CHAPTER 1

1. INTRODUCTION

1.1. NANOTECHNOLOGY

The term nano originated from the Greek nanos which means ‘dwarf’. It is one
billionth of a meter. Therefore, whenever we think about nanoscience or
nanotechnology, very small objects come to the mind. Nanotechnology is science,
engineering, and technology conducted at the nanoscale, which is about 1 to 100
nanometers. Nanotechnology deals with various structures of matter having
dimensions of the order of a billionth of a meter. While the word nanotechnology is
relatively new, the existence of functional devices and structures of nanometer
dimensions is not new, and in fact such structures have existed on Earth as long as life
itself

The ideas and concepts behind nanoscience and nanotechnology started with a
talk entitled “There’s Plenty of Room at the Bottom” by physicist Richard Feynman.
Nanomaterials are expected to have a wide range of applications in various fields such
as electronics, optical communications and biological systems. These applications are
based on factors such as their physical properties, huge surface area and small size
which offers possibilities for manipulation and room for accommodating multiple
functionalities Nanoscience and nanotechnology involve the ability to see and to
control individual atoms and molecules. Everything on Earth is made up of atoms—
the food we eat, the clothes we wear, the buildings and houses we live in, and our own
bodies. But something as small as an atom is impossible to see with the naked eye. In
fact, it’s impossible to see with the microscopes typically used in a high school
science classes. The microscopes needed to see things at the nanoscale were invented
relatively recently—about 30 years ago. Once scientists had the right tools, such as
the scanning tunnelling microscope (STM) and the atomic force microscope (AFM),
the age of nanotechnology was born.

1.2. NANOPARTICLES

Nanomaterials or nanoparticles are the set of particles or the substances where

atleast one dimension is in between 1 and 100 nanometers in size with a surrounding

1
interfacial layer. The term “nanoparticle” is not usually applied to individual
molecules; it usually refers to inorganic materials. Nanoparticles are of great interest
as they are effectively a bridge between bulk materials and atomic or molecular
structures. A bulk material should have constant physical properties regardless of its
size, but at the nano-scale this is often not the case. Nanoparticles exist in the natural
world and are also created as a result of human activities. Because of their
submicroscopic size, they have unique material characteristics, and manufactured
nanoparticles may find practical applications in a variety of areas, including medicine,
engineering, catalysis, and environmental remediation Nanoparticles can be classified
into different types according to the size, morphology, physical and chemical
properties. Some of them are carbon-based nanoparticles, ceramic nanoparticles,
metal nanoparticles, semiconductor nanoparticle, polymeric nanoparticles and lipid-
based nanoparticles.

 Carbon Based Nanoparticles: Carbon-based nanoparticles include two main

materials: carbon nanotubes (CNTs) and fullerenes. CNTs are nothing but
graphene sheets rolled into a tube. CNTs can be classified into single-walled
carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs).
Fullerenes are the allotropes of carbon having a structure of hollow cage of sixty
or more carbon atoms.

 Ceramic Nanoparticles: Ceramic nanoparticles are inorganic solids made up of

oxides, carbides, carbonates and phosphates. These nanoparticles have high heat
resistance and chemical inertness. They have applications in photocatalysis, photo
degradation of dyes, drug delivery, and imaging.

 Metal Nanoparticles: Metal nanoparticles are prepared from metal precursors.

These nanoparticles can be synthesized by chemical, electrochemical, or
photochemical methods. In chemical methods, the metal nanoparticles are
obtained by reducing the metal-ion precursors in solution by chemical reducing
agents. These have the ability to absorb small molecules and have high surface
energy.

 Semiconductor Nanoparticles: Semiconductor nanoparticles have properties like

those of metals and non-metals. They are found in the periodic tables in groups.

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 These particles have wide bandgaps, which on tuning shows different properties.
They are used in photocatalysis, electronics devices, photo-optics and water
splitting applications.

 Polymeric Nanoparticles: Polymeric nanoparticles are organic based

nanoparticles. Depending upon the method of preparation, these have structures
shaped like nanocapsular or nanospheres. A nanosphere particle has a matrix-like
structure whereas the nanocapsular particle has core-shell morphology. Some of
the merits of polymeric nanoparticles are controlled release, protection of drug
molecules, ability to combine therapy and imaging, specific targeting and many
more.

 Lipid Based Nanoparticles: Lipid nanoparticles are generally spherical in shape

with a diameter ranging from 10 to 100nm. It consists of a solid core made of lipid
and a matrix containing soluble lipophilic molecules. The external core of these
nanoparticles is stabilized by surfactants and emulsifiers. These nanoparticles
have application in the biomedical field as a drug carrier and delivery and RNA
release in cancer therapy.

1.3. PROPERTIES OF NANOPARTICLES

Nanoparticles consist of three layers: the surface layer, the shell layer, and the
core. The surface layer usually consists of a variety of molecules such as metal ion,
surfactants, and polymers. The principal parameters of nanoparticles are their shape,
size, surface characteristics and inner structure. Nanoparticles may contain a single
material or maybe consists of a combination of several materials. Nanoparticles can
exist as suspensions (solids in liquids), colloids, or dispersed aerosols (solids or
liquids in air) depending on their chemical and electromagnetic properties.

Nanoparticles often have unique physical and chemical properties. At the

nanoscale, materials behave very differently compared to larger scales and it is still
very difficult to predict the physical and chemical properties of such a very small size.
The properties of nanoparticles are dependent their size.

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Various properties are;

 Magnetic properties:

1. Magnetic nanoparticles are used in a range of applications like imaging,

bioprocessing, refrigeration as well as high storage density magnetic memory
media.
2. The large surface area to volume ratio results in a substantial proportion of
atoms having different magnetic coupling with neighboring atoms leading to
differing magnetic properties.
3. Bulk gold and platinum are non magnetic but at the nano size they act as
magnetic particles. Au nanoparticles become ferromagnetic when they are
capped with the appropriate molecules such as thiol.
4. Giant magnetoresistance (GMR) is a phenomenon observed in nanoscale
multilayers consisting of strong ferromagnet (Fe,Co,Ni)and a weaker magnetic
or non magnetic buffer(Cr,Cu).It is usually employed in data storage and
sensing.

 Optical properties:

1. In small nano clusters the effect of reduced dimensionality on electronic

structure has the most profound effect on the energies of highest occupied
molecular orbital (HOMO) which is valence band and the lowest unoccupied
molecular orbital (LUMO), essentially the conduction band.
2. The optical emission and adsorption occurs when the transition of the
electrons occur between these two states.
3. Semiconductors and many metals show large changes in optical properties
such as colour, as a function of particle size.
4. Colloidal suspense of gold nano particles have a deep red colour which
becomes progressively more yellow as the particle size increases.

 Electronic properties:

1. The changes which occur in electronic properties as the system length scale is
reduced are related mainly to the increasing influence of the wave-like

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 property of the electrons (quantum mechanical effects) and the scarcity of
scattering centres.
2. As the size of the system becomes comparable with the de Broglie wavelength
of the electrons, the discrete nature of the energy states becomes apparent once
again, although a fully discrete energy spectrum is only observed in systems
that are confined in all three dimensions.
3. In certain cases, conducting materials become insulators below a critical
length scale, as the energy bands cease to overlap. Owing to their intrinsic
wave-like nature, electrons can tunnel quantum mechanically between two
closely adjacent nanostructures, and if a voltage is applied between two
nanostructures which aligns the discrete energy levels in the DOS, resonant
tunnelling occurs, which abruptly increases the tunnelling current.
4. Conduction in highly confined structures, such as quantum dots, is very
sensitive to the presence of other charge carriers and hence the charge state of
the dot.

1.4. APPLICATIONS OF NANOPARTICLES

Nanotechnology applications in many fields have the potential to profoundly

change the world of everyday experience. Nanotechnology is being used in
developing countries to help treat disease and prevent health issues. The umbrella
term for this kind of nanotechnology is Nanomedicine. Nanotechnology is also being
applied to or developed for application to a variety of industrial and purification
processes. Purification and environmental cleanup applications include
the desalination of water, water filtration, wastewater treatment, groundwater
treatment, and other nanoremediation. In industry, applications may
include construction materials, military goods, and nano-machining of nano-wires,
nano-rods, few layers of graphene, etc., Also, recently a new field arisen from the root
of Nanotechnology is called Nanobiotechnology. Nanobiotechnology is the biology-
based, application-oriented frontier area of research in the hybrid discipline of
Nanoscience and biotechnology with an equivalent contribution.

