GREEN SYNTHESIS OF Co3O4/BiOCl@AC AND ITS

PHOTOCATALYTIC POTENTIAL

MUHAMMAD AWAIS

DEPARTMENT OF CHEMISTRY
VEHARI CAMPUS
UNIVERISTY OF EDUCATION
LAHORE

2024
Green Synthesis of Co3O4/BiOCl@AC and its Photocatalytic
Potential

MUHAMMAD AWAIS
Reg. No.: 20-UE-07862
Roll No.: BSF2005878
Session: 2020-2024

A thesis submitted in partial fulfillment of the

requirements for the award of the degree of
Bachelor of Science (Chemistry)

DEPARTMENT OF CHEMISTRY
VEHARI CAMPUS
UNIVERISTY OF EDUCATION
LAHORE

2020-2024
@Copyright MUHAMMAD AWAIS 2024
“I hereby declare that I have read this thesis and in my opinion this thesis is sufficient
in terms of scope and quality for the award of the degree of BS (Chemistry)”

Name of Supervisor: Dr. Muhammad Asim Farid

Signature: __________________________

Date: ____________________________
 DECLARATION
I declare that this thesis entitled “Green Synthesis of Co3O4/BiOCl@AC and its
Photocatalytic Potential” is the result of my own research except as cited in the
references. The thesis has not been accepted for any degree and is not concurrently
submitted in candidature for any other degree. At any time if my staVVFaement is found
to be incorrect even after award of BS degree, the university has the right to withdraw my
BS degree.

Name: Muhammad Awais

Signature: ________________________

Date: ___________________________
 PLAGIARISM UNDERTAKING

I solemnly declare that research work presented in the thesis entitled “Green Synthesis
of Co3O4/BiOCl@AC and its Photocatalytic Potential” is solely my research work with
no significant contribution from any other person. Small contribution/help wherever
taken has been duly acknowledged and that complete thesis has been written by me.
I understand the zero-tolerance policy of the HEC and University of Education, Lahore
towards plagiarism. Therefore, I as an Author of the above titled thesis declare that no
portion of my thesis has been plagiarized and any material used as reference is properly
referred/cited.

I undertake that if I am found guilty of any formal plagiarism in the above titled thesis
even after award of BS degree, the University reserves the rights to withdraw/revoke my
BS degree and that HEC and the University has the right to publish my name on the
HEC/University Website on which names of students are placed who submitted
plagiarized thesis.

Name: Muhammad Awais

Signature: ________________________

Date: __________________________
 ACKNOWLEDGEMENT

First and foremost, I am profoundly grateful to Allah, the Almighty, for providing me
with the strength, knowledge, and perseverance to undertake this research journey and
bring it to a successful completion. Without His blessings, none of this would have been
possible.

I owe my deepest gratitude to my beloved parents, my father, Zahoor Ahmad and my

mother. Their unwavering love, support, and encouragement have been my greatest
source of motivation throughout my academic journey. My mother's constant prayers and
my father's relentless belief in my abilities have been instrumental in achieving this
milestone. Their sacrifices and dedication have laid the foundation for all my
accomplishments, and for that, I am eternally thankful.

I am also immensely grateful to my supervisor, Dr. M. Asim Farid, whose insightful

guidance, invaluable feedback, and continuous support have been pivotal in shaping this
research. His expertise and encouragement have significantly contributed to my personal
and professional growth, for which I am profoundly thankful.

Lastly, I would like to extend my heartfelt thanks to my friends and group members,
whose camaraderie and collaboration have made this journey enjoyable and enriching.
Their support, both academically and personally, has been indispensable, and I am
grateful to have shared this experience with such an incredible group of individuals.
 ABSTRACT

The use of dyes is increasing day-by-day and the run-off of these dye wastewater in
freshwater bodies damage the aquatic as well as human life. This study is based on the
green synthesis of Bimetallic nanoparticles Co3O4 and BiOCl which are supported on
Activated Carbon for the effective removal of dye content from wastewater. Cobalt
nitrate and bismuth nitrate salts were mixed with the Azadirachta indica (Neem) extract
and conditions were optimized to obtain nanoparticles. Activated Carbon was prepared
from walnut shells which were calcinated to obtain Biochar. Activating agent KCl was
added into Biochar to synthesize Activated Carbon. AC was mixed with Co 3O4/BiOCl
nanoparticles to obtain final nanocomposite Co3O4/BiOCl@AC.

The nanocomposite was subjexted to FTIR and UV to characterize the sample. FTIR
shows the Co-O peak at 662 cm -1 and Bi-O and Bi-Cl at 529 cm -1 and 1354 cm-1
respectively. The Optical band gap found through UV is about 2.6 eV.

The nanocomposite is subjected to the degradation of Organic dyes such as Methyl Green
and Methyl Red. The nanocomposite showed exceptional photocatalytic activity bye
degradaing the harmful dye content from wastewater. The nanocomposite effectively
degraded MG and MR dye to 87 % and 74 % respectively.
TABLE OF CONTENTS
Chapter 1Introduction
1.1 Introduction to Photocatalytic degradation of Dyes:.......................................................13
1.2 Classification of Dyes:......................................................................................................14
1.3 Methods of dye degradation:..........................................................................................18
1.3.1 Ion Exchange method:.................................................................................................20
1.3.2 Adsorption:..................................................................................................................21
1.3.3 Membrane filtration:...................................................................................................21
1.3.4 Coagulation and flocculation.......................................................................................22
1.3.5 Ozonation....................................................................................................................22
1.3.6 Fenton:........................................................................................................................22
1.3.7 Sonolysis:.....................................................................................................................23
1.3.8 Photocatalysis:............................................................................................................24
1.4 Introduction to Nanoparticles..........................................................................................25
1.4.1 Organic Nanoparticles:............................................................................................25
1.4.2 Inorganic Nanoparticles:.........................................................................................26
1.4.3 Metal nanoparticles:...............................................................................................26
1.4.4 Metal oxide nanoparticles:......................................................................................26
1.4.5 Ceramic nanoparticles:............................................................................................26
1.4.6 Bio-nanoparticles:...................................................................................................27
1.5 Introduction to Nanomaterials:.......................................................................................27
1.6 Classification of nanomaterial on the basis of dimension:...............................................28
1.7 Synthesis of nanoparticles:..............................................................................................29

1.7.1 Top-down approach

1.7.1 Top-down approach:

1.7.2 Bottom-up approach:

1.7.3 Chemical Method:

1.7.4 Biological synthesis:

1.7.4.1 Plant-mediated Green Synthesis:

1.7.4.2 Microorganism-mediated Green Synthesis:

3.1 Apparatus Used:

3.2 Chemicals Used:

3.2.1 Chemicals used for Co3O4 Nanoparticles:

3.2.2 Chemicals used for BIOCI:

3.2.3 Chemicals used for Activated Carbon:

3.3 Preparation of Neem plant extract:

3.4 Green Synthesis of Nanoparticles:

3.5 Green Synthesis of Activated Carbon:

3.6 Green synthesis of Nanocomposites:

3.7 Preparation of Dye Solution:

3.8 Degradation of Prepared samples:

3.9 Characterization Techniques:

 TABLE OF FIGURES
Figure 1.1 Methods of degradation...........................................................................18
Figure 1.2 AOPs for Dye degradation......................................................................19
Figure 1.3 Membrane Filtration Process..................................................................21
Figure 1.4 Ozonation Process for Degradation........................................................22
Figure 1.5 Mechanism of Fenton’s Process.............................................................22
Figure 1.6 Mechanism of snonolysis........................................................................23
Figure 1.7 Mechanism of Degradation using Co3O4/BiOCl/AC nanocomposite.. .24
Figure 1.8 Top-Down and Bottom-up approaches of synthesis of nanoparticles.. . .30
Figure 3.1 Preparation of Plant Extract....................................................................47
Figure 3.2 Green Synthesis of Cobalt Oxide (Co3O4) Nanoparticles......................48
Figure 3.3 Green Synthesis of BiOCl Nanoparticles...............................................48
Figure 3.4 Physical Activation process of Activated Carbon Synthesis..................49
Figure 3.5 Activated Carbon Synthesis through physical and Chemical
Activation………………………………………………………………………………...50
Figure 3.6 Mixing of Co3O4/BiOCl/AC...................................................................52
Figure 3.7 Process of UV-Visible Spectroscopy......................................................56
Figure 3.8 Function of Monochromator..................................................................58
Figure 3.9 Photomultiplier tube detector.................................................................59
Figure 3.10 Phototube................................................................................................60
Figure 4.1 FTIR Spectrum of Co3O4 Nps.................................................................61
Figure 4.2 FTIR Spectrum of BiOCl Nps................................................................62
Figure 4.3 FTIR Spectrum of AC............................................................................62
Figure 4.4 FTIR Spectrum of Co3O4/BiOCl Nanocomposite..................................63
Figure 4.5 FTIR Spectrum of Co3O4/BiOCl@AC nanocomposite..........................63
Figure 4.6 Bandgaps of Co3O4, BiOCl and AC.......................................................64
Figure 4.7 Bandgap of Co3O4/BiOCl, Co3O4/BiOCl@AC nanocomposite………..65
Figure 4.8 Degradation of Methyl Green Dye (a) Absorbance time graph of Co3O4,
BiOCl and AC (b) Absorbance time graph of Co 3O4/BiOCl and Co3O4/BiOCl@ AC (c)
C/Cₒ graph of Co3O4, BiOCl and AC (d) C/Cₒ graph of Co 3O4/BiOCl and Co3O4/
BiOCl@ AC. (e) UV graph of degradation of Methyl Green using Co 3O4/BiOCl@ AC...
...........................................................................................................................................66
Figure 4.9 Degradation of Methyl Red Dye (a) Absorbance time graph of Co 3O4,
BiOCl and AC (b) Absorbance time graph of Co 3O4/BiOCl and Co3O4/BiOCl@ AC (c)
C/Cₒ graph of Co3O4, BiOCl and AC (d) C/Cₒ graph of Co3O4/BiOCl and Co3O4/ BiOCl@
AC. (e) UV graph of degradation of Methyl Red using Co3O4/BiOCl@ AC....................68
1. INTRODUCTION

1.1 Introduction to Photocatalytic degradation of Dyes:

In the last hundred years or more, millions of different colored chemical compounds have
been created, of which 10,000 are manufactured industrially. Global production of
organic synthetic dyes amounts to about 0.7 million tons annually, with the primary
markets being textiles, leather products, food, plastics, cosmetics, and consumer
electronics. [1] Dye presence, even at low amounts, is extremely noticeable and
undesirable in effluent. It results in major issues for aquatic life as well as health
difficulties for people. These concerns have prompted the creation of more effective
treatment technology as well as new, strict rules governing the release of colored
wastewater. [2]

A number of techniques, including biodegradation, coagulation, adsorption, advanced

oxidation process (AOP) and membrane process, have been proposed to deal with the
removal of dye from water. Every one of these procedures has certain benefits or
drawbacks in comparison to the alternative. Therefore, it is necessary to take a balanced
approach when determining whether it is worthwhile to select a suitable technique for
deteriorating the dye in issue. These methods include advanced oxidation processes,
which seem to be a promising area of research since they may virtually completely
degrade soluble organic pollutants from fluids and soils, as found to be effective for near-
ambient degradation. [3]

