Fabrication and Characterization of CuBi2O4/TiO2

Heterojunction Piezocatalyst for Effective Ultrasonic

Degradation of Textile Dye

M.M.F RUMANA

This dissertation is submitted to the Department of Chemical Sciences

Faculty of Applied Sciences of the South-Eastern University of Sri Lanka
In partial fulfillment of the awards of the Degree of Bachelor of Science,
Special in Chemistry

Department of Chemical sciences

Faculty of Applied Sciences
South Eastern University of Sri Lanka
Sammanthurai

April 2021.
 i

DECLARATION

This dissertation is my original work and has not been submitted previously for a degree at this
or any other university/ institute. To the best of my knowledge, it does not contain any material
published or written by another person, except acknowledged in the text.

Author’s name: M.M.F RUMANA

Date: ………………………. Signature: ………………………………

 ii

CERTIFICATION

This is to certify that this dissertation is based on the work carried by Ms. M.M.F Rumana
under my supervision. The dissertation has been prepared according to the format stipulated
and is of acceptable standard.

Certified by

Supervisor Name: Dr. A.Manjceevan

Date: …………………….. Signature: ……………...

 iii

ACKNOWLEDGEMENTS

I would like to express my deepest gratitude and appreciation to my supervisor, Dr. A

Manjceevan, Lecturer, Department of Chemistry, Faculty of Sciences, University of Jaffna,
Sri Lanka for suggesting this research and for his continuous encouragement and support while
supervising this research work.

My deepest thanks to Dr. M.H Haroon, Senior Lecturer, Head of the Department of Chemical
Sciences who has always been sincere and helpful to carry out my research successfully.

I would also like to thank the Head of the Department of Biological Sciences, Faculty of
Applied Sciences for providing permission to carry out my project work in the Biology
laboratory.

Also, I would like to express my sincere appreciation to Dr. UL Zainudeen, Dean of Faculty
of Applied Sciences for permitting to carry out my research and for his constant
encouragements.

Furthermore, I owe my greatest thanks to Mr. AL Fairooz (Technical Officer) and other staffs
of the chemistry laboratory and Mrs. ILF. Shahitha (Technical Officer) and other staffs of
biology laboratory for their supports innumerous ways and provide lab facilities.

I also acknowledge with a deep sense of reverence, my gratitude towards my parents and
members of my family, who has always supported me morally as well as economically.

Finally, I would like to thank all the academic and non-academic staff of the Faculty of
Applied Science, South Eastern University of Sri Lanka, and my colleagues for their helps in
numerous ways to complete this work successfully.
 iv

ABSTRACT

Removal of hazardous pollutants by piezocatalytic degradation process is an eco-friendly

method and alternative to the conventional methods such as chemical and physical process.
Rhodamine B is one of the azo dye discharged from the garment industry and mixed with water
reservoirs in huge concentration. In this study, 𝐶𝑢𝐵𝑖2 𝑂4 /TiO2 composite, TiO2 and 𝐶𝑢𝐵𝑖2 𝑂4
materials have been prepared and the piezocatalytic degradation ability of such materials
evaluated by using Rhodamine B azo dye, under ultrasound irradiation. 𝐶𝑢𝐵𝑖2 𝑂4 / TiO2
nanocomposite were synthesized by a facile sol-gel method using copper bismuth pentahydrate
and titanium isopropoxide as a precursor with different molar ratios. The piezocatalytic activity
of 𝐶𝑢𝐵𝑖2 𝑂4 / TiO2 nanocomposite toward the degradation of Rhodamine B was investigated.
Beside of other composites in the acidic medium, almost 98.4 % of Rhodamine B was degraded
in the presence of nanocomposite mixture, 𝐶𝑢𝐵𝑖2 𝑂4 and TiO2 in the ratio of 1:10. This is due
to the formation of nanorod increase the piezocatalytic efficiency.

