A

Research Proposal on

Synthesis and Characterization of Metal (Ni and Fe) Oxide

for various applications

For Registration to the Degree of Doctor of Philosophy

IN THE FACULITY OF SCIENCE

THE IIS UNIVERSITY, JAIPUR

Submitted By:

JYOTI YADAV

ICG/2017/24609

Under the Supervision of

Dr. RIMPY SHUKLA

Assistant Professor

DEPARTMENT OF PHYSICS

The IIS University, Jaipur

May, 2018

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 CONTENTS :
Ø Introduction of Nanotechnology
Ø Metal Oxide Nanomaterials
§ Importances
Ø Target Metal Oxide Nanomaterials
§ NiO
§ Fe2O3
Ø Application of Oxides
Ø Review of Literature
Ø Motivation/ Justificstion
Ø Research gap
Ø Objectives
Ø Research Methodology
Methods of preparation of nanoparticles
§ Sol-gel Method
§ Hydrothermal Method
Ø Characterization techniques of nanoparticles
§ XRD
§ SEM
§ TEM
§ FTIR
§ UV-Vis Spectroscopy
§ VSM
Ø Plan of work
Ø References

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1. Introduction of Nan
Nanotechnology

Nanoscience is an interdisciplinary field of the sciences of physics, chemistry and materials

sciences, meant for the design and fabrication of nanomaterials and their application. This
branch of science is meant to understand the fundamental physical and chemical pro properties
and the phenomenon of nanomaterials and nanostructures, and because of the novel
application of nanomaterials, the science of nanomaterials has evolved as a frontline research
area.
a. Feynman pointed out the importance of nanotechnology at the annual meeting of the
American Physical
ysical Society in 1959, in the classic science lecture entitled ‘‘There is plenty of
room at bottom”.. In the last three decades, many discoveries and inventions have been made
in the field of nanosciecne in terms of fabricating nnew ew materials and utilizing them for
applications. Various new experimental techniques, with unique and desired properties of
nanomaterials fabrication
cation have been discovered.
Considerable
erable research efforts with different synthesis methods have given brith to different
classs of nanomaterials, typically classified into three categories based on their dimensionality:
0 dimensional, one dimensional, two and three dimensional. Quantum dots and the individual
molecules fall in the 0-dimensional
dimensional structures where the nanoparticles
articles are isolated from each
other. One dimensional nanostructures where atleast one of the dimension goes in the range
of nanoscale order are being highly utilized and have versatile application in the nanodevice
fabrications. Thin nano films lie in the two dimensional structures and are studied extensively
for the utilization of nanodevice application. Three Three-dimensional
dimensional nanomaterials include
powders, fibrous, multilayeryer and polycrystalline materials in which the 0D, 1D and 2D
structural elements arere in close contact with each other and form interfaces. An important
type of three-dimensional
dimensional nanostruct
nanostructured materials is a compact or consolidated (bulk)
polycrystal
ycrystal with nanosize grains, whose entire volume is filled with those nanograins.

Figure1
Figure1: Nanoscale according to size of materials

Almost all materials system including material, insulator and semiconductors show size
dependent electronic or optical properties in the quantum size regime. Among these, the
modification in the energy band gap of semiconductor is the most attractive one because of

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the fundamental as well as technological importance. The band gap can be observed from the
same material. Nanoparticles are becoming key components in a wide range of applications.
Research encompasses numerous disciplines, e.g. nanotechnology, molecular engineering,
medicine, pharmaceutical drug manufacture, biology, chemistry, physics, optical
components, polymer science, mechanical engineering, toxicology, cosmetics, energy, food
technology and environmental and health sciences.

2. Metal oxide nanomaterials

Metal oxides because of their electronic structure differences, exhibit metallic,
semiconductor, or insulator character. Preparation of these materials through the novel
synthesis procedures can be described as physical and chemical methods. In general, two
approaches have been used for the synthesis of these metal oxide nanostructures, top-down
and bottom-up fabrication techniques. These approaches involve liquid–solid or gas–solid
transformations. Metal oxide nanostructures among the most versatile groups of
semiconductor nanostructures stand out as one of the most common, most diverse and most
probably richest class of materials due to their extensive structural, physical and chemical
properties and functionalities. In recent times metal oxides have been at the heart of many
dramatic advances in the materials science. These materials display most fascinating and
widest range of properties.
Due to the unique and tunable properties of these metal oxides such as optical, optoelectronic,
magnetic, electrical, mechanical, thermal, catalytic, photochemical etc. made themselves
excellent candidates for various high level technological applications. For instance, fuel cells,
secondary battery materials, ceramics, chemical sensors, gas sensors and biosensor, solar
cells, alkaline and lithium ion batteries, pyroelectric, piezoelectric, ferroelectric, magnetic,
actuator, super capacitors, optical devices, lasers, waveguides, infrared(IR) and solar
absorbers, gate dielectric, dielectrics in dynamics random access memories, High TC
superconductivity, decoupling capacitors, magneto- resistance and so on. Hence metal oxide
nanostructure materials have been actively studied in a broader perspective by the
researchers. Therefore it is essential to explore its understanding in great details interms of
their synthesis, properties and applications.

