electron-hole pairs . BiOI, with its smaller size and wider valence band, had
a better photocatalytic performance than BiOI because it had a lower
electron-hole pairs recombination rate. BiOI, which is often difficult to
differ with BiOI, was also reported to have excellent photocatalytic activity
under visible light irradiation.which exhibited a twice higher photocatalytic
activity than BiOI because of its pores and different band structure.it has not
been compared yet with BiOI activity. Many reports on BiOI and its
derivatives for photocatalytic application have been reported. However, to
the best our knowledge, there is no study in the screening of BiOI and its
derivations for photovoltaic device application, even though BiOI can be
considered as the promising material for the future photovoltaic devices
owing to its longer lifetime which up to 2.7 ns.
 CHAPTER 2

SYNTHESIS OF BiOI

Materials
Bismuth Nirate,Potassium Iodide,Ethylene Glycol,Distilled Water,Ethanol.

Prepration Of BiOI
Experimental Synthesis of layered BiOI nanodiscs All chemical reagents
used in this experimental procedure were of analytical grade and used
without further purification. In a typical experiment, 0.1mmol KI was
dissolved in double distilled water (DW), and 0.1mmol Bi(NO3)3 was
dissolved in ethylene glycol, in separate glass beakers. The aqueous KI
solution was added drop wise to bismuth nitrate solution and the resulting
suspension was stirred rigorously. The suspension exhibited gradual colour
change from yellow to red. After continuous stirring for 2 h, the final
product was collected via filtration, washed several times with anhydrous
ethanol, followed by drying in air at 60 C for 2 h.

Bismuth Nitrate Bismuth Nitrate + KI After 2hrs Stirring Bismuth Oxyiodide

(Final Product)
No. Of Reaction Bismuth Nitrate Potassium Iodide Ratio Ethylene
Glycol:Distilled Water
BiOI 1 0.1mmol 0.1mmol 1:1
BiOI 2 0.5mmol 0.5mmol 1:1
BiOI 3 0.5mmol 0.5mmol 5:1
BiOI 4 0.5mmol 0.5mmol 10:1

No. Of Reaction Bismuth Nitrate Sodium Iodide Ratio Ethylene

Glycol:Distilled Water
BiOI 5 0.1mmol 0.1mmol 1:1

Thin films of Bismuth oxyiodide (BiOI) were deposited on slide glass

substrates.The formation of nanostructured BiOI thin films have been
confirmed through XRD, UV, and FESEM. The structure properties were
investigated by XRD. The optical properties were measured by UV-VIS
spectrophotometer. The absorption coefficient is calculated from recorded
data and it is best fitted for direct band gap. The direct band gap was in
range 3.8-4.0 eV
The photocatalytic activity of as-prepared samples was studied via catalytic
degradation of Dye in water under visible illumination. Before irradiation,
the dispersed catalyst was magnetically stirred in the dark for 1 h to reach
adsorption–desorption equilibrium of dye on the catalyst surface.The
concentration of Dye chromophores was estimated from the absorbance at
465 nm on UV-visible spectrophotometer.
CHARACTERIZATION TECHNIQUES

XRD (X-Ray Diffraction)

Introduction
In a crystalline solid, the constituent particles (atoms, ions or molecules) are
arranged in a regular order. An interaction of a particular crystalline solid
with X-rays helps in investigating its actual structure. Crystals are found to
act as diffraction gratings for X-rays and this indicates that the constituent
particles in the crystals are arranged in planes at close distances in repeating
patterns. The phenomenon of diffraction of X-rays by crystals was studied
by W. L. Bragg and his father W. H. Bragg in 1913. The distance between
two atoms is nearly 1-2 A0. The wavelength of X rays much similar to that.
Bragg gave a mathematical equation to establish a relationship between
wavelength of the incident X-ray, the distance between the layers and the
angle of diffraction.
n λ= 2 d sinθ
Here, ƛ= wavelength of X-ray used, Ɵ=Angle between incident X-rays and
plane of the crystal. The diffracted beam makes an angle 2θ. d= Distance
between planes of the constituent particles in a crystal. n= An integer (1, 2,
3, 4, …etc) which represents the serial order of diffracted beams. Bragg's
equation can be used to calculate the distances between repeating planes of
the particles in a crystal. Similarly, if inter 24 planar distances are given, the
corresponding wavelengths of the incident beam of X-ray can be calculated.
The powder method.The powder method is used to determine the value of
the lattice parameters accurately. The interplanar spacing for different (h, k,
l) planes in the crystal give rise to peaks at different Bragg angle.For every
set of crystal planes, by chance, one or more crystals will be in the correct
orientation to give the correct Bragg angle to satisfy Bragg’s equation.
Every crystal plane is thus capable of diffraction. Each diffracted line on a
photographic plate is made up of a large number of small spots, each from a
separate crystal. Each spot is so small as to give the appearance of a
continuous line. If the crystal is not ground finely enough, the diffraction
lines appear speckled.
Field Emission Scanning Electron Microscope
FESEM is the abbreviation of Field Emission Scanning Electron
Microscope. A FESEM is microscope that works with electrons (particles
with a negative charge) instead of light. These electrons are liberated by a
field emission source. The object is scanned by electrons according to a zig-
zag pattern.
A FESEM is used to visualize very small topographic details on the surface
or entire or fractioned objects. Researchers in biology, chemistry and
physics apply this technique to observe structures that may be as small as 1
nanometer (= billion of a millimeter). The FESEM may be employed for
example to study organelles and DNA material in cells, synthetical
polymeres, and coatings on microchips. The microscope that has served as
an example for the virtual FESEM is a Jeol 6330 that is coupled to a special
freeze-fracturing device (Oxford Ato).
Electrons are liberated from a field emission source and accelerated in a
high electrical field gradient. Within the high vacuum column these so-
called primary electrons are focussed and deflected by electronic lenses to
produce a narrow scan beam that bombards the object. As a result secondary
electrons are emitted from ech spot on the object. The angle and velocity of
these secondary electrons relates to the surface structure of the object. A
detector catches the secondary electrons and produces an electronic signal.
This signal is amplified and transformed to a video scan-image that can be
seen on a monitor or to a digital image that can be saved and processed
further.