Nanotechnology has brought a revolution in manufacturing materials, creating

a vast number of new devices, drug delivery systems and monitoring and diagnosing
systems. but the implications if this technology are very diverse, impacting

5
consumers, clinicians and the practice of informatics. A major area of concern for
health care providers is the ethical use of nanomaterials. Nanotechnology has brought
a new era in healthcare but the challenges is to develop it by overcoming various
difficulties and implications. New opportunities have provide us with a powerful tool
in the field of genomics, proteomics, molecular diagnostics and high throughout
screening. Nanoparticles have the properties to become the most versatile materials
for developing diagnostics. Advances in nanotechnology will provide a good inside
view of our human systems. It has a bright future with the emergence of several
promising approaches for delivery of therapeutics agent and imaging using the
advantage of nanoscale carriers. Future studies will now be addressing a no. of
challenges faced in nanomedicine application. Greater funds are being allocated for
clinical and preclinical studies but still are studies are lacking in safety data that
includes toxicity studies. Also the cost of nanomedicine should be in acceptable range
so that it is successful in clinics. Nanotechnology is being applied at all stages of drug
development, from formulations for optimal delivery to diagnostic applications in
clinical trials. Actual utilization of nanotechnology novel drug delivery techniques lag
behind because of perception that such technologies could delay products due to
technical or regulatory reasons. So oral drug delivery remains a prefered option.
Further the cost factor becomes a hinderance in its daily use.

In recent years, major progress has been achieved in molecular electronics. As

the physical limits of the conventional silicon chips are being approached, researchers
are seeking the next small thing in electronics through chemistry. By making devices
from small groups of molecules, researchers may be able to pack computer chips with
billions of transistors, more than 10 times as many as the current technology can
achieve.

Researchers in molecular-electronics think that it is possible to make complex

circuitry by utilizing DNA’s ability to recognize molecules and self-assemble. They
hope to use DNA as a template for crafting metallic wiring, or even to wire circuits
with strands of DNA itself. Makers of computer chips are concerned with the
wavelength-limits of light. As the wavelength of the light is reduced, smaller features
can be printed on the chip. As a general rule of thumb, a given wavelength can make
features about half its length. Typically, light of 248 nm wavelength was used in the
past in optical lithography devices, and the smallest features that could be made by

6
these devices were about 120 nm. Chipmakers are trying to build devices which use
much shorter wavelengths (e.g., 157 nm). Features as small as 80 nm have already
been created on silicon wafers. Researchers expect that the technology will be able to
turn out features as small as 10 nm.

A very promising and rapidly-growing field of application of nanotechnology

is in medicine. One interesting application involves the use of nano-scale devices
which may serve as vehicles for delivery of therapeutic agents and act as detectors or
guardians against early disease. They would possibly repair the metabolic and genetic
defects. They would seek out a target within the body such as a cancer cell and
perform some functions to fix it. The fixing can be achievedby releasing a drug in the
localized area. The potential side effects of general drug therapy can be reduced
significantly in this manner. As nanotechnology becomes more sophisticated, gene
replacement, tissue regeneration or nanosurgeries are the promising future
developments

1.5. COPPER OXIDE

Copper oxide or cupric oxide inorganic compound with formula CuO. A black
solid, it is one of the two stable oxides of copper, the other being 𝐶𝑢2 𝑂 or cuprous
oxide. As a mineral, it is known as tenorite. It is product of copper mining and the
precursor to many other copper-containing products and chemical compounds.

(1.1.a) (1.!b)

Fig. 1.1a Copper oxide nanoparricles and Fig 1.1b structure of Copper Oxide

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 Copper oxide nanoparticles appear as a brownish-black powder as in figure
1.1a and an figure 1.1b represents the structure of copper oxide. They can be reduced
to metallic copper when exposed to hydrogen or carbon monoxide under high
temperature. They are graded harmful to human and as dangerous for the environment
with adverse effect on aquatic life.

1.6. PROPERTIES OF COPPER OXIDE

T Formula
Chemical CuO
h
Group Copper 11
e
Oxygen 16
Electronic Configuration Copper [Cu] 3𝑑10 4𝑠1
p
Oxygen [O] 2𝑠 2 2𝑝6
r
Density
o 6.31 𝑔/𝑐𝑚3
p
Molar Mass 79.55 g/mol
e
Solubility In Water Insoluble
r
t
Solubility Soluble in ammonium chloride, potassium
i
cyanide
e
Insoluble in alcohol, ammonium hydroxide,
s
ammonium carbonate

Band
a Gap 1.2 Ev

r
Magnetic Susceptibility +238.9× 10−6 𝑐𝑚3 /𝑚𝑜𝑙
e
Melting Point 1201 ℃ (2194 ℉, )
d

Table 1.1- Properties of Copper Oxide

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 Table 1.1 represents the physical and chemical properties of copper oxide.
The properties are depend on the synthesis method selected and they are very
important for their applications in various areas, such as biomedical research, which is
the most predominant. The most important feature is the size of the nanoparticles
(which may be controlled during the synthesis) because it allows the tailored
modeling of their optical, catalytic, electrical, and biological properties. These
properties make them useful for multiple applications such as the development of
cosmetics, pharmacological alternatives, paints, coatings, etc.. Therefore, the applied
synthesis method, the modulation of the reaction parameters and the composition of
bulk material represent key aspects in the direct control of size and direct or indirect
control of other important physical, chemical and biological properties

1.7. APPLICTIONS OF COPPER OXIDE NANOPARTICLES

CuO nanoparticles can be synthesized by various methods, and by using

various bulk materials and coating agents to obtain different types of nanosystems
with various applications. All these aspects may significantly impact on their physico-
chemical and biological properties and may affect their biomedical applications. The
use of CuO nanoparticles in drug delivery formulations is still limited due to the
enhanced toxicity, however other applications, such as topic formulations, dressings
and coated textiles are of a great interest among the medical environments and others.
The main application of such nanoformulations relies on their antimicrobial ability
that allows for the development of multiple products, from antimicrobial solutions
utilized to disinfect the surfaces and medical devices to antimicrobial wound
dressings, textiles and coatings. For improving their applications on the biomedical
field, researchers are striving to find optimal synthesis approaches in order to decrease
the toxicity of CuO NPs but at the same time to keep or even improve their efficiency
in diagnosis and therapy It can greatly improve the homogeneous propellant burning
rate, lower pressure index, and also perform better as a catalyst for the AP composite
propellant. It can be applied to the catalyst, superconducting materials, thermoelectric
materials, sensing materials, glass, ceramics and other fields. It can be used as
ceramic resistors, magnetic storage media, gas sensors, near-infrared tilters,
photoconductive and photothermal applications. It can be as semiconductors, solar
energy transformation, and high-tech superconductors.

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 CHAPTER 2

2. LITERATURE REVIEW

2.1. INTRODUCTION
A detailed literature survey is made on synthesis , preparation and characterization on
synthesis of Copper Oxide nanoparticles and this part discuss the literature survey that’s done

R. Etefagh et al. have been synthesized Copper oxide (CuO) nanoparticles and nanolayers
by sol–gel and spray pyrolysis methods, respectively. The structure and morphology of the
prepared samples were characterized using XRD, SEM and TEM analysis. As per gillus
niger fungi were grown in an appropriate medium and exposed to the synthesized samples in
a closed glass vessel. The boisoning properties of the nano systems were investigated by
measuring their electrical resistance at regular time intervals and different temperatures.
Further studies were made on the effects of CO2 and humidity on the sensing properties,
using CaCo3 and Silica gel. The considerable changes observed in the electrical resistance of
the prepared samples, in the presence of As per gillus niger fungi, support our proposed
system as a biosensor.

Y Aparna et al. CuO Nano particles are prepared by novel sol gel technique. In this
technique CuCl2.6H2O is added with acetic acid and heated to 100 °C with continuous
stirring. Control the pH of solution, NaOH is added to the solution till pH reaches desired
value. The color of the solution changed from blue to black with precipitation. The black
precipitation was washed 3-4times with distill water. Finally it was centrifuged and dried in
air for one day. The CuO Nano particles were characterized for the studying of their structure
and composition from X-ray diffraction, Energy Dispersive X-ray analysis and size with
Particle Size Analyzer. The thermal analysis was carried by TG-DTA. Catalytic nature
parameter zeta potential was also measured, For the morphology test SEM and TEM carried
out.