2.1 Importance of Metal Oxide Nanostructures

Nanoparticles of metal oxides have attracted increasing technological and industrial interest
due to the changes in their optical, magnetic, electrical and catalytic properties accompanied
with improved physical properties of stability or chemical passivity. Many physical
properties of nanoparticles differ drastically from that of a single crystal of the same chemical
composition. At nanoscale size, due to the confinement effect of electronic states and large
number of surface atoms, many physical properties are influenced compared to their bulk
phases.
Metal oxide nanoparticles have technological applications in areas such as catalysts, passive
electronic components and high performance ceramics. These materials play important role in
the selective surface modification of different substrates in the form of coatings. In comp-
arison to that of bulk metaloxide phase nanomaterial metal oxides contain large fraction of

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total atoms as surface atoms, which makes a distinct contribution to the free energy and
results in the large changes in the thermodynamic properties (melting temperature depression,
solid-solid phase transition elevation). Also the intrinsic properties of metal oxide are
transferred by quan-tum size effect, that is changes in the optical and electrical properties
with size arises because of the transformation in the density of electronic energy levels.

2.2 Target metal oxide nanomaterials

1. Nickle oxide (NiO):

Nickel is a strong, lustrous, silvery-white metal that is a staple of our daily lives and can be
found in everything from the batteries that power our television remotes to the stainless steel
that is used to make our kitchen sinks. Nickel oxide catches much intension due to its unique
physical and chemical stability. Nickel oxide with chemical formula NiO found rarely in
nature as bunsenite mineral form.
As like all other transition metal oxide, nickel oxide has been especially investigated in the
degradation of several environmental pollutants & due to its properties, the interest in NiO as
a photocatalyst has increased. Nickel oxide appears to be especially efficient as catalyst for
wastewater pollution abatement. Nickel oxide based materials proved to be more effiecient
for photocatalytic degradation of dyes. In brief, nickel oxide nano particles have received
significant attention in the recent years for various applications.
Nickel is a Block D, Period 4 element, while oxygen is a Block P, Period 2 element. Nickel
oxide nanoparticles appear in green powder form, and are graded as very toxic. They can
cause an allergic skin reaction, prolonged harmful effects to aquatic life, and possible damage
to organs due to prolonged or repeated exposure.
Chemical Properties:
Table:1 Properties of Nickel Oxide Nanoparticles
Chemical symbol NiO
CAS No. 1313-99-1
Group Nickel 4
Oxygen 16
Electronic configuration Nickel [Ar]3d8 4s2
Nickel 78.55
Oxygen 21.40

Physical Properties:
The physical properties of nickel oxide nanoparticles are given in the following table.

Density 6.67 g/cm3 0.240 lb/in3

Molar mass 74.71 g/mol -

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Thermal Properties:
The thermal properties of nickel oxide nanoparticles are provided in the table below.

Melting point 1955°C 3551°F

2. Iron Oxide (Fe2O3) :

Iron oxides are chemical compounds composed of iron and oxygen. All together, there are
sixteen known iron oxides and oxy-hydroxides. Iron oxide NPs are found naturally in the
environment as particulate matter in air pollution and in volcanic eruptions. Either magnetite
or maghemite – the two most commonly studied iron oxides − particles can be generated as
emissions from traffic, industry and power stations but can also be specifically synthesised
chemically for a wide variety of applications (so-called engineered nanoparticles). Iron
oxides play an important role in many geological and biological processes, and are widely
utilized by humans, e.g., as iron ores, pigments, catalysts, in thermite , Hemoglobin. Common
rust is a form of iron(III) oxide. Iron oxides are widely used as inexpensive, durable pigments
in paints, coatings and coloured concretes.
Although Iron oxide is found in nature in different forms, Magnetite (Fe3O4), Maghemite (γ-
Fe2O3) and Hematite (α-Fe2O3) are the most common among them.
Iron oxide magnetic nanoparticles differ with their atoms and bulk counter parts in their
physical and chemical properties. As each nanoparticle is considered a single magnetic
domain, large surface area and quantum size effects lead to some dramatic change in
magnetic properties resulting in super paramagnetic phenomena and quantum tunnelling of
magnetization. Based on their unique physical, chemical, thermal and mechanical properties,
super para-magnetic nanoparticles offer a high potential for different applications. These
applications demand nanomaterials of specific sizes, shapes, surface characteristics, and
magnetic properties, fields of high- density data storage, ferrofluids, magnetic resonance
imaging, waste water treatment, bio separations and biomedicines.

Table:2 Properties of Iron Oxides

Chemical symbol Fe2O3
Group Oxygen 16
Iron 8
Electronic Configuration Iron[Ar] 3d6 4s2
Oxygen[He] 2s22p6
Element Content(%)
Iron 69.93%
Oxygen 30.06%
Density 5.34g/cm3
Boiling point 1,897ºc
Melting Point 1,566ºC
Physical properties
Metric Imperial