A lot of work has gone into creating an effective degradation technique that can quickly
eliminate these organic pollutants that are resistant to biodegradation. Due to partial
elimination in primary and secondary treatment procedures, they are widely present in
low concentration secondary wastewater effluents. These pollutants have caused
significant worry for regulatory authorities and the general public despite their low
concentration because of their exceptionally high genotoxicity and endocrine disrupting
potency. [4]
For the breakdown of organic colors and contaminants, photocatalysis is one of the most
effective and affordable techniques available. In addition to offering a viable method for
eliminating hazardous organic pollutants from industrial waste water, photocatalysis may
also be able to address some of the main environmental problems brought on by the
polluted water. A number of benefits, such as cheap cost, minimal consumption of
energy, non-toxic properties, and the capacity to efficiently use UV and/or visible light,
have made semiconductor photocatalysis a feasible technique.[5]

At this point, it is important to discuss the significance of this issue. The reasons include
the following:

 Several researchers are engaged in this area. As a result, it is preferable to review

the literature.
 Photocatalytic degradation of pollutants is one approach that has several
advantages, including complete pollutant degradation and the possibilityof cost
effective.
 Degraded components, including water and carbon dioxide, are non-toxic.
 Pollutant degradation may be predicted based on numerical values of oxidation
potential and reagents like OH• radical, which have a typical reduction potential
of roughly 2 V.[6]

1.2 Classification of Dyes:

The blue dye known as indigo was discovered in the mummy wrappings of Egyptian
tombs approximately 4,000 years ago, marking the first documented usage of an organic
pigment. Approximately 100,000 dyes are available for purchase, and approximately
7,107 tons of dye-related materials are produced globally each year. Many industries,
including food, cosmetics, paper printing, and textiles, utilize these dyes extensively; the
textile sector is the biggest user of dyes. Textiles are quite complex due to the wide range
of dyes and chemicals used to try and create more appealing, popular shades for a
competitive market.

The term "natural dye" refers to any dye that comes from plants, animals, or minerals in
nature. Since most natural dyes are not strong, they must be applied to textiles with the
aid of mordants, which are mostly metallic salts that have a like for both fiber and the
coloring material. Many different industries utilize synthetic dyes extensively; the textile
processing industries are the main users of these dyes. Cotton fiber dyeing and printing
mostly require the use of reactive, vat, and azo dyes. Reactive dyes and direct dyes, with
respective shares of 16% and 11%, and disperse dyes, with roughly 21% of the market,
are the two largest segments. Textile dyes are often categorized based on their chemical
makeup or how they are used to color textile fibers and other materials. This review's
primary goal is to critically examine current advancements in textile dye chemistry and
their uses in textile coloring.[7]
 Molecu
Dye Name Chemical Structure lar
Weight
(g/mol)

Methyl
458.5
Green
C26H33N3Cl2

Methylene
Blue 319.85
Cationic
C16H18N3SCl
Dye

Methyl Red
C15H15N3O2
 Molecular
Dye Dye Name Chemical Structure
Weight
Type
(g/mol)

Acid
Orange 10 452.36
C16H10N2Na2
O7S2

991.8

Reactive
Black 5
Anionic
C16H21N5Na
4O19S6

289.28

Disperse
Yellow 54
C18H11NO3
 Molecular
Dye Dye Name Chemical Structure
Weight
Type
(g/mol)

Disperse 304.32
Orange3
C16H16N2O4

Nonionic
Sudan Black B
C29H24N6O 472.59

Acid Red 1 509.421

C18H13N3Na2O8S2

Table 1 Classification of Dyes.

 1.3 Methods of dye degradation:

In the late 1990s, due to the lack of a dye effluent discharge restriction, dye removal
techniques only included initial water purification procedures including equalization and
sedimentation. Improvements were achieved by implementing more efficient dye
removal techniques, such as dye-degrading filter beds and activated sludge processes,
once allowable dye effluent emission guidelines were set. [8]

Figure 1.1 Methods of degradation

The elimination of dye from industrial effluent has become a significant environmental
concern and difficulty in recent years. However, in order to meet the demands for clean
water and remove color from wastewater, a number of contemporary technologies and
procedures have recently been developed. AOPs (photo-Fenton, ozonation,
photocatalytic, sono-catalytic), biological (enzyme-assisted, bacteria-assisted, fungal-
assisted), chemical (coagulation-flocculation, photolysis, electrochemical), physical
(adsorption, ion exchange, membrane filtration), and hybrid techniques are among the
quickly used methods for dye removal. The benefits of a physical, chemical, and
biological approach are straightforward, adaptable, effective, and environmentally
benign. Additionally, it has several drawbacks such being pH dependent, costly, having a
problem disposing of secondary sludge, and taking longer. Nonetheless, because of their
ability to remove dye from wastewater, improved oxidation treatment methods are
currently being used extensively.

AOPs have several noteworthy benefits, including quick dye removal, increased
practicality, affordability, environmental friendliness, efficacy against persistent
pollutants, reduced time requirements, and high production. AOPs' primary drawback is
their decreased efficacy in alkaline wastewater and visible light. The formation of
secondary sludge, disposal issues, and high operating costs are the current constraints on
hybrid treatment, which, on the other hand, demonstrates greater efficiency and energy
savings. These techniques offer a range of color removal and degradation rates for
contaminants based on different benefits, drawbacks, requirements, and limitations.[9]

Figure 1.2 AOPs for Dye degradation.

1.3.1 Ion Exchange method:
The ion-exchange approach involves the removal of dyes by utilizing the strong
interactions between the functional groups of ion exchange resins and charged dye
molecules. The establishment of robust chemical connections between the resins and the
dye molecules leads to the extraction of dyes from wastewater.

The purpose of ion exchange in the treatment of dye effluent is to decrease the amount of
hazardous waste by transforming it into a reusable form, while also leaving behind fewer
toxic substances. Additionally, ion exchange can aid in the final disposal of the effluents
by reducing the flow of the stream that carries the toxic substances. Another notable
characteristic of the ion exchange process is its capacity to both separate and concentrate
contaminants. Considering the significant capacity and selectivity of ion exchange resins
towards various dyes, they appear to be suitable materials for effectively removing colors
from textile effluents.

1.3.2 Adsorption:
The process of interphase accumulation or concentration of chemicals on the surface of a
solid or liquid (adsorbent) is known as adsorption. When molecules (adsorbate) come
into contact with the adsorbent, their imbalanced inward forces of attraction, or free
valences, at the surface of the adsorbent, have the ability to draw and hold the molecules
onto their surface. Any two phases, such as liquid-liquid, gas-liquid, or liquid-solid
interfaces, might experience this process. Adsorption is a common technique in the
purification of water and operates in a variety of systems, including chemical, biological,
and physical ones.[10]

1.3.3 Membrane filtration:

A membrane is a phase that is either semi-permeable or permeable, sometimes referred to
as a thin polymeric solid, that limits the movement of specific species. The purpose of a
membrane is to prevent other components from passing through while permitting one
component of the mixture to pass through freely. The direction of the feed stream and the
membrane's orientation are the two main modes of operation for membrane separation.
They go by the names cross flow and dead-end filtration. Clarification, concentration,
and most importantly the continuous separation of dye from effluent are all possible with
the membrane separation method.[11]

Figure 1.3 Membrane Filtration Process.

 1.3.4 Coagulation and flocculation
Electrostatic attraction occurs during coagulation between the molecules of the coagulant
and the oppositely charged soluble dyes of the effluents. Using chemical coagulation and
flocculation in wastewater treatment involves adding chemicals to modify the suspended
and dissolved particles' physical states, which then makes it easier for the sedimentation
process to remove those solids later. In wastewater treatment, coagulation is the most
effective pre-treatment process because it removes pollutants from suspended or colloidal
forms that do not settle out on their own or settle slowly. [12]

1.3.5 Ozonation
Ozonation is an oxidative process in which ozone (O3) is the oxidizing agent. Ozone
treatment has garnered significant attention in the wastewater industry in recent times
owing to its many benefits. These include ozone's strong oxidation potential, even at low
concentrations, its great efficiency in the breakdown of organic matter, its ability to give
oxygen to water, and its low temperature sensitivity. Ozonation-related reactions can
happen indirectly through OH-radicals or directly between ozone and the organic
compounds in wastewater.[13]

Figure 1.4 Ozonation Process for Degradation.

1.3.6 Fenton:
Fenton's reagent produces hydroxyl radicals by combining H2O2 with ferrous iron (Fe 2+).
The breakdown of H2O2 is initiated and catalyzed by ferrous iron (Fe +2), which produces
hydroxyl radicals. In an aqueous solution, a complicated chemical cascade is involved in
the formation of these radicals. H2O2 is both an initiator and an OH scavenger. Fenton's
oxidation reactions typically include pH correction, oxidation, neutralization, and
coagulation to produce precipitate. Therefore, the oxidation and coagulation processes
eliminate the organic materials at two different phases. It is possible to degrade gaseous
dichloromethane (DCM) using a continuous photo-Fenton process.[14]

Figure 1.5 Mechanism of Fenton’s Process

1.3.7 Sonolysis:
Sonolysis is a simple AOP that produces no sludge and no secondary pollutants [47]. To
treat the water or wastewater, ultrasonic sound waves with frequencies in the range of 20
kHz−10 MHz are passed through the wastewater to be treated. This hydrodynamic
characteristic creates cavitation bubbles, which when they burst break down the organic
compounds in the water that needs to be treated.

Figure 1.6 Mechanism of snonolysis

At high temperatures and pressures of 500–10,000 atm and 3000–5000 K, this is
microscopic pyrolysis. This causes the water molecules to separate, generating ∗OH
radicals that attack the contaminant. When the free radicals produced at the bubble-liquid
interface go into the liquid's bulk, further reactions occur. Sonolysis is less common than
other AOPs since it requires a lot of energy and produces a lower mineralization
efficiency. The suggestion is to intensify it and/or combine it with other AOPs to perhaps
make it more active. Ultrasonic wave hybridization with ultraviolet light speeds up ROS
production, increasing efficiency. Improved bubble cavitation is also a result of the
combined action of ultrasonic waves and a photocatalyst that is UV light sensitive.

1.3.8 Photocatalysis:
By generation of electrons and holes on their lattice, semiconductor materials can create
surface-activated regions on which redox reactions occur when exposed to UV or visible
light. Typically, the redox cycle's byproducts generate radicals during this process, which
is known as photocatalysis. This process is dual in nature, meaning it can both
significantly change the physical state of the reactants and excite the semiconductor
materials. Band theory provides an explanation of how to measure this capacity in terms
of band-gap energy (Eg). Upon exposure to light or UV irradiation, semiconductor
materials undergo photonic energy absorption from an electron in the valence band. This
results in the creation of an electron hole and its subsequent excitation to the conduction
band[15].

