Sol-gel Synthesis of Yttrium Molybdenum Co-doped

Mullite Type BFO for Highly Efficient Visible Light

Driven Photodegradation of Cationic Dye.

University Of Narowal
Submitted to
University of Narowal
To partially meet the conditions for the degree's conferment.

Bachelor of Science (BS)

in
CHEMISTRY
by
Ahmad Umair
Roll Number: 0034-BS-CHEM-2019
Session: 2019-2023
Department of Chemistry
University of Narowal

1
 DECLARATION

I, Ahmad Umair, bearing Roll No. 0034-BS-CHEM-2019, enrolled as a

student pursuing a Bachelor of Science degree in Chemistry, within the academic
tenure spanning from 2019 to 2023, hereby affirm that the content presented in the
thesis entitled "Sol-gel Synthesis of Yttrium Molybdenum co-doped Mullite type
BFO for highly efficient visible light driven photodegradation of cationic dye." is
a direct outcome of my personal research endeavors conducted at the Department of
Chemistry, University of Narowal. This thesis has not been previously disseminated
and does not include any material sourced from published works that could infringe
upon international copyright regulations. Additionally, I assert my understanding of
the concepts of 'copyright' and 'plagiarism', and I acknowledge my accountability for
any potential breach of copyright that might emerge within this work.

Deponent,

__________________ Dated: _________________

Ahmad Umair

Roll No. 0034-BS-CHEM-2019

Department of Chemistry,

University of Narowal,

Narowal, Pakistan

2
 PLAGIARISM UNDERTAKING

I solemnly affirm that the research work presented in the thesis entitled "Sol-
gel Synthesis of Yttrium Molybdenum co-doped mullite type BFO for highly
efficient visible light driven photodegradation of cationic dyes." is the product of
my individual research endeavors, devoid of any significant contributions from
external parties. Any modest assistance or guidance received during its completion
has been appropriately acknowledged, and I confirm that the entire thesis has been
authored by me.

I am well aware of the unequivocal stance held by both the Higher Education
Commission (HEC) and the University of Narowal (UON) in relation to plagiarism.
Therefore, I, as the author of the aforementioned thesis, unequivocally declare that no
portion of my work is plagiarized, and any sources utilized for reference have been
accurately attributed and cited.

I undertake the responsibility that, should any form of formal plagiarism be

detected in the aforementioned thesis, even subsequent to the conferment of my BS
degree, the University retains the authority to rescind and revoke said degree.
Furthermore, I acknowledge that the HEC and the University reserve the right to
publicly list my name on their respective websites, among students whose theses have
been determined to be plagiarized.

__________________

Ahmad Umair

Dated: ____________

3
 RESEARCH COMPLETION CERTIFICATE

This serves to confirm that the research endeavor encapsulated within the
thesis entitled "Sol-gel Synthesis of Yttrium Molybdenum co-doped mullite type
BFO for exceptionally efficient photodegradation of cationic dyes under visible
light," has been conducted and successfully concluded by Ahmad Umair, identified
by Roll No. 0034-BS-CHEM-2019, within the course of his Bachelor of Science
studies in Chemistry, under my direct guidance. The presented work has been
endorsed for submission to the University of Narowal (UON), signifying its alignment
with the requisites for the conferral of a Bachelor of Science degree in Chemistry.

Date:________________

Supervisor
Dr. Mehboob Hassan
Assistance professor,
Dept. of Chemistry,
University of Narowal,
Narowal

Submitted Through

Controller of Examination

Dr. Mehboob Hassan

Coordinator
Department of Chemistry
University of Narowal

4
 Acknowledgment
All gratitude and reverence are directed towards Allah Almighty, the Infinitely
Merciful and Compassionate, the Originator of the expanding cosmos and the
Sovereign of the Final Judgment. His attributes know no bounds, and He has granted
me the competence to bring this task to fruition. Utmost respect and homage are also
extended to the Holy Prophet Muhammad (peace be upon Him), the radiant source of
every virtue, who has illuminated our path to recognizing our Creator. My entire
existence is devoted in homage to Him.
I wish to convey my deepest appreciation to those who have provided
unwavering support and guidance on this journey of completing my thesis. Their
motivation, insights, and aid have been of immeasurable worth in shaping this
endeavor.
Foremost, I extend my heartfelt gratitude to my thesis mentor, Dr. Mehboob
Hassan, for their steadfast guidance, patience, and expertise. Their constructive
feedback and enlightening conversations have profoundly enriched my research and
writing process. Gratitude is also extended to Dr. Mirza Mehmood Baig for their
valuable contributions as a guide and mentor, and for serving as my co-supervisor in
this comprehensive undertaking.
Acknowledgment is owed to the esteemed faculty members of the Department
of Chemistry, whose commitment to education and the cultivation of a scholarly
atmosphere has been pivotal. Their lectures, deliberations, and feedback have been
instrumental in shaping my comprehension of the subject.
Appreciation is extended to my family, friends, and seniors for their
continuous encouragement, understanding, and unwavering support. Their
unwavering faith in my abilities provided the impetus to persevere through the
challenges encountered on this path.
My colleagues and peers also merit gratitude for their enlightening discussions,
valuable insights, and the camaraderie that pervaded this academic odyssey.
Furthermore, I express my gratitude to the Department of Chemistry at the
University of Narowal for their financial support, which facilitated the necessary
research and experimentation integral to this thesis.
Finally, I acknowledge the wider academic community, whose reservoir of
knowledge formed the bedrock upon which this work stands.

5
 In closing, this thesis owes its existence to the contributions of all those
mentioned above. To each of you, I extend my sincere gratitude for being an integral
part of this expedition and for aiding me in achieving this significant milestone.

Ahmad Umair S/O Sajjad Ahmad

University of Narowal
August, 2023.

6
 Abstract:
The escalating concern of water pollution has taken center stage on the global
platform, with an alarming statistic of approximately 14,000 daily fatalities attributed
to the repercussions of contaminated water. Among the culprits, organic pollutants,
specifically organic dyes, have garnered significant attention. This pertains to the
exacerbation of the issue, especially due to the hazardous nature of cationic dyes,
which can potentially lead to grave health conditions such as cancer. Consequently, it
is imperative to eliminate these dyes from the environment, transforming them into
benign compounds.
Various approaches exist to undertake this critical task; however,
photocatalysis emerges as a promising, economically viable, and efficacious method
for dismantling these dyes into innocuous byproducts such as carbon dioxide and
water. To this end, a pioneering solution has been crafted through the preparation of a
novel Y-Mo co-doped mullite type BFO via the sol-gel synthesis technique. The
confirmation of successful synthesis and the distinctive rhombohedral morphology of
the Y-Mo co-doped mullite type BFO were affirmed through XRD analysis.
The efficacy of the photocatalyst was assessed through rigorous
experimentation involving several cationic dyes, namely crystal violet, methylene
blue, methyl violet, and rhodamine B. Employing a comprehensive methodology, the
dyes were subjected to a period of incubation with the catalyst in darkness, followed
by a series of measurements taken at 15-minute intervals under visible light
irradiation. Remarkably, the photocatalyst exhibited an impressive degradation
efficiency, yielding rates of 98%, 98%, 99%, and 19% for the respective dyes.
Notably, these reactions unfolded at ambient temperature and neutral pH conditions,
obviating the need for pH adjustments.
This endeavor imparts a fresh perspective on the synthesis of specialized
catalysts tailored for the optimization of photocatalytic applications, thereby paving
the way for heightened efficiency in addressing the critical challenge of organic dye
pollution.
Keywords: Sol-Gel, Mullite, BFO, Photocatalysis, Efficiency.

7
Table of Contents
1. Introduction to Nanoparticles: ---------------------------------------------------------- 15

1.1. Nano-Science: ------------------------------------------------------------------------ 15

1.2. Nanotechnology: --------------------------------------------------------------------- 15

1.2.1. Applications: -------------------------------------------------------------------- 16

1.3. Nanoparticles: ------------------------------------------------------------------------ 16

1.3.1. Types of Nanoparticles: ------------------------------------------------------- 17

1.3.1.1. Carbon Based Nanoparticles: ------------------------------------------- 17

1.3.1.2. Metal and Metal Oxide Nanoparticles: -------------------------------- 18

1.3.1.3. Semiconductor type Nanoparticles: ------------------------------------ 18

1.3.1.4. Ceramics type Nanoparticles: -------------------------------------------18

1.3.1.5. Polymer type Nanoparticles: -------------------------------------------- 18

1.3.1.6. Bio-molecules derived Nanoparticles: ---------------------------------19

1.3.2. Properties of Nanoparticles: -------------------------------------------------- 19

1.3.3. General Properties of Nanoparticles: ---------------------------------------- 20

1.3.3.1. Size of Nanoparticles: ----------------------------------------------------20

1.3.3.2. Shape of Nanoparticles: --------------------------------------------------20

1.3.3.3. Surface of Nanoparticles: ------------------------------------------------20

1.3.4. Physiochemical Properties of Nanoparticles: ------------------------------ 20

1.3.4.1. Thermal Properties: --------------------------------------------------------- 20

1.3.4.2. Magnetic Properties: ----------------------------------------------------- 21

1.3.4.3. Mechanical Properties: ---------------------------------------------------21

1.3.5. Synthesis of Nanoparticles: --------------------------------------------------- 21

1.3.5.1. Top-Down Method: --------------------------------------------------------- 22

1.3.5.1.1. Ball Milling process: ----------------------------------------------------- 22

1.3.5.1.2. Thermal Evaporation Method: ------------------------------------------23

1.3.5.1.3. Laser Ablation Method: --------------------------------------------------23

8
 1.3.5.1.4. Sputtering Method: ------------------------------------------------------- 24