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Molar Mass 1.569g/mol -
Solubility in water Insoluble
Solubility Soluble in diluted acids
Cordination geometry Octahedral
Odour Odourless
Appearance Red-brown solid
.
2.3 Application Of Target Oxides
Iron oxide (Fe2O3) has a range of applications such as:In magnetic resonance imaging to
provide enhanced contrast at very low concentrations in the nanomolar range for studying
tumors. As a targeted delivery vehicle and as a drug delivery coating for nanoscale anti-
cancer drugs.For magnetic data storage In coatings, plastics, nanowires, nanofibers, and
textiles and in specific alloy and catalyst applications.For Magnetic Resonance Imaging
(MRI) As drug carriers for target specific drug delivery As gene carriers for gene therapy As
therapeutic agents for hyperthermia based cancer treatments As magnetic sensing probes for
in-vitro diagnostics (IVD) As Nanoadjuvant for vaccine and antibody production.Magnetite
and maghemite are preferred in biomedicine because they are biocompatible and potentially
non-toxic to humans. Iron oxide is easily degradable and therefore useful for in vivo
applications. Results from exposure of a human mesothelium cell line and
a murine fibroblast cell line to seven industrially important nanoparticles showed a
nanoparticle specific cytotoxic mechanism for uncoated iron oxide. Solubility was found to
strongly influence the cytotoxic response. Labelling cells (e.g.stem cells, dendritic cells) with
iron oxide nanoparticles is an interesting new tool to monitor such labelled cells in real time
by magnetic resonance tomography.

Nickel oxide (NiO) has a range of applications such as:For making electrical ceramics such
as thermistors and varistors e.g. ferrites (nickel zinc ferrite). In Pigments for ceramic, glasses
and glazes. Nickel oxide can be reacted with acids to form salts and other compounds e.g.
nickel sulfamate for electroplating and nickel molybdate for hydrodesulfurisation catalysts.
Gold doped nickel oxide films can be used as transparent electrodes in optoelectronic device.
In lithium nickel oxide cathodes for lithium ion microbatteries. In electrochromic coatings,
plastics and textiles, nanowires, nanofibers and specific alloy and catalyst applications. As a
catalyst and as anti-ferromagnetic layers. In light weight structural components in aerospace,
adhesive and coloring agents for enamels.In active optical filters, automotive rear-view
mirrors with adjustable reflectance, in cathode materials for alkaline batteries, Electro
chromic materials, energy efficient smart windows. Materials for gas or temperature sensors,
such as CO sensor, H2 sensor, and formaldehyde sensors

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3. Review Of Literature

Sharma et al [2018] determined Nickel oxide has been synthesized by solution combustion
technique. The nickel oxide ceramic was annealed at 600°C and 1000°C for 2 hours.
Structural, electrical, dielectric and magnetic properties were analyzed which are strongly
dependent upon the synthesis method. Structural properties were examined by X-ray
diffractometer (XRD), which confirmed the purity and cubic phase of nickel oxide. XRD data
reveals the increase in crystallite size and decrease in full width half maximum (FWHM) as
the annealing temperature increases. Electrical conductivity is found to increase from 10-6 to
10-5 (Ω-1cm-1) after annealing. Dielectric constant is observed to increase from 26 to 175
when the annealing temperature is increased from 600°C to 1000°C. Low value of coercive
field is found which shows weak ferromagnetic behavior of NiO. It is observed that all the
properties of NiO particulate improve with increasing annealing temperature.

Lassoued et al [2018] Studied the synthesized products have been studied by TGA,
Differential Thermal Analysis (DTA), X-ray diffraction (XRD), Transmission Electron
Microscopy (TEM), Scanning Electron Microscopy (SEM), Fourier Transform Infra-Red
(FT-IR), Raman spectroscopy, Ultraviolet–Visible (UV–Vis) analysis and Vibrating Sample
Magnetometer (VSM). The TGA showed three mass losses, whereas DTA resulted in three
endothermic peaks. XRD measurements confirm that all the prepared nanocrystals consist
only in nanocrystalline hematite phase. TEM and SEM show that the size of the nanoparticles
decreases with Ni-doping. FTIR and Raman spectroscopies confirm the phase purity and the
phonon modes of the synthesized nanoparticles. The UV–Vis absorption measurements
confirm that the decrease of particle size is accompanied by a decrease in the band gap value
from 2.02 eV for α-Fe2O3 down to 1.81 eV for 8 mol% Ni-doped α-Fe2O3.

Khan et al [2017] Studied Haematite (Fe2O3) nanorods are synthesized by reflux assisted
coprecipitation method in two steps. In the first step, spherical nanoparticles of ferric
oxyhydroxide (FeOOH) are synthesized. In the second step, FeOOH nanoparticles are
converted into Fe2O3 nanorods by calcination of 4 h. These products (FeOOH and Fe2O3) are
subjected to x-ray diffractometry to analyze their lattice structure, lattice parameters,
diffraction planes and miller indices. Both of these products are also subjected to scanning
electron microscopy (SEM) and transmission electron microscopy (TEM) to analyze their
morphology. SEM and TEM observations have revealed that products are monodisperse and
hollow. The dimensions of FeOOH nanoparticles and Fe2O3 nanorods are also measured from
SEM and TEM observations. The heat transport properties of FeOOH are compared with that
of Fe2O3. The value of thermal conductivity, thermal diffusivity and specific heat of FeOOH
and Fe2O3 are measured to analyze their heat transport/storage characteristics. These products
are also used as fuel additive.