Figure 1.7 Mechanism of Degradation using Co3O4/BiOCl/AC nanocomposite.

 Homogenous Catalysis:

The oxidative method of producing both bulk and fine compounds has made considerable
use of homogeneous catalyst. This is as a result of its effectiveness in catalyzing chemical
conversions via same-phase reactions with significant effects. Certain transition metal ion
complexes have demonstrated excellent selectivity, efficiency, and repeatability in recent
times when it comes to catalyzing reactions in mild environments. In homogeneous
catalysts, the single catalytic unit might function as a single active site, accelerating the
reaction and shortening its duration. On the other hand, homogeneous catalytic
procedures result in massive waste products, seriously upsetting ecological and
environmental stability. Additionally, homogeneous catalysts corrode industrial
materials, some of which end up deposited on the reactor wall.The preparation of
homogeneous catalysts, which would eliminate these issues and reduce environmental
risks, would include dispersing metal on insoluble solid supports through covalent
anchoring, which would hold the metal in place on the surface where the catalysis
reaction occurs.[16]

 Heterogenous Catalysis:

The reactants and catalysts in a heterogeneous catalysis reaction are in distinct phases. As
a matter of fact, most heterogeneous catalysts are solids, while most reactants are either
liquids or gasses. Reactant, product, and catalyst separation at the end of the reaction are
all substantially aided by a phase separation catalysis reaction. Additionally,
heterogeneous catalysts are simpler to handle and produce. These catalysts are made up
of powders at the nanoscale that are supported on oxide substrates that are technically
inert and have every conceivable crystallographic face. To improve efficiency and/or
selectivity, structural promoters or toxins are frequently added to metal catalysts.
Heterogeneous catalysis is currently the industry standard for energy production and
chemical transformation. 90% of industrial processes use heterogeneous catalysis.[16]

1.4 Introduction to Nanoparticles

Nanoparticles are classed according to their morphology, size, and form. Main types of
Nps are given below:

1.4.1 Organic Nanoparticles:

Organic nanoparticle are mostly ferritin, micelles, dendrimers, and liposomes. Organic
nanoparticles are non-toxic and biodegradable. Some have a hollow sphere known as
micelles and liposomes. It is also known by the term of nano capsules that are heat and
light sensitive.
Organic nanoparticles are useful for medication delivery due to their properties.
Nanoparticles are routinely employed for targeted medication delivery. Organic
nanoparticles are also known as polymeric nanoparticles. The most common shape of
organic or polymeric nanoparticles is a nanosphere or nano capsule. Matrix particles have
a solid bulk and a spherical surface that may adsorb molecules. In the latter scenario,
particles enclosed the solid mass.

1.4.2 Inorganic Nanoparticles:

Carbon is absent in inorganic nanoparticles. Inorganic nanoparticles are non-toxic. The
inorganic nanoparticles are both biocompatible and hydrophilic. Inorganic nanoparticles
have a higher stability than organic ones. There are two types of inorganic nanoparticles:
metal and metal oxide.

1.4.3 Metal nanoparticles:

Metallica nanoparticles can be manufactured using destructive or constructive processes
with metals. Metal precursors are used to produce pure metal nanoparticles. Metal
nanoparticles have distinct optoelectrical capabilities as a result of plasma resonance
features. Shape, facet, and size all have an impact on metal nanoparticle synthesis (19).
Nanoparticles of all metals can be produced (20). Metal nanoparticles such as aluminum,
gold, iron, lead, silver, cobalt, zinc, cadmium, and copper are widely known.
Nanoparticles have unique properties due to their small size (10-100 nm), surface
properties (surface area to volume ratio, surface charge, pore size, surface charge
density), structure (crystalline or amorphous), shape (spherical, rod, hexagonal,
tetragonal, cylindrical, irregular), color, and environmental factors (sunlight, moisture,
air, and heat).

1.4.4 Metal oxide nanoparticles:

Metal oxide nanoparticles are synthesized to affect the properties of their respective
metals. For example, iron nanoparticles are oxidized to produce iron oxide nanoparticles.
Iron oxide nanoparticles exhibit higher reactivity compared to iron nanoparticles. Metal
oxide nanoparticles can be produced due to their increased reactivity and efficiency (21).
Examples of metal oxide nanoparticles include zinc oxide, silicon dioxide, iron oxide,
aluminum oxide, cerium oxide, titanium oxide, and magnetite.

1.4.5 Ceramic nanoparticles:

Ceramic nanoparticles are sometimes known as nonmetallic solids. Ceramic
nanoparticles are created through heating or subsequent cooling. Ceramic nanoparticles
may be polycrystalline, amorphous, porous, dense, or hollow. Researcher focuses on
nanoparticles for their wide range of applications, such as dye degradation,
photocatalysis, catalysis, and imaging.

1.4.6 Bio-nanoparticles:
Biological or bio-nanoparticles are assemblies of atoms or molecules generated in
biological systems with at least one dimension ranging from 1 to 100 nm. Bio
nanoparticles are naturally occurring nanoparticles. There are two types of nanoparticles:
intracellular and extracellular. Magnetosomes are an example of an intracellular structure,
while lipoproteins and viruses are examples of external structures. Biological
nanoparticles include magnetosomes, exosomes, ferritin, lipoproteins, and viruses.

1.5 Introduction to Nanomaterials:

Nanomaterials are materials with structural components or units smaller than one
micrometer in at least one dimension. Nanomaterials are matter's building blocks
(approx. 0.2 nm in size).

1.5.1 Carbon-based nanomaterial:

Carbon-based nanomaterials consist entirely of carbon. Carbon-based nanoparticles
include fullerenes, carbon nanotubes (CNTs), graphene, carbon black, and nanofibers.

1.5.2 Fullerene:
the fullerenes are C60 or C70. Fullerenes are nanomaterials that have the shape of hollow
cages. Electrical conductivity, structure, strength, and adaptability make it a
commercially significant interest. Fullerenes are carbon units that have pentagonal or
hexagonal shapes. Fullerenes use sp2 hybridization to bond their carbon atoms.
Fullerenes constructed of C60 or C70 have diameters of 7.114 or 7.648 nm. Fullerenes
can be single or multi-layered.

1.5.3 Carbon nanotubes (CNT):

Carbon Nano Tubes are tubular structures with 1-2 nm diameter (26). Carbon nanotubes
can be expected as semiconducting or metallic based on their diameter (27). CNT's
structure resembles a graphite sheet rolling on itself. Rolling CNTs are classified into
three types: single-walled (SWNTs), double-walled (DWNTs), and multiwalled
(MWNTs).
  Single-walled carbon nanotubes (SWTs). Single-walled Nanotubes (SWTs) made
up of single rolled sheet. The diameter of nanotubes for single walled ranges to
0.7 nm.
 Double-walled carbon nanotubes (DWNTs). Double Walled Nanotubes (DWNTs)
composed of double rolled sheet.
 Multiwalled carbon nanotubes (MWNTs): Multiwalled Nanotubes (MWNTs)
made up of multiple rolled sheets. The least diameter of Multi-walled CNT is
100nm.

Nanotubes are formed by winding graphene nano foils with honeycomb carbon lattices
into hollow cylinders. Carbon tubes can be anywhere from a few micrometers to many
millimeters long. CNT is quite strong. CNT is flexible and returns to its original shape
without becoming brittle when released. CNTs come in a variety of shapes, thicknesses,
lengths, and layers, but are based on graphene sheets.

1.5.4 Graphene:
Graphene is an allotrope of carbon. It is a hexagonal network of honeycomb carbon atom
lattice with a two-dimensional flat surface. The graphene is 1 nanometer thick.

1.5.5 Carbon nanofiber:

The same graphene nano foils are translated into carbon nanofibers as carbon nanotubes,
but the nano foils are coiled into cup or cone shapes rather than elongate cylindrical
tubes.

1.5.6 Carbon black:

Carbon-based amorphous material. The shape of carbon black is spherical. The diameter
spans between 20 and 70 nm. There is a high level of interaction between the particles in
carbon black, which causes them to form an aggregate of the material.

1.6 Classification of nanomaterial on the basis of dimension:

Nanomaterials are categorized into

 One-dimension (1D) nanomaterials.

 Two-dimension (2d) nanomaterials.
 Three Dimension (3D) nanomaterials.
1.6.1 One-dimension nanomaterial:
The number 109 represents the one billionth of a unit, resulting in the development of
one-dimensional nanomaterials like a thin film. These nanoparticles offer a wide range of
uses in chemistry, pharmaceuticals, electronics, and engineering. The monolayers or thin
films range in size from 1 to 100 nm. Nanomaterials have a significant role in various
fields, including electronics, storage systems, optoelectronics, biosensing, magneto
optics, fiber optics, and optical devices. One-dimensional nanomaterials are used to
create nanoscale materials such nanotubes, nanobelts, nanowires, nano-ribbons, and
hierarchical nanostructures.

1.6.2 Two-dimension nanomaterial:

2D nanostructures have two dimensions that are larger than nanometric and have a
unique shape, and they are used as building blocks for important components of
nanodevices (42). Nanocontainers, sensor photocatalysts, nanoreactors, and 2D structure
templates are all examples of two-dimensional nanomaterial uses. Carbon nanotubes are a
type of two-dimensional nanoparticle.

1.6.3 Three-dimension nanomaterial:

Three-dimensional nanomaterials have been increasingly popular in medical science and
research during the last decade. The behavior of nanomaterials is determined by their
shape, size, and morphology, which are the fundamental parameters for nanostructure
application and performance. These nanoparticles have a wide range of uses, including
catalysis, batteries, and magnetic materials for reactant and product transport. Three-
dimensional nanoparticles include fullerenes, dendrimers, and quantum dots.[17]

1.7 Synthesis of nanoparticles:

Nps are synthesized by various methods. These methods are subdivided into two main
classes Top Down and Bottom-up approach.
 Figure 1.8 Top-Down and Bottom-up approaches of synthesis of nanoparticles.
1.7.1 Top-down approach:
The top-down technique is destructive, breaking down huge molecules into tiny bits
before turning them into the appropriate nanoparticles. This technique employs
decomposition strategies such as chemical vapor deposition (CVD), grinding, and
physical vapor deposition (PVD). Milling is a method for extracting nanoparticles from
coconut shells, with the crystallite size decreasing with time. This approach has produced
nanoparticles of iron oxide, carbon, dichalcogenides, and cobalt (III) oxide.

1.7.2 Bottom-up approach:

This method includes gradually forming nanoparticles from simple materials. It is
environmentally benign, less toxic, practical, and low-cost. The materials utilized are
typically green synthesis, bio-chemical, spin coating, sol-gel, and other reduction and
sedimentation processes use this approach. This technique has been used to produce
nanoparticles of titanium dioxide, gold, and bismuth.

1.7.3 Chemical Method:

Some chemical processes used to synthesize nanoparticles include sol gel, precipitation,
hydrothermal, thermal decomposition, solvothermal, and vapor synthesis.