A cryo-FESEM looks like a cylindrical column (1) that is mounted on a

desk. The column hosts the electron beam. Knobs for the regulation of the
electron beam can be found at various levels on the column. There are also
tubes present to mainatin the cacuum and the temperature in the instrument
and the cryo-unit.The microscope is operated from the steering panel (2; on
the desk). A close copy of this panel has been used for the simulations. The
cryo-unit with a binocular (3) is located left of the column. When
conventional (not cryo) microscopy is applied the exchange chamber in
front, below the columns (4) is used to introduce the object into the high
vacuum area. The object can be observed on the large screen (5) while it is
scanned. The small screen (6) serves to watch the object chamber. The
computer for image archiving and processing is located right (7). The
cupboards below the desk contain (LOT OF) electronics (8). On the
background the sound of the pumps that maintain the vacuum in the
caolumsn canbe heared as well as the sissing of the boiling nitrogen for the
freeze-unit and the cooling of the column.

UV-Visible (UV-Vis) Spectroscope

Ultraviolet and visible spectrometers have been in general use for the last
35 years and over this period have become the most important analytical
instrument in the modern day laboratory. In many applications, other
techniques could be employed but none rival UV Visible spectrometry for
its simplicity, versatility, speed, accuracy and cost-effectiveness.
Lambert's Law- when a beam of light is allowed to pass through a
transparent medium, the rate of decrease of intensity with thickness of
medium is directly proportional to the intensity of light.
It=I0e-kt . . . . . ..(1)
Lamert-beer law: The intensity of a beam of a monochromatic light
decreases exponentially with the increase in the concentration of of the
absorbing substance arithmetically. from eq.n (1),
log(I0/ It)=act . . . . . (2)
UV-Visible spectroscopy measures the intensity of absorption of
nearultraviolet and visible light by a sample. Ultraviolet and visible light are
energetic enough to promote the outer electrons in an atomic, 26 molecular
or material system to higher energy levels depending on the specific nature
of the electronic states of a given material. In semiconductors, when the
incident photon energy exceeds the band gap energy of the materials,
absorption takes place and signal is recorded by the spectrometer whereas in
metals when the surface free electrons vibrate coherently with the incident
frequency then resonant absorption takes place.
The energies associated with UV-visible ranges are sufficient to excite
molecular electrons to higher energy orbitals. Photons in the visible range
have wavelengths between 800-400 nm, which corresponds to energies
between 36 and 72 kcal/mol. The near UV range includes wavelengths
down to 200 nm, and has energies as high as 143 kcal/mol. UV radiations of
lower wavelengths is difficult to handle for safety reasons and is rarely used
in routine UV-Vis spectroscopy.
Ultraviolet-visible (UV-VIS) spectroscopy is widely utilized to
quantitatively characterize organic and inorganic nanosized molecules. A
sample is irradiated with electromagnetic waves in the ultraviolet and
visible ranges and the absorbed light is analyzed through the resulting
spectrums. It can be employed to identify the constituents of a substance,
determine their concentrations, and to identify functional groups in
molecules. Consequently, UV-Vis spectroscopy not only is used for
characterization, but also for sensing applications.
Different sized materials can be characterized, ranging from transition
metal ions and small molecular weight organic molecules, whose diameters
can be several Angstroms’, to polymers, supra molecular assemblies,
nanoparticles and bulk materials. Size dependents properties can also be
observed in a UV-visible spectrum, particularly in the nano and atomic
scales. These include peak broadening and shifts in the absorption
wavelength. Many electronic properties, such as the band gap of a material,
can also be determined by this technique.
Source-Tungsten filament lamp, Hydrogen Discharge Lamp, Deuterium
Lamp, Mercury Arc.
Detectors-barrier layer cell, photo cell, photomultiplier tube.
 Typical setup for UV-Visible spectrophotometer for liquid samples.
Working 28 Figure shows a typical UV-Vis absorption experiment for a
liquid sample. A beam of monochromatic light is split into two beams, one
of them is passed through the sample, and the other passes a reference (in
this figure, a solvent in which the sample is dissolved). After transmission
through the sample and reference, the two beams are directed back to the
detectors where they are compared. The difference between the signals is
the basis of the measurement. Liquid samples are usually contained in a cell
(called a cuvette) that has flat, fused quartz faces. Quartz is commonly used
as it is transparent to both UV and visible lights.
Photocatalytic Activity
The term photocatalyst is a combination of two words: photo related to
photon and catalyst, which is a substance altering the reaction rate in its
presence. Therefore, photocatalysts are materials that change the rate of a
chemical reaction on exposure to light. This phenomenon is known
as photocatalysis. Photocatalysis includes reactions that take place by utilizing
light and a semiconductor. The substrate that absorbs light and acts as a catalyst
for chemical reactions is known as a photocatalyst. All the photocatalysts are
basically semiconductors. Photocatalysis is a phenomenon, in which an
electron-hole pair is generated on exposure of a semiconducting material to
light.
The photocatalytic reactions can be categorized into two types on the basis of
appearance of the physical state of reactants.