Riasat et al [2016] Studies the hollow spheres of iron oxide ( -Fe2O3) were successfully
synthesized synthesis by using hydrothermal method. Iron salt was dissolved together with
glucose in water and then the mixture was heated to 180ºC in an autoclave at 12 and 24 hours
of synthesis time separately. Hollow -Fe2O3 spheres of around 200 to 300 nm size were
formed after the calcination that lead to the removal of carbon. Increasing the reaction time
will decrease the shell thickness. Phase confirmation and crystalline structure of these
nanoparticles were done by XRD. Surface morphology was characterized by SEM and TEM
analysis showed the hollow spheres inside and a shell of -Fe2O3.
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Manisha et al [2016] Studied Nickle oxide (NiO) nanoparticles have been synthesized via
modified Sol-gel method. In this modified method, oxalic acid was replaced with citric acid
which was mixed with ethylene glycol to form a homogenous gel and replaced ethyl alcohol
with ethylene glycol. The metal nanoparticles were characterized by XRD, UV-Vis and FT-
IR spectroscopy. The results obtained from XRD, UV-Vis and FT-IR spectra analysis
confirms the formation of nickle oxide nanoparticles.

Mirzaei et al [2016] Studied Fe2O3 nanoparticles (NPs) have been synthesized by using a
sol-gel method from iron nitrate, citric acid as complexing agent and ethylene glycol as
polymerization agent. The calcined Fe2O3 NPs were fully characterized by different
techniques. It was confirmed that ultrafine and highly crystalline Fe2O3 NPs with high purity
and mesoporous nature can be obtained after calcination at 550 °C for 3 h. In addition, the
results of electrical resistance measurements of the fabricated Fe2O3 thick films showed that
Fe2O3 thick films have stable electrical properties which are beneficial for electrical
applications such as gas sensing and field effect transistors.

Dang et al [2015] Studied the NiO p-type semiconducting nanowires with polycrystalline
structure were prepared by a facile and scalable hydrothermal method. Morphology and
crystal structure of the NiO nanowires were investigated by scan electron microscopy, X-ray
diffraction, and transmission electron microscopy. The nanostructured material was then
tested as hydrogen sensor showing very good performance in terms of sensor response,
stability, absence of drifts, and speed of response and recovery.The selectivity of the NiO
sensor to hydrogen towards other gases (ethanol, ammonia, and liquefied petroleum gas) was
found to be good.

Rahdar et al [2015] Studied the Nanostructured NiO were synthesized by co-precipitation

method using Nickel(II) Chloride Hexahydrate (NiCl2.6H2O) and sodium hydroxide (NaOH)
as starting material. Structural, optical and magnetic properties of nanostructures were
characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Atomic
force microscope (AFM), UV–Vis absorption; Fourier transformed infrared (FTIR) and
vibrating sample magnetometer (VSM) technique. The X-ray diffraction pattern studies
revealed the NiO have a face-centered cubic (FCC) structure and confirmed the presence of
high degree of crystallinity nature NiO nanoparticles that their average size is found to be 26
nm. The composition of nanostructures confirmed by analysis of FTIR spectra. The average
size of the NiO nanoparticle observed from scanning electron microscopy images is found to
be dimensions about 24 nm. Magnetic measurement confirmed the Nickel Oxide
nanostructures superparamagnetic behavior at room temperature (RT) after calcinations.

Marbella et al [2015] discuss recent developments in the application of NMR techniques to

the study of noble metal nanoparticle growth, surface chemistry, and physical properties.

Shaker et al [2013] investigated Magnetite (Fe3O4) nanoparticles have been successfully

synthesized by Sol–Gel method by using Ferric nitrate (Fe (NO3)3.9H2O) and Ethylene glycol
(C2H6O2) as precursors in different annealing temperatures. The obtained nanoparticles have
been characterized by X-Ray diffraction (XRD), Scanning Electron Microscope (SEM), X-
ray energy dispersive spectrometer (EDS) and Particle Size Analyzer. XRD measurements

9
indicate that the obtained nanoparticles are single phase and the particle size increased by
increasing the temperature. Environmental pollution such as dyes has been excessively
released into the environment and has created a major global concern. Congo Red is a
benzidine-based anionic diazo dye with two azo groups. It is toxic to many organisms and is
a suspected carcinogen and mutagen. The presence of Congo Red (CR) in water even at very
low concentration is highly visible and undesirable. Present work is focused on synthesis of
magnetite nanoparticles which showed a high adsorption capacity of Congo Red and is useful
in removal of CR from wastewater.

Cheng et al [2012] investigated the applicability of maghemite (γ-Fe2O3) nanoparticles for

the selective removal of toxic heavy metals from electroplating wastewater. The maghemite
nanoparticles of 60nm were synthesized using a coprecipitation method and characterized by
X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with energy
dispersive X-ray spectroscopy (EDX).