1.3.5.2. Bottom-Up Approach: --------------------------------------------------- 24

1.3.5.2.1. Chemical Vapor Deposition Method: ----------------------------------25

1.3.5.2.2. Sol-Gel Method: ---------------------------------------------------------- 25

1.3.5.2.3. Co-Precipitation Method: ------------------------------------------------26

1.3.5.2.4. Hydrothermal Method: ---------------------------------------------------27

1.3.6. Applications Nanoparticles: -------------------------------------------------- 28

1.3.6.1. Drugs and Medicine: ----------------------------------------------------- 29

1.3.6.2. Manufacturing of Material or Material Synthesis: -------------------29

1.3.6.3. Environment: -------------------------------------------------------------- 29

1.3.6.4. Electronics: ---------------------------------------------------------------- 29

1.3.6.5. Energy Storage: ----------------------------------------------------------- 30

1.3.6.6. Energy Conversion: ------------------------------------------------------ 30

1.3.6.7. Mechanical Industry: ----------------------------------------------------- 30

1.4. Mullite (��������) type Bismuth Ferrite Nanoparticles: ------------------- 30

1.4.1. Synthesis of Mullite (��������) type Bismuth Ferrite: ----------------31

1.4.1.1. Sol-Gel Method: ---------------------------------------------------------- 32

1.4.1.2. Co-Precipitation Method: ------------------------------------------------32

1.4.1.3. Hydrothermal Method: ---------------------------------------------------33

1.4.1.4. Solid-State Reaction Method: -------------------------------------------33

1.5. Doped Mullite (��������) type Bismuth Ferrite: ---------------------------- 33

1.6. Photocatalysis: ----------------------------------------------------------------------- 35

1.6.1. Introduction: -------------------------------------------------------------------- 35

1.6.2. Mechanism: --------------------------------------------------------------------- 35

1.7. Waste Water Treatment: ------------------------------------------------------------ 36

2. Literature Review: ------------------------------------------------------------------------ 42

3. Characterization Techniques: ----------------------------------------------------------- 47

9
 3.1. X-Ray diffraction: ------------------------------------------------------------------- 47

3.2. UV-Visible Spectrophotometer: --------------------------------------------------- 49

4. Synthesis method: -------------------------------------------------------------------------52

4.1. Material Required: ------------------------------------------------------------------- 52

4.2. Synthesis Experiment: -------------------------------------------------------------- 52

4.3. Photocatalytic experiment: --------------------------------------------------------- 53

5. Results and Discussions: -----------------------------------------------------------------56

5.1. X-Ray Diffraction Technique: ----------------------------------------------------- 56

5.2. Photocatalytic activity: --------------------------------------------------------------57

5.2.1. Crystal Violet: ------------------------------------------------------------------ 57

5.2.2. Methylene Blue: ---------------------------------------------------------------- 59

5.2.3. Methyl Violet: ------------------------------------------------------------------ 61

5.2.4. Rhodamine B: -------------------------------------------------------------------62

5.2.5. 4-Nitrophenol: ------------------------------------------------------------------ 63

6. Conclusion: -------------------------------------------------------------------------------- 65

7. References: ---------------------------------------------------------------------------------66

10
Table Of Figures:
Figure 1: Fields of Nano Science .................................................................................15
Figure 2: Applications of Nanotechnology. .................................................................16
Figure 3: Types of Nanoparticles. ............................................................................... 17
Figure 4: Properties of Nanoparticles. ......................................................................... 19
Figure 5: Synthesis Methods for Nanoparticles. ..........................................................21
Figure 6: Top-Down Method for nanoparticles synthesis. .......................................... 22
Figure 7: Thermal Evaporation Method. ..................................................................... 23
Figure 8: Laser Ablation Method. ............................................................................... 24
Figure 9: Bottom-Up approach synthesis. ................................................................... 25
Figure 10: Sol-Gel Synthesis. ...................................................................................... 26
Figure 11: Co-precipitation Method ............................................................................ 27
Figure 12: Hydrothermal Method ................................................................................28
Figure 13: Applications of nanoparticles .....................................................................28
Figure 14: Methods used for mullite type BFO synthesis. .......................................... 31
Figure 15: General Photocatalytic Mechanism illustration. ........................................ 36
Figure 16: Solution preparation. .................................................................................. 52
Figure 17: Synthesis Method. ...................................................................................... 53
Figure 18 : XRD Graph of pure mullite type BFO. .....................................................56
Figure 19 : XRD Graph of Y-Mo Co-doped mullite type BFO. ................................. 56
Figure 20: (a) Degradation profile of pure mullite type BFO over Crystal violet, (b)
Percentage degradation of mullite type BFO over Crystal violet, (c) Degradation rate
and rate constant of Crystal Violet by mullite type BFO, (d) Order of reaction for
degradation of Crystal Violet with mullite type BFO. ................................................ 57
Figure 21: (a) Degradation profile of Crystal Violet with Y-Mo co-doped mullite type
BFO, (b) Percentage degradation of Crystal Violet by Y-Mo co-doped mullite type
BFO, (c) Degradation rate and rate constant of Crystal Violet with Y-Mo co-doped
mullite type BFO, (d) Order of reaction. ..................................................................... 58
Figure 22: (a) Degradation profile of Methylene Blue with pure mullite type BFO, (b)
Percentage degradation of Methylene Blue with pure mullite type BFO, (c)
Degradation rate and rate constant of Methylene Blue with pure mullite type BFO, (d)
Order of reaction. .........................................................................................................59

11
Figure 23: (a) Degradation profile of Methylene Blue with Y-Mo co-doped
��2��4�9, (b) Percentage degradation of Methylene Blue Y-Mo co-doped
��2��4�9, (c) Degradation rate or rate constant of Methylene Blue with Y-Mo co-
doped ��2��4�9, (d) Order of reaction. .....................................................................60
Figure 24: (a) Degradation profile of Methyl Violet with ��2��4�9, (b) Degradation
profile of Methyl Violet with Y-Mo co-doped ��2��4�9. ........................................ 61
Figure 25: (a) Degradation profile of Methyl Violet by Y-Mo co-doped ��2��4�9, (b)
Percentage degradation of Methyl Violet by Y-Mo co-doped ��2��4�9, (c)
Degradation rate or rate constant of Methyl Violet by Y-Mo co-doped ��2��4�9, (d)
Order of reaction. .........................................................................................................61
Figure 26: Degradation profile of Rhodamine B with pure mullite type BFO. ...........62
Figure 27: Degradation profile of Rhodamine B with pure mullite type BFO. ...........62

12
Table of Abbreviations:
AOP _______________________ Advance Oxidation Process.
POP _______________________ Persistent Organic Pollutants.
BFO _______________________ Bismuth Ferrite.
VB _______________________ Valence Band.
CB _______________________ Conduction Band.
CV _______________________ Crystal Violet.
MB _______________________ Methylene Blue.
Rh-B _______________________ Rhodamine B.

13
Chapter 01
Introduction

14
 1. Introduction to Nanoparticles:
1.1. Nano-Science:
The word "nano" comes from the Greek word for "dwarf," and it means "very
small." Nanoscience is the study of extremely small particles, or those that are on the
nanometer scale. A nanometer is one billionth of a meter, which is about 100,000
times smaller than the width of a human hair.
Nanoscience is a cross-disciplinary field that combines the principles of physics,
chemistry, biology, and engineering these fields are represented in fig 1. It studies the
unique properties of matter at the nanoscale, and how these properties can be used to
create new materials and devices with improved performance.

Figure 1: Fields of Nano Science

For example, nanoscience is being used to develop new drugs that can target
specific cells in the body, new materials that are stronger and lighter than traditional
materials, and new sensors that can detect diseases at an earlier stage. The field of
nanoscience is still in its early stages, but it has the potential to revolutionize many
industries, including medicine, electronics, and energy [1].
1.2. Nanotechnology:
Richard Feynman, a Nobel Prize-winning physicist, first introduced the concept of
nanotechnology in a 1959 paper titled "There's Plenty of Room at the Bottom." In this
paper, Feynman proposed that it was possible to manipulate matter at the atomic and
molecular level, and that this could lead to the development of new materials and
devices with unprecedented properties.

15
 Feynman's ideas were not widely accepted at the time, but they helped to lay the
foundation for the field of nanotechnology. Today, nanotechnology is a rapidly
growing field with applications in a wide range of industries, including medicine,
electronics, and energy [2].
1.2.1. Applications:
Nano science and nanotechnology don’t have its applications limited to one or two
fields it has a very vast range of applications in nearly everything around us from a
hand-held device mobile phone to modern characterization instruments. It has its
applications in large number of fields i.e., immunology [3], food industry [4], energy
production (Nano Generators)[5] and harvesting [6], agriculture [7], waste water
treatment [8], drugs and medicines [9], petrochemical industry [10], biotechnology
[11], textile [12], dermatology [13], and construction [14]. This enhancement in the
applications of nano structures and nanotechnology in different fields is due to and
according to their chemical and physical properties and structure i.e., melting point,
light scattering and adsorption, electric and thermal conductivity, catalytic activity,
photocatalysis as shown in figure 2 below [15].

Figure 2: Applications of Nanotechnology.

1.3. Nanoparticles:
Nanoparticles are tiny particles that have three dimensions in the nanoscale range
[15]. This size difference gives them unique properties that are different from both
smaller particles and larger materials [16].

16
 1.3.1. Types of Nanoparticles:
Nano particles are classified into different classes on the bases of the type of
bonding nature, structure, dimensions etc. but for general we divide nano particles
into following classes as represented in the fig 3 below. At first nano particles are
classified into two main types or groups inorganic nano particles and organic nano
particles. Organic particles are further divided into two types polymer particles and
biomolecules nano particles. The name of types of nano particles are clarifying their
uses and applications in specific sides. Inorganic nano particles are further divided
into four types and these are carbon based nano particles, metal and metal oxide nano
particles, semiconducting nano particles and the last type is ceramics type nano
particles. These classes can also be further divide into many more types but these are
some major classes that cover nearly complete area of nano particles types. The
applications of all these types of nano particles also vary from each other and they
may be used for multiple applications also [17, 18].

Figure 3: Types of Nanoparticles.

1.3.1.1. Carbon Based Nanoparticles:

The nano materials that are made up of carbon are called as carbon-based
nanoparticles. There are multiple types of carbon-based nanoparticles i.e., nano
diamonds, carbon nanofibers, carbon nano cones, graphene, fullerenes, and nano

17
tubes [19]. These carbon nano structures are used in different fields according to the
requirement of time i.e., EM interference shielding [20], ecotoxicology [21],
biomedical [22], fuel cell catalyst [23] etc. Nanoparticles are useable in many modern
fields due to their excellent biocompatibility, surface area, less-toxic effect and low
cost, their diameter ranges less than 100nm and are spherical [24].
1.3.1.2. Metal and Metal Oxide Nanoparticles:
Metal and metal oxide nanoparticles have vast and uncommon limit of
physiochemical characteristics and occupy improved chemical and physical characters
because they have loose material. These nanoparticles possess large surface area,
modifications in morphology and surface. Nanoparticles of Zn, ZnO, Au, Cu, Pt etc.
are used in different processes [25].
1.3.1.3. Semiconductor type Nanoparticles:
The term "Quantum Dots" (QDs) is another name for these nanoparticles. The
uses of these nanoparticles in DNA labelling, proteins, and cells are outstanding.
When used with spectral arrays for the UV, visible, near-infrared, and mid-infrared
ranges, they provide customizable discharge spectra. These nanoparticles' sizes affect
the released spectrum. These nanoparticles QDs have been used in a wide variety of
applications, including the creation of cellular pictures, photocatalysis, optical devices,
solar energy conversion, and the detection of trace levels of analytes. Some well-
known semiconductor QDs include HgSe (mercuric selenide), ZnO (zinc oxide), and
ZnS (zinc sulphide) [26].
1.3.1.4. Ceramics type Nanoparticles:
Ceramic nanoparticles have a solid core consisting of metalloids like silicon and
titanium as well as oxides, carbides, and carbonates. Ceramic nanoparticles,
sometimes referred to as nano-phase ceramics, can be further subdivided into nano-
clays and nano-scaffolds. These heat-resistant nanoparticles are mostly employed in
biological applications [27].
1.3.1.5. Polymer type Nanoparticles:
These 10 nm-sized solid colloidal nanoparticles are colloidal in appearance. These
particles serve primarily as drug carriers by aiding the medication's chemical and
physical absorption above the surface. Hydrophilic polymers found in nature are used
to make polymeric NPs [28].