Key words: 𝐶𝑢𝐵𝑖2 𝑂4 / TiO2 nanocomposite, sol-gel, piezocatalytic degradation, Rhodamine B.

 v

TABLE OF CONTENTS

DECLARATION .............................................................................................................................. i
CERTIFICATION .......................................................................................................................... ii
ACKNOWLEDGEMENTS............................................................................................................ iii
ABSTRACT .................................................................................................................................... iv
LIST OF TABLES......................................................................................................................... vii
LIST OF FIGURES...................................................................................................................... viii
LIST OF ABBREVIATIONS......................................................................................................... ix
LIST OF SYMBOLS ....................................................................................................................... x

CHAPTER 01 INTRODUCTION ................................................................................................. 1

1.1 Dyes ........................................................................................................................................ 3
1.1.1 Natural dyes ...................................................................................................................... 4
1.1.2 Synthetic dyes ................................................................................................................... 4
1.1.3 Rhodamine B .................................................................................................................... 6
1.1.4 Methods of Dye Removal .................................................................................................. 7
1.1.5 Advanced oxidation process (AOP) ................................................................................... 9
1.2 Semiconductor ..................................................................................................................... 10
1.2.1 Semiconductor Nano particles ......................................................................................... 10
1.2.2 Heterojunction ................................................................................................................ 10
1.2.3 Photocatalysis ................................................................................................................. 10
1.3 Piezoelectric effect................................................................................................................ 12
1.3.1 Types of piezoelectric materials ...................................................................................... 13
1.3.2 Applications of the piezoelectric materials / piezoelectric effect....................................... 14
1.3.3 Piezoelectric in chemical catalysis (PZEC) ...................................................................... 14
1.3.4 Piezocatalytic degradation of organic pollutants .............................................................. 15
1.3.5 Copper bismuth oxide as a semiconductor ....................................................................... 17
1.3.6 Titanium dioxide as a semiconductor ............................................................................... 17
1.3.7 p-CuBi2O4/n-TiO2 nancomposites .................................................................................... 18

CHAPTER-02 EXPERIMENTAL DETAILS ............................................................................. 19

2.1 Materials .............................................................................................................................. 19
2.2 Apparatus............................................................................................................................. 19
2.3 Sample preparation ............................................................................................................. 19
2.3.1 Preparation of CuBi2O4 nanoparticle .............................................................................. 19
 vi

2.3.2 Preparation of CuBi2O4/TiO2 nanocomposite materials .................................................... 20

2.3.3 Preparation of TiO2 bare nanomaterial ............................................................................. 22
2.3.4 Characterization of the CuBi2O4/TiO2 nanocomposite materials ....................................... 22
2.3.5 Piezocatalytic degradation of dye .................................................................................... 22

CHAPTER-03 RESULTS AND DISCUSSIONS ......................................................................... 25

3.1 Prepared CuBi2O4/TiO2 nanocomposite materials ............................................................. 25
3.2 Piezocatalytic activities of CuBi2O4/TiO2 nanocomposite materials ................................... 26
3.3 The influencing factors in piezocatalytic degradation process ........................................... 30
3.3.1 Effect of ultrasonic catalyst dosage.................................................................................. 31
3.3.2 Effect of ultrasonic irradiation time ................................................................................. 31
3.3.3 Effect of Initial pH .......................................................................................................... 31
3.3.4 Effect of initial dye concentration .................................................................................... 32
3.3.5 Effect of Reaction temperature ........................................................................................ 33
3.3.6 Effect of Formation of Hydrogen Peroxide during Ultrasonic irradiation. ........................ 33

CHAPTER-04 CONCLUTION.................................................................................................... 35
REFERENCES .............................................................................................................................. 36
 vii

LIST OF TABLES

Table 1: Molar ratios and amount of reactants used for synthesis of nancomposites .......................... 21
 viii

LIST OF FIGURES

Figure 1: Water usage of different field.............................................................................................. 2

Figure 2: Application of dyes............................................................................................................. 3

Figure 3: Different types of xanthene dyes (Saeed, Shabir, & Shehzadi, 2015) ................................... 6

Figure 4: Physical properties of Rhodamine-B ................................................................................... 7

Figure 5: Treatment methods for textile waste waster ......................................................................... 8

Figure 6: The relationship between the piezoelectric, pyroelectric, ferroelectric ............................... 13

Figure 7: Piezocatalytic degradation of Rhodamine-B ...................................................................... 16

Figure 8: Scheme of the pure CuBi2O4 nanoparticle preparation method ......................................... 20

Figure 9: Sonicator, Homemade reaction system to maintain dark condition and Genesys 10S UV-

Visible spectrophotometer ............................................................................................................... 23

Figure 10: Prepared CuBi2O4/TiO2 nanocomposite, pure Cubi2O4 and pure TiO2.......................... 25

Figure 11: Absorption spectra showing piezocatalytic degradation of Rhodamine-B dye .................. 27

Figure 12: (A) Piezocatalytic degradation of Rhodamine-B dye with respect to initial dye

concentration with the increasing time in the presence of different ratio of CuBi2O4/TiO2

nancomposite under Ultrasonic irradiation (B) Graph of –ln(At/A0) vs irradiation time for different