Rogojan et al [2011] studied by the sol-gel method, the synthesis started from different
chemical nature precursors – inorganic (aluminum chloride, AlCl3) and organic (aluminum
triisopropylate, (C3H7O)3)Al). The powders obtained after drying the gel were heat treated at
1000ºC and 1200ºC for 2 hours. X-ray diffraction was used in order to characterize the
powders in terms of their crystallinity degree and crystallite size. Microstructural and
morphological characterization was performed using electron-microscopic techniques -
scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

Basavaraja et al [2011] Studied the nanometer-sized α -Fe2O3 particles have been prepared
by a simple solvothermal method using ferric acetylacetonate as a precursor. The products
were characterized by X-ray diffraction (XRD), energy dispersive X-ray microanalysis
(EDAX), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM),
transition electron microscopy (TEM), infrared spectroscopy (IR) and thermal analysis (TG–
DTA). XRD indicates that the product is single-phase α -Fe2O3 with rhombohedral structure.
Bundles of acicular shaped nanoparticles are seen in TEM images with an aspect ratio ~ 12;
typically 8–12 nm wide and over 150 nm long. The α -Fe2O3 nanoparticles posses a high
thermal stability, as observed on thermal analysis traces.

Changyu et al [2011] Studied the Mesoporous nanosheets of single-crystalline β-nickel

hydroxide (β-Ni(OH)2) were successfully synthesized via a facile hydrothermal method using
Ni(NO3)2 .6H2O as precursor in a mixed solution of sodium hydroxide (NaOH) and sodium
dodecylbenzenesulfonate (SDBS). Single-crystalline nickel oxide (NiO) mesoporous
nanosheets can be obtained through a thermal decomposition method using β-Ni(OH)2
mesoporous nanosheets as precursor. The influences of SDBS and hydrothermal treatment
were carefully investigated; the results showed that they played important roles in the
formation of β-Ni(OH)2 mesoporous nanosheets. The as-obtained β-Ni(OH)2 and NiO were
characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), thermal
gravity-differential thermal analysis (TG-DTA), and specific surface area, and pore size test.

Wenqing Qin et al [2010] Studied Single-crystalline α-Fe2O3 nanocubes were successfully

obtained in large quantities through a facile one-step hydrothermal synthetic route under mild
conditions. In this synthetic system, aqueous iron (III) nitrate (Fe(NO3)3࡮9H2O) served as
iron source and triethylamine served as precipitant and alkaline agent. By prolonging reaction

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time from 1 h to 24 h, the evolution process of α-Fe2O3, from nanorhombohedra to nano
hexahedron, and finally nanocube, was observed. The products were characterized by Powder
X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron
Microscopy (TEM), Highresolution Transmission Electron Microscopy (HRTEM), Selected-
Area Electron Diffraction (SAED), and Fourier Transform Infrared Spectrometry (FTIR)

4. Motivation /Justification
Nickel and Iron oxides has major applications. They exhibit magnetic properties. They are
generally used for optical properties as pigments for paints, plastics, ceramic glazes and
enamels, as photoelectric, recording materials, catalysts, sensors, ceramic materials etc. Other
uses include oxygen sensors, photovoltaics and antimicrobial coatings, water purification. For
making electrical ceramics such as thermistors and varistors. Magnetic properties of NiO
nanoparticles with different sizes and at different temperatures are compared. The nickel
oxide nanoparticles are mostly used in batteries like lithium ion batteries, nickel-iron battery,
nickel-Zinc battery, nickel- cadmium battery etc. Iron oxide nanoparticles include terabit
magnetic storage devices, catalysis, sensors, super paramagnetic relaxometry (SPMR), and
high-sensitivity biomolecular magnetic resonance imaging (MRI) for medical diagnosis and
therapeutics. Common rust is a form of iron(III) oxide. Iron oxides are widely used as
inexpensive, durable pigments in paints, coatings and colored concretes.

4.1 Research Gap

In the above works review by us most of them have prepared the materials and recorded their
properties by characterization. Some of them ( Cheng.et al, Shaker.et al) have investigated the
(Ni, Fe) oxide material for their application in water purification. However work on the
removal of metallic ions (lead, copper, zinc etc.) are very limited. Therefore, there is a need
for further research in this area.
The drinking water obtain from well, ponds it generally contain heavy metal ions which is
mercury, cadmium, lead, copper, chromium, nickel, zinc etc. These metal ions cannot be
detected by naked eye, smell or taste. For example mercury, cadmium, lead, copper,
chromium, nickel, zinc etc. The source of heavy metals are – acidic rain ,detergent and
refined petroleum products, industrial and consumer wastes, copper occurs in drinking water
from copper pipes and algal growth. In current era, pH value measurement, thrmogravimetric
analysis, differential scanning calorimetry and UV-Visible spectroscopy techniques are
usually employed for detection and identification and identification of ionic impurities in
water. Research on environmental health risks is also limited but suggests that multiphase
metal oxide may have a minor adverse impact on human or environmental healthand further
research is necessary to determine the impact.
Keeping in view of above exciting research area with fulfilling the gaps of available reviews,
the proposed research will be very potential and innovative to scientists and engineers
working in this field, particularly in purification of water.