Narongdet Wongpisutpaisan et al. has been synthesized Copper oxide (CuO) nanoparticles
by a sonochemical process using copper nitrate and sodium hydroxide in the presence of
polyvinyl alcohol (PVA) as a starting precursor. The precipitated product was calcined at
various temperature ranging from 400-700 °C.The physical microstructure and morphology of
as-calcined nanoparticles were characterized by X-ray diffraction (XRD) and scanning
electron microscope (SEM). From XRD observation, it is evident that the high purity CuO

10
nanoparticles were obtained by this synthesis process. It was additionally revealed that its
crystallization and particle size was strongly dependent on the reaction time and calcination
temperature.

Amrut.S.Lanje et al. Copper oxide (CuO) nanoparticles are synthesized by aqueous

precipitation method using copper acetate as a precursor and NaOH as a stabilizing agent.
This gives a large scale production of CuO nanoparticles easily. X-ray diffraction pattern
(XRD) reveals single phase monoclinic structure. Scanning electron microscopy (SEM)
showed the rectangular morphology of as prepared CuO nanoparticles. The transmission
electron microscopy (TEM) showed 5-6 nm size of as prepared CuO nanoparticles.
Photoluminescence (PL) showed band edge emission at 398 nm and green emission at 527
nm. The band edge-absorption peak is found to be at 355 nm.

Kanikanit Phiwdang et al. CuO nanoparticles were synthesized by precipitation method

using different precursors as copper nitrate (Cu(NO3)2) and copper chloride (CuCl2) with
post-heating comparing between as-synthesized and after calcinations. Relevant properties of
as-synthesized nanoparticles were investigated by X-ray diffraction (XRD), scanning electron
microscope (SEM) and Fourier Transform Infrared (FTIR) Spectroscopy. Overall results
suggest that the formation of CuO nanostructures with different shape, size and morphology
can be achieved using different precursors via this process. The improvement in their
crystallinity and purification can be further attained by post calcinations process

Sanjay Srivastava et al. has been prepared Cupric oxide (CuO) nanoparticles by the
chemical route by calcinations at a higher temperature from 300oC to 400 oC. For the
comparison transmission electron microscopy (TEM) and x-ray diffraction (XRD)
measurements were made through JCPDS. There is good agreement between data produced
by spectroscopy and the microscopic measurements.

Pankaj Kumar et al. cupric oxide (CuO) nanoparticles were synthesized by electrochemical
discharge process. The experiments were carried out separately using NaOH and KOH
electrolytes. The nanoparticles are investigated by SEM, FTIR and UV-vis-NIR
Spectroscopy. Scanning electron microscopy images revealed that flower-like and caddice
clew-shaped CuO nanocrystalline particles were synthesized by the electrochemical discharge
process. Fourier transform infrared spectrum showed that the CuO nanoparticles have a pure
and monolithic phase. UV–vis–NIR spectroscopy was used to monitor oxidation course of
Cu→CuO and the band gap energy was measured as 2 and 2.6 eV for CuO nanoparticle
synthesized in NaOH and KOH solutions, respectively.

11
P. Angelina mary et al. have been formed Copper oxide multilayer nanosheets thin films
using chemical bath deposition method. These films were characterised using X-ray
diffraction (XRD), Field emission scanning electron microscope (FESEM), FTIR, optical
absorption and wettability test. The XRD pattern revealed that the copper oxide films are
amorphous. Formation of copper oxide compound was confirmed from the FTIR studies. The
FESEM images revealed the development of hierarchical multilayer nanosheets. Surface
wettability with liquid interface showed hydrophilic nature with water contact angle 530 . The
optical absorption showed the existence of direct optical band gap energy 2.18 eV. The
supercapative properties of copper oxide thin films investigated in 1M 𝑁𝑎2 𝑆𝑂4 electrolyte
showed supercapacitance of 43 F𝑔−1 at the scan rate 10 mV𝑠 −1

K. Borogohin et al. has been synthesized copper oxide (CuO) nanoparticles through a
sonochemical assisted precipitation followed by thermal treatment. As prepared CuO
nanoparticles have been anchored on surface of graphene oxide (GO) nanosheets through a
simple electrostatic coprecipitation. Prepared samples have been characterized using XRD,
FTIR, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and energy dispersive
X-ray analysis (EDX). Morphology of the samples has been characterized by FESEM and
transmission electron microscopy (TEM). The composite material shows better
electrochemical supercapacitive behavior and lower charge transfer resistance compared to
other samples. It also shows better specific capacitance (245 F g−1) at current density of
0.1 A g−1 compared to the pure components (125 F g−1 for CuO and 120 F g−1 for GO) and the
layer-by-layer coated electrodes (155 F g−1). Conducting charge/discharge measurements for
1000 cycles and in different current densities, it has been found that the composite material is
a promising candidate for supercapacitor application, in terms of cycle ability and rate
capability.

K. Kannaki et al. The CuO nano particles were synthesized from copper sulfate pentahydrate
aqueous solution under the low hydrothermal condition at 80°C.The average crystallite size
was calculated from De-Bye Scherrer’s equation. SEM/EDS,XRD were used to characterize
the structure features of the product. FTIR spectra confirmed the adsorption of ammonia on
the surface of the CuO nanoparticles. In addition, UV-visible absorption spectra were
employed to estimate the band gap energy of the CuO nanoparticles. This method may be
suitable for large scale production of nano CuO particles for practical applications
Asha Radhakrishnan et al. Copper oxide nano materials are of interest on account of their
potential uses in many technological fields. In this study CuO nanoparticles were synthesized
via simple sol gel method using basic CuSO4 as wet chemically synthesized precursor and
NaOH as stabilizing agent. Samples were characterized by X-ray diffraction (XRD), infrared

12
spectrum (IR), scanning electron microscope (SEM), transmission electron microscopy
(TEM) and UV-visible spectrum. Using this method CuO nanoparticle could be
synthesized without using organic solvent, expensive raw materials and complicated
equipments.

Seyed Javad Davarpanah et al. has been used Copper sulfate as a precursor to prepare CuO
nanoparticles in reverse micelles (o/w microemulsion). This is a technique which allows the
preparation of ultrafine metal oxide nanoparticles within the size ranging from 50 to 60 nm.
The preparation of copper (II) oxide nano particles was investigated in the inverse
microemulsion system. Therefore, the nucleation of metal particles proceeds in the water
capsules of the microemulsion. Tween 80 was added as surfactant. The products were
characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and
transmission electron microscopy (TEM). The study provides a simple and efficient route to
synthesize CuO nanoparticles at room temperature.

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REFERENCE

1. Y. Aprna, K. V. Enkateswara Rao And P. Srinivasan , “Synthesis And

Characterisation Of Cuo Nano Particles By Sol-Gel Method”, 2012 2nd
International Conference On Environment Science And Biotechnology , Vol.
48, Pages 156-160.
2. Pankaj Kumar, Manowar Hussain, Alok Kumar Das, “Synthesis And
Characterization Of Cuo Nanoparticles Using Strong Base Electrolyte
Through Electrochemical Discharge Process”, Vol-39,Page No:469-477.
3. R. Etefagh,E. Azhir, N. Shahtahmasehi, “Synthesis Of Cuo Nanoparticles
And Fabrication Of Nanostructural Layer Biosensors For Detecting
Aspergillus Niger Fungi”, 2012- Sharif University Of Technology”, Vol-23,
Page No: 1055-1058.
4. Amrut S Lange, Satish J. Sharma, Ramachandran B. Pode; “Synthesis And
Optical Characterization Of Copper Oxide Nanoparticles”; 2010- Advance In
Applies Science Research – Pelagia Research Library; Vol-1, Page No: 36-
40.
5. Narongdet Wongpisutaisam, Piyanut Charonn Suk, Naratip Vittayakorn,
Wisanu; “Sonochemical Synthesis And Characterization Of Copper Oxide
Nanoparticles”; 2011-9th Eco Energy And Material Science And Engineering
Symposium”; Vol-9; Page No: 404-409.
6. Asha Balakrishnan, B. Bhaskaran Beena; “Structural And Optical
Absorption Analysis Of Cuo Nanoparticles”; 2010-Advances In Chemical
Science; Vol-2; Page No: 158-161.
7. Seyed Javad Davarpanah, Ramin Karmian, Vahabodin Goodarzi, Farideh
Piri; “Synthesis Of Copper Oxide Nanoparticles And Its Applicvation As Gas
Sensor”; 2015- Journal Of Applied Biotechnology Reports; Vol-2; Page No:
329-332.
8. Sanjay Srivastava, Mahendra Kumar, Aravind Agarwal, Sudhanshu Kumar;
“Synthesis And Characterization Of Copper Oxide Nanoparticles”; 2013-
ISOR Journal Of Applied Physics; Vol-5; Page No:61-65
9. Kankanit Phiwdang, Sineenart Suphankij, Wanichaya Mekprasart, Wisanu
Pecharapa; “Synthesis Of Cuo Nanoparticles By Precipitation Method Using

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 Different Precursors”; 2013- 10th Eco Energy And Materials Science And
Engineering.
10. P. Angelina mary, a thaminum ansari, r. Subramanian; “synthesis of copper
oxide and its application as supercapacitor”; 2010- journal of king saud
university; vol-3; page no: 56-61.
11. K. borogohain, j. b. singh, m. v. rama rao, t. shripathi, s. mahamuni; “
preparation of copper oxide through sonochemical method”; 2008- pelagia
research library; vol-5; page no: 88- 95.
12. K Kannaki, PS Ramesh, D Geetha; “Hydrothermal synthesis of CuO
nanostructure and their characterizations”; 2012-International Journal Sci
Eng Res; vol-3; page no: 1-4.