 The sol-gel method is a simple way of manufacturing nanostructures by

homogeneously combining precursors in a solvent to form a gel substance, which
is then heated to make the desired nanoparticle. It begins with the preparation of a
sol, which then goes through the gelation process to remove the solvent. The wet
chemical/precipitation method is a quick and simple way to synthesize large-scale
nanoparticles.
  Hydrothermal technique uses high pressure and temperature to drive
heterogeneous reactions in aqueous solvents such as water. The type of pressure,
pH, and temperature used influences the properties of the produced nanoparticles.
Because of their hydrophilic surface, these nanoparticles are ideal for
biotechnological applications.
 Thermal decomposition is the process of oxidizing a solid material at the proper
temperature.
 The solvothermal process employs a solvent to manufacture a variety of materials
such as polymers, semiconductors, and metals under moderate or high pressure. It
generates unique and stable nanoparticles of controllable thickness and
temperature.

In vapor synthesis, gaseous molecules chemically react to form a phase that condenses
and causes particle development. The higher the temperature, the faster the particles
develop. Condensing inert gasses or vaporizing a supersaturated substance using a pulsed
laser, creating spark discharge by energizing electrodes and sputtering the material with
inert gaseous ions; or by using chemical processes such as chemical vapor deposition,
photothermal method, flame synthesis, or spray pyrolysis.[18]

1.7.4 Biological synthesis:

Biological synthesis involves the synthesis of nanoparticles by using plant extract and
microorganisms such as bacteria and fungi.

1.7.4.1 Plant-mediated Green Synthesis:

Phyto-nanotechnology has shown a new field for the synthesis of nanoparticles which is
eco-friendly, simple, cost effective. Scalability, bio-compatibility and synthesis of
nanoparticles via universal solvent (water) as reducing agents are advantages of phyto-
nanotechnology. Nanoparticles are synthesizes using different part of plant such as root,
fruit, stem, seed and leaf. The exact mechanism for synthesis of nanoparticles using plant
remain to be elucidated. It has been illustrated that organic acid, proteins vitamins and
secondary metabolites such as alkaloids, flavonoids, terpenoids, polysaccharides and
heterocyclic compound are responsible for synthesis of various types nanoparticles.
 1.7.4.2 Microorganism-mediated Green Synthesis:
Microorganism is considered as nano factories that hold wide potential as cost-effective
tool, eco-friendly, avoid toxic and harsh chemicals and energy demand for the synthesis
of nanoparticles. Various reductase enzymes present in the microorganism due to which
microorganism have ability to accumulate and detoxify heavy metals. These reductase
enzymes play vital role in reduction of metal salt into the nanoparticles. Over past few
years, various microorganism such yeast, fungi and bacteria. Proteins, reducing cofactor,
metal resistant gene, enzyme and organic material play important role in synthesis of
nanoparticles as reducing and capping agent. [17]
2. LITERATURE REVIEW
C. Mallikarjunaswamy et.al used green synthesis to prepare multifunctional nanoscale
material Bismuth oxychloride (BiOCl) for the removal of different dyes through
photodegradation and antimicrobial activity. They used hydrothermal method and extract
of jackfruit as a reducing agent. The crystal structure and phase composition were studied
by X-ray diffraction and confirmed tetragonal structure. FTIR analysis showed Bi-O band
at 508 cm-1 and Bi-Cl at 1457 cm -1. Energy Dispersive spectra and Scanning electron
microscope were used to study surface morphology and elemental composition. EDS
revealed the percentage of bismuth (77.84), oxygen (9.27) and chlorine (12.89) which
confirms the purity of BiOCl. By optimizing the parameters, photocatalytic activity
confirms the photodegradation of methylene blue. Destruction of bacterial cell wall
shows the antibacterial activity of BiOCl nanoparticles.[19]

Muhammad Saeed et.al performed photocatalytic degradation technique for treatment of

dye contaminated wastewater, the photocatalytic ability of TiO 2 was enhanced by
formation of p–n Co3O4-TiO2 hetero-junction prepared by wet incipient impregnation
method. The synthesized composite was characterized by X-ray diffraction (XRD),
Energy-dispersive X-ray spectroscopy (EDS), ultraviolet/visible diffuse reflectance
spectroscopy (DR UV–Vis) and scanning electron microscopy (SEM) analysis. The
broadened and shortened diffraction peaks in XRD confirmed the existence of Co3O4 and
TiO2 in crystalline nature. The average crystal size of composite according to Sherrer’s
equation was 103 nm. The atomic percentages of cobalt, titanium and oxygen were 30.34,
10.37 and 58.21 with 1.08 % aluminum as impurity. The greater photo catalytic activity
of Co3O4- TiO2 is due to separation of photo generated electrons and positive holes by
synergetic effects of p–n junction. The first order kinetics model was found as applicable
to degradation data of methyl orange. When treated with 0.1 g of Co3O4, TiO2, and
Co3O4-TiO2 at 40 °C, respectively, around 25, 41, and 88% of methyl orange (50 mL,
100 mg/L) decomposed. [20].

Machrouhi et.al prepared Activated Carbon/Zinc Oxide through green synthesis for the
removal of methyl orange dye from aqueous solution using photocatalytic degradation.
Activated carbon derived from Thapsia transtagana stems (TTS) was loaded using the
hydrothermal technique with several percentages (15 %, 30 %, 50 %, and 75 %) of ZnO
as possible catalysts for the UV irradiation-induced degradation of methyl orange. The
chemical activation was done by phosphoric acid to prepare activated carbon and then
using hydrothermal method for obtaining different percentages of ZnO. XRD, FTIR, and
SEM-EDX were used to characterize the produced composite materials. The
ZnO/ACTTS (75 %) catalyst exhibits enhanced activity with a MO dye degradation of
52.10, slightly higher than those other ZnO/ACTTS composite. ThepH initial= 3.5, 90 min
of irradiation, and 0.5 g/L were found to be ideal for catalysis. The MO dye
photodegradation process followed pseudo first-order kinetics in the presence of all
photocatalysts.[21]

Souhaila Meneceur et.al used three different plant extracts (Mentha Pulegium L., and
Artemisia herba-alba and Punica Granatum L.) to prepare iron oxide
nanoparticlesfor the degradation of diazo dyes Evans blue and Congo red.
Characterization was done using XRD, SEM, and infrared spectroscopy. The crystallite
sizes of Mentha Pulegium L, Artemisia herba-alba, and Punica Granatum L were
calculated to be 42.37, 31.68, and 30.17 nm respectively, and the average diameter of the
generated Fe3O4 NPs is near to spherical. Basic pH was maintained to get efficient
results. The compound Fe3O4 NPs was proved efficient in the treatment of wastewater
(dye degradation) [22].

Parwathiraja Chelliah et.al prepared environmental favorable biosynthesis of cobalt oxide

(Co3O4) nanoparticles using Curcuma longa plant extract. Characterization was done
using UV, XRD, FTIR, TEM and EDX. The Co3O4 nanoparticles' optical and chemical
valencies projected the Co2+ and Co3+ valencies across the oxygen vacancies. The
Curcuma longa plant extract enhanced the material interface and the electronic transitions
of the Co3O4 nanoparticles indicate the creation of Co and O stabilization. During the 40-
minute radiation exposure, 90 % of the MB dye degraded. Co3O4 nanoparticles in the
amount of 10 mg is used for better photocatalytic dye degradation. When applied to
gram-positive bacterial strains, biogenic Co3O4 nanoparticles demonstrated increased
antibacterial efficacy. The results obtained support the usage of Co 3O4 nanoparticles for
development and applications in the field of biomedical research and water treatment.[23]

Amel Taha et.al worked on environmentally friendly Ag nanoparticles (AgNPs), ZnO

nanoparticles (ZnONPs), and Ag/ZnO nanocomposites supported on activated carbon
using neem leaves extract. simple impregnation, successive precipitation, and co-
precipitation were different techniques used for preparation. Different analytical
techniques were used to examine sample such as XRD, SEM, FTIR, and UV. The
catalytic degrading activity of Ag/AC and Ag-ZnO/AC nanocomposites toward 4-
nitrophenol showed great efficiency. These samples also exhibited strong antibacterial
activity against both Gram classes of bacteria.[24]

P.A. Luque et.al used green synthesis to prepare SnO2 nanoparticles (NPs) by using
varying concentrations of Camellia sinensis (1, 2, and 4 %). Characterization techniques
e.g. attenuated total reflection infrared spectroscopy (ATR-IR), scanning electron
microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction
(XRD) were used. After 180 minutes of exposure to UV radiation, the greenly
synthesized SnO2 NPs achieved a significant proportion of MO degradation (81%) and a
complete degradation of 100 % of organic dyes, such as Methylene blue and Rhodamine
B. In addition to being an affordable and ecologically responsible solution, the
nanocomposite shown to be an effective method for treating water tainted by the textile
industry.[25]

Konstantinos Kouvelis et.al studied the shape, crystallographic structure, and optical
characteristics of a bismuth oxychloride (BiOCl) photocatalyst using fabrication process.
Using a solar simulator, the photocatalytic efficiency of the substance was evaluated in
relation to the hydrolysis of the blood pressure drug Losartan in water.After only 15 to 30
minutes of irradiation, the as-prepared BiOCl completely degraded 0.3 mg/L LOS,
demonstrating notable photocatalytic efficiency. 500 mg/L of BiOCl and pH 3 were the
best concentrations of efficiency for the system under investigation. BiOCl demonstrated
notable stability in the course of five subsequent experiments, continuously retaining its
effectiveness in attaining a 100 % LOS removal during 30 minutes of radiation exposure.
Through these studies it is confirmed BiOCl is suitable as a potential photocatalytic
material.[26].