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5. Objectives
Scope of this work is focused on the following steps:

Ø To synthesize the NiO and Fe2O3 by using chemical synthetic methods ( sol-gel
method and hydrothermal method).
Ø To investigate various properties of the samples, it has to undergo a number of
characterisation techniques. It is proposed to use the following techniques:
· Crystals structure by using XRD diffraction patterns.
· Particle size and crystalline nature by using Transmission Electron Microscopy.
· Surface morphology by Scanning Electron Microscopy.
· Optical properties by UV-Vis Spectroscopy.
· Various characteristic functional groups in molecules of synthesized
nanomaterial by FTIR spectroscopy analysis.
· Magnetic properties by Vibrating Sample Magnetometer.
Ø To compare the properties of the samples of above materials obtain from sol-gel and
and hydrothermal method.
Ø To investigate effect of temperature on Crystallographic phases and Morphologyof
the sample.
Ø To find out optimum calcination temperature for the use of above materials in water
treatment application.
Ø
6. Research Methodology

6.1 Methods of preparation of nanoparticles

1. Sol-gel Method:
The sol-gel process may be described as:
”Formation of an oxide network through polycondensation reactions of a molecular
precursor in a liquid.”
A sol is a stable dispersion of colloidal particles or polymers in a solvent. The particles may
be amorphous or crystalline. An aerosol is particles in a gas phase, while a sol is particles in a
liquid, A gel consists of a three dimensional continuous network, which encloses a liquid
phase, in a colloidal gel, the network is built from agglomeration of colloidal particles. In a
polymer gel the particles have a polymeric sub-structure made by aggregates of sub-colloidal
particles. Generally, the sol particles may interact by vander Waals forces or hydrogen bonds.
A gel may also be formed from linking polymer chains. In most gel systems used for
materials synthesis, the interactions are of a covalent nature and the gel process is
irreversible. A sol consists of a liquid with colloidal particles which are not dissolved, but do
not agglomerate or sediment. Agglomeration of small particles are due to vander Waals
forces and a tendency to decrease the total surface energy. Vander Waals forces are weak,
and extend only for a few nanometers. The gelation process may be reversible if other
interactions are involved. The idea behind sol-gel synthesis is to “dissolve” the compound in

12
 a liquid in order to bring it back as a solid in a controlled manner. Multi component
compounds may be prepared with a controlled stoichiometry by mixing sols of different
compounds. The sol-gel methodethod prevents the problems with co-precipitation,
precipitation, which may be
inhomogeneous, be a gelation reaction. Enables mixing at an atomic level. Results in small
particles,
icles, which are easily sinterable. Sol-gel synthesis may be used to prepare materials with
a varietyy of shapes, such as porous structures, thin fibers, dense powders and thin films.

Figure 2: sol –gel process

If the gel is dried by evaporation, then the capillary forces will result in shrinkage, the gel
network will collapse, and a xerogel is formed. If drying is performed under supercritical
conditions, the network structure may be retained and a gel with large pores may be formed.
This is called an aerogel, and the density will be very low. A record is < 0.005 g/cm3.

2. Hydrothermal
al Method

Hydrothermal synthesis is normally conducted in steel pressure vessels called autoclaves

with or without Teflon liners under controlled temperature and/ or pressure with the reaction
in aqueous solution. The temperature can be elevated above the boiling ppoint of water,
reachingg the pressure of vapour saturation. This method is widely used for the production of
small particles in the ceramics industry.
The use of Hydrothermal method in preparing metals or metal oxides has become a recent
trend. This is because
use the resultant powder needs no more highhigh-temperature
temperature calcinations and
thus can avoid the nano-particles
particles from rere-clustering and from being contaminated. In the
process of preparing
aring nano
nano-powderr by hydrothermal method, any of the operating
ssure and reaction
temperature, pressure tion path affects the shape and size of the particle.

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 Figure 3: Setup of Hydrothermal process

Advantages of Hydrothermal Method

Does without the high-temperature
temperature calcinations process or crushing thus saving much cost on
energy. The product are homogeneous in composition, easy to control the purity,
composition, sizee and crystal shape of the powder. Makes it possible for the heating path to
avoid transition from
m meso phasa to sub
sub-state phase.

6.2 Characterization
acterization techni
techniques of Nanoparticles

1. X-ray diffraction (XRD)

A very useful and widely used technique for characterizing solid materials is X X-ray
diffraction (XRD). The technique reveals detailed information about the chemical
composition, crystallographic
stallographic structure, orientation and various
ious defects in a crystalline
material. The process of interaction between X X-rays
rays and the electrons in a matter is governed
by inelastic or elastic scattering. When monochromatic X X-rays
rays impinge onto a surface plane
of a crystal lattice, some are ref
reflected
lected off the plane with an angle of reflection equal to the
angle
le of incidence, while the rest are transmitted and subsequently reflected by deeper lying
crystal planes. The reflected X X-rays
rays interfere with each other either constructively or
destructively.
y. Constructive interference occurs when two waves are in phase and add together
to produce stronger intensity. This condition is shown schematically in fig. 13 for an X X-ray
with an incidentt and scattering angle of . The two reflected rays are in phase whe when the
distance ABC, i.e. the difference in distance travelled by the reflected rays from the adjacent
planes,, is equal to a whole number of wavelengths. From these conditions one can derive
Bragg’s Law, which is expressed by
nλ=2 dhkl sin Ɵ
where n is thee order of reflection (n = 1,2,3…), is the wavelength of the X rays,
d is thee distance between the planes with the Miller indices ((hkl).
The resulting wave interference pattern is the basis of diffraction
fraction analysis valid for any beam,
e.g.. ions, electrons and neutrons, having a wavelength similar to the inter-atomic
inter distance in
the lattice.