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 CHAPTER 3

3. EXPERIMENTAL TECHNIQUES(CHEMICAL
METHODS)

3.1. INTRODUCTION

Nanocrystalline materials can be synthesized either by consolidating

atoms/molecules/clusters or breaking down the bulk material into smaller and smaller
dimensions. The former is known as the ‘Bottom up’ approach whereas the latter is
referred to as the ‘Top down’ method. Many techniques including both Top-down
and Bottom-up approaches have been developed and applied for the synthesis of the
nanoparticles. In the Top-down approach a block of a bulk material is whittled or
sculptured to get the nanosized particle. The Top-down approaches include milling or
attrition, lithography etc. The main disadvantage of the Top-down approach is the
imperfection of the surface structure. The nanoparticles produced by the attrition have
a relatively broad size distribution and various particle shape or geometry. In addition
they may contain significant amount of impurities. In the Bottom-up approach, the
individual atoms and molecules are placed or self assembled precisely where they are
needed. Here the molecule or atomic building blocks fit together to produce
nanoparticles. Bottom-up approaches are more favourable and popular in the
synthesis of nanoparticles and many preparation techniques of Bottom-up approach
have been developed

3.2. SOL-GEL METHOD

Sol–gel method is one of the well-established synthetic approaches to prepare

novel metal oxide NPs as well as mixed oxide composites. This method has potential
control over the textural and surface properties of the materials. Sol–gel method
mainly undergoes in few steps to deliver the final metal oxide protocols and those are
hydrolysis, condensation, and drying process. The formation of metal oxide involves
different consecutive steps, initially the corresponding metal precursor undergoes
rapid hydrolysis to produce the metal hydroxide solution, followed by immediate
condensation which leads to the formation of three-dimensional gels. Afterward,

16
obtained gel is subjected to drying process, and the resulting product is readily
converted to Xerogel or Aerogel based on the mode of drying. Sol–gel method can be
classified into two routes, such as aqueous sol–gel and nonaqueous sol–gel method
depending on the nature of the solvent utilized. If water is used as reaction medium it
is known as aqueous sol–gel method; and use of organic solvent as reaction medium
for sol–gel process is termed as nonaqueous sol–gel route. The reaction pathway for
the production of metal oxide nanostructures in the sol–gel method. In the sol–gel
approach, nature of metal precursor and solvent plays a remarkable role in the
synthesis of metal oxides NPs.

3.3. CHEMICAL VAPOUR DEPOSITION

Chemical vapor deposition (CVD) is parent to a family of processes whereby a

solid material is deposited from a vapor by a chemical reaction occurring on or in the
vicinity of a normally heated substrate surface. The resulting solid material is in the
form of a thin film, powder, or single crystal. By varying experimental conditions,
including substrate material, substrate temperature, and composition of the reaction
gas mixture, total pressure gas flows, etc., materials with a wide range of physical,
tribological, and chemical properties can be grown. A characteristic feature of the
CVD technique is its excellent throwing power, enabling the production of coatings of
uniform thickness and properties with a low porosity even onsubstrates of
complicated shape. Another important feature is the capability of localized,
or selective deposition, on patterned substrates. CVD and related processes are
employed in many thin film applications, including dielectrics, conductors,
passivation layers, oxidation barriers, conductive oxides, tribological and corrosion-
resistant coatings, heat-resistant coatings, and epitaxial layers for microelectronics.
Other CVD applications are the preparation of high-temperature materials (tungsten,
ceramics, etc.) and the production of solar cells, high-temperature fiber composites
and particles of well-defined sizes. Recently, high Tc superconductors, and more
recently carbon nanotubes, have also been made by this technique [1]. Since oxygen
activity in the vapor can be precisely controlled during the deposition, no annealing in
oxygen is needed to achieve superconductivity. There exists a multitude of CVD
processes. In thermally activated CVD (TACVD), the deposition is initiated and
maintained by heat.

17
3.4. CHEMICAL BATH DEPOSITION
The chemical bath deposition method is one of the easiest methods used to deposit
thin films and nanomaterials which are working for large area batch dispensation or
continuous declaration. Chemical deposition techniques are comparatively low cost
processes and can be easily scaled for industrial applications. Most of the chemical
bath consists of one or more metal salts 𝑀𝑛−1, a source for the chalcogenide X (X =
S, Se, Te ) and typically a complexion agent, in aqueous solution

3.5. HYDROTHERMAL METHOD

Hydrothermal synthesis refers to the synthesis of substances via chemical
reactions in a sealed and heated solution above ambient temperature and pressure. The
concept ‘hydrothermal’ originates from earth science in the nineteenth century, where
it implies a regime of high temperatures and water pressures (Byrappa and
Yoshimura, 2001). In fact, our planet itself is a huge hydrothermal vessel, in which
some precious crystals such as quartz crystal are formed. In the artificial hydrothermal
synthesis process, the crystal growth is normally performed in an apparatus consisting
of a steel pressure vessel called autoclave. Hydrothermal synthesis offers many
advantages such as relatively mild operating conditions (reaction temperatures
< 300 °C), one-step synthetic procedure, environmental friendliness, and good
dispersion in solution. Moreover, hydrothermal synthesis is inexpensive in terms of
the instrumentation, energy and material precursors compared with other solution
synthesis methods. In general, this method allows the synthesis of nanostructures
requiring relatively
high temperatures for its formation, and therefore, the synthesis of small nanoparticles
is almost impossible, that is, the case of barium hexaferrite powders prepared at
temperatures around 900 °C. Nanoparticles less than 10 nm wide have been obtained
at 150 °C by using the hydrothermal method.
3.6. SOLVOTHERMAL METHOD
The Solvothermal method is identical to the hydrothermal method except that a
variety of solvents other than water can be used for this process. This method has
been found to be a versatile route for the synthesis of a wide variety of nanoparticles
with narrow size distributions, particularly when organic solvents with high boiling
points are chosen. The solvothermal method normally has better control of the size
and shape distributions and the crystallinity than the hydrothermal method.
18
Solvothermal synthesis of nanowires is a high-pressure solution-based nanowire
growth method that does not employ any catalyst. An organic solution of
semiconductor precursors and surfactants is heated up above the boiling point of the
solvent (typically < 250°C) in a reactor able to withstand high pressures. The increase
of pressure in the liquid phase, due to the partial evaporation, can go up to hundreds
of bars, therefore favouring the conditions for precursor decomposition and crystal
nucleation. Then, the growth of nanowires proceeds at high rates by crystal growth in
preferred directions with surfactant adsorbed onto sidewalls preventing
agglomeration. If the solvent employed is water, it is referred to as hydrothermal
synthesis, which involves higher temperature and pressure, resulting in a safer
manipulation due to the absence of a toxic/flammable solvent. Using the solvothermal
route gains one the benefits of both the sol-gel and hydrothermal routes. Thus,
solvothermal synthesis allows for the precise control over the size, shape distribution,
and crystallinity of metal oxide nanoparticles or nanostructure products. These
characteristics can be altered by changing certain experimental parameters, including
reaction temperature, reaction time, solvent type, surfactant type, and precursor type.
3.7. ELECTRODEPOSITION
This is a simple and well-established process and can be easily adopted to
produce nanocrystalline materials. Electrodeposition of multilayered (1-D) metals can
be achieved by using either two separate electrolytes or much more conveniently from
one electrolyte by appropriate control of agitation and the electrical conditions
(particularly voltage). Also, 3D nanostructure crystallites can be prepared using this
method by utilizing the interference of one ion with the deposition of the other.
Recently many researchers extensively used this process to study the synthesis and
properties of nanocrystalline materials (Gu and Suh 2010; Song et al 2009; Zhang et
al 2008). It has been shown that electrodeposition yields grain sizes in the nanometer
range when the electrodeposition variables (e.g., bath composition, pH, temperature,
current density, etc.) are chosen such that nucleation of new grains are favoured rather
than growth of existing grains. This is achieved by using high deposition rates,
formation of appropriate complexes in the bath, addition of suitable surface-active
elements to reduce surface diffusion of ad-atoms, etc. This technique can yield
porosity-free finished products that do not require subsequent consolidation
processing. Further, the process requires low initial capital investment and provides
high production rates with few shape and size limitations.