Amit Kumar Singh et.al worked on making composites of bismuth oxychloride (BiOCl)
nanoplatelets, and lignin-based biochar through a one-step hydrolysis synthesis. The
photocatalytic degradation efficiency of the Biochar–BiOCl composites was investigated
by removal of methyl orange dye (MO). The optimal conditions such as catalyst dosage,
initial dye concentration, and pH was observed and carried out. scanning electron
microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction
(XRD), thermogravimetric analysis (TGA), nitrogen sorption, and UV–Vis diffuse
reflectance spectroscopy (DRS) were different analytical techniques carried out. The 100
% degradation of MO was observed at a catalyst dosage of 1.39 g/L, an initial dye
concentration of 41.8 mg/L, and a pH of 3.15 after 60 min of light exposure. The
incorporation of Biochar improved the photocatalytic performance of BiOCl. The
nanocomposite is a cost effective and ecofriendly catalyst for wastewater treatment
applications.[27]

Mahitha Udayakumar investigated A hydrothermal process that was used to prepare the
nanocomposites of bismuth oxychloride (BiOCl) and porous carbon foam (CF) made
from leftover polyurethane (PU) elastomers. The photocatalytic activity of the materials
was examined. The photocatalytic activity was analyzed by investigating the degradation
of methylene blue (MB) under UV-A irradiation. Excellent photocatalytic activity was
seen even at a high MB concentration (0.5 mmol/L), with an overall elimination
efficiency of 99.0 % after 100 minutes of irradiation. The well-connected heterojunction
interface, increased hydrophilicity, increased number of reactive sites, and efficient
separation of photogenerated charges were the causes of the composites' increased
activity.[28]

Syed Taj Ud Din et.al prepared a three-dimensional (3D) hierarchical microsphere of

Bi12O17Cl2 through a facile solvothermal method using a binary solvent for the
photocatalytic degradation of Rhodamine-B (RhB) and Bisphenol-A
(BPA).Microstructural, physical, and chemical examination revealed that the BOC
microspheres comprised of high surface area, 3D hierarchical design, and thin (~20 nm
thick) nanosheets. RhB (97.4 %) and BPA (88.4 %) were more efficiently degraded by
the 20- Co3O4/BOC heterostructure than by the pure BOC photocatalyst. In comparison to
pure BOC and other nanocomposite samples, the results demonstrated that the 20-
Co3O4/BOC heterostructure displayed a remarkable degradation efficiency of RhB (97.4
%) and BPA (88.4 %) after 140 min and 175 min of visible light irradiation, respectively.
A greater active area of the hierarchical microsphere, the extended light absorption to
visible light range with Co3O4 NPs, and a decrease of electron hole recombination due to
the p-n junction formation of Co3O4/BOC could all be contributing factors to the
enhanced photocatalytic degradation efficiency.[29]

Wendari, T.P., et al prepared CuFe2O4/activated carbon (CuFe/AC) composite by

Utilizing oil palm empty bunches of waste as the source of AC and green betle leaf
extract as a bio-capping agent. The nanocomposite was characterized by different
analytical techniques like XRD, FT-IR, DRS UV–Vis, SEM-EDX, and VSM. The XRD
proves the existence of each phase, while the TEM visualizes the spherically-shaped
nanoparticles. The Fe–O, Cu–O, and AC vibration modes in the composite are validated
by the IR spectra. The optimum parameters for the photocatalytic degradation of
rhodamine B dyes were obtained using 0.2CuFe/0.8 AC catalyst, at a concentration of 10
mgL−1, within 2 h of irradiation with a catalyst amount of 25 mg. The catalyst is
ecofriendly and can be reused again[30].

Kombaiah et al. used the hot plate combustion method to prepare Co3O4 nanorods from
V. vinifera seed extract. Their catalytic activity was then examined for use in the
photocatalytic degradation of textile dye waste water and the catalytic hydrogenation of
4-nitroaromatic systems (4-nitrophenol and 4-nitroanilne). the antibacterial properties
against strains were also studied. Analysis using XRD, Raman, and EDX revealed the
pristine single crystal structure. Through the presence of organic components, FT-IR and
TEM examination revealed that the plant extract is essential for the reduction and
stability of nanorods. Textile dying wastewater was subjected to photocatalytic
degradation using Co3O4 nanorods at a starting concentration of 750 mgL −1, a catalyst
dosage of 50 mg/L, and an irradiation period of 150 min. The nanorods' tiny size
breakdown cell membrane immediately and result in the loss of proteins, minerals, and
genetic material, which ultimately results in the death of the cell. It was also discovered
that the generated cobalt oxide nanorods are an improved catalyst for the reduction of 4-
nitrophenol and 4-nitroanile and may also be utilized to break down the waste water from
textile dyeing. Also, cobalt oxide nanoparticles have the ability to combat both Gram-
positive and Gram-negative bacteria with efficient antibacterial properties.[31]

The green approach of producing Co 3O4 spinel nanoparticles (Co3O4-NPs) from neem
(Azadirachta indica) leaf involves utilizing an easy and effective hot plate combustion
method (HPCM). The Co3O4-NPs were created by HPCM using an aqueous solution of
cobalt (II) nitrate (Co (NO3)2·6H2O), glycine (C2H5NO2), and leaf extract from
Azadirachta indica (A. indica) (5 mL). Using well-known and analytical methods like
photoluminescence spectroscopy (PL), vibrating sample magnetometry (VSM), diffuse
reflectance spectroscopy (DRS), high resolution transmission electron microscopy
(HRTEM), energy dispersive X-ray analysis (EDX), and Raman spectroscopy, the as-
prepared Co3O4-NPs have been characterized. Co3O4-NPs were explored for a number of
applications; for instance, toxic textile dye waste (TDW) gathered from the dyeing
industry was broken down using a multi-lamp photocatalytic reactor. Additionally, the
antibacterial activity of the produced Co3O4-NPs was investigated against both Gram-
negative and Gram-positive microorganisms. At nanoscale concentrations, Co3O4-NPs'
antibiotic capability has a stronger impact on the eradication of microorganisms.
Therefore, we have put forth a brand-new, affordable, and environmentally friendly
synthesis of Co3O4-NPs, which is crucial for the elimination of dangerous compounds in
the modern world.[32]

Seema Garg et.al used plant extracts from Azadirachta indica (Neem), Ocimum sanctum
(Tulsi), and Saraca indica (Ashoka) to envision a cost-effective and environmentally
friendly method for producing BiOCl. the ability of the chemically and
biosynthesisedBiOCl-N (Neem), BiOCl-T (Tulsi), BiOCl-A (Ashoka), and BiOCl-C
(without any extract) to degrade MO and BPA by photocatalysis under visible light was
investigated. Visible light irradiation demonstrated the effect of the kind of plant extract
on the structural, morphological, optical, and photocatalytic characteristics of BiOCl-N,
BiOCl T, BiOCl-A, and BiOCl-C. Under visible light irradiation, the biosynthesized
BiOCl increased the degradation of methyl orange (MO) and bisphenol A (BPA) by 21.5
% and 18.2 %, respectively, in 90 and 600 minutes. Electrochemical impedance spectrum
(EIS), photoluminescence (PL), and photocurrent response investigations showed that the
biosynthesized BiOCl had increased photocatalytic efficiency and effectively inhibited
electron-hole pair recombination. The obtained MO degradation data showed that the
percentage of MO degradation was significantly influenced by the photocatalytic dose
and the duration of visible light irradiation.[33]

S. Kaushal et.al used Psidium guajava (P. guajava) leaf extract as a reducing agent and a
capping agent for the synthesis of ferrous oxide-copper oxide nanocomposite
(CuO/Fe2O3) in an inexpensive and environmentally friendly green synthesis process. The
prepared CuO/Fe2O3 nanocomposite were characterized using different analytical
techniques and their efficiency as photocatalyst for photocatalytic degradation of
Tetracycline antibiotic and organic dyes such as rhodamine B (RhB) and methylene blue
(MB). By maintaining optimal conditions such as contact, catalyst dosage and pH, the
CuO/Fe2O3 nanocomposite displayed remarkable performance in the breakdown of TC
antibiotics (88% removal in 80 min), RhB (96 % removal in 40 min), and MB (93 %
elimination in 40 min) With an apparent rate constant of 0.048, 0.068, and 0.032 per
minute. liquid chromatography mass spectrometry (LC-MS) studies were also included to
further elaborate the degradation process of tetracycline.[34]

Raja Abdul Basit et.al worked on effective synthesis of ZnO nanoparticles (NPs), CuO
NPs, and ZnO/CuO nanocomposite utilizing an environmentally friendly method that
uses leaf extract from Corriandrum sativum as a capping agent. The produced materials
were assessed for structural analysis, functional group identification, spectroscopic
measurements, and morphological examination using XRD, FTIR, UV-Vis, and SEM
methods. With the application of Energy Dispersive X-ray (EDX), The sample in
consideration contains 72.38 % Cu and 23.59 % O. SEM revealed irregular and elongated
forms with an average length of 11 nm, and FTIR's peak at 485 cm−1 verified the
ZnO/CuO nanocomposite's production. After examining the photocatalytic degradation of
methylene blue,the composite performed excellent results than the other two materials in
terms of photodegradation out of all three photocatalysts. ZnO/CuO nanocomposite
proved to be a as a potential photocatalyst against methylene blue dye.[35]

Shazia Nouren et.al utilized green synthesis to prepare Copper oxide nanoparticles using
Jasmin sambac extract for the photocatalytic degradation of Methylene Blue dye. The pH,
temperature, reaction time and concentration of salt were optimized to get efficient
results. Characterization techniques included UV–Vis, SEM, XRD, FTIR. EDX analysis
showed a peak at 243 nm in UV–Vis, and an FTIR band at 590 cm −1 confirmed Cu (II)
ion reduction to CuO Nanoparticles. 50 mg dose of CuO increased degradation efficiency
of MB dye up to 80.67% and at 210 min of irradiation time the degradation increased up
to 97.67%. The catalyst also gave better results on reusability. Using Jasminum sambac
leaf extract in the green synthesis process is a highly effective way to customize CuO
NPs for photocatalytic uses.[36]

Helen Rathi V et.al worked on the synthesis of Ag/TiO 2 via co-precipitation approach for
degradation of dye and antimicrobial activity. This Green synthesis method involved the
use of flowers from C. pulcherrima as a reducing agent and a stabilizer. X-ray diffraction
(XRD) showed Ag/TiO2 NPs exhibited a tetragonal and cubic structure. Through
scanning and transmission electron microscopy (SEM and TEM), the shape and size
changes of the Ag/TiO2 NPs were about 27 nm. Energy-dispersive Xray spectroscopy
(EDX) analysis was employed to investigate the elements’ chemical composition in the
produced NPs. A Fourier transform infrared spectroscopy (FTIR) study was carried out to
identify functional groups. The findings of the experiment comparing the antibacterial
activity of Ag/TiO2 NPs on S. aureus revealed greater antibacterial activity. It was
demonstrated that Ag/TiO2 (94%) had higher catalytic activity in the MB dye
degradation. [37]

Herbin Basalius et.al synthesized silver nanoparticles using Syzygiumsamarangense

flower extract for multifaceted applications in biomedical field and photocatalytic
degradation of methylene blue dye. Different concentrations of S. samarangense flower
extract (5, 10, and 15 mL) were used as a reducing agent. UV- vis spectroscopy, (FTIR),
(XRD), SEM with EDS, and Transmission Electron Microscopy were used to analyze the
structural vibrational and morphological properties of silver nanoparticles. In UV–visible
spectrum the absorbance of silver nanoparticles spectra was observed at 440 nm. 15 mL
concentration and pH 7 and 10 was found to be ideal for higher degradation efficiency.
At 120 min of sunlight irradiation, about 80 percent degradation of methylene blue dye
was accomplished. Results have shown that silver nanoparticles have high antibacterial
action against E. coli and S. aureus[38].

Sadia Aroob et.al used leaf extract of Perihelium wolverine as a stabilizing agent to
prepare CuO nanoparticles. The characterization of CuO was done via XRD, SEM, PL
and FTIR. A monoclinic CuO phase with a crystallite size of 12.44 nm was found via
PXRD analysis. CuO NPs with oxygen vacancies present showed two distinct bands in
their PL spectra at 421 and 597 nm, respectively, enhancing the photocatalytic activity.
For both the MG and MO dyes, the photocatalytic reduction had a degradation rate of
65% and followed pseudo-first-order kinetics. These encouraging findings gave scientists
a new avenue to pursue in their quest to create inexpensive, eco-friendly photocatalysts
that effectively remove dyes from water[39].