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 Figure 4 :Digram of XRD

2. Fourier Transform Infrared (FTIR) Spectroscopy

The physics of the individual atoms and simple molecules can be understood by studying
their interaction with electromagnetic radiations. This study is called as spectroscopy. In
spectroscopy, electromagnetic radiation of a particular frequency or a range of frequencies is
allowed to fall on a sample. The radiation coming out of the sample is then analyzed in terms
of the intensity at different frequencies. This indicates about the line absorbed or emitted by
the molecule, and hence giving a picture of the molecular energy levels.
Here the term FTIR refers to Fourier transform Infrared spectroscopy, when intensity time
output of the interferometer is subjected to a Fourier transform to convert it to a familiar
infrared spectrum (intensity frequency). The energy of infrared radiation corresponds to the
difference of vibrational energy modes in a molecule. Infrared spectroscopy is therefore a
probe of vibrational motion of a molecule. The technique works on the fact bonds and groups
of bonds vibrate at characteristic frequencies. FTIR analysis provides information about the
chemical bonding or molecular structure of materials, whether organic or inorganic.

15
 Figure 5: Picture of Fourier transform Infrared spectrometer

3. Scanning
ing Electron Microscope (SEM)

Scanning electron microscope (SEM) is basically a type of electron microscope that images
the sample surface
ace by scanning it with a highhigh-energy y beam of electrons in a raster scan
pattern.
The experimental
mental setup is shown in fig
figure3.4. The electron interact with the atoms that make
up the sample producing
ducing signals that contain information about the sample’s surface
topography,
hy, composition and other properties such as electrical conductivity. SEM is used for
various purposes like Topographic studies and microst
microstructureure analysis, Elemental analysis (if
equipped with appropriate detector (energy/ (energy/wavelength gth dispersive x-ray).
x Chemical
compositionn and elemental mapping. In SEM, Primary electron are thermonically or field
emitted by a cathode filament (W or LaB) or a filled emission gun (W-tip) (W and after that
acceleratedd with high energy typically 11-30 KeV. The electron beam is steered with scanning
coils over the area of the interest. Upon interaction with material, the primary electrons
decelerate as well as losing his
is ene
energy, transfer it in elastically
tically to other atomic electron and to
the lattice.

Figure 6 : Setup of SEM

16
Due to continuous scattering events the primary beam spread up with different energies
dependingg on source origin as the interaction volume with vvarious
ous electron emitted and their
respective energy. Secondary electron (1 (1-50 eV) are mostly used for the imaging the
topography
hy and to reproduce the surface. High energy elastically backscattered electrons
depends on the atomic number (Z) of the element, which is useful to obtain X-ray
characteristic
acteristic can be used to qualitatively and quantitatively analyze the elemental
compostion and distribution in the sample as shown in figure 3.5.

Figure 7: Experimental process of SEM

3.1 SEM setup

The experimental setup consists of an electron gun, column, scanning system, substrate
chamber and dectectors.
3.2 Electron gun
It is based on the themal emission. The electron source is commonly a tungsten (W) or
lanthanium hexaboride (LaB6) tip. Elect
Electron are emitted during heating.
3.3 Column
The column consist of two electromagnetic lenses acting on the electron beam. The first lens,
the condenser lens produces most of the beam demagnification, while the second, objective
lens focuses the beam onto the sample. In co columns,
lumns, a beam shaper called stigmator, the
stigmator can createe a magnetic field around the beam to restore it in a circular cross section.
3.4 Scanning system
To get image on the display the beam should be scanned over the specimen information from
any point on thee sample can then reproduced in the same relative position on the display.

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3.5 Substrate chamber
The substrate holder depends on the different size and shape of the sample. The sample can
be moved in three dimensions, as well as rotated and titled
3.6 Detector
The most detector types used for secondary electrons are the scintillation detector. It can also
be used for primary electrons.

3.7 X-ray detector

Spectrometers for detection and analysis of X-ray are based on either of two principles are
wavelength dispersive X-ray (WDX); determines the wavelength of the X-rays.Energy
dispersive X-ray (EDS); determine the energy of the X-rays.

4. Transmission electron microscope (TEM)

Electron Microscopes are scientific instruments that use a beam of highly energetic electrons
to examine objects on a very fine scale. This examination can yield the information like
topography, morphology, composition as well as crystallographic information’s. Working
principle is exactly as their optical counterparts except that they use a focused beam of
electrons instead of light to "image" the specimen and gain information as to its structure and
composition. The main use of this technique is to examine the specimen structure,
composition or properties in sub microscopic details so that this microscopy technique is
significantly involved in numerous fields. In TEM there is no change in the refractive index
of the medium when the illumination beam is deflected, the vacuum in the lens is the same as
the vacuum in the column. Deflection is in this case only due to the electromagnetic
properties of the lens which are defined by electromagnetic plates that are only able to
influence the path direction of the electrons, since all of the electrons carry a negative charge.
Those electrons that pass through the sample go on to form the image while those that are
stopped or deflected by dense atoms in the specimen are subtracted from the image.In this
way a black and white image is formed. Remaining other electrons which passes close to
heavy atom and get only slightly deflected make their way down the column and contribute
to the image.. There are three main reasons why the microscope column must be operated
under very high vacuum. The first of these is to avoid collisions between electrons of the
beam and stray molecules. Such collisions can result in a spreading or diffusing of the beam
or more seriously can result in volatization event if the molecule is organic in nature. Such
volatizations can severely contaminate the microscope column especially in finely machined
regions such as apertures and pole pieces that will serve to degrade the image.