CuBi2O4/TiO2 nancomposite under Ultrasonic irradiation .............................................................. 28

Figure 13: (A) Rate constants of different ratio of CuBi2O4/TiO2 nanocomposite under Ultrasonic

irradiation (B) Comparison of Comparison of degradation efficiency of different CuBi2O4/TiO2

nancomposite after irradiation for 3 hours ........................................................................................ 29

Figure 14: p–n junction formation model and the schematic ............................................................. 30

Figure 15: (A) Changes in the absorbance with time, during the degradation of Rhodamine-B. (b):

Effect of time on sonocatalytic degradation of Rhodamine-B. (Initial dye concentration = 25 mg/L,

Catalyst loading = 200 mg, Ultrasonic frequency = 30 kHz, pH= 6.5 ............................................... 34

Figure 16: Effect of (A) CuBi2O4/TiO2 nanocomposite added amount, (B) pH, (C) Temperature and

(D) initial concentration on sonocatalytic degradation of Rhodamine-B. .......................................... 34

 ix

LIST OF ABBREVIATIONS

UV Ultraviolet

PZEC Piezoelectric catalysis

AOP Advanced Oxidation Process

VB Valance band

CB Conduction band

OH. Hydroxide radical

O.2- Superoxide radical

H2O2 Hydrogen peroxide

EtOH Ethanol

Rh-B Rhodamine-B

HOMO Highest Occupied Molecular Orbital

LUMO Lowest Unoccupied Molecular Orbital

Photon energy
ℎ𝜐
Scanning Electron Microscope
SEM
Transmission Electron Microscope
TEM

XRD X-ray Diffraction

Fourier-transform infrared spectroscopy

FTIR
Diffuse Reflection Spectroscopy
DRS

Eg Band gap energy

Np Nanoparticles

Fp Fine particles
 x

LIST OF SYMBOLS

oC Degree Celsius

h Hours

Mins Minutes

G Grams

ml Milliliter

nm Nanometer

% Percentage

Rpm Rotations per minute

eV Electric volt

W Watts

° Degree

𝑐𝑚 Centimeter

A Amperes

F Faraday

V Voltage

Mol Moles

𝑑𝑚 Decimeter
 CHAPTER 01

INTRODUCTION

In any ecosystem makes water is an essential component of sustaining life, as it is the

fundamental building block that supports the biochemistry of all life in this world (Brenner,
Laurie, 2021). However, water pollution problems pose escalating threat to the earth’s
ecosystem. Because a fast development in industrial era improves human living standard but
at the same time it plays a major role in earth pollution. Water pollution means, the release of
the excess amount of substances or harmful substances into water bodies such as groundwater,
streams, rivers, and oceans to where the substances interfere with the quality of the water.

Usually, most Industrial wastewaters are discarded directly or indirectly into environmental
water bodies without further treatment. Various aqueous pollutants such as pathogenic
microorganisms, biodegradable wastes, plant nutrients (phosphates and nitrates), dyes, heat,
sediments, radioactive substances, hazardous and toxic chemicals, etc. pollute the water bodies
and deteriorate the quality of water Dwivedi (2017).

1
Dyes are being increasingly used in several industries worldwide. Including textile, chemicals,
pharmaceuticals, foods, cosmetics, and laboratories. The textile industry is the most polluting among
all industries. The discharge of colored wastewater from such industries creates serious problems for
the environment.(K. Singh, Kumar, & Srivastava, 2017; Zabłocka-Godlewska, Przystaś, & Grabińska-
Sota, 2014). Many different types of dyes consisting of varied chemical compounds are
used in production, depending on the type of textile or product being dyed.

Figure 1: Water usage of different field

There are three basic types of water pollution based on source and impact of pollution.

1. Point source pollution.

2. Nonpoint source pollution.
3. Trans-boundary pollution.

Point source pollution.

When a single source produced the contaminants and affects a specific area. It is called point
source pollution. Examples include wastewater discharged legally or illegally by a
manufacturer, oil refinery, or wastewater treatment facility, as well as contamination from
leaking septic systems, chemical and oil spills, and illegal dumping., this type of water
pollution relatively easy to remediate itself.

Nonpoint source

Multiple sources have produced pollutants in water bodies and affect both the immediate area
and close area. It is known as Nonpoint source pollution. A good example of this sort of
pollution is runoff from meadows or farmland. Compared to the point source, the identification
and regulation of non-point source pollution are often more complex.(X. Liu et al., 2015)

2
Trans-boundary water pollution

Trans - boundary water pollution is the most widespread and affects large areas of the
environment. Radiation from nuclear waste is an example of trans-boundary pollution. This
kind of water pollution is typically the most complex to treat .