18
 1.3.1.6. Bio-molecules derived Nanoparticles:
Biomolecules such as proteins, nucleic acids, polysaccharides, and lipids have
special features that can be exploited to create nanoparticles (NPs). These bio-
molecules are becoming well-known due to the growing need for materials that are
biodegradable and biocompatible. By conjugating with NPs that are inorganic in
origin, biomolecules have the ability to create unique biomolecule nanoparticles (NPs)
[18].
1.3.2. Properties of Nanoparticles:
The characteristics of nanoparticles are distinct. The size of nanoparticles and the
substance they are made of both have a significant impact on a small number of
nanoparticles' characteristics. certain nanoparticles' qualities depend on their form and
surface area, while others depend on their optical, magnetic, mechanical, or thermal
characteristics. However, certain NPs lack these characteristics. General qualities of
nanoparticles include size, surface area, shape, and physiochemical properties
including thermal, magnetic, mechanical, electric, and optical. Seen in picture 4 below
[18].

Figure 4: Properties of Nanoparticles.

19
 1.3.3. General Properties of Nanoparticles:
1.3.3.1. Size of Nanoparticles:
The size of nanoparticles is crucial to understanding their characteristics. The size
of nanoparticles may be determined by a variety of methods, including: The synthesis
process and reaction have a significant impact on the size of the nanoparticles.
Consider the hydrothermal process used to create iron oxide nanoparticles, which
exhibit high iron oxide crystallinity and a mix of magnetite and magnetite crystalline
phases. By enlarging nanoparticles, the magnetite phase in its pure form at 123±44
nm particle size is obtained. So, band gap and stain are likewise impacted by changes
in these nanoparticles' sizes [29].
1.3.3.2. Shape of Nanoparticles:
Nanoparticle shapes are crucial in a variety of technological applications. Some
nanoparticles have unique forms, including dimensional shapes (1D, 2D, and 3D). To
make exact applications, several nanoparticles made of the same materials but with
different forms can be produced. Shape-controlled nanoparticle manufacturing is
currently a widely used research technique in nanoscience. The main application of
this shape-controlled technique is the detection of inorganic nanoparticles in solutions
[30].
1.3.3.3. Surface of Nanoparticles:
Nanoparticle surface area is crucial for electrochemical reactions, reactivity,
adsorption catalysis, and other processes. ��3 �4 nanoparticles, used as coating
particles on super paramagnetic ascorbic acid, were created using the hydrothermal
approach method and have a diameter less than 10 nm. They were used for heavy
metal adsorption and demonstrated essentially effective adsorption abilities. High
surface area nanoparticles have strong photocatalytic activity while degrading
Rhodium B [31].
1.3.4. Physiochemical Properties of Nanoparticles:
1.3.4.1. Thermal Properties:
Having a high heat conductivity, nanoparticles. Cu has a thermal conductivity that
is 3000 times greater than motor oil and 700 times more than water. Due to the fact
that nanoparticle oxides like alumina oxide have better thermal characteristics than
water. Additionally, thermal conductivity is greater in nano-fluids than it is in
equivalent fluids when they are solid [32].

20
 1.3.4.2. Magnetic Properties:
In the field of research known as heterogeneous range, which includes
homogeneous and heterogeneous catalysts, magnetic storage, MRI, etc., magnetic
characteristics of nanoparticles play a significant role. A few synthesis techniques are
employed to create these nanoparticles, including co-precipitation, micro-emulsion,
and flame spray synthesis [33].
1.3.4.3. Mechanical Properties:
The investigation of mechanical characteristics has important applications in the
fields of nanofabrication, surface engineering, and nanomanufacturing. Numerous
mechanical parameters, including stress, hardness, friction, and elastic modules, may
be used to describe the mechanical character of nanoparticles. These characteristics
demonstrate how the size of nanoparticles affects performance; for instance, the
mechanical qualities of micro nanoparticles differ from those of large nanoparticles
[34].
1.3.5. Synthesis of Nanoparticles:
Since their sizes typically fall between one and one hundred nanometers,
nanoparticles are sometimes referred to as nanostructures. By synthesizing atoms or
by shrinking micro sized particles to nanosized particles, these nanostructures can be
created. Different synthesized processes can be used to create various nanoparticles.
Different nanoparticles are created utilizing various techniques, such as dry
nanoparticles or liquid dispersion nanoparticles. Figure 5 below shows:

Figure 5: Synthesis Methods for Nanoparticles.

21
 1.3.5.1. Top-Down Method:
Using this process, large, bulky particles are reduced to tiny, nano-sized particles.
The manufacture of very tiny and atypically shaped nanoparticles is accomplished
using this method. This method involves the use of an additional method for the
manufacture of nanoparticles. These top-down techniques are sometimes referred to
as the chemical method for producing nanoparticles. The following are these chemical
techniques:

Figure 6: Top-Down Method for nanoparticles synthesis.

1.3.5.1.1. Ball Milling process:

Ball milling is the most straightforward mechanical top-down method for attrition-
based nanoparticle production. Kinetic energy is imparted to the substance created in
this process by grinding raw materials. This method is used to create several kinds of
nanoparticles, including metal nanoparticles. The interaction between the vessel and
the balls in this process creates temperature and pressure, which results in a high
transformation phase at a high temperature. By contact and friction between the balls
and vessels of the milling device, a predetermined number of powdered materials are
added to the milling as well as synthesized. This technique is mostly used to
agglomerate particles and modify their shape, size, and structure. High energy milling
powder with particle sizes of 10–40 nm is used in the manufacture of zinc oxide
nanoparticles [35].

22
 1.3.5.1.2. Thermal Evaporation Method:
Endothermic means that heat is used to break down the chemicals in this process.
This approach is one of the most popular for creating the most stable mono-disperse
particles with the ability to self-assemble into inorganic nanoparticles. The use of heat
evaporation on thin films produces a variety of NPs [36].

Figure 7: Thermal Evaporation Method.

1.3.5.1.3. Laser Ablation Method:

The term "laser" refers to electromagnetic radiation with an elevated, high-
intensity beam. Einstein was the first to present a laser hypothesis. This method is
employed for the creation of nanoparticles from solvent in various forms. When
Maiman initially introduces a functional laser in the 1960s, it is widely employed in
many industries and by the military as well as in medical procedures. In essence, this
procedure creates micro nanostructured particles using a pulsed laser, which are then
employed in a variety of applications, including ceramics, glasses, and polymers.
When using various lasers in various applications, including those involving ceramics,
glasses, and polymers.
The ablation process continues continuously when various laser machining
operations, including laser cutting, milling, and others, are carried out. Vaporization

23
and metal ejection are involved in the ablation process. Graphite was the target
material employed to synthesize carbon-based nanoparticles using this method [37].

Figure 8: Laser Ablation Method.

1.3.5.1.4. Sputtering Method:

The process of sputtering is non-thermal. A vacuum pump is used to maintain low
pressure during the sputtering process. The nanoparticles are applied to the surface in
this procedure utilizing high-energy ions. Substrates are deposited on the surface of
nanomaterials via the sputtering process, which involves attacking high energy ions
ejecting particles from the substrates. The main applications of this technique include
coating, surface etching, and thin layer deposition. Plasma ions are the most typical
source employed in this technique. Direct current sputtering, ion beam sputtering, gas
flow sputtering, and more variations of this method exist to create various
nanoparticles with various characteristics [38].
1.3.5.2. Bottom-Up Approach:
As nanoparticles are created from very common components using this procedure,
it is often referred to as the building-up approach. Examples of this strategy include
the sedimentation and reduction methods. Graphene-containing anatase nanoparticles,
like ���2 , are created using this method [39, 40].

24
Figure 9: Bottom-Up approach synthesis.

1.3.5.2.1. Chemical Vapor Deposition Method:

For creating nanostructured particles, chemical vapor deposition is a great method.
Most micro-electric enterprises employ this method. This method uses a
straightforward material to create nanostructured particles. This method fixes the
substrate with a relatively thin layer of reactant in gaseous form. In this procedure, a
chemical reaction takes place when the thin layer comes into contact with the heated
substrate, producing a thin layer on the substrate's surface. The layer was then deleted
and saved for later usage. The product quality and rate of deposition in this process
are significantly impacted by pressure. The majority of CVD is done at extremely
high temperatures, usually above 100°C [41].
1.3.5.2.2. Sol-Gel Method:
One of the best methods for creating high-quality nanoparticle oxides, such as
metal oxide NPs and mix-oxide nanoparticles, is the sol-gel procedure. Because this
technique has control over several NP qualities, such as texture and surface, a superior
texture particle is produced [42].

25
Figure 10: Sol-Gel Synthesis.

1.3.5.2.3. Co-Precipitation Method:

One of the most used wet chemical techniques for the synthesis of NPs is this one.
Impurities from the solution are eliminated during this procedure. Small-size
homogenous nanoparticles have been directly synthesized in this approach. Drop by
drop, dissolved precipitants serve as preparation and separation agents in this
procedure. The main precipitating agents employed in this method include sodium
hydroxide, chlorides, hydroxides, and carbonates. Oleic acid is applied to the surface
for 30 minutes at 30°C while sodium hydroxide is used to balance the pH. The
mixture is then rinsed, centrifuged, and dried for an entire night to produce 28-
nanometer-sized nickel nanoparticles [42].

26
Figure 11: Co-precipitation Method

1.3.5.2.4. Hydrothermal Method:

This method, which results in the deposition of nanostructured particles, involves the
interaction of solid materials in contact with an aqueous solution at high temperatures
and pressure. This technique produces 86 nm crystals of silver using a stabilizing
agent called Nano-cellulose and a precursor called silver nitrate. The temperature used
in this process is higher than typical, and the solvent utilized in this approach is water.
Crystal growth is the primary use for this technique [43]. Figure 12 below depicts the
straightforward hydrothermal process.