Elham A. Alzahrani et.al worked on ecologically safe bio-based semiconductor zinc

oxide nanoparticles (ZnO NPs) and plasmonic Ag-supported ZnO nanocomposite (ZnO–
Ag) by utilizing the Carthamus tinctorius aqueous extract as a substitute for dangerous
production methods. Characterization was done via UV-DRS, PL, FTIR, SEM-EDX,
XRD, TGA. Using a proposed photocatalytic system using a ZnO–Ag nanocomposite,
the photocatalytic activity primarily causes •OH radicals caused photocatalytic
degradation. The catalyst also gave better results on reusability. 50 mg of ZnO–Ag
nanocomposite, 20 ppm dye concentration and pH 8 were found to be ideal for maximum
degradation. At 60 min irradiation time, 98.51 % of degradation of Mb dye was observed.
[40]

Emi Kurnai Sari et.al worked on green synthesis of magnetite/carbon dots

nanocomposites (GS-Fe3O4/C dots) Using watermelon peel waste and Moringa oleifera
leaf extract which rapidly degraded the methylene blue (MB) dye. GS-Fe3O4 and C dots
were synthesized by coprecipitation and hydrothermal techniques, respectively. C dots
was linked on Fe3O4 surface via sonication method. XRD, EDX, FTIR and UV were used
for characterization. The TEM showed most uniform size of nanocomposites at 13.4 nm.
The addition of C dots resulted in changes to the saturation magnetization and coercivity
value, which demonstrated good magnetic characteristics, in the range of 29.2–38.3
emu/g and 59–65 Oe, respectively. MB was used for a photocatalytic process; the
degradation efficiency was increased to 98% for 30 min photocatalytic process under UV
irradiation. The nanocomposite can be used three times for higher degradation. GS-
Fe3O4/C dots nanocomposites is a practical, affordable and reusable photocatalyst for
treating wastewater in the future and also other environmental uses.[41]

Dineo A. Bopape et.al successfully synthesized CuO-TiO2 nanocomposites using the C.

benghalensis plant extract as a reducing agent. The impact of varying photocatalyst
compositions on the degradation of methylene blue, ciprofloxacin, and sulfisoxazole,
among other contaminants was investigated. Structural, electrochemical and
photocatalytic degradation efficiency were studied using characterization techniques like
UV-vis, FTIR, SEM, XRD, TGA, BET, and CV. In comparison to the other two samples,
the CuO-TiO2 30/70 electrode's voltammogram had a greater response current density,
which may indicate a larger specific capacitance. When exposed to UV light, these
materials showed a significant propensity for degradation against the antibiotics CIP and
SSX. 67.3% and 93.64%, respectively, were reported as the degrading efficiency of CIP
and SSX. The materials can be recycled and reused again.[43]

Is Fatimah et.al NiO/g-C3N4 photocatalyst using Tinosphora cordifolia stem extract under
ultrasound-assisted method to examine rhodamine B and tetracycline photocatalytic
oxidation. The results obtained showed that both photocatalytic oxidation processes
benefit from the efficient enhancement of NiO photocatalytic activity by graphitic carbon
nitride. It was discovered that the composite with a 10% weight percentage of nickel had
the most photoactivity. Degradation efficiencies of 98% for tetracycline and 95% for
rhodamine B indicated the great effectiveness. The reusability of catalyst is determined
by running in into five cycles. On first cycle the degradation is 95% and on fifth cycle the
degradation is 84.7 % and the DE of TC degradation changes from 98.9 % to 90 %,
respectively.[44]

Mekdes Tenkolu Maru et.al observed photocatalytic degradation of the pollutants using
the green synthesis approach. ZnO and CuO nanoparticles (NPs) and ZnO/CuO
nanocomposites (NCs) with different CuO weight percents were created by researchers
employing fruit peel extract from Musa acuminata as the stabilizing and capping agent.
Using TGA/DTA, XRD, SEM, TEM, SAED, HR-TEM, UV-DRS, and FTIR methods,
the produced nanomaterials were studied. Examined under a visible light source was the
catalysts' ability to degrade the methylene blue (MB) dye. The degradation efficiencies of
the photocatalysts CuO, ZnO, and ZnO/CuO were 50%, 57%, and 90%, respectively. The
pH of the dye solution, the dye solution's initial concentration, the catalyst loading, and
the quantities of CuO in the nanocomposites all have a significant impact on the
photocatalytic activity.[45]

Deska Lismawenning Puspitarum et.al prepared CoFe2O4/TiO2 hybrid

magnetic/semiconductor nanocomposites that were greenly synthesized using Moringa
oleifera leaf extract. Under ultraviolet (UV) light, the photocatalyst showed excellent
photocatalytic activity and reuse. This work examined CoFe2O4/TiO2 nanocomposites as
magnetic/semiconductor photocatalysts. XRD, FTIR, UV-Vis, SEM,TEM and EDX were
different analytical techniques used to characterize the results. Nanocomposites
effectively decomposed methylene blue, a common organic contaminant, in under 2
hours of irradiation time with a 97.4% efficiency. Greenly synthesized hybrid magnetic/
semiconductor nanocomposites exhibited excellent catalytic activity and can be used in
other applications in future.[46]

Hemmat A. Elbadawy et.al utilized A green economical method was used to prepare
silver nanoparticles from chitosan biopolymer. Under UV irradiation, a combination of
heterogeneous nano photocatalysts TiO2 and ZnO (1:1 weight ratio) were combined with
the nanoparticles at different concentrations (0.02-0.18 g/L) to speed up the
photocatalytic breakdown of Acid Red 37 dye to make clean water. V–Vis, FTIR, XRD,
HR-TEM, and EDX analysis were used to characterize AgNps. The UV-vis spectra of
UV/Ag were compared with UV/TiO2, UV/ZnO and UV/(TiO2–ZnO).ZnO, TiO2, and
silver nanoparticles working together could result in promising candidates for
environmental applications, particularly in wastewater treatment.[47]

M. Mylarappa et.al effectively created environmentally friendly ajwain honey (AH)

loaded cerium oxide (CeO2) nanoparticles by using a simple reflux method. XRD, FT-
IR, DRS UV–Vis and EDX were used to characterize materials. effectiveness of ajwain
honey (AH) doped CeO2 in a range of applications, such as photocatalytic research,
cyclic voltammetry (CV), antioxidant, and chemical sensor detection was also studied.
With degradation rates of 100% and 82% for MV and CR dyes, respectively, the sample
showed high photocatalytic performance. The electrochemical studies demonstrated the
material's excellent specific capacitance, proton diffusion coefficient, and cyclic
reversibility. Analyzed utilizing the DPPH free radical scavenging test, the synthetic
compound's antioxidant activity exhibited an 81% activity level and an IC50 value of
102.51 mg/ml. [48]

Suryani Eka Safitri et.al successfully synthesized Y2O3 decorated with ZnFe2O4 using
Citrus limon (L.) Osbeck leaf extract. Despite having a band gap value that is greater than
ZnFe2O4, the ZnFe2O4/ Y2O3 nanocomposite is still active in the spectrum of visible light.
According to TEM data, ZnFe2O4 particles have a mixture of nanocube and hexagonal
structures and have a size of 37.84 nm. Y 2O3 surrounded the nanocube, creating a
ZnFe2O4/ Y2O3 nanocomposite with 49.61 nm particle size and resembling a nanosphere.
These results suggest that using ZnFe2O4c as a modifier may improve Y2O3's
photocatalytic performance. The efficient photodegradation 95.44 % was observed using
5 mg of ZnFe2O4/ Y2O3. The degradation was Also efficient under natural and basic
condition. Following four reusing experiment cycles, the photocatalyst efficiency reduced
just to 88%. The findings show that adding ZnFe 2O4 to Y2O3 decreases leaching while
increasing the composite's overall durability and strength.[49]

Abdul Raouf Malik et.al prepared ZnO nanoparticles using Ocimumbasilicum extract as a
reducing and stabilizing agent. Using a one-step procedure, greenly synthesized ZnO NPs
driven by Ocimumbasilicum extract was decorated on the reduced graphene oxide (RGO)
sheet. The prepared nanoparticles were characterized via X-ray diffraction (XRD),
Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM),
and UV–visible spectroscopy. The average crystallite size of ZnO was 25 nm, confirming
its wurtzite hexagonal structure. Scanning Electron Microscopy verified the spherical
form of the 31 nm particles. ZnO NPs and RGO-ZnO NCs demonstrated photocatalytic
activity, degrading Rh-B dye by 91.4% and 96.7%, accordingly, under UV-visible light.
With increasing levels, RGO-ZnO NCs shown antibacterial activity against gram-positive
(Cocci) and gram-negative (E. coli) bacterial strains. The results suggest that
Ocimumbasilicum extract-mediated eco-friendly RGO-ZnO NCs can be effective not
only for major biomedical issues like diabetes, as an antibacterial agent for wound
dressing, and to prevent bacterial contamination in food packaging, but also for the
purification of wastewater.[50]
 CHAPTER NO 3:
3. RESEARCH METHODOLOGY
Co3O4/BiOCl/AC Nanocomposites were synthesized by following method:

3.1Apparatus Used:
 Beaker.
 Pipette.
 Funnel.
 Whatman filter paper.
 Oven.
 Stirrer.
 Hot plate.
 Magnetic Stirrer.
 Measuring Cylinder.
 Furnace.

3.2Chemicals Used:
3.2.1 Chemicals used for Co3O4 Nanoparticles:
 Cobalt Nitrate hexahydrate Co (NO3)2.6H2O
 Neem plant extract
 Sodium hydroxide NaOH

3.2.2 Chemicals used for BiOCl:

 Bismuth Nitrate Bi (NO3)2.5H2
 HCl solution
 Potassium Chloride KCl
 Sodium hydroxide NaOH

3.2.3 Chemicals used for Activated Carbon:

 Potassium Hydroxide KOH
 0.1M HCl solution
 3.3Preparation of Neem plant extract:
Neem leaves was collected from trees and washed several times with distilled water to
remove dirt and impurities. 20 g leaves were ground in the grinder and added to the
beaker. Added 200ml distilled water into the beaker and placed on hot plate for stirring.
The beaker was covered with aluminum foil and set the temperature 60-70 ⁰C.Stirred the
solution for 2 hours.The solution was filtered using Whatman filter paper. The filtrate
was stored in acontainer at 4⁰C for later use.

Figure 3.9 Preparation of Plant Extract.