18
 Figures 8 :Diagram of TEM

5. UV-Vis Spectroscopy
Ultraviolet Visible Near-Infra red (UV-Vis-NIR) spectroscopy is useful to characterize the
absorption, transmission, and reflectivity of a variety of technologically important materials,
such as pigments, coatings, windows, and filters. This more qualitative application usually
requires recording at least a portion of the spectrum for characterization of the optical or
electronic properties of materials. Absorbance spectroscopy, commonly referred to as
spectroscopy, is the analytical technique based on measuring the amount of light absorbed by
a sample at a given wavelength. Spectroscopy, particularly in the visible and UV portions of
the electromagnetic spectrum, is one of the most versatile and widely used techniques in
chemistry and the life sciences. Molecular absorption spectroscopy in the ultraviolet (UV)
and visible (VIS) is concerned with the measured absorption of radiation in its passage
through a gas, a liquid or a solid. The wavelength region generally used is from 190 to about
1000nm, and the absorbing medium is at room temperature. Ultraviolet-visible spectroscopy
(UV-Vis) refers to absorption spectroscopy or reflectance spectroscopy in the ultraviolet-
visible spectral region. UV-Vis absorption spectroscopy measures the percentage of radiation
that is absorbed at each wavelength. Typically this is does by scanning the wavelength range
and recording the absorbance. It is widely used in organic chemistry to investigate the extent
of multiple bond or aromatic conjugation within molecules. The technique can be expended
to gases and solids, and also beyond absorption, to include measure reflected rather than
transmitted light.It is also used for the measurement of electronic band gap of semiconductor
films

19
 Figure 99: UV-Visible Spectrometer instrument, UV800

UV-Vis refers to absorption spectroscopy or reflectance spectroscopy in the ultraviolet -

visible spectral region. This means it uses light in the visible and adjacent (near
(near-UV and near-
infrared [NIR] ranges.
ges. The absorption or reflectance in the visible range directly affects the
perceived colourr of the chemicals involved. In thithiss region of the electromagnetic spectrum,
molecules undergo go electronic transitions.
This technique is complementary to fluorescence spectroscopy,, in that fluorescence deals
with transitions from the excited state to the ground state,, while absorption measures mea
transitions from the ground state to the excited state
Band gap energy is calculatedd using the relationship of photon n energy and frequency
Eg = hc/λ
where h is the Planck’s constant (6.626*10-34Js), c is the speed of light (2.998*108m/s) and λ
is the wavelength of light.

6. Vibrating Sample
ample Magnetometer
MicroSense VSMs are thee easiest to use vibrating sample magnetometers with the widest
range of options available.
ailable. Whether you are measuring magnetic moment and coercivity of
thin films or studying
dying the magnetic properties of liq
liquids,
uids, powders, or bulk samples, the
VSMs will give ive you the easiest and most accurate magnetic measurements. The magnetic
properties
ties of solids are very important, and attempts to understand them have led to a deep
insight into the fundamental
ental structure of many solids, both metallic and non
non-metallic. The
VSM is the instrument used to measure the magnetic moment, the most fundamental
fundam
quantityy in magnetism, of solid samples.When a sample material is placed in uniform
magnetic
netic field, a dipole moment proportional to the product of sample susceptibility aand
applied field is induced
duced in thee sample.If the sample is made to undergo sinusoidal motion as
well,
l, an electrical signal will be induced in suitable located stationary pick
pick--coils. This signal,
which is at the vibration
tion frequency, is proportional to the m
magnetic moment,
moment vibration
amplitude and vibration frequency. The instrument displays the magnetic moment in e.m.u.
units.

20
Specifications:
1.Range: 0.00001 to 10000 e.m.u.
2.Magnetic field :-10 to +10 kOe
3.Temperature range : 77 to 1050 K

Figure 10:Diagram of VSM

7. Plan Of Work
Timeline/Research Planning – an outline of the timescale of the research, indicating how
long different tasks are envisaged to take, and the sequence of different task in the time
available is given below :
Ø Three months, to review literature and learn of sol-gel and hydrothermal methods for
synthesis of materials.
Ø In next six months, the different structural phases of NiO will be synthesize by sol-
gel and hydrothermal method and calcinate them at different temperature to get a low
dimension varities of shaped with controlled morphology (-Nps, -wires, -flakes etc.)
and size (1-100 nm) and characterize the samples by different techniques (XRD,
SEM, TEM, UV-Vis, FTIR, VSM)
Ø Meanwhile, we will publish the results in conferences and journals.
Ø In next six months, we will synthesized Fe2O3 by sol-gel and hydrothermal method
with varying calcinations temperature To get different phases will change the
calcinations temperature and characterize the samples by different techniques.
Ø Then, we will publish the results in conferences and journals.
Ø Next, three months we compare the properties of the above samples obtain from both
the synthesis method.
Ø Keeping the view of above study we will see these material impact on human and
environmental health particularly for the heavy metal ions in purification of water.

21
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