19
3.8. CHEMICAL PRECIPITATION AND CO-PRECIPITATION
A chemical precipitation process consists of three main steps: chemical
reaction, nucleation and crystal growth. Chemical precipitation is generally not a
controlled process in terms of reaction kinetics and the solid phase nucleation and
growth processes. Therefore, solids obtained by chemical precipitation have a wide
particle size distribution plus uncontrolled particle morphology, along with
agglomeration. To obtain nanoparticles with a narrow size distribution, the necessary
requirements are (i) a high degree of supersaturation, (ii) a uniform spatial
concentration distribution inside a reactor and (iii) a uniform growth time for all
particles or crystals.The other commonly used solution method for the synthesis of
multi component oxide ceramics is co-precipitation method, which produces a
“mixed” precipitate comprising two or more insoluble species that are simultaneously
removed from solution. The precursors used in this method are mostly inorganic salts
(nitrate, chloride, sulfate, etc.) that are dissolved in water or any other suitable
medium to form a homogeneous solution with clusters of ions. The solution is then
subjected to pH adjustment or evaporation.. After precipitation, the solid mass is
collected, washed and gradually dried by heating to the boiling point of the medium.
The washing and drying procedures applied for co-precipitated hydroxides affect the
degree of agglomeration in the final powder and must be considered when nanosized
powders are the intended product. Generally, a calcination step is necessary to
transform the hydroxide into crystalline oxides. In most of the binary, ternary and
quaternary systems, a crystallization step is necessary, which is generally achieved by
calcinations or, more elegantly, by a hydrothermal procedure in high-pressure
autoclaves.

3.9. SONOCHEMICAL SYNTHESIS

Currently, ultrasound irradiation has become an important tool in chemistry. It

provides an unusual mechanism for generating high-energy chemistry with extremely
high local temperatures and pressures and an extraordinary heating and cooling rate.
Sonochemistry drives principally from acoustic cavitations: the formation, growth and
implosive collapse of bubbles in liquids. When solutions are exposed to strong
ultrasound irradiation, bubbles are implosively collapsed by acoustic fields in the
solution. Hightemperature and high-pressure fields are produced at the centers of the

20
bubbles. The implosive collapse of the bubbles generates a localized hotspot through
adiabatic compression or shock wave formation within the gas phase of the collapsing
bubbles. The conditions formed in these hotspots have been experimentally
determined, with the transient temperature of ~5000 K, pressure of > 1800 atm and
cooling rates in excess of 1010 K/s. These extreme conditions enable many chemical
reactions to occur. The products are sometimes nano amorphous particles and, in
other cases, nanocrystalline (Bang and Suslick 2010, Gedanken 2004). This depends
on the temperature in the ring region where the reaction takes place. Ultrasound
irradiation differs from traditional energy sources (such as heat, light, or ionizing
radiation) in duration, pressure and energy per molecule. Ultrasound irradiation has
also been used to induce hydrolysis to produce various metal oxide nanoparticles.
Ultrasound irradiation also offers a very attractive method for the preparation of
various nanosized metal chalcogenides (Praharaj et al 2006). They vary in size, shape,
structure and in their solid phase (amorphous or crystalline), but they are always of
nanometer size.

3.10. PHOTOCHEMICAL SYNTHESIS

Absorption of photo energy can change the structure of molecules and induce
a variety of photochemical reactions. During recent years, a photochemical technique
has emerged as an effective synthetic technique for the preparation of nanosized metal
chalcogenides with various morphologies. This method has the advantages of mild
reaction conditions and convenient operations and the equipments involved are simple
and cheap. Generally speaking, a low-pressure mercury pillar lamp and a high-
pressure column-like indium lamp are most commonly used as the ultraviolet
irradiation and visible photo irradiation source, respectively. Zhu’s (2001) group
reported the photochemical synthesis of CdSe nanoparticles by employing a high-
pressure indium lamp as the visible photo irradiation source. Wang et al (2000)
established an ultraviolet irradiation method for in-situ synthesis of nanocrystalline
CdS particles. CdS nanocrystallites with cubic or hexagonal phase structures were
prepared at room temperature via precipitation of Cd2+ ions with homogeneously
released Sí ions, generated from the decomposition of thioacetamide by ultraviolet
irradiation reduction. This technique may be extended to prepare other sulfide
semiconductor nanoparticles, including ZnS, Ag2S, PbS, NiS and CuS. This method

21
can be extended to the preparation of nanocrystalline CdS with different
morphologies. Mo et al (2001) established a morphology-controlled synthesis of CdS
nanocrystallites by introducing poly vinyl alcohol (PVA) as the protecting agent,
which self-assemble into desirable shapes. CdS spherical nanoparticles, nanodisks and
nanowires have been obtained conveniently and there are some CdS nanotubes that
appeared in the CdS nanodisk sample. This method gives a mild chemical route to
fabrication of semiconducting nanowires which may be applied in many fields.

22
 CHAPTER 4

4. PREPARTION AND CHARACTERISATION

TECHNIQUES

4.1. PREPARATION

CuO nanostructures were synthesized CuO nanostructures were synthesized

by hydrothermal method using copper nitrate (Cu(NO)3.6H2 O). First, precursor of
2.42 gm was dissolved in 20 ml deionized water to form 0.5 M concentration.
NaOH(0.5 M) of 2.47gm was dissolved in 120 ml of deionized water. Both the
solutions were stirred for 1 hour. Then NaOH solution was slowly dropped into the
precursor solution until pH reached to desired pH value. After adding 43 ml of
NaOH solution the pH value became 14. Initially the colour of precursor solution was
sky blue which was then turned into dark blue. Then the solution was transferred into
autoclave and was maintained at 120℃for 14 hours. Black precipitates were obtained
and repeatedly washed by deionized water and absolute ethanol for several times till
pH reached 10. Subsequently, the washed precipitates were dried at 80 °C for 30
minutes. After that it was transferred into Petri dish and again dried for 15 minutess.
Then the sample is grained and packed. The sample was investigated by X-Ray
Diffractrometry (XRD). The optical absorption characteristics were investigated by
UV-Vis spectroscopy. Chemical properties were investigated by Fourier transform
infrared spectroscopy (FTIR).

4.2 CHARACTERISATION TECHNIQUES

4.2.1. FOURIER TRANSFORM INFRARED SPECTROSCOPY(FTIR)

4.2.1a. INFRARED SPECTROSCOPY

Infrared absorption spectrum There must be a change in the dipole moment of

the vibrating molecule in order for IR absorption to occur. For a diatomic molecule
this means that the molecule must have a dipole moment. The dipole moment of
uncharged diatomic molecule derives from the partial charges of the atoms which can
be approximated by comparison of electronegativities of the atoms. Homonuclear
diatomic molecules i.e. molecules build from a pair of identical atoms, such as: O2,

23
H2, N2 etc. have no dipole moment and therefore can’t absorb IR radiation.
Heteronuclear diatomic molecules, such as: CO, HCl, NO etc. have a permanent
dipole moment. The change of the interatomic distance caused by vibration results in
a change of the dipole moment of the molecule which enables the absorption of an
IR photon. If the frequency of the IR photon matches the vibrating frequency of the
molecule, then the photon will be absorbed, resulting in a change in the vibrational
frequency of the molecule. Generally, molecules consist of multiple groups of atoms
rather than just a two atom pair. Each of these groupsof atoms has its own vibrational
transitions and has influence on the energy of vibrational transitions of the other
atomic groups that are part of the molecule. The infrared spectrum of a sample is
recorded with a spectrometer that examines the transmitted light of an infrared beam
which is used to illuminate the sample. Each molecule in the sample absorbs photons
of certain energies, characteristic for that molecule which are then revealed in the IR
spectrum as a well-defined and reproducible absorption bands