27
Figure 12: Hydrothermal Method

1.3.6. Applications Nanoparticles:

Nanoparticles has their applications in multiple fields and these are given below in
fig 12. In each field nanoparticles are playing an extra ordinary role due to their
efficient properties.

Figure 13: Applications of nanoparticles

28
 1.3.6.1. Drugs and Medicine:
Nanoparticles have been extensively employed to precisely target illness and its
therapy. Disease diagnosis and therapy are both possible with the use of NPs as
theragnostic. These nanoparticles have a significant impact on both the detection and
therapy of brain disorders. Due to their tiny size, certain nanoparticles develop
magnetic domains. These particles have been employed in medication delivery, tissue
healing, cancer treatment, fish medicine, drug delivery, antimicrobial agent, cell
labelling, biological imaging, and cellular treatment, among other applications [44-47].
1.3.6.2. Manufacturing of Material or Material Synthesis:
Manufacturing NPs have physicochemical characteristics that provide distinctive
capabilities like as electrical, mechanical, etc. that are widely applied in a variety of
domains, including commercial and ecological. These nanoparticles are utilized in the
food industry as packaging and food protection. Among all of these ingredients, the
categories of house, computer, and garden come in second place, followed by items
for health and fitness [32].
1.3.6.3. Environment:
Utilizing photo-degradation, certain nanoparticles are often utilized in
environmental remediation to identify and eliminate contaminants. Targeted
contaminants were collected by these nanoparticles. Metal nanoparticles can increase
the capability of light absorption to a wider wavelength range. Some oxides of
semiconductor nanoparticles, such as ���2 & ZnO, have been used extensively for the
photocatalytic destruction of pollutants. More over now a days perovskite type BFO,
mullite type BFO and other ���3 and �2 �4 �9 type of materials is used for
photocatalysis [48-53].
1.3.6.4. Electronics:
Because these electronics, particularly printed electronics, are employed in a
variety of industries, their use was particularly demanding in last years. Metallic and
ceramic nanoparticles were present in the inks used in printed electronics. The
important quality of those nanoparticles with manipulable and reversible construction
for electronic devices with the potential for inclusion. Nanomaterials and
nanoparticles are used in various electronics in the form of nanotechnology i.e.,
photovoltaics, sensors, optoelectronics, diagnostics, bioelectronics, transistors, [32,
54-57].

29
 1.3.6.5. Energy Storage:
Due to their non-renewable nature, recent studies have shown that there will be a
scarcity of fossil fuels in the future. Scientists therefore begin to investigate ways to
produce renewable energy from inexpensive and accessible materials. Scientists have
shown that nanoparticles are an excellent alternative to fossil fuels because of
qualities including huge size, surface area, strong optical performance, and catalytic
nature. Specifically designed nanoparticles are utilized to produce energy by photo-
and electrochemical water splitting [58, 59].
1.3.6.6. Energy Conversion:
There are different materials and their nanoparticles that are used in energy
conversion from one form of energy to other. There are a few devices that are used for
energy conversion i.e., photovoltaic cell, nanogenerators. Perovskite type and mullite
type materials also possess applications in this field. These nanogenerators are
piezoelectric, and triboelectric [60-63].
1.3.6.7. Mechanical Industry:
These nanoparticles have outstanding mechanical properties, including stress,
young modulus, and strain characteristics, as indicated by their name. These
nanoparticles are mostly employed in industrial settings for coating lubricants and
adhesive purposes [32].
1.4. Mullite (��� ��� �� ) type Bismuth Ferrite Nanoparticles:
As we already know water on earth is in limited amount that is useable for
drinking and other human uses and if this continued to get contaminated at this pace,
we will be soon out of water sources and face water scarcity. So, we need to clean
water and make it re-useable and for this purpose organic pollutants and dyes are
needed to be fully degraded and eradicated from environment. And can be done by
fenton reaction, photocatalytic oxidation and electrochemical oxidation due to
generation of highly active radical in these processes [64]. Development of
nanomaterials has opened a new gate towards the progression of water treatment
technologies. In all these latest developed technologies metal catalysts for degradation
are the most suitable, effective, environmental friendly, and economical methods
because of their suitable band gaps [65, 66]. Photocatalytic degradation with the help
of metal catalyst can also be helpful in this regard [67].

30
 Bismuth ferrite normally has orthorhombic structure (space group Pbam) and has
a lattice constant of � = 7.965 Å, � = 8.440 Å, � = 5.994 Å and crystallographic
properties detriment many properties of material synthesized [68]. BFO is
paramagnetic at room temperature, ferroelectric and its state changes to
antiferromagnetic at 264K which is also its Neel temperature making it a multiferroic
or multiferromagnetic material around room temperature[69]. As ��2 ��4 �9 is
classified as a mullite-type compound with �9 -structures, which are distinguished by
���6 octahedral that share edges and align parallel to the crystallographic c-axis.
These octahedral chains are interconnected by ��2 �7 dimers, which are composed of
two ���4 tetrahedral. Within the framework, the channels are formed, and they
accommodate ��3+ cations. The channels are characterized by the presence of stereo
chemically active 6�2 lone electron pairs (LEPs) of the ��3+ cations, which are
oriented towards the vacant sites within the channels [70, 71].
1.4.1. Synthesis of Mullite (������ �� ) type Bismuth Ferrite:
The synthesis of mullite type BFO involves multiple chemical and physical
processes. These procedures deliver a flawless system with an accurate size
distribution and stoichiometry. Each of these methods has particular requirements in
terms of energy use, safety, pricing, etc. These techniques are mostly used to create
materials with volume ratio nano-structures from micro-sized nanoparticles.

Figure 14: Methods used for mullite type BFO synthesis.

31
 1.4.1.1. Sol-Gel Method:
All of the chemicals were of the analytical grade and were used directly out of the
package. Typically, at room temperature, ethylene glycol (30 mL) was stirred rapidly
while being dissolved in stoichiometric amounts of ��(��3)3 5�2 � (10 mmol) and
��(��3 )3 9�2 � (20 mmol). After forming a stable translucent sol, it was heated at
140 °C for 24 hours to produce a fluffy dry gel. The dry gel was ground in an agate
mortar, transported to a crucible, ramped up to a certain temperature at a rate of 5
C/min, and kept at that temperature for 4 hours. The cool powders were then
centrifuged and vacuum-dried at 60 °C after being repeatedly rinsed with deionized
water and 100% alcohol. In a nutshell, iron oxide (��2 �3 ) and bismuth oxide
(��2 �3 ) were fully combined stoichiometrically, compressed, and then heated to
850 °C for 12 hours in an alumina crucible. The reacted product was compressed,
finely powdered, and heated to 900 °C for ten hours [72].
1.4.1.2. Co-Precipitation Method:
Chemical used in this method to synthesis mullite type BFO are given here.
Reverse chemical co-precipitation was successfully used to create ��2 ��4 �9 (BFO)
nanoparticles. All chemical reagents, including sodium hydroxide NaOH (Scharlau
99%), bismuth subnitrate (��5 �9 �4 �22 ) (Sigma-Aldrich 98%), nitric acid ���3
(Scharlau 65%), and high-purity analytical grade iron nitrate nonahydrate
��(��3 )3 9�2 � (Scharlau 98%), were used as raw materials without any additional
purification.
The experimental method followed is here.
For 0.2M solutions of ��3+ and ��3+ , iron nitrate was dissolved in deionized
water, while bismuth subnitrate was dissolved in 2M nitric acid (���3 ). To create a
homogenous, transparent mixture, these solutions were combined and agitated at
stoichiometric molar ratio (Fe: Bi = 2:1) for 40 minutes. As a precipitant, 2M sodium
hydroxide (NaOH) was utilized. To achieve pH values of 8, 9, 10, 11, and 12, the
cations solution was then introduced dropwise into the precipitating agent while being
vigorously stirred. After the chemical co-precipitation procedure, which took around
15 minutes in total, the suspension was agitated for an additional 10 minutes to
homogenize it. The suspension was then filtered and repeatedly rinsed with distilled
water until the pH level was 7. The precipitate was then dried for two days at 80 °C in

32
an oven. Finally, the powders were crushed and calcined for 1 hour at 600, 650, 700,
750, and 800 °C for crystallization and phase formation [73].
1.4.1.3. Hydrothermal Method:
In hydrothermal synthesis method following procedure can be followed.
Hydrothermal synthesis was used to create the ��2 ��4 �9 samples. Without
additional purification, all of the compounds employed are analytical grade reagents.
In a typical synthesis of ��2��4 �9 micro platelets, 10 mL of 1 M ���3 was used to
dissolve 2 mmol of ��(��3 )39�2 � and 1 mmol of ��(��3 )3 5�2 �. NaOH was used
to modify the solution's alkalinity. For the production of samples S1, S2, and S3,
respectively, the concentrations of NaOH were 4, 8, and 12 M. The precursor solution
was put into a steel autoclave with Teflon lining after 15 minutes of magnetic stirring.
The autoclave was sealed, heated for 24 hours at 200°C, and then allowed to naturally
cool to ambient temperature. To get rid of any potential residues, the finished product
was washed multiple times with pure alcohol and deionized water. It was then dried
for 24 hours at 65°C. ��3+ and ��3+ were used in a 1:1 molar ratio to create sample
S4 along with 1 M NaOH [74].
1.4.1.4. Solid-State Reaction Method:
In this study, the ��2 ��4 �9 precursor was made using a solid-state process at ambient
temperature. As raw materials, sodium hydroxide (NaOH), ferric nitrate
( ��(��3 )3 9�2 � ), and bismuth nitrate ( ��(��3)3 5�2 � ) of analytical grade were
employed. ��(��3 )3 5�2 � (��(��3 )3 9�2 �) and NaOH were combined in an agate
mortar and pestle and pounded for 40 minutes at room temperature (25°C) in a molar
ratio of 1:2:10. During the mixing procedure, the reaction quickly began, and heat was
released as well. The mixture was rinsed and filtered multiple times with deionized
water, then dried for three hours at 80°C. The precursor was then calcined in air for
two hours at various temperatures to produce ��2 ��4 �9 . To eliminate the unreacted
reactants, the resulting product was leached with 20% ���3 before being repeatedly
washed with deionized water and dried at 80°C for three hours [75].
1.5. Doped Mullite (��� ����� ) type Bismuth Ferrite:
We need to treat water properly but traditional wastewater treatment methods
have limitations, such as secondary pollution, low performance, and high energy cost.
And to avoid these reasons advanced oxidation processes (AOPs) are a promising
alternative, as they are effective, efficient, and environmentally friendly. Photo-