1.1 Dyes

Dyes are used mainly in the production of consumer products, as well as paints, textiles,
printing inks, paper, and plastics. They add color and patterns to materials. Natural dyes
extracted from the fruits. Vegetables and flowers are used color fabrics and different materials
Kant (2012). These dyes were replaced by chemical dyes that bond with the fabric, providing
and holding richer color throughout laundry and exposure.

Figure 2: Application of dyes

The dyestuff lost in the textile trade poses a serious problem to wastewater sources.The textile
trade produces high levels of dye and floating solids. This discharge of effluents produces
compounds that are toxic to aquatic organisms (Verma, Dash, & Bhunia, 2012). Decolorization
and detoxification of industrial dye waste is the most important aspect and is of great concern
to meeting environmental regulations.

3
There are two types of dyes namely natural dyes and synthetic dyes.

1.1.1 Natural dyes

Natural dyes are obtained from vegetables, such as plants, trees, and lichens, with very little
from insects. Alizarin and indigo, hold great importance among all-natural dyes (Ferreira,
Hulme, McNab, & Quye, 2004; Křížová, 2015). Alizarin is a red dye extracted from the roots
of the madder plant, Rubia tinctorium, indigo is a well-known blue color and was obtained by
fermenting the leaves of plants. Both alizarin and indigo have very good dyeing properties,
and indigo is mainly used for dyeing denim, although natural indigo has been replaced by
synthetic indigo dye.
The Industrial Revolution led to the growth of the textile industry, which also increased the
demand for cost-effective, readily available, and easy-to-apply dyes. As a result, the economic
limitations of harnessing natural dyes such as the vast area of land required for their production
and the consistency and durability of the color they produce have been revealed.

1.1.2 Synthetic dyes

Synthetic dyes, which are manufactured from organic and inorganic molecules, are playing
more and more important roles in our fashionable life with applications primarily in both fields
textile and paint industry. Synthetic dyes are sometimes referred to as "coal tar dyes", as they
are made from coal tar (Asim Kumar & Chowdhury, 2018).

In 1876, German chemist Otto Witt suggested that dyes contain sequences of conjugated
double bonds: X = C - C = C - C = C―…, where X is carbon, oxygen, or nitrogen. The
conjugate systems of benzene rings carrying simple unsaturated groups (for example, NO2, N
= N―, C = O), which he called chromophores, and polar groups (for example, -NH2, -OH, –
CO2H, NH3 and –SO3H), which he called auxochromes(Christie, 2014), (Benkhaya, M' rabet,
and El Harfi (2020). Acid dye, basic dye, reactive dye, direct dye, sulfur dye, disperse dye are
types of synthetic dyes.
1.1.2.1 Disperse dyes
Most disperse dyes are based on azo structures, However, violet and blue are most often
obtained from anthraquinone derivatives(Shamey, 2009). These dyes are non-ionic, and thus
insoluble or slightly soluble in water, and can be applied to hydrophobic fibers(Clark, 2011),
acetate, cellulose, cellulose acetate, nylon, polyamide, polyester, polyester, cotton and plastics
(Hassan, Awwad, & Aboterika, 2009). Examples of disperse dye are Disperse blue 27,
Dispersed Red 4.

4
1.1.2.3 Direct dyes
In 1884 first direct dye (Congo red), was discovered(Marzec, 2014)(R.L. Allen,2013). Direct
dye’s chromophoric group includes azo, Stibene, Oxazin and Phthalocyanine, with some
Thiazole and Copper complex (Chattopadhyay, 2011). These are water-soluble dyes that are
used on, coloring paper products, cotton, leather, wool, silk and nylon (Katheresan, Kansedo,
& Lau, 2018). When washing these dyes have appeared in solid form. Example of direct dye
is Direct Orange 26.