4.2.1b. FROM IR TO FT-IR SPECTROSCOPY

Most of the components in present infrared spectrometers were already

described during the nineteenth century. The field of infrared spectroscopy did not
develop at that time due to difficulties in building suitable detectors for measuring IR
radiation. In the begining of the 20th century William W. Coblentz conducted
measurements in the IR spectral region of the transitions between different vibrational
states of molecules for hundreds of inorganic and organic compounds. The
recognition of the high potential of IR spectroscopy and the advances in electronics
during and after World War II led to establishing IR spectroscopy as a key analytical
method in academic and industrial labs by the middle of the 20th century. Most IR
instrumentation used through the 1970s was based on prism or grating
monochromators. A major breakthrough in IR spectroscopy was the introduction of
FT-IR spectrometers which used an instrument called interferometer that was
discovered almost a century ago by Albert Michelson. At the time of the construction
of the Michelson interferometer (1891), Lord Rayleigh recognized that the output
from an interferometer could be converted to a spectrum using a mathematical
operation that was developed by the french mathematician Fourier in the 1820s. The
combination of those discoveries led to the development of a whole new technology
for measuring and calculating the IR spectrum which was used in FT-IR
24
spectrometers. In spite of the advantages of FT-IR over dispersive instruments such
as: high speed data collection, increased resolution, lower detection limits and greater
energy throughput, the acceptance of FT-IR spectroscopy was slowed by the
complexity of the calculation required to transform the measured data into a spectrum.
With the discovery of the Fast Fourier Transform algorithm by James Cooley and
John Tukey (1964), the time for spectrum calculation was reduced from hours to just
a few seconds. The development of the first commercial FT-IR spectrometer in 1969
by Digilab enabled spectroscopists to see a spectrum plotted shortly after the
interferogram was collected. Today there are large number of commercial FT-IR
spectrometers on the market that are used for different applications of FT-IR
spectroscopy, such as: quantitative analysis of complex mixtures in liquid, solid or
gaseous state; determination of the quality of a sample; biological and biomedical
spectroscopy etc.

4.2.1c. PRINCIPLE OF FTIR

Transform Infrared Spectroscopy (FTIR) provides specific information about

the vibration and rotation of the chemical bonding and molecular structures, making it
useful for analyzing organic materials and certain inorganic materials. An infrared
spectrum represents a fingerprint of a sample with absorption peaks which correspond
to the frequencies of vibrations between the bonds of the atoms making up the
material. Because each different material is a unique combination of atoms, no two
compounds produce the exact same infrared spectrum. Therefore, infrared
spectroscopy can result in a positive identification (qualitative analysis) of every
different kind of material. In addition, the size of the peaks in the spectrum is a direct
indication of the amount of material present. With modern software algorithms,
infrared is an excellent tool for quantitative analysis. The IR region is commonly
divided into three smaller areas: near - IR (400 - 10 cm-1), mid - IR (4000 - 400 cm-
1), and far - IR (14000 – 4000 cm-1). Infrared photons have enough energy to cause
groups of atoms to vibrate with respect to the bonds that connect them. Like
electronic transitions, these vibrational transitions correspond to distinct energies, and
molecules absorb infrared radiation only at certain wavelengths and frequencies.
Chemical bonds vibrate at characteristic frequencies, and when exposed to infrared
radiation, they absorb the radiation at frequencies that match their vibration modes.
Measuring the radiation abs frequency produces a spectrum that can be used to

25
identify functional groups and compounds. Some impurities produce their own
characteristic bands in infrared region. Spectral measurements of these bands are used
to determine conce the impurities and their bonding with the host materials.
identification, the measured interferogram signal can not be interpreted directly. A
means of “decoding” the individual frequencies is required. This can be accomplished
via a well-known mathematical technique called the transformation is performed by
the computer which then presents the user with the desired spectral information for
analysis.

4.2.1d. INSTRUMENTATION - MICHELSON INTERFEROMETER

There are three basic spectrometer components in an FTIR system: a radiation

source, an interferometer, and a detector.

Interferometer divides radiant beams, generate an optical path difference

between the beams and the recombines them in order to produce repetitive
interference signals measured as a function of optical path difference by a detector.

Figure 4.1- Michelson Interfrometer

As its name implies, the interferometer produces interference signals, which

contain infrared spectral information generated after passing through a sample. The
most commonly used interferometer is a Michelson interferometer (fig4.1). It

26
consists of three active components: a moving mirror, a fixed mirror, and a beam
splitter. The two mirrors are perpendicular to each other. The beam splitter is a semi-
reflecting device and is often made by depositing a thin film of germanium onto a flat
KBr substrate. Radiation from the broadband IR source is collimated and directed into
the interferometer, and impinges on the beam splitter.

4.2.1e. WORKING OF AN FTIR SPECTROMETER

The basic instrument design is quite simple. Fig 4.1 illustrates the schematic
diagram of FTIR. The normal instrumental process is as follows:

 The Source: Infrared energy is emitted from a glowing black-body source. This
beam passes through an aperture which controls the amount of energy presented to
the sample (and, ultimately, to the detector).
 The Interferometer: The beam enters the interferometer where the ‘spectral
encoding’ takes place. The resulting interferogram signal then exits the
interferometer.
 The Sample: The beam enters the sample compartment where it is transmitted
through or reflected off of the surface of the sample, depending on the type of
analysis being accomplished. This is where specific frequencies of energy, which
are uniquely characteristic of the sample, are absorbed.
 The Detector: The beam finally passes to the detector for final measurement. The
detectors used are specially designed to measure the special interferogram signal.
 The Computer: The measured signal is digitized and sent to the computer where
the Fourier transformation takes place. The final infrared spectrum is then
presented to the user for interpretation and any further manipulation.

27
 Fig- 4.2 Schematic Diagram Of FTIR

4.2.1f. ANALYTICAL INFORMATION OF FTIR

FTIR can be analysed by two techniques namely: Qualitative and

Quantitative.

 Qualitative analysis :

The combination of the fundamental vibrations or rotations of various functional

groups and the subtle interactions of these functional groups with other atoms of the
molecule results in the unique, generally complex IR spectrum for each individual
compound. IR spectroscopy is mainly used in two ways: structural elucidation and
compound identification.

 Structural Elucidation:

Because of complex interactions of atoms within the molecule, IR

absorption of the functional groups may vary over a wide range. However, it has
been found that many functional groups give characteristic IR absorption at
specific, narrow frequency ranges regardless of their relationship with the rest of
the molecule. Generalized tables of the positions and relative intensities of
absorption bands have been established and used to determine the functional
groups present or absent in a molecule. Correlation charts are available in many
data books.

28
  Compound Identification:

Since the IR spectrum of every molecule is unique, one of the most

positive identification methods of an organic compound is to find a reference IR
spectrum that matches that of the unknown compound. Transmittance (T) is the
ratio of radiant

power (I) transmitted by the sample to the radiant power (I0) incident on the
sample. Absorbance (A) is the logarithm to the base 10 of the reciprocal of the
transmittance.

𝟏 𝑰
𝑨 = 𝒍𝒐𝒈𝟏𝟎 (𝑻) = −𝒍𝒐𝒈𝟏𝟎 𝑻 = −𝒍𝒐𝒈𝟏𝟎 (𝑰 )
𝟎

The transmittance spectra provide better contrast between intensities of strong

and weak bands because transmittance ranges from 0 to 100 % T whereas
absorbance ranges from infinity to zero.

 Quantitative analysis

The basis for quantitative analysis of absorption spectrometry is the Bouguer–

Beer–Lambert law, commonly called Beer’s law . For a single compound in a
homogeneous medium, the absorbance at any frequency is expressed as,

𝑨 = 𝒂𝒃𝒄

where A is the measured sample absorbance at the given frequency, a is the

molecular absorptivity at the frequency, b is the path length of source beam in the
sample, and c is the concentration of the sample. This law basically states that the
intensities of absorption bands are linearly proportional to the concentration of each
component in a homogeneous mixture or solution.

4.2.1g. ADVANTAGES AND LIMITATIONS OF FTIR SPECTROMETER

 ADVANTAGES

The FT-IR spectrometer has several major advantages over the dispersive
instrument. Its sensitivity is better because it measures all frequencies simultaneously
rather than scanning through the individual frequencies. Less energy is needed from
the source and less time (typically 1 to 2 seconds) is needed for a scan. Several scans

29
can be completed in a few seconds and averaged to improve the signal. Resolution
and accuracy are also improved because a laser beam is used alongside the IR beam to
control the speed of the moving mirror and to time the collection of data points. The
light beam is a precise frequency reference that keeps the spectrometer accurately
calibrated.

 LIMITATIONS

Few limitations of FTIR spectrometer are listed below:

 Minimal elemental information is given for most samples.