3.4Green Synthesis of Nanoparticles:

3.4.1 Green Synthesis of Cobalt Oxide (Co3O4) Nanoparticles:
2g of Co (NO3)2.6H2O was added in 100 ml distilled water to make 0.007 M solution in
500 ml beaker. The beaker containing solution was placed on the hotplate and set on
stirring. 50 ml neem extract was added into the solution and stirred for 1 hour. 1 M
NaOH solution was added to maintain pH 9-10. The solution was again set of stirring for
2 hours. The solution was allowed to stand for one day. The precipitate was settled down
and filtered using filter paper. The Filter paper was dried in oven at 60 ⁰C for 3 hours to
completely dry Co3O4 nanoparticles. 1.4 g of Cobalt Oxide nanoparticles was obtained.
The nanoparticles were stored in sample bottle for later use.
 Figure 3.10 Green Synthesis of Cobalt Oxide (Co3O4) Nanoparticles:

3.4.2 Green Synthesis of BiOCl nanoparticles:

2.42 g bismuth nitrate pentahydrate in 100 ml distilled water to make 0.005 M solution.
Added some drops of Hydrochloric acid (HCl) to dissolve salt in it. 50 ml extract was
added into the beaker and stirred the solution for 1 hour. 2M NaOH was added into the
solution to maintain pH from 3.5-5. After this, added 0.1 M KCl into the solution. Stirred
the solution for 2 hours. The solution was allowed to stand for 1 day. The nanoparticles
settled down. The nanoparticles were filtered using filter paper. The filter paper was dried
in oven at 60 ⁰C for 3 hours. 0.4 g of Bismuth oxychloride nanoparticles was obtained.
The dried nanoparticles were stored inn sample bottles for later use.

Figure 3.11 Green Synthesis of BiOCl Nanoparticles

3.5 Green Synthesis of Activated Carbon:
Activated Carbon was prepared from walnut shells. It was washed with distilled. I placed
walnut shells in oven at 60 ⁰C for 12 hours to dry.100 walnut shells were weighed and
put into crucibles. The crucibles were placed in furnace for 2 hours at 400 ⁰C.The burned
walnut shells were allowed to cool down and crushed using a pestle and mortar.

Figure 3.12 Physical Activation process of Activated Carbon Synthesis.

3.5.1 Chemical Activation Process:

Chemical activation offers widespread uniform pore development for microdomains

containing carbon particles. In contrast, physical activation results in inhomogeneous
gasification from the outer surface of the carbon particles and their microdomains, which
lowers the degree of pore development and the activation yield.[51]

The process of Chemical activation is as follows:

Took 30 g of burned walnut shells in a beaker and added 135 ml 1 M KOH. Stirred the
solution for 30 minutes at 80 ⁰C. After stirring, heated the slurry in furnace for about 3
hours at 650 ⁰C. 5ml HCl was added to maintain pH. The solution present in the beaker
was filtered. The nanoparticles were washed with distilled water to remove any acid.
Filter paper was dried in oven at 60 ⁰C for 3 hours. I stored the activated carbon in 100
mL beaker and cover with aluminum foil for later use.
 Figure 3.13 Activated Carbon Synthesis through physical and Chemical Activation.

3.6 Green synthesis of Nanocomposites:

3.6.1 Green synthesis of Co3O4/BiOCl nanocomposite:

Step 1: Preparation of Cobalt Oxide nanoparticles:

0.8 g of Co (NO3)2.6H2O was added in 100 ml distilled water. The beaker containing
solution was placed on the hotplate and set on stirring. 50 ml neem extract was added into
the solution and stirred for 1 hour.1 M NaOH solution was added to maintain pH 9-10.
The solution was again set of stirring for 2 hours. The solution was Allowed to stand for
one day.

Step 2: Preparation of BiOCl nanoparticles:

Took 100 ml distilled water in a 500 ml beaker and added 3g bismuth nitrate
pentahydrate salt in it. After this, added some drops of Hydrochloric acid (HCl) to
dissolve salt in it. 50 ml extract was added into the beaker and stir the solution for 1 hour.
2M NaOH was added into the solution to maintain pH from 3.5-5. Added 0.1 M KCl into
the solution. Stirred the solution for 2 hours. The solution was allowed to stand for 1 day.
The nanoparticles settled down.
Step 3: Mixing of Co3O4 and BiOCl:

The precipitates of both solutions were collected in a beaker. Added 30 ml ethanol in the
beaker. The solution was placed on a hotplate and stirred for 30 minutes. Collected the
nanoparticles on filter paper. The filter paper was dried in oven at 60 C for 3 hours. 1.2 g
of Co3O4/BiOCl nanocomposite was obtained. The dried nanoparticles were stored inn
sample bottles for later use.

3.6.2 Green synthesis of Co3O4/BiOCl/AC nanocomposite:

Step 1: Preparation of cobalt nitrate nanoparticles:

Weighed 0.8 g of Co(NO3)2.6H2O and add in 100 ml distilled water. The beaker
containing solution was placed on the hotplate and set on stirring. After this, added 50 ml
neem extract was into the solution and stirred for 1 hour.1 M NaOH solution was also
added to maintain pH 9-10. The solution was again set of stirring for 2 hours. The
solution was allowed to stand for one day.

Step 2: Preparation of BiOCl nanoparticles:

Took 100 ml distilled water in a 500 ml beaker and added 3g bismuth nitrate
pentahydrate salt in it. I added some drops of Hydrochloric acid (HCl) to dissolve salt in
it. 50 ml extract was added into the beaker and stir the solution for 1 hour. 2M NaOH was
added into the solution to maintain pH from 3.5 - 5. After this,added 0.1 M KCl into the
solution. Stirred the solution for 2 hours. The solution was allowed to stand for 1 day.
The nanoparticles settled down.

Step 3: Mixing of Co3O4/BiOCl/AC:

The precipitates of both solutions were collected in a beaker.0.6 g prepared Activated

carbon was also added in the solution and added 30 ml ethanol in the beaker. The
solution was placed on a hotplate and stirred for 30 minutes. Collected the nanoparticles
on filter paper. The filter paper was dried in oven at 60 C for 3 hours. As a result of
mixing 1.8 g of Co3O4/BiOCl/AC nanocomposite was obtained. The dried nanoparticles
were stored in sample bottles for later use.
 Figure 3.14 Mixing of Co3O4/BiOCl/AC

3.7 Preparation of Dye Solution:

3.7.1 Preparation of Methyl Green Solution:

Weighed 0.003 g of Methyl Green in 500 ml beaker and add 100 ml distilled water. Stir
the solution to completely dissolve dye. Complete the flask up to the mark with deionized
water. 3 ppm solution of dye was prepared. Added 0.005 g of the prepared sample and
performed degradation.

3.7.2 Preparation of Methyl Red Solution:

Weighed 0.01 g of Methyl Red in 500 ml beaker and add 100 ml distilled water. Stir the
solution to completely dissolve dye. Complete the flask up to the mark with deionized
water. 10 ppm solution of dye was prepared.

3.8 Degradation of Prepared samples:

 Dark environment:

100ml solution of dye was collected in a 250 ml beaker. Added 0.005g of the prepared
nanoparticles in 250 ml beaker. The beaker was covered with aluminum foil to perform
degradation in dark environment. Stirred the solution using a magnetic stirrer for 20
minutes. After 20 minutes, 7 ml of sample was separated from the sample and filtered
using filter paper. The filtrate was added in sample vial.
  Light environment:

Aluminum foil was removed and solution was brought to light. Stirred the solutionat
room temperature. After 10 minutes, 7 ml of the solution was separated and filtered using
filter paper. The filtrate was stored in sample vial. Continuously stirred the solution for
60 minutes and after 10 minutes 7ml of the sample was filtered and placed in the sample
vial. UV-Vis spectrum was performed of the sample vials.

This Degradation process was applied to all the prepared Samples (Co3O4, BiOCl, AC,
Co3O4/BiOCl, Co3O4/BiOCl/AC)

3.9 Characterization Techniques:

3.9.1 Fourier Transform Infrared spectroscopy (FTIR):

A device based on infrared spectroscopy is the Fourier transform infrared spectrometer

(FTIR). Compared to other dispersive spectrometers, it is the most advanced model. Its
exceptional sensitivity, speed, accuracy, ease of use, and sample non-destructiveness are
the reasons for it. Dispersive's inability to measure individual infrared frequencies and its
poor scanning speed were its limitations.

3.9.1.1 Working principle:

Radiation interference between the two beams produces an interferogram, which is the
basis for FTIR spectroscopy. The latter is a signal that is generated by the difference in
path length between the two beams that are reflected off of two mirrors (which are
located within the interferometer block).

3.9.1.2 Instrumentation:

Different parts of FTIR instrumentation include:

 The source
 The interferometer
 The sample
 Detector

3.9.1.2.1 The Source:

The light source is a broadband emitter, such as a near-infrared halogen lamp, a far-
infrared mercury lamp, or a mid-IR ceramic source.

3.9.1.2.2 The Interferometer:

The interferometer, which consists of a beamsplitter, a stationary mirror, and a moving

mirror, is the heart of an FTIR spectrometer. A semi-transparent mirror called a
beamsplitter splits a collimated light beam into two optical channels. The moving mirror
receives half of the light, while the stationary mirror receives the other half. The two light
beams are reflected by the moving and fixed mirrors and then recombined at the
beamsplitter before passing through the sample chamber and onto the detector. Over
time, the phase difference shifts as a result of the moving mirror's repeating movements
and changes in the optical path difference to the fixed mirror. Recombining the light
beams in the Michelson interferometer produces interference light. An interferogram
measures the interference light's intensity and logs the optical path difference along its
horizontal axis.

3.9.1.2.3 The sample:

The beam enters the sample chamber and is either transmitted through or reflects off the
sample's surface, depending on the sort of analysis being done. This is the location of
energy absorption for particular frequencies specific to the sample.

3.9.1.2.4 Detector:

FTIR detectors measure and produce an electrical signal from a sample's transmitted or
reflected light. The kind and composition of the detector dictate its sensitivity and the
range of wavelengths of data it can record. The beam is transformed into photons by the
detector, and the computer can subsequently interpret these photons into quantifiable
electrical signals.

3.9.1.3 Steps in getting FT-IR spectrum of the sample with interferometer:

1. The first stage involves recording an interferogram in computer memory without using
any sample in the beam. This interferogram, which is typical of the experimental setup,
shows how the spectrometer responds to water and carbon dioxide present on the optical
bench in terms of source performance.

2. Another recording of the interferogram is made, but this time a sample is added to the
beam and is kept in computer memory. It comprises background solvent or air, as well as
signals from the sample.

3. Using a computer, subtract the first interferogram from the second.

4. The spectrum is obtained by Fourier transforming the resultant difference

interferogram.
The removal of gas absorption occurs during the process of calculating the difference of
the two interferograms.

3.9.2 UV-Visible Spectroscopy:

Johann Ritter experimented in 1801, trying to find out if there was energy present in the
visible spectrum that extended past the violet end. He exposed the paper to light beyond
violet as he knew that photographic paper would turn black more quickly in blue light
than in red light. Since the excitation of electrons produces UV-Vis spectra, UV-Vis
spectroscopy is also frequently referred to as "electron spectroscopy." All forms of
electron excitation by visible or ultraviolet light fall under the umbrella term of "electron
spectroscopy". Thus, the molecular spectra include the UV-Vis spectra.

Spectrophotometry, often known as UV-Vis Spectroscopy, is a quantitative method for

determining how much light a chemical compound absorbs. A potent method for
analyzing nanoparticles, UV-Vis spectroscopy offers important information about the
optical characteristics and structural characteristics of the particles.