1.1.2.4 Reactive dyes

These dyes are the second largest class of dyes(Ghiyasiyan-Arani, Masjedi-Arani, & Salavati-
Niasari, 2016),(Rauf & Hisaindee, 2013).Reactive dyes have become very popular due to their
high wet fastness, brilliance and color gamut.Reactive dyes are used for dyeing cellulosic
fibers, in addition to a small percentage of silk and wool fibers(Shankarling, Deshmukh, &
Joglekar, 2017). About 50% of these dyes are lost in their hydrolyzed and unfixed form during
the washing process. An Example of reactive dyes Reactive Blue 19, Reactive Red 1

1.1.2.5 Vat dye

Vat dye is known for better color fastness, usually excellent wet and light fastness properties.
(Khatri et al., 2017). Vat dyes are mainly soluble in hot water and some are soluble in the
presence of little Na2CO3.It can be applied to cotton, cellulosic fibers, polyester-cotton, rayon
and wool. An example of Vat dye is Vat Blue 4 (A. Gürses et al., Dyes and Pigments, 2016).

1.1.2.6 Basic dyes

Basic (cationic) dyes are very bright but have poor color fastness. This is applied in a dye bath
with acidic conditions. Acetic acid is usually added to the dye bath to help the dye absorb into
fibers.(Jia et al., 2009).Basic dyes have a quaternary amine group. Sometimes, a positively
charged oxygen or sulfur atom can replace the nitrogen atom. When dissolved in water, basic
dyes will produce colored cations in the solution. These cations are electrically attracted to
substrates of negative charge. These dyes are usually applied to wool, silk, acrylic, paper and
nylon substrates, but they can also be used on some modified polyester substrates. (Katheresan
et al., 2018)
Examples of a localized charge dye (Basic Blue 22), delocalized charge dye (Basic Violet 2)
and Methylene Blue are basic dye.
1.1.2.7 Acid dye
Acid (anionic) dyes are soluble in water. It can be applied to wool, silk, nylon, modified rayon,
modified acrylic and polyester fibers, textile materials, medicine, printing, leather and paper
due to its bright color and high solubility (Ji Wu et al., 2020).The molecule has one or more
acidic functional groups (SO3H sulphonic acid or and COOH carboxylic acid).Examples of
acid dye are Alizarine Pure Blue B, Acid red 88, etc.

5
1.1.2.8 Sulfur Dyes
Sulfur dyes are a type of vat dye. Which is insoluble in water but becomes soluble in sodium
polysulfide. sulfur dyes have become very popular due to their excellent color fastness in
water, low cost and ease of application(Benkhaya et al., 2020). Dark shades-black, brown,
navy blue-are available colors of sulfur dyes. They are susceptible to damage by chlorine
bleaches .Sulfur dyes can be used for dyeing cellulosic, such as heavyweight cotton and viscose
rayon.

An Example of sulfur dye is Sulfur Black 1 (Katheresan et al., 2018).

1.1.2.9 Xanthene dyes

The importance of xanthene dye is due to a wide range of biological and pharmacological
properties such as bactericidal and anti-inflammatory activity(Saeed et al., 2015).

Chromophores of Xanthene dyes are xanthylium or di‐benzo‐g‐pyran nucleus with amino or

hydroxyl group meta to the oxygen. They are used as dyes for paper, paints, textiles, anticancer
agents, inks, antibacterial, insecticides, biomarkers, and stains.
Xanthene cationic and other anionic dyes are effective fluorescent dyes. Their fluorescent
colors are controlled by functional groups of the xanthene moiety. An example of red
fluorescent dye is cationic dyes of Rhodamine B with a dialkylamino group and green
fluorescent dye is an anionic dye of eosin.(Saeed et al., 2015)

Figure 3: Different types of xanthene dyes (Saeed, Shabir, & Shehzadi, 2015)

1.1.3 Rhodamine B
Rhodamine B is commercially the most important aminoxanthenes.It is a reddish violet colored
synthetic alkaline dye. Which is belongs to the class of xanthene dye. This is denoted by Rh-
B. It is usually synthesized by the condensation of two moles of m-diethylaminophenol with
phthalic anhydride ("<wight2000.pdf>,"). This dye consists carboxylic acid and amine group.
Commercially useful dyes are yields by Esterification of the carboxyl group. If Rhodamine B
is esterified with ethyl chloride or ethanol at 160–170◦C under pressure, Basic Violet 11 forms.

6
Rhodamine B (Rh-B) is widely used in industrial purposes, such as printing and dyeing in
textile, paper, paints, leathers etc.(Kaur & Kaur, 2014) However, the organic dyes will cause
serious biological and environmental problems, even capable of irritating, for the skin and eyes
and is suspected to be carcinogenic and mutagenic.(Merouani, Hamdaoui, Saoudi, & Chiha,
2010).