33
catalysis is one of the most effective AOPs, and has been used to treat wastewater
since the 1970s [76]. In this regard bismuth ferrite (BFO-mullite type) is a promising
material for solar, photocatalytic and other applications due to its narrow bandgap and
chemical stability more over mullite type BFO is the most stable of all the three
phases of BFO (selenite, mullite and perovskite) [77], it has high magnetic frustration
and its similarity with �����3 and α − ��2�3 in terms of lattice parameters [78].
Compared to TiO2-based photocatalysts, BFO has a narrower bandgap and can be
activated by visible light, which makes it more efficient. However, the photocatalytic
performance of BFO is still limited by the fast recombination of charge carriers and
low quantum yield [79, 80]. In case of BFO or other photocatalysts this recombination
can be slowed by the help of doping, heterojunction formation etc.
Now a days semiconductor-based photocatalysts are widely available and
cheaply recyclable, they have previously been used to destroy organic dyes. In this
field both n-type and p-type semiconductors function as photocatalysts [81].
��2 ��4 �9 has gained great attention because of it being dramatically magnetic,
electronic, electronic, dielectric, non-toxic and chemically stable[82, 83]. Mullite type
BFO is a p-type semiconductor and is being the Multiferroic material that has both
magnetic and ferroelectric properties existing spontaneously at room temperature and
is also suitable for photocatalytic degradation reactions moreover in case of
multicomponent system it has enhanced photocatalytic activity with synergistic
photocatalytic efficiency [84-87]. BFO has two clear absorption edges for visible light
in the range from 610nm to 850nm [74, 88, 89]. BFO ( ��2 ��4 �9 ) has its potential
applications in the development of modern technologies for human development i.e.
water splitting, spintronics, energy storage, energy conversion, gas sensors,
electronics and photocatalysis giving out efficient results in every field [90, 91]. The
dimensionality or crystallite size of a given structure can have a significant impact on
its piezoelectric, magnetic, or optical properties. In some cases, a critical nano size
can be reached where the properties of the material change drastically, such as the
development of magnetism in a conventional nonmagnetic oxide [91-93]. As highly
efficient results are noticed in photocatalytic degradation by BFO ( ��2��4 �9 ), it is
used in the degradation of ammonia to NO, degradation of methyl orange, phenols
and other dyes present in the environment, sometimes small amount of �2 �2 or other
initiators are added, and this was affected by the shape or morphology of crystals,

34
hence its photocatalytic activity is morphologically controlled [52, 74, 94, 95]. This
makes it a catalyst that can be used for all different pollutants degradation just by
varying its morphology.
1.6. Photocatalysis:
1.6.1. Introduction:
The terms photo, which has to do with photons, and catalyst, which is a chemical
that affects the pace of a process when it is present, are combined to form the phrase
"photocatalyst." As a result, photocatalysts are substances that, when exposed to light,
alter the pace of a chemical process. The term "photocatalysis" refers to this
occurrence. The term "photocatalysis" refers to chemical processes that use light and
a semiconductor. A photocatalyst is a substance that absorbs light and serves as a
catalyst for chemical processes. In essence, all photocatalysts are semiconductors. A
semiconducting substance will produce an electron-hole pair when exposed to light in
a process known as photocatalysis.
On the basis of how the reactants appear physically, two types of photocatalytic
reactions may be distinguished.
Homogeneous photocatalysis: This type of photocatalytic reaction occurs when
the semiconductor and reactant are both in the same phase, such as a gas, solid, or
liquid.
Heterogeneous photocatalysis: These photocatalytic processes are referred to as
heterogeneous photocatalysis when the semiconductor and reactant are in distinct
stages [96].
1.6.2. Mechanism:
When an appropriate wavelength of light is absorbed, the electron in the valence
band (VB) is excited into the conduction band (CB). Band gap is the name for the
space between VB and CB. As a result, the lowest energy needed to excite one
electron is the same as the energy of the band gap. Thus, a photon with energy equal
to or greater than the photocatalyst's band gap may be absorbed to start a
photocatalytic reaction such as oxidation or reduction. On the surface of the
photocatalyst, the excitation of an electron results in the production of a pair of charge
carriers (e- - h+ pair), which are a hole and an electron in the valence band and
conduction band, respectively. There are two options at current time:

35
 1. The created charge carriers unite once more and release energy in the form of
heat.
2. An electron donor or electron acceptor on the photocatalyst surface may
further react with the charge carrier.
In the first instance, nothing happens. In the second scenario, dissolved oxygen or
⦁−
water is combined with an electron or hole to produce free radicals called �2 , ���⦁ ,

or ��⦁ . These reactive oxidizing species, in addition to others like �2 and �2 �2 , are
crucial to the photooxidation process [96].

Figure 15: General Photocatalytic Mechanism illustration.

1.7. Waste Water Treatment:

This is a major problem that must be solved in its best possible and cheapest way
so that clean water should be available to every single person on this planet earth. In
the last few decades, due to vigorous growth in the industrial developments to meet
human requirements, the amount of waste water is increasing worldwide. This
industrial waste water is directly drained into the water streams, especially in
developing countries i.e., Pakistan, India, Colombia, Brazil, Cambodia, and Malaysia.
This uncontrolled production of persistent organic pollutants (POP) in water has
produced a devastating increase in risks to human health, animal health and especially
aquatic life. In developing countries and low-income countries water pollution has

36
caused 1.4 million premature deaths according to a report in Lancet, 6% of deaths in
low-income countries are due to unsafe polluted water and its 1.2 million deaths each
year. Water pollution causes approximately 14000 deaths every day in developing
countries [97-101].
As water being the most precious gift existing in this world it is very important
for biotic survival on our planet [102]. In developing countries industries are
increasing at a high pace i.e. machinery manufacturing, printing, textile, chemicals,
electronic, pesticide and pharmaceutical industries [103] these industries are giving
their part in water pollution [104]. These are responsible for release of untreated water
into the water reservoirs that contains pollutants i.e., dyes, heavy metals, phenols,
pesticides, insecticides, and drugs [102, 105-107]. The existence of these pollutants in
the water bodies above recommended level by WHO and environmental organizations
can lead to devastating health issues in land life and aquatic life i.e., neural toxicity,
cancer, reproduction incapability, fish gills clogging, eutrophication and incapability
to photosynthesis [108-110].
We know that dyes from textile industries are non-biodegradable and
synthetically stable in water hence are primary danger to nature, and around 0.1
million dyes are available worldwide for commercial use with 7 × 105 ���� of annual
production[101]. These Organic dyes in polluted water create stable secondary
pollutants, harming aquatic ecosystems by depleting dissolved oxygen and reducing
sunlight penetration, leading to decreased photosynthesis in water flora [111]. So,
these dyes and their intermediates are in some of such compounds that are called
xenobiotic and recalcitrant, these compounds stay in the environment for long time
and are not degraded proving damaging and cause of destruction of environment and
biosphere. These dyes are the components coming out from industries and major
cause of pollution [112]. The global dye industry is complex and fragmented, with
production and use occurring in a variety of settings. This makes it difficult to
accurately estimate the total amount of dye produced each year. However, a rough
estimate suggests that the annual production of various classes of dyes is on the order
of 0.75 million metric tons [113, 114]. From which, the textile industry is a major
source of pollution, releasing millions of tons of dyes and other pollutants into the
environment each year. The dyeing process itself is very water-intensive, requiring up
to 150 liters of water to dye a single kilogram of cotton. In addition, a significant
amount of dye is not actually fixed to the fabric, and instead ends up in the
37
wastewater. This unfixed dye can be harmful to aquatic life and can also contribute to
algal blooms. The wastewater from textile factories also contains high levels of
inorganic salts, acids, and bases. These pollutants can make it difficult to treat the
wastewater, and can also have negative environmental impacts. The heterogeneous
nature of textile wastewater makes it difficult to treat with a single treatment process.
This is because the wastewater can contain a wide variety of pollutants, each of which
requires a different treatment method. As a result, multiple treatment processes are
often used in combination to treat textile wastewater. Despite the challenges, it is
important to find effective ways to treat textile wastewater. The textile industry is a
major economic driver, and it is essential to protect the environment while continuing
to produce textiles [115-119].
Azo dyes are widely used globally, accounting for approximately 60% of all
dyes. When present in aquatic environments, these dyes, including azo compounds,
have negative effects on photosynthesis, contribute to the depletion of dissolved
oxygen, and pose toxicity risks to plants and animals. Although the acute toxicity of
dyes is generally low, certain purified azo dyes are directly mutagenic and
carcinogenic. Moreover, the breakdown of dye compounds can generate intermediate
substances that are more toxic than the original molecules. In the case of azo dyes, a
chemical reaction called azo cleavage occurs in the environment. Under oxygen-
deficient conditions, redox mediators of abiotic or biotic origin facilitate the transfer
of redox equivalents from a donor to the azo bond, resulting in the reduction of dyes.
Consequently, when these compounds enter the environment, their native forms are
reduced, forming constituent aromatic amines that are recognized as more toxic or
carcinogenic than the parent compounds, and harmful to cellular mechanisms.
According to Saratale et al. (2011), the bacterial toxicity of azo dyes depends on the
mechanisms involved in their degradation. Firstly, several azo dyes only become toxic
after their azo bonds are reduced, leading to the generation of aromatic amines,
primarily under anaerobic conditions. These aromatic amines are subsequently
oxidized to form reactive electrophilic species that bind covalently to DNA. Secondly,
oxidation of azo dyes without cleaving the azo bonds produces free aromatic amines.
Lastly, azo bonds can be directly oxidized to create highly reactive electrophilic
diazonium salts of azo dyes. All three mechanisms are specific to the compound
(and/or bacteria) involved. Thus, the toxicity of azo dyes may be caused by a single
mechanism or a combination of different degradation processes. The toxicity or
38
mutagenicity of reduced dyes or aromatic amines is strongly influenced by their three-
dimensional molecular structure. The nature and position of substitutions, such as
amino, carboxy, halogen, and methyl, methoxy, nitro, or sulfonate groups, on
aromatic rings greatly impact the toxicity of the dye molecules to varying degrees. For
instance, Acid Red 18 and Acid Red 27 were found to be non-mutagenic, whereas
structurally similar Acid Red 26 was carcinogenic due to the presence of a methyl
group and the position of the sulfonate group substitution. However, studies on dye
toxicity have yielded contradictory observations. Ferraz et al. (2011) discovered that
3-methoxy-4-aminoazobenzene was a potent mutagen in a bacterial system and a
hepato-carcinogen in rat studies, whereas 2-methoxy-4-aminoazobenzene exhibited
weak mutagenicity in bacteria and appeared to be non-carcinogenic. The
understanding of azo toxicity is well-established in bacterial systems, but further
research is needed to establish a correlation between mutagenicity and carcinogenicity
in animal models. The lack of correlation is likely due to the existence of complex
metabolic pathways in mammalian systems. Additionally, physicochemical treatments
also generate toxic intermediates. The products resulting from the oxidation of indigo
blue through processes like coagulation with ��2 (��4)3 , electro incineration, or the
use of laccase have been shown to be more toxic than the dye itself [113, 117, 120-
128].
Similarly in waste water from pharmaceutical industries water contains
hormones, consumer products and organic waste water compounds that result in
problems for human and fishes where it resulted in increased female as compared to
male fishes and also psychological alteration and this alternation or imblancement in
male and female proportion can cause damage to environment [129]. If we move
towards agriculture where pesticides are used in agriculture to kill unwanted insects
and only 10-15% of them reach their target while the rest are drained or seeped down
to fresh water reservoir hence contaminating it [130]. With all these above problems
we discussed with respect to water pollution antibiotic resistance is also a growing
problem, and ciprofloxacin is a common antibiotic that has been detected in drinking
water. During its purification, bromate is a byproduct that can cause cancer and
mutations. The World Health Organization has set a safe limit of 10 mg/L for bromate
in drinking water, but levels as high as 60 mg/L have been detected [131-135]. We are
also using plastic products in our daily life and this is the reason for production of
micro-plastic in environment. These are all major problems because, it is really tough
39
to degrade them, these are of small size and their effect on environment are
devastating due to their presence in huge amount in the world around us [67].
In the field of environmental remediation photocatalysis is the most effective,
useful and low cost way to convert harmful organic pollutants into harmless
carbonaceous products in the end [136, 137]. Now a days researchers are interested in
the synergistic effect which is present in ternary composites [136]. We are not using a
single phased photocatalyst because in single phase photocatalyst charge carrier
transfer is randomized leading towards higher recombination probability of excited
carrier that will reduce photocatalytic efficiency [138]. The separation of photo-
induced charge carriers is the fundamental and most important idea in the
photocatalytic process, and this can be enhanced by enhancing the delocalization of
electrons [139]. Adsorption or capturing of photons to create reactive electron and
positive hole to begin the oxidation or reduction of dye molecular structure that
results in its degradation is incriminated in photocatalytic reaction [140].
This work aims toward creation of a new ��2 ��4 �9 based material with
doping using sol-gel method. There is only small amount of work is done on this base
material while it has properties like paramagnetism, antiferromagnetism,
ferroelectricity or multiferroic properties around room temperature and it shows a
synergistic effect of adsorption and visible light degradation with good efficiency
making it a suitable material to work on. And up to the best of our knowledge there
are no reports on the synthesis of yttrium and molybdenum doped ��2 ��4 �9 . The
successful synthesis of this material is confirmed by the characterization techniques
i.e., XRD, SEM, and applications by UV-visible spectrophotometer model CECILE
CE7200. It has given very good results in dye degradation.