3.9.2.1 Principal of UV-Visible Spectroscopy:

This follows the principle of the Beer lambert law which states:
Absorption of the light by the sample is directly proportional to the path length and
concentration of the sample.
Mathematically,
A = log (I0/I) = €cb
A=absorbance
I0=intensity of light incident upon sample cell
I=intensity of light leaving sample cell
C=molar concentration of solute
b=length of sample cell (cm.)
€=molar absorptivity

3.9.2.2 INSTRUMENTATION:
A spectrophotometer only measures the intensity of light as a function of wavelength, in
contrast to a spectrometer, which is any device that can measure the characteristics of
light throughout a variety of wavelengths.

The key components of a spectrophotometer are:

• Light source

• Monochromator

• Sample area

• Detector and Recorder

Figure 3.15 Process of UV-Visible Spectroscopy

3.9.2.2.1 Light Source:

The most suitable sources of light are:

  Deuterium lamp: A deuterium lamp emits light in the UV range (between 160
and 375 nm) and is made up of an anode and tungsten filament placed on opposite
sides of a nickel box structure designed for output spectrum.
 Xenon arc lamp: Each has a tungsten metal electrode at either end of a fused
quartz or other heat-resistant glass arc tube. Exhaust the glass tube and then
replace it with xenon gas. A third "trigger" electrode typically encircles the
outside of the arc tube in xenon flashtubes.
 Tungsten lamp/Tungsten-halogen lamp: The construction of the lamps is
identical to that of traditional gas-filled tungsten filament lamps, with the
exception of a minor halogen (usually bromine) presence in the fill gas. The
tungsten that has evaporated, moved outward, and settled on the lamp wall
combines with the halogen gas to produce radiation in the visible and near-
infrared wavelength range (350–2500).

3.9.2.2.2 Monochromator:

The main function of the monochromator is to disperse the beam of light obtained from
the primary source, into its component. The principle components of monochromator are:

 An entrance slit
 A collimating lens
 A dispersing device
 A focusing lens
 An exit slit
 Figure 3.16 Function of Monochromator.

Through the entrance slit, polychromatic light from the primary source enters the
monochromator. After collimating, the beam strikes the dispersing element (grit or prism)
at a specific angle.

3.9.2.2.3 Sample Area:

 The sample solution receives one of the two divided beams, while the reference
solution receives the other beam.
 The most typical samples used to record spectra are liquids, although it is also
possible to quantify the absorbance of gases and even solids. A clear cell called a
cuvette holds the sample and reference solutions.
 The cuvettes are typically rectangular in shape and have an interior width of one
centimeter. Transparency of the cell material to radiation over the studied region
is a requirement. The materials used to make the cells include glass, plastic,
quartz or silica.

3.9.2.2.4 Detector and Recorder:

The transformation of a light signal into an electrical signal occurs in a detector. The
intensities of the corresponding transmitted beams are then compared across the whole
wavelength range of the instrument after the beams have gone through both the reference
cell and the sample under examination. The reference cell's radiation beam has a higher
intensity than the sample cell's beam. As a result, the pulse forms.
Chapter 4

Results and Discussion

4.1 FTIR Spectrum Studies

The prepared sample of Co3O4, BiOCl, AC, Co3O4/BiOCl, Co3O4/BiOCl@AC was

analyzed under FTIR Spectrum studies.

FTIR spectrum of Co3O4 shown in figure 4.1 reveals the Co-O bond at 661cm -1 and Co-
ONO bond at 1380 cm-1. Presence of organic functional groups C=O identify the use of
Neem extract. A broad band ranging from 3100-3500 represented the breakage of water
molecule through OH- Stretching Peak at 1074cm-1 confirms the presence of NO3-1.

Figure 4.17 FTIR Spectrum of Co3O4 Nps

In the figure 4.2, the Bi-O and Bi-Cl bonds was observed at 529 cm -1 and 1354 cm-1
respectively. At 1593 cm-1 C=O stretching is observed to identify the presence of organic
functional group confirming the use of neem extract. A broad band from 3000-3500 cm -1
corresponds to OH-stretching indicating the absorption of water molecules on the surface
of Nps.
 Figure 4.18 FTIR Spectrum of BiOCl Nps
FTIR spectrum of AC shown in figure 4.3 involved the twisting and bending of C-H
bonds at 1367 cm-1 and 662 cm-1. C=O bending was occurred at 1050 cm -1 confirming the
formation of Activated Carbon. The C=C stretching at 1540cm -1 involves conjugation
which confirm the use of Neem extract.

Figure4.19 FTIR Spectrum of AC

FTIR spectrum of Co3O4/BiOCl shown in figure 4.4 involves the presence of both Bi-O
and Bi-Cl bond at 529 cm-1 and 1354 cm-1 respectively. Cobalt oxide peak was confirmed
at 662 cm-1. Peak at 1061 cm-1 confirms the presence of NO3-1. In the FTIR spectrum a
broad peak was observed at 3362 confirming the adsorption of water molecule on the
surface of nanocomposite.

Figure 4.20 FTIR Spectrum of Co3O4/BiOCl Nanocomposite

The final nanocomposite Co3O4/BiOCl @AC shown in figure 4.5 gives the information
about Co3O4 through Co-O bond at 666 cm-1. BiOCl was confirmed through Bi-O and Bi-
Cl bond at 525 cm-1 and 1367 cm-1. The CH-bending was observed at 1048 involving the
change in bond angle leading to the formation of AC. The C=C stretching at 1540cm -1
involves conjugation which confirm the use of Neem extract.

Figure 4.21 FTIR Spectrum of Co3O4/BiOCl@AC nanocomposite

4.2 UV visible Analysis
After analyzing the results obtained from UV visible Spectrum, we have come to know
that Cobalt oxide nanoparticles absorb UV visible light in the range from 350-380 nm
with maximum absorption at 380 nm.

4.2.1 Calculation of Band gaps

The two most important factors that primarily control a semiconductor's photocatalytic
activity under simulated sunlight radiation are its band gap and the locations of its VB
and CB edge positions.(Opoku, Govender et al. 2017). Because of their nano size,
nanoparticles have distinct characteristics from larger particles. The energy difference
that separates a material's valence band, where electrons are in their ground state, and
conduction band, where they can be stimulated to conduct electricity, is known as the
bandgap. The optical and electrical properties of a material are significantly influenced
by this energy gap.

To calculate band gap of semiconductor we used uv visible spectrum to obtain band gap
using tauc plot method. It gives information about optical bandgap of the prepared
nanoparticle and nanocomposite by plotting a graph between (ahv) 2 and (hv). Optical
bandgap of Co3O4 nanoparticles synthesized through green synthesis came out to be 2.2
eV. Band gap of BiOCl was observed at 2.3 eV while the band gap of AC was calculated
to be 1.85 eV as shown in figure.

Figure 4.22 Bandgaps of Co3O4, BiOCl and AC

Band gap calculation of Co3O4/BiOCl nanocompsite was analyzed and it was 3.25
forming a p-n junction to generate electron hole pair for effective degradation. The
nanocomposite relatively offers lesser band gap of 2.6 eV and more easily electron can
jump from valance band into the conduction band. A lesser band gap gives more efficient
results. The photocatalytic activity is enhanced by the recombination of electron hole pair
and forming junction through photocatalysis as shown in figure.

Figure 4.23 Bandgap of Co3O4/BiOCl, Co3O4/BiOCl@AC nanocomposite

4.3 Degradation of Methyl Green Dye

Methyl green dye degradation is investigated by the UV analysis of the different

nanoparticle and nanocomposite sample mixed in methyl green dye solution. The sample
results are collected at different time intervals.

A comparison of degradation of given nanoparticles Co3O4, BiOCl and AC is represented

by absorbance-time and C/Cₒ-time graph. The degradation of AC gave the best result in
absorbance-time graph shown in figure starting from 0.37 a.u and ending at 0.02 a.u. The
C/Cₒ graph shows the difference is concentration of Co3O4, BiOCl and AC starting from 1
to 0.23, 0.20 and 0.08 respectively.

In comparison of Co3O4/BiOCl and Co3O4/BiOCl@AC nanocomposite shown in figure,

the nanocomposite Co3O4/BiOCl@AC showed efficiency from 0.3 a.u to showing
degradation efficiency of 87 %. The value of C/Cₒ graph of Co 3O4/BiOCl and
Co3O4/BiOCl@AC starts from 1 and ends at 0.28 and 0.13 respectively.
The uv analysis of Co3O4/BiOCl@AC nanocomposite shown in figure showed a rapid
decrease in the peak at 657 cm -1 which shows an effective degradation of the Methyl
green dye. The degradation efficiency of the nanoparticles and the final nanocomposite is
given in table

Figure 4.24 Degradation of Methyl Green Dye (a) Absorbance time graph of Co3O4,
BiOCl and AC (b) Absorbance time graph of Co 3O4/BiOCl and Co3O4/BiOCl@ AC (c)
C/Cₒ graph of Co3O4, BiOCl and AC (d) C/Cₒ graph of Co 3O4/BiOCl and Co3O4/
BiOCl@ AC. (e) UV graph of degradation of Methyl Green using Co3O4/BiOCl@ AC.
 4.4 Degradation of Methyl Red dye

Methyl green dye degradation is investigated by the UV analysis of the different

nanoparticle and nanocomposite sample mixed in methyl green dye solution. The sample
results are collected at different time intervals.

A comparison of degradation of given nanoparticles Co 3O4, BiOCl and AC is represented

by absorbance-time and C/Cₒ-time graph. The degradation of AC gave the best result in
absorbance-time graph shown in figure starting from 0.45 a.u and ending at 0.1 a.u. The
C/Cₒ graph shows the difference is concentration of Co3O4, BiOCl and AC starting from 1
to 0.43, 0.4 and 0.2 respectively.

In comparison of Co3O4/BiOCl and Co3O4/BiOCl@AC nanocomposite shown in figure,

the nanocomposite Co3O4/BiOCl@AC showed efficiency from 0.3 a.u to 0.11 showing
degradation efficiency of 87 %. The value of C/Cₒ graph of Co 3O4/BiOCl and
Co3O4/BiOCl@AC starts from 1 and ends at 0.32 and 0.28 respectively.

The uv analysis of Co3O4/BiOCl@AC nanocomposite shown in figure showed a rapid

decrease in the peak at 508 cm -1 which shows an effective degradation of the Methyl
green dye. The degradation efficiency of the nanoparticles and the final nanocomposite is
given in table
Figure 4.25 Degradation of Methyl Red Dye (a) Absorbance time graph of Co 3O4,
BiOCl and AC (b) Absorbance time graph of Co 3O4/BiOCl and Co3O4/BiOCl@ AC (c)
C/Cₒ graph of Co3O4, BiOCl and AC (d) C/Cₒ graph of Co3O4/BiOCl and Co3O4/ BiOCl@
AC. (e) UV graph of degradation of Methyl Red using Co3O4/BiOCl@ AC.
Conclusion
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