 Background solvent or solid matrix must be relatively transparent in the
spectral region of interest.
 Molecule must be active in the IR region; i.e. when exposed to IR radiation, a
minimum of one vibrational motion must alter the net dipole moment of the
molecule in order for absorption to be observed.

4.2.2. UV-VIS SPECTROSCOPY

Ultraviolet-visible spectroscopy (UV–Vis ) refers to absorption

spectroscopy or reflectance spectroscopy in part of the ultraviolet and the full,
adjacent visible spectral regions. This means it uses light in the visible and adjacent
ranges. The absorption or reflectance in the visible range directly affects the
perceived colours involved. In this region of the electromagnetic
spectrum, atoms and molecules undergo electronic transitions. Absorption
spectroscopy 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.

4.2.2a. PRINCIPLE OF UV-VIS SPECTROSCOPY

This technique involves the absorption of near-UV or visible

lightAbsorption spectroscopy is employed to determine the presence of a particular
substance in a sample and, in many cases, to quantify the amount of the substance
present [3], When organic compounds absorb UV or visible light,energy from the
light is used to promote an electron from a bonding or non-bonding orbital into one of
the empty anti-bonding orbitals. In each possible case, an electron is excited from a

30
full orbital into an empty anti-bonding orbital. Each jump takes energy from the light,
and a big jump needs more energy than a small one. Figure 4.3 showing the possible
electron jumps that light may cause.

Fig 4.3- Possible electron jump

Each wavelength of light has a particular energy associated with it. If that particular
amount of energy is just right for making one of these energy jumps, then that wavelength
will be absorbed its energy will have been used in promoting an electron. The relationship
between the frequency of light absorbed and its energy,

𝐸 = ℎ𝜐

where, E is the energy of each quanta of light, h is the Planck’s constant and 𝜈 is the
frequency of light For higher energy jump, light of a higher frequency is to be absorbed

UV-visibJe spectrophotometer measures both intensity and wavelength. It is usually

applied to molecules and inorganic ions in solution. For each wavelength of light passing
through the spectrometer, the intensity of the light passing through the reference cell is
measured. This is usually referred to as l0 .The intensity of the light, I passing through the
sample cell is also measured for that wavelength. If l is less than l0l then obviously the
sample has absorbed some of the light. The Beer-Lambert Law gives, the relationship
between A (the absorbance) and the two intensities is given by

𝐼0
𝐴 = 𝑙𝑜𝑔10
𝐼

An absorbance of 0 at some wavelength means that no light of that particular

wavelength has been absorbed. An absorbance of 1 happens when 90% of the light at that
wavelength has been absorbed that means that the intensity is 10% of what it would otherwise
be.

31
4.2.2b. INSTRUMENTATION

The basic components of a UV-vis spectrophotometer are described in the figure 4.4
shown below,

Fig 4.4- Schematic representation representing different components of an

absorption spectrophotometer

 Light source: The most general source of Ultraviolet light is a deuterium arc that offers
light in the range of 190 - 380 nm. While a tungsten lamp or a quartz-iodine lamp is used
as a source for obtaining Visible light. Xenon lamp source also serve as a potential
candidate for light source as it covers the UV as well as visible range. Moreover, it
ensures a long lifetime as it is consumed only during the actual measurement cycle. The
major requirement of any source is its stability or in other words its intensity should not
fluctuate during the measurements.
 Wavelength selector: In order to enhance the selectivity and specificity of the
technique a narrow band of wavelength must be supplied. Most of the instruments
generally use a filter for desired beam of light and thus are unable to provide a narrow
band of the wavelengths. Most of the sophisticated instruments utilize a monochromator.
A monochromator can be defined as a device used to provide light of single wavelength
out of range of wavelengths emitted by the source. It comprises of an entrance slit, a
collimating device which facilitates production of parallel light, a wavelength selection
system, a mirror or a focusing lens and finally an exit slit. The two types of
monochormators are prism and diffraction grating.
 Sample handling: Generally samples in solution or vapor phase are analyzed in a cell
called cuvette which must be transparent to the wavelength of light passing through it.
Various cuvettes are available for the spectral determination, but generally they are made
of glass or quartz. A cuvette must have the following characteristics;

 The entrance and exit surfaces must be exactly parallel and orthogonal.
 Light path must be tightly controlled.
 Optical windows of cuvette must be highly smooth, parallel and flat.

32
 Generally, cuvettes of path length1.0 cm are used, though cuvettes with smaller path
lengths (0.1 mm or 0.05 mm) are also available.
 Detectors: The function of a detector is to convert a received light signal into an
electrical signal which can be transformed into a readable output. The signal generated by
the detector is linear in transmittance. The most commonly used detectors are the
photomultiplier, the silicon diode and the diode array.
 Signal Processing and Output Devices: Finally the transducer sends the generated
electrical signal to the recorder. The spectrum of solvent is electronically subtracted from
the solution so as to determine the spectrum of particles under investigation only. Thus
the output plot between the wavelength and the intensity of absorption is characteristic of
the absorbing species. Schematic diagram of uv-vis spectroscopy is shown by the figure
4.5.

Fig 4.5- UV-Vis spectroscopy

4.2.2c. ADVANTAGES AND DISADVANTAGES

 Advantages

The biggest advantage for chemists and astronomers who use UV-VIS spectrometers is
the accuracy of the device. Even small UV-VIS spectrometers can give extremely accurate
readings, which is crucial when you are preparing chemical solutions or recording the
movement of celestial bodies. UV-VIS spectrometers are easy to use. Most UV-VIS

33
spectrometers used in astronomy attach to telescopes. Most of the ones used in chemistry are
comparable in size to electron microscopes and require the same basic skills to use. Because
they are simple to operate, there is little chance of a UV-VIS spectrometer being used
improperly.

 Disadvantages

Just as the human ear can only hear certain frequencies of sound, the human eye can only
see certain kinds of light. The light we can see is referred to as the visible spectrum of light.
Beyond the visible spectrum of light is infrared light and ultraviolet light. Although these two
kinds of light cannot be seen directly by the human eye, certain devices can detect them. UV-
VIS spectrometers measure light in both the visible spectrum and the ultraviolet
spectrum.Elements make up all matter on earth. These elements reflect wavelengths of light.
Different wavelengths of light appear to the human eye as different colors. For the
wavelengths we can't see, such as ultraviolet wavelengths, a UV-VIS spectrometer can be
used to measure the wavelengths reflected off of or emitted by matter.

4.2.3. X-Ray DIFFRACTION SPECTROSCOPY

X-ray Diffraction (XRD) is one of the classical methods for identification and
characterization of crystalline solids. Each crystalline solid has its unique
characteristic X-ray powder pattern which is used as a” fingerprint” for its
identification. The method is based on the diffraction of X-rays by the sample in
different directions. Waves of wavelength comparable to the crystal lattice spacing are
strongly scattered (diffracted).

4.2.3a. PRINCIPLE

When a crystal with an interplanar spacing d (crystal lattice constant) is

irradiated by X-ray beam with a comparable wavelength λ, the X-ray diffraction, or
the constructive interference between elastically scattered X-ray beams can be
observed at specific angles 2θ when the the Bragg’s Law is satisfied

𝑛𝜆 = 2dsinθ

where n is any integer. In most diffractometers the X-ray wavelength λ is fixed and
the diffraction angle θ is measured by goniometer, therefore the crystal lattice
constants can be decided by above equation.

34
 Fig- 4.6 Bragg’s law

4.2.3b INSTRUMENTATION

Ray Diffractometer and Experimental Procedure Basically, this method

involves the diffraction of monochromatic X-ray by a powdered specimen. The
instrument used for the method is X-ray diffractometer, which consist of three basic
elements, (i) an X-ray tube, (ii) a sample holder, and (iii) an X-ray detector. Figure 4.7
shows the schematic presentation of powder x-ray diffraction

Fig-4.7 Schematic Diagram Of Powder XRD

X-rays are generated in a cathode ray tube by heating a filament to produce

electrons, accelerating the electrons toward a target by applying a high voltage, and
bombarding the target material with electrons. When electrons have sufficient energy
to dislodge inner shell electrons of the target material, characteristic X-ray spectra are
produced. These spectra consist of several components, the most common being Kα
(α-doublet) and Kβ. Kα consists, in part, of Kα1 and Kα2. Kα1 has a slightly shorter
wavelength and twice the intensity as Kα2. The specific wavelengths are

35
characteristic of the target material. The most common laboratory X-ray tube uses a
copper anode, but cobalt and molybdenum are also popular. Filtering, by foils or
crystal monochrometers, is required to produce monochromatic X-rays needed for
diffraction. Kα1 and Kα2 are sufficiently close in wavelength such that a weighted
average of the two is used. Copper is the most common target material for single-
crystal diffraction, with CuKα radiation = 1.54184 Å. The basic purpose of the
monochromatization is to obtain an experimental pattern from a single, unique
wavelength.