40
Chapter 02
Literature Review

41
 2. Literature Review:
The degradation of different dyes by the mullite type BFO depends upon its
shape. Yang, Dai [141] et al. prepared ��2 ��4 �9 flower like spheres with enhanced
photocatalytic activity by hydrothermal method and tested it on Methyl orange. This
synthesized photocatalyst showed satisfactory results in degradation of MO.
Psathas, Georgiou [142] et al. prepared controlled phase of mullite and
perovskite type BFO by flame spray pyrolysis method and evaluated them over 4-
nitrophenol and it gave satisfactory results.
Kebir, Boudjemaa [143] et al. prepared ��2 ��4 �9 by sol gel method and
carried out chromium VI photo reduction under visible light and sun light irradiation.
This mullite type BFO reduced chromium VI from 98% to 5% in the given solution. It
changed to less toxic form of its chromium III only 5% wasn’t changed and it was
better than most of the previously used photo-reduction catalysts.
Tong, Jin [144] et al. worked on controllable synthesis of different bismuth
ferrite by a PVA modified hydrothermal method and did their photocatalytic
characterization. In their work mullite type BFO gave impressive results in
degradation methyl orange.
Casanova Monteiro, Caetano [145] et al. worked on ��2 ��4 �9 in pellet
form as an alternative of wastewater treatment process. They prepared it by two
methods Pechini method and solid-state reaction and successfully prepared about
93.5% pure form of it by Rietveld refinement. Material prepared by solid state
reaction method showed 85.86% of degradation of tartrazine dye. And the other gave
above 90% results which one was prepared by Pechini method.
Liang and Yang [146] et al. worked on control-growth and photocatalytic
activities of low-dimensional ��2 ��4 �9 crystals, nano sheets were prepared by
hydrothermal method and micro rods were prepared by co-precipitation method and
checked their photocatalytic activities. For an impressive degradation of methylene
blue nano sheets took 12h and micro rods took 8h.
Glinskaya, Petrov [147] et al. worked on crystal structure, magnetic and
photocatalytic properties of solid solution ��2−� ��� ��4 �9 . Where it is doped with
lanthanum and this doping is between 5-10%. After checking material’s

42
photocatalytic activity, it found out that its efficiency was around 37.4% at its best for
400mg/L. They prepared this material by solid phase reaction method.
Rao, Kamath [148] et al. worked on delineating the photocatalytic properties
of doped mullite ��2 ��4 �9 by virtue of ��3+ ions. Gd doped mullite BFO powder
was prepared by ball milling route. The doping was between 1-5% and muffle furnace
was used for calcination process at 850 degrees Celsius for 12h. The photocatalytic
efficiency of it was 77% maximum after 80mins.
Wang, Zhang [72] et al. worked on a facile approach to pure phase ��2 ��4 �9
nanoparticles sensitive to visible light. They used sol-gel synthesis method for mullite
BFO preparation. They used this prepared mullite on Rhodamine-B dye and it was
degraded by photocatalyst with an efficiency of around 90%.
Xian, LJ [149] et al. worked on the synthesis and photocatalytic activity of
��2 ��4 �9 using KOH as mineralizer via hydrothermal method and their prepared
material showed 74% degradation efficiency of methylene blue and they were able to
get same efficiency after repeated three cycles. Maximum obtained efficiency was of
85% after 8h of irradiation with visible light.
Monteiro, de Jesus Cubas [150] et al. studied the effect of pH variation on
synthesis and photocatalytic activity of ��2 ��4 �9 by preparing this using sol-gel
method at different pH values. It provided maximum results at pH 3 with an efficient
result in photocatalytic degradation around 90%.
Wu, Liu [151] et al. worked on enhanced magnetic and photocatalytic
properties of ��2 ��4 �9 semiconductor with a large exposed surface. They carried out
hydrothermal preparation method for this. They obtained 40% degradation of Rh-B
dye with ��2 ��4 �9 microplates.
Zhang, Lv [68] et al. worked on formation and photocatalytic properties of
bismuth ferrite sub microcrystals with tunable morphology. They used hydrothermal
method to prepare ��2 ��4 �9 . It showed an efficiency around 76.4% under UV-light
and around 11% efficiency in visible light for methyl orange.
Ma, Liu [152] et al. worked on hydrothermal synthesis of single crystalline
��2 ��4 �9 photocatalyst with enhanced photocatalytic activity. And they obtained
above 90% efficiency in methylene blue degradation under visible light in 90mins of
irradiation time.

43
 Liu, Wu [153] et al. worked on microwave hydrothermal synthesis of
��2 ��4 �9 crystals with visible light photocatalytic activity. After their preparation
their photocatalytic efficiency methyl orange was 71% after 8h of illumination time
under visible light.
Shuyan, Guan [154] et al. prepared Mn doped ��2 ��4 �9 photocatalyst and
this doping resulted in enhancement of photocatalytic properties. Hydrothermal
method was used for the preparation of Mn doped ��2 ��4 �9 and it gave efficiency of
around 85% on rhodamine-B. In the first step rhodamine-B was converted into an
intermediate which resulted into horizontal peak shifting and later formed carbon
dioxide and water.
Liu and Zuo [155] et al. worked on morphology and optical absorption of
��2 ��4 �9 crystals via mineralizer-assisted hydrothermal synthesis. They checked
photocatalytic activity of the prepared sub-micron particles and rod-like particles the
efficiency was 45% and 10% respectively on MO.
Hu, Lua [156] et al. put their efforts on Nanostructured hexahedron of
bismuth ferrite clusters: delicate synthesis processes and an efficient multiplex
catalyst for organic pollutant degradation. They prepared mullite type BFO
nanostructured clusters by using low temperature co-precipitation and hydrothermal
method together. And they produced above 90% efficiency on MO by using mullite
type BFO with an initiator i.e., hydrogen peroxide.
Wu, Miao [157] et al. made efforts on novel multiferroic ��2 ��4 �9
nanoparticles: the interesting optical, photocatalytic, and multiferroic properties. They
synthesized it by using glycine combustion method. They proved that efficiency of
this material greatly depends upon surface area and provided an efficiency between
93-98% between temperature ranges of 650 degree Celsius to 900 degrees Celsius.
Gheorghiu, Tanasa [158] et al. worked on preparation of ��2 ��4 �9 particles
by hydrothermal synthesis and functional properties. They preparation was confirmed
by respective techniques. They analyzed photocatalytic efficiencies which was found
to be 52-61% under visible light for Rh-B.
Zhang, Yang [159] et al. worked on polyacrylamide gel synthesis and
photocatalytic performance of ��2 ��4 �9 nanoparticles. The ��2 ��4 �9 system is
effective at degrading MR under visible light. After 6 hours of irradiation, the MR
degradation rate reached 40% and 38% for the two samples.

44
 Xian, Yang [160] et al. worked on photocatalytic mechanism of ��2 ��4 �9
nanoparticles in degradation of methylene blue.
Zhang, Gong [161] et al. worked on size-dependent magnetic, photo
absorbing, and photocatalytic properties of single-crystalline ��2 ��4 �9
semiconductor nanocrystals. They prepared mullite type BFO by sol-gel synthesis
method and checked its activity on methylene blue which found to be maximum at
91% after 4h of visible light irradiation out of all the prepared samples.
Tong, Cai [162] et al. worked on Synthesis and Photocatalytic Property of
Preferred-oriented ��2 ��4 �9 Crystals by Using Different Organic Additives. They
prepared it using hydrothermal method and tested its photocatalytic activity that was
found to be 93% on methyl orange in the presence of hydrogen peroxide after around
3h of visible light irradiation.
Sun, Wang [52] et al. worked no visible light-induced photocatalytic
oxidation of phenol and aqueous ammonia in flowerlike ��2 ��4 �9 suspensions. They
prepared it by using solid state reaction method at pH 13.5 and tested its
photocatalytic activity on phenol and ammonia water which was found to be 30% and
32% without any other initiator while with hydrogen peroxide it changed to 74% and
16% after 4h and 6h respectively.
Ruan and Zhang [74] et al. worked on tunable morphology if ��2 ��4 �9
crystals for photocatalytic oxidation. They prepared it using hydrothermal synthesis
method. These plate’s thickness decreased with pH increasing and after testing its
photocatalytic activity on MO in UV irradiation it was found to be 93% efficient after
90mins and in visible region its efficiency was just 2-3% after 24h.