Homogeneous photocatalysis: When both the semiconductor and reactant

are in the same phase, i.e. gas, solid, or liquid, such photocatalytic reactions
are termed as homogeneous photocatalysis.
Heterogeneous photocatalysis: When both the semiconductor and reactant
are in different phases, such photocatalytic reactions are classified as
heterogeneous photocatalysis.
The energy difference between the valence band (HOMO) and the conduction
band (LUMO) are known as the band gap (Eg). On the basis of band gap, the
materials are classified into three basic categories
Semiconductors are capable of conducting electricity even at room
temperature in the presence of light and hence, work as photocatalysts.
When a photocatalyst is exposed to light of the desired wavelength
(sufficient energy), the energy of photons is absorbed by an electron (e−) of
valence band and it is excited to conduction band. In this process a hole (h+)
is created in valence band. This process, leads to the formation of photo-
excitation state, and e− and h+ pair is generated. This excited electron is used
for reducing an acceptor in which a hole is used for oxidation of donor
molecules.
 CHAPTER 3

RESULTS AND DICUSSION

X-Ray Diffraction (XRD)

Crystal structure The XRD patterns of the BiOI composites with different ratios
were The diffraction peaks of all the samples were relatively sharp and strong,
indicating the high crystallinity of the as-prepared products. No miscellaneous
peaks were observed, indicating that the products were relatively pure.
Compared with the standard spectrum, the XRD pattern of BiOI was consistent
with the standard spectrum which was tetragonal.
If taken different reactions ratios still selective same peak points cames.And
these points are (001),(002),(102),(110),(004).It is found beause of the variation
of Ethylene glycol.
Product Plane 2θ 2θ 2θ Crystal Size
BiOI 5:1 001 9.61 9.81 9.72 799.42nm
BiOI10:1 001 9.56 9.95 9.77 408.84nm
 FESEM

UV-VISIBLE SPECTROSCOPY
UV-Visible spectroscopy confirmed the presence of nanoparticles by reduction
of bismuth oxyiodide ions in the solution.The bismuth oxyiodide nanoparticles
were placed in a quartz cuvette and observed for wavelength scanning between
300 to 800 nm with distilled water as a reference. The absorption peak was
observed at 440 nm, which is characteristic bismuth oxyiodide. UV-Visible
spectroscopy is similar.
Photocatalytic activity
The photocatalytic activity of as-prepared BiOI nanocomposite samples
towards the degradation of Dye was investigated under visible illumination.

(A)Water + Dye, (B) Liquid 5:1 + Dye, (C) Liquid 5:1 +Drop of Dye

A B C A B C AA BB C
C

After 5mins After 15mins

Initial

When we added Dye in Liquid 5:1 after certain period of time degradation is
formed like as shown in figure.
 CHAPTER 4
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