A fine powder of the material under investigation should be placed in the

sample holder - a small disc like container and its surface carefully flattened. The X-
rays are collimated and directed onto the sample. The fundamental law, which
governs the x-ray diffraction phenomenon, is the Bragg’s Law. The interaction of the
incident X-rays with the crystalline powdered sample produces constructive
interference when conditions satisfy Bragg's Law and it gets diffracted in the form of
cones, which is exhibited. The cones may emerge in all directions, forwards and
backwards. A circle of film is used to record the diffraction pattern as shown. Each
cone intersects the film giving diffraction lines. The lines are seen as arcs on the film.
Each diffraction line 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. These
diffracted X-rays are then detected, processed and counted. The geometry of an 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, mounted on an arm to collect the diffracted X-
rays, rotates at an angle of 2θ, which is known as Bragg-Brentano configuration. The
intensity of diffracted Xrays is continuously recorded as the sample and detector
rotate through their respective angles. A peak in intensity occurs when the mineral or
crystallinematerial contains lattice planes with d-spacing appropriate to diffract X-
rays at that value of θ. The instrument used to maintain the angle and rotate the
sample is termed a goniometer. For typical powder patterns, data is collected at 2θ in
the range of angles from ~5° to 70°, angles that are preset in the Xray scan. By
scanning the sample through a range of 2θ angles, 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 dspacing allows identification of the mineral or

36
crystalline material because each mineral has a set of unique d-spacing. Typically, this
is achieved by comparison of d-spacing with standard reference patterns. Resultant
diffraction pattern contains a good deal of information of which three parameters are
of special interest – (i) the position of the diffraction maxima,

(ii) the peak intensities and

(iii) the intensity distribution as a function of diffraction angle. Results of the

procedure are commonly presented as peak positions at 2θ and X-ray counts
(intensity) in the form of a table or an x-y plot, known as diffractogram. For
determination of unit cell parameters, each reflection must be indexed to specific
Miller indices (h, k, l). Nowadays, many types of software are available in market for
powder XRD data analysis. Figure 4.8 show the single crystal XRD.

Fig-4.8 Single crystal -XRD

4.2.3c. APPLICATIONS

Powdered XRD has a wide range of applications in material science, geology,

environmental science, chemistry, forensic science, and the pharmaceutical industry,
etc. This method has been conventionally used for phase identification, quantitative
analysis and the determination of structure imperfections. Various types crystalline
materials can be characterized by powder XRD, including organic and inorganic
materials, minerals, drugs, zeolites, catalysts, metals and ceramics. In the

37
pharmaceutical industries the powder XRD is popular for identification of drug
molecule and its polymorphs. The physical states of the materials can be loose
powders, thin films, poly-crystalline and bulk materials. By properly using this
technique one can yield a great deal of structural information about the material under
investigation. For most applications, the amount of information which is possible to
extract depends on the nature of the sample microstructure (crystallinity, structure
imperfections, crystallite size and texture), the complexity of the crystal
structure(number of atoms in the asymmetric unit cell and unit cell volume) and the
quality of the experimental data (instrument performances and counting statistics) The
powder method can be used as a tool to identify crystals, since the powder XRD
patterns produced by a crystalline substance is a characteristic of that particular
substance. One of the most important uses of the powder method is in the
identification of an unknown material. The ASTM (American Society for Testing and
Materials) data cards as well as JCPDS (Joint Committee of Powder Diffraction
Standards) data files are available for large number of substances for identifications
and comparison. Statistical study of the relative orientations of the individual crystals
of an aggregate is one of the important secondary uses of the powder method.

4.2.3d. ADVANTAGES AND DISADVANTAGES

 ADVANTAGES
 It is reliable and powerful tool for crystalline sample identification.
• It is a non-destructive technique.
• Ability to analyze mixed phases.
• For the purpose of simultaneous and quick measurement of the positions and
intensities of diffraction lines the diffractometers are advantageous. It is a fast
technique (< 20 min) for identification of an unknown sample.
• In most cases, it provides an unambiguous sample determination.
• Simplicity in sample preparation, i.e., required sample preparation is minimal and
extensive sample preparation is not needed.
• XRD units are widely available.
• Data interpretation is relatively straight forward.
 LIMITATIONS
• Homogeneous and single phase material is best for material identification.

38
• Must have access to a standard reference file of compounds.
• Requires tenths of a gram of material which must be ground into a powder.
• The sensitivity of the powder diffraction method is not comparable in sensitivity
to the other X-ray-based techniques.
• A phase present in quantities lower than 5% by weight is usually not detected.
For mixed materials, detection limit is ~ 2 - 5% of sample
• Peak overlay may occur and worsens for high angle 'reflections'.
• Can not identify amorphous materials.

39
 CHAPTER 5

RESULT AND DISCUSSION

5.1 FTIR ANALYSIS OF CuO NANOPARTICLE

Fourier Transform Infrared spectroscopy is a technique used to measure the vibrational

frequencies of bonds in the molecule. The infrared spectrums of synthesized samples of
cupric oxide nanoparticle is shown in the figure 6.1.

Fig 6.1- FTIR Spectrum

This spectra of nano-sized CuO sample is mainly presented in three regions. The
obtained spectra show an sharp absorbed band of 503.77 𝑐𝑚−1, which shows the
characteristic band of monoclinic phase of pure CuO. There are bands between 400 𝑐𝑚−1
and 600 𝑐𝑚−1 corresponding to CuO vibration, conforming the formation of highly pure
CuO nanoparticle. The strong intensity peak at 2928.17 𝑐𝑚−1 and at 2854.52 𝑐𝑚−1 assigned
to alkane (C-H ) stretching. The broad peak at 3437.65 𝑐𝑚−1corresponds to (O-H) stretching

40
of alcohol group. The peaks at 1637.99 and 1366.78 shows C=C stretching band of alkene
and S=O stretching band of sulfonate respectively.

41
5.2 UV-VIS ANALYSIS OF CuO NANOPARTICLE

UV-Vis spectroscopy was used to find qualitative information and to estimate the direct band
gap of CuO nanoparticle sample. The scan distance range was set between 200 nm and 1200
nm.

The optical band gap energy(𝐸𝑔 ) can obtained by using fundamental law,

𝐸𝑔 = ℎ𝑐/𝜆𝑚𝑎𝑥

where 𝜆𝑚𝑎𝑥 is maximum absorption wave length of CuO nanoparticles in nm. The maximum
absorption power of sample are observed at 983 nm and corresponding the band gap energy
is 1.263 eV. UV-Vis absorbtion spectrum is show in the figure 6.2.

Fig 6.2- UV-Vis Absorption Spectrum

42
5.3. XRD ANALYSIS OF CuO NANOPARTICLE

Structural, phase purity and crystallinity of the prepared CuO sample were
characterised by XRD as shown in figure 6.3. All diffraction patterns are indexed to the
cubic structure of CuO (JDPDS Card Number 89-5895) and the main diffraction peaks(
34.99, 38.43, 48.39,61.26, 67.90) corresponds to (110),(200),(202),(113),(220) planes of CuO
phase respectively. No other impurity peaks are observered.this suggest the pure formation of
CuO nanoparticles. Crystalline size was estimated using well known Scherre formula,

0.9𝜆
𝑑=
𝛽 cos 𝜃

Where 0.9 is Scherrer’s constant, 𝜆 is the wavelength of X-rays, 𝜃 is the Bragg diffraction
angle, and 𝛽 is the full width at half-maximum (FWHM) of the diffraction peak

And the calculated crystalline size was around 37.08 nm.

Fig 6.3- XRD spectrum

43
 CHAPTER 6

CONCLUSION

The CuO nanoparticles were successfully prepared via hydrothermal method. These
prepared nanoparticles were characterised by different characterisation techniques.

The XRD analysis revealed the monoclinic phase of CuO nanoparticle and the
formation f pure CuO nanoparticle. The crystalline size of CuO was found to be 37.08 nm
from the XRD analysis. The optical characterisation was did by UV-Vis analysis and the band
gap energy was found to be 8.60 eV which is very large. The FTIR studies revealed the
existence of different functional groups and the presence of Cu-O vibrating modes.

In future idea of the research is due to use the CuO nanoparticles for the application
of supercapacitor.

44