45
Chapter 03
Characterization

46
 3. Characterization Techniques:
There are several characterization techniques that are used to confirm the
formation of our specified product or material XRD or X-ray diffraction technique is
the most important in them that is used here as a prove for the material is synthesized
successfully. XRD was used to analyze crystal structure and its crystallinity. It was
also used to get a hint of geometry of the synthesized material. CECILE CE7200 UV-
visible spectrophotometer was used to check out the activity of material on multiple
dyes preferably on cationic dyes i.e., crystal violet, methyl violet, methylene blue,
rhodamine B, 4-nitrophenol and EBT.
3.1. X-Ray diffraction:
Because we often have some basic knowledge, such as potential component
elements and their volume in a sample, there are relatively few situations when
structural analysis for wholly unknown compounds is required. Additionally, the
obtained diffraction data may be quickly and easily compared with those of a large
number of standard compounds thanks to recent advancements in database search
tools. About 50,000 chemicals are included in the powder diffraction database, which
was created by the JCPDS cards (Joint Committee on Powder Diffraction Standards)
with the assistance of several societies in the United States, Canada, the United
Kingdom, and France. Then, by scanning the diffraction data for one that perfectly fits
the pattern of the unknown chemical stored in the database, we may identify an
unknown compound of interest. Hanawalt et al. first proposed this method based on
the idea that a substance's powder diffraction pattern is distinctive to that substance,
similar to a fingerprint, and that if a sample contains two or more components, the
measured powder diffraction pattern is quite likely to be reproduced by the simple
sum of those of pure substances. The d-values of the three strongest diffraction peaks
used by the Hanawalt technique to describe each material. Below is a description of
this approach's key components, sometimes known as the Hanawalt method.
To find the relevant pattern in the database, the values of �1 , �2 , and �3 , for
�
the three greatest diffraction peaks together with their respective intensities ( � ) are
1

utilized. If the diffraction data of interest and the data from the reference materials
exactly match each other, analysis is considered to be complete. about course, prior
knowledge about the kind of elements presents in a sample and their relative

47
proportions, as determined, for instance, by fluorescence X-ray analysis, is essential
when using the Hanawalt approach.
The "Search Manual" index tables, which identify compounds according to the
d-values of their three strongest peaks as well as their d-spacings and intensities for a
total of eight peaks for each chemical, were used to manually compare the substances.
There is another guidebook that lists drugs alphabetically by name.
However, using a computerized automated search rather than a manual one is
increasingly quite common. It is important to keep in mind "what work should be
carried out" or "what you are going to do" while doing an automatic search using the
Hanawalt technique and automatically calculating d values from an automatic
diffractometer.
It is recognized that a variety of variables can impact the d values and their
relative intensities. For instance, if a sample contains some water molecules, the
sample may react with oxygen, water vapor, carbon dioxide, etc. in the environment,
or the sample may be received in a certain orientation. In such cases, the automated
search procedure may inadvertently match a desired sample with the reference data,
leading to an incorrect identification. As such, attention is once again highly advised.
When applying the Hanawalt approach, it is important to remember that some
experimental uncertainty is involved and that not all reference data is accurate, even if
it was recently produced. Remember that certain substances have a very similar
diffraction profile, as demonstrated by Au and Ag, Si and ZnS, a ferrite and a
compound of spinel, etc. In other words, the Hanawalt approach is quite useful for
identifying unknown substances, but it's vital to keep in mind that it only works for
relative comparisons.
When an unknown substance is a single component, the search process is
fairly simple. However, when an unknown substance is a mixture, the analysis
process becomes more challenging because the three strongest peaks in the pattern of
the unknown substance are made up of such mixed d-values.
It is reasonable to say that the Hanawalt technique can only be used to
examine a sample's maximum three components. The creation of software of the next
generation, which enables us to demonstrate a nearly equal execution of the search
operation by human eyes, may resolve this constraint in the near future.
There is no need to repeat information on the JCPDS cards that has already
been covered in other monographs, such as B.D. Cullity's Elements of X-ray
48
Diffraction, 2nd edition, Addison-Wesley, Reading Massachusetts, (1978).
Nevertheless, this chapter's Questions 4:4–4:9 help readers comprehend "how to use
the Hanawalt method for determining the structure of unknown samples." Obviously,
irrelevant diffraction data will be removed by proper sample preparation and effective
experimental setup. The following is a summary of some considerations that should
be made while utilizing the Hanawalt technique to analyze data:
1. If a powder crystalline sample's particle size is more than a few 10 m,
strong repeatability of the intensity pattern is not always verified, and it is
common to observe differences of more than a few 10% across
measurements.
2. Remember the X-ray wavelength that was utilized for the measurement
(such as Cu-Kα or Mo-Kα), since there may be changes in the relative
intensities based on the wavelength owing to anomalous dispersion effects.
3. A sample that is easily detected under the desired orientation, such as clay
minerals, may have the reverse order of the relative intensities.
4. A specific shift toward the lower angle in the peak locations is highly
likely to show up when impurities are present in a sample. (This shift often
manifests itself in the peak that is noticed at higher angles.
5. The diffraction peaks' positions are easily off from the JSPDS reference
values if the goniometer's zero point or center is discovered to be eccentric.
Slits that are not properly aligned might potentially be the cause of a
similar discrepancy.
6. Careful judgment should be used when the diffraction peak, which is not
defined by the JCPDS data, is seen. Some considerations to take into
account include impurity contamination and the existence of a phase of
solid solution or an arranged phase (super-lattice). [163].
3.2. UV-Visible Spectrophotometer:
The band between > 1019 (γ-rays) and 103 Hz (radio waves) is where the most
usable energy frequencies are found in the electromagnetic spectrum. A small portion
of the spectrum is visible, and visible light differs from other types of radiation in
terms of the frequency and energy of its photons. Numerous compounds, including a
large number of organic molecules, regularly absorb light in the UV-Vis range
(between 180 and 800 nm). � → �∗ and � → �∗ transitions need higher energy and are

49
associated with absorption in the UV region, whereas � → �∗ transition is associated
with absorption in the UV-Vis area. The primary energy changes occur at the
electronic level, although they can also occur at vibrational quantum levels.
The chromophore is the region of the molecule where the electronic changes take
place. Derivatization (Schiff base creation, complexation processes, enzymatic and
other catalytic reactions, azodyes derivatization, charge transfer complexation, ion-
pair analysis, solid phase derivatization) can be employed when the molecule is
transparent in this area. Derivatization increases the UV-Vis methodology's sensitivity
and, occasionally, selectivity. The same thing occurs when sample
preconcentration/enrichment (based on solvent, sorbent, or membrane extraction
extraction) is applied.
The method of measuring the attenuation of electromagnetic radiation by an
absorbing material is called ultraviolet and visible absorption spectrophotometry. The
spectral range of this radiation, which is around 190–800 nm, varies along with the
energy ranges and the kind of excitation from other adjacent areas. This attenuation is
caused by interferences, reflection, scattering, or absorption. However, precise
attenuation measurements may be made by just measuring the absorbance. Within
certain bounds, the absorbance is inversely correlated with the concentration of the
target analyte and the length of the light's path through the sample during irradiation.
Beer's law is the name of this connection, which is usually expressed as � = � ×
� × �. Where A stands for absorbance, is the molar absorbance coefficient
(wavelength-dependent) in ���−1 ���−1 , b is the route length in cm, and c is the
absorber concentration in ��� �−1 , c is the relationship's unit of measurement. The
characteristics of the spectrophotometer, photodegradation of the molecules, the
presence of scattering or absorbing interferences in the sample, the presence of
fluorescent compounds in the sample, interactions between the analyte and the solvent,
and the pH can all have an impact on this linear relationship. [164].

50
Chapter 04
Experimental
Section

51
 4. Synthesis method:
In synthesis of this mullite type BFO we followed Sol-Gel synthesis method.
4.1. Material Required:
Bismuth nitrate (��(��3 )3 5�2 �), Iron nitrate (��(��3 )3 9�2 �), Yttrium nitrate
(�(��3 )3 6�2 �), Ammonium hepta-molybdate ((��4 )6 ��7�24 ), Ethylenediamine
acetic acid (EDTA), Ethylene Glycol (solvent), Nitric acid.

Figure 16: Solution preparation.

4.2. Synthesis Experiment:

To prepare ��2 ��4−�+� �� ��� �9 two solutions were prepared in which one was
pure mullite type BFO ( ��2 ��4 �9 ) was prepared labelled as C1, and other was the
solution with dopants up to 3% each being yttrium and molybdenum
(��2 ��3.88 �0.6 ��0.6 �9 ) labelled as C2 with EDTA by Sol-Gel synthesis method. To
prepare these solutions at first stock solution of Bismuth nitrate ( ��(��3 )3 5�2 � )
and Iron nitrate (��(��3 )3 9�2 �) of 0.2 molarity were prepared in ethylene glycol
and magnetically stirred for 90 minutes, at 40°C for first 25 minutes. Then 100ml
solution of each salt was mixed together in a breaker and equimolar solution of EDTA
was and the solution was again magnetically stirred. Preparation of other solution was
quite different from C1. A known amount of iron nitrate (88ml) from stock solution
was taken into beaker and equimolar solutions of yttrium nitrate and ammonium
hepta-molybdate were added into it, then bismuth nitrate 100ml was added into it and
stirred. After this, 0.2 molar of equimolar solution of EDTA in equal volume was
added and then placed on hot plate and magnetically stirred to prepare

52
��2 ��3.88 �0.6 ��0.6 �9 . Moreover, 12ml ���3 was added to the solution to maintain
the pH of the solution at 2.
To obtain gel, all solutions were placed in sterilizer oven for 48 hours for 110°C
until gel forms. For the formation of nanoparticles, gel was calcined at 550°C for 3
hours in muffled furnace. After these nanoparticles were obtained and material was
crushed to fine powder.

Figure 17: Synthesis Method.

4.3. Photocatalytic experiment:

Photocatalytic degradation experiment was conducted on multiple organic dyes,
crystal violet, methylene blue, 4-nitrophenole, methyl violet, rhodamine B, and
Eriochrome black-T.
10ppm solutions of each dye were prepared at neutral pH and 30ml solution
was taken into a flask where 20mg of prepared catalyst after proper dose optimization
was added into 30ml, 10ppm solution of respective dyes. Then the solution with
photocatalyst was kept in photocatalytic chamber in the dark for 1 hour to maintain
adsorption and desorption equilibrium and the first reading was taken in using UV-
Visible spectrophotometer. Later on, 200-watt yellow light bulb was turned on that
emits visible light radiations and solutions were shake in the presence of this visible
light. After this it was centrifuged for 5 minutes to set the particles down. The device
used to check out the absorbance of solution and degradation of dye was CECILE
CE7200 UV-visible spectrophotometer. To calculate the percentage adsorption after

53
placing the solution dark following formula is used:
�0−��
���������� ���������� = × 100
�0

Or in the form of absorption as both absorption and concentration are directly

�0 −��
proportional to each other: ���������� ���������� =
�0
× 100

54
Chapter 05
Results and
Discussions

55
 5. Results and Discussions:
5.1. X-Ray Diffraction Technique:

The graph of XRD is drawn between intensity and 2Ɵ and it is because that the
between incident rays and measuring device is 2 degrees.
According to JCPDS
card no. 25-0090 the
peaks at 28, 29, 31, 34,
39, 44, 46, and 55
degrees represents the
rhombohedral structure
of pure mullite type BFO,
other peaks represent the
minor number of
impurities present in the
Figure 18 : XRD Graph of pure mullite type BFO. powder of prepared
material.

In this graph it can

also be seen that it
follows the same pattern
as above XRD graph and
this shows us that this
has the same
rhombohedral geometry
but it can be seen that the
peak intensity 45 degrees
is high as compared to
Figure 19 : XRD Graph of Y-Mo Co-doped mullite type BFO.
the graph of pure sample
it is due to the presence of dopants added in it.

56
 5.2. Photocatalytic activity:
Photocatalytic activity of the catalyst was studied in the presence of 200-watt
tungsten bulb in a photocatalytic chamber. Two prepared sample one being the pure
mullite type BFO and other being Y-Mo co-doped mullite type BFO were taken to
check the degradation of dyes. Photocatalytic degradation experiment was applied
over multiple cationic dyes.
5.2.1. Crystal Violet:

Figure 20: (a) Degradation profile of pure mullite type BFO over Crystal violet, (b) Percentage degradation of
mullite type BFO over Crystal violet, (c) Degradation rate and rate constant of Crystal Violet by mullite type BFO,
(d) Order of reaction for degradation of Crystal Violet with mullite type BFO.

In the above figure the degradation profile of pure mullite type BFO over
crystal violet dye is provided. Each reading was taken after 15 minutes of visible light
irradiation except the first reading was taken after 1 hour in dark. It can be seen from
above graphs that there has been an effective decrease in concentration of crystal
violet dye in the solution with the passage of time. From degradation profile it is
cleared that material showed an adsorption of about 60% and the final degradation of
82% after 1 hour and 45 minutes, giving a synergistic effect of adsorption and

57
photocatalytic degradation. The rate constant observed during this reaction was
0.0172 per minute. After this time there was no decrease in concentration of crystal
violet as it was the maximum degradation possible by the pure sample prepared.

Figure 21: (a) Degradation profile of Crystal Violet with Y-Mo co-doped mullite type BFO, (b) Percentage
degradation of Crystal Violet by Y-Mo co-doped mullite type BFO, (c) Degradation rate and rate constant of
Crystal Violet with Y-Mo co-doped mullite type BFO, (d) Order of reaction.

In the above graphs degradation profile, percentage degradation, degradation

rate, and order of reaction of crystal violet dye with Y-Mo co-doped mullite type BFO
were given. First reading was taken after placing 10ppm solution of dye in dark with
prepared photocatalyst to maintain the adsorption and desorption equilibrium and
concentration was measured with the help of UV-visible spectrophotometer.
Degradation profile shows effective decrease in the concentration of dye with the
passage of time there is an impressive increase in adsorption crystal violet dye as
compared to pure mullite type BFO and now the adsorption is about 90%. Solution
concentration was checked after 15 minutes of irradiation from L1 to L6 and there
have been a noticeable decease in the concentration of dye giving out an efficiency of
98%, with a rate constant of 0.02272 per minute. The total time given was 2 hours and

58
30 minutes for this efficient degradation of crystal violet dye and after this there was
no decrease in concentration was observed.
5.2.2. Methylene Blue:

Figure 22: (a) Degradation profile of Methylene Blue with pure mullite type BFO, (b) Percentage degradation of
Methylene Blue with pure mullite type BFO, (c) Degradation rate and rate constant of Methylene Blue with pure
mullite type BFO, (d) Order of reaction.

It can be seen in above figure from degradation profile of methylene blue dye
with pure mullite type BFO that there is an adsorption of about 28% and after that
readings were taken every 15 minutes of irradiation time and maximum degradation
of around 31% is observable after total time of 1 hour 45 minutes of reaction time.
Degradation in value of absorbance was only observed from L1 to L3 later on there
was no decrease in the value of absorbance that indicates the maximum degradation
limit of photocatalyst (Pure mullite type BFO ( ��2 ��4 �9 ) ). From the graph of
degradation rate, it can be seen that there is a rate constant of 0.00375 per minute.

59
Figure 23: (a) Degradation profile of Methylene Blue with Y-Mo co-doped ��2 ��4�9 , (b) Percentage degradation
of Methylene Blue Y-Mo co-doped ��2 ��4�9 , (c) Degradation rate or rate constant of Methylene Blue with Y-Mo
co-doped ��2 ��4�9, (d) Order of reaction.

In above figure degradation profile of methylene blue dye with Y-Mo co-
doped ��2��4 �9 is given. It can be noticed that there is an effective decrease in the
concentration methylene blue dye with the passage of time. At first the solution was
kept in dark and then absorbance was taken after an irradiation time of 15 minutes for
each reading. It is observable in the percentage degradation graph that there is an
adsorption of around 82% after keeping the solution in dark for 1 hour and then
moving from L1 to L7 it is noticeable that the percentage degradation of methylene
blue increases a lot which means the absorbance of solution decreases with time. And
after 2 hours and 45 minutes the percentage degradation observed was above 98%.
After L7 at 98% degradation there was no decrease in the absorbance of solution
observed which indicates the maximum attainable degradation efficiency of
photocatalyst. The rate constant for this reaction can be observed in degradation rate
graph where it is 0.01888 per minute.

60
 5.2.3. Methyl Violet:

Figure 24: (a) Degradation profile of Methyl Violet with ��2��4 �9 , (b) Degradation profile of Methyl Violet with
Y-Mo co-doped ��2��4 �9 .

It can be seen in the above figure that there is only adsorption around 42% of
crystal violet dye with pure ��2 ��4 �9 , and there is an effective increase in the activity
of photocatalyst after doping in the form of Y-Mo co-doped ��2 ��4 �9 . The
adsorption after 1 hour of placing the reaction mixture in dark is around 91% and after
the reaction time of 2 hours and 45 minutes the efficiency observed is 99%. There was
no observed degradation of methyl violet dye by pure
material.

Figure 25: (a) Degradation profile of Methyl Violet by Y-Mo co-doped ��2��4 �9 , (b) Percentage degradation of
Methyl Violet by Y-Mo co-doped ��2 ��4�9 , (c) Degradation rate or rate constant of Methyl Violet by Y-Mo co-
doped ��2��4�9, (d) Order of reaction.

61
 It can be observed from the above figure there is an efficient decrease in the
absorbance of dye solution with photocatalyst that is Y-Mo co-doped ��2 ��4 �9 . In
dark it shows about 91% adsorption and after that from L1 to L7 readings were taken
after an irradiation time of 15 minutes and absorption value of methyl violet solution
decreases as irradiation time progresses. The final observed degradation is around
99% after time of 2 hours and 45 minutes. After this there was no decrease in
concentration it became constant that shows maximum degradation limit of catalyst.
The rate constant for this whole process is 0.0229 per minute.
5.2.4. Rhodamine B:
In the side figure degradation profile
of rhodamine b is given and it can be
seen that there is only adsorption of dye
with pure mullite type BFO and there is
no degradation observed in light as value
of absorbance remains the same as in
dark. After placing the reaction in dark
for 1 hour the observed adsorption is
Figure 26: Degradation profile of Rhodamine B with pure
mullite type BFO. 18% with no degradation of dye.
Figure 27:
(a)

Figure 27: Degradation profile of Rhodamine B with Degradation

pure mullite type BFO. profile of
Rhodamine
B with Y-Mo
co-doped
mullite type
BFO, (b)
Percentage
degradation
of
Rhodamine
B with Y-Mo
co-doped
mullite type
BFO, ©
Degradation
rate and rate constant of Rhodamine B with Y-Mo co-doped BFO, (d) Reaction Order.

62
 In above figure a small amount of degradation is observed in the presence of
light and irradiation time of 15 minutes. And after total time of 1 hour and 15 minutes
we got around 19% of degradation of rhodamine B with Y-Mo co-doped mullite type
BFO. Degradation profile and percentage degradation in figure indicates it very well.
This all reaction happened with a rate constant of 0.00259 per minute.
5.2.5. 4-Nitrophenol:
4-Nitrophenol
shows degradation in
two steps in the first
step it is in the form of
phenol with a lambda
max around 318 nm,
and during degradation
process this phenol
changes into phenolate
ion which has a
lambda max around
Figure 28: Degradation profile of 4-Nitrophenol.
401 nm. In the
degradation profile it can be seen that the peak around 318 nm is decreasing with time.
This decrease in the peak shows that 4-nitrophenol is being degraded to phenolate ion.
In 2 hours, the value of 4-nitrophenol peak decreased so efficiently. The value of
absorbance of 4-nitrophenol ion decreased by 83% with Y-Mo co-doped mullite type
BFO.

63
Chapter 06
Conclusion

64
6. Conclusion:
Mullite type BFO nanoparticles with proper doping of Yttrium and Molybdenum
are successfully synthesized that is confirmed by the XRD technique. More over these
nanoparticles gave impressive and efficient degradation of cationic dyes that are more
hazardous to human and animal health as compared to any other dye. Y-Mo co-doped
mullite type BFO gave impressive efficiency over the degradation of Crystal Violet,
Methylene Blue and Methyl Violet, of 98%, 98%, and 99%. These nanoparticles also
managed to degrade Rhodamine B dye up to 19% and 4-nitrophenol is also
successfully converted into phenolate ion that needs a reducing agent for its
degradation.

65
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