Common name Rhodamine-B

IUPAC name [9-(2-carboxyphenyl)-6-diethylamino-

3xanthenylidene] diethylammonium
chloride

Molecular formula C28H31ClN2O3

Molecular weight 479.02 gmol-1

Color Reddish violet

Figure 4: Physical properties of Rhodamine-B

1.1.4 Methods of Dye Removal

Water pollution is one of the biggest and most important problems of the modern world.
Phytonutrients, dyes, heat, sediments and etc are polluting water bodies. Among these, dyes
are mainly involved in water pollution because a very small amount of synthetic dyes present
in the water causes serious problems with the water quality. Thus, the dye containing the
wastewater must be effectively removed by the physical, chemical as well as biological process
to prevent the harmful effect on the environment. The main purpose of the physico-chemical
processes is to remove undissolved chemicals and particulate matter present in waste water(K.
Singh et al., 2017).

7
 Figure 5: Treatment methods for textile waste waster

1.1.4.1 Biological Methods

When compared to physical and chemical processes biological treatment is most cost effective
and environmentally friendly. (P. Singh, Iyengar, & Pandey, 2012).
When biological treatment process organic pollutants undergo complete mineralization such
as fungal decolorization, microbial decomposition and adsorption of microbial biomass (living
or dead) and final products of mineralization are non-toxic. However, biological methods
cannot be applied to all types of dye waste water because modern dyes are more stable and
most industrial dyes are toxic to microorganisms.(Forgacs, Cserháti, & Oros, 2004).
1.1.4.2 Physical method
Physical treatment includes membrane filtration, coagulation ,flocculation, flotation,
adsorption, ion exchange, sedimentation, reverse osmosis and electro chemical treatments. (K.
Singh et al., 2017). But these methods are not destructive, they only transfer contamination
from one phase to another which causes a new and a different kind of pollution known as
secondary pollution (Kansal, Singh, & Sud, 2007).
1.1.4.2.1 Adsorption
Among the physical processes, adsorption technology is one of the most effective and proven
techniques. Which has potential applications in both water and wastewater treatment. In
adsorption technology, activated carbon is the most widely used as an absorbent because of its
large surface.(K. Singh et al., 2017).The rate of adsorption depends on the parameters affecting
the adsorption process such as adsorbent dosage, contact time, pH value, agitation speed, ionic
strength, temperature and initial dye concentration etc
1.1.4.2.2 Coagulation and flocculation
Coagulants are also widely used in decolorizing textile wastewater. Although this process
partially removes the color and also reduces the chemical oxygen demand. In the textile
industry, this method is usually chosen because of the more effective and less expensive
treatment processes (Golob, Vinder, & Simonic, 2005).The surfactants and dyes with high

8
molecular weights are successfully removed through coagulation / flocculation processes
followed by sedimentation, flotation and filtration respectively. This method generates large
quantities of concentrated sludge, which is not suitable for acidic, basic, and reactive dyes
effluents.
1.1.4.2.2.3 Membrane filtration

Membranes play a very important role in any advanced dye wastewater treatment system.
During this treatment, different kinds of membranes were used like microfiltration (MF),
ultrafiltration (UF), nanofiltration (NF), and reverse osmosis membranes (RO). Membrane
separations take center stage in the third stage of wastewater treatment. Membrane processes
MF and UF are used to remove large particles and biodegradable products. Membrane
bioreactors also use MF and UF membranes. RO is used to remove all organic and inorganic
impurities from water. NF membranes containing nanopores are used to isolate salt solutions
containing monovalent cations and anions from dye wastewater
(Thamaraiselvan & Noel, 2015).Factors affecting membrane contamination such as feed water
composition, membrane properties, and hydrodynamic operational conditions (Tang, Chong,
& Fane, 2011).Disadvantage of this methodology is concentrated sludge is created and ,block
the membrane and maintenances cost is very high.
1.1.4.3 Chemical methods
Chemical technology includes conventional oxidation, chlorination, bleaching, ozonation and
advanced oxidation processes with homogeneous, heterogeneous catalysts (photochemical),
Fenton’s and piezoelectric methods.
In general, chemical treatment has feasibility and efficiency, but the main disadvantage is that
the costs of chemicals are very expensive.

1.1.5 Advanced oxidation process (AOP)

A new method known as the Advanced Oxidation Process (AOP) has become a trending
technique for the degradation of dye completely and non-selectively. AOP is defined as a
process that involves in situ generation of free radicals such as hydroxyl radicals.
Piezocatalytic dye, degradation is an emerging AOP than the conventional AOP such as
hydrogen peroxide oxidation, ozonation, photolysis, Fenton process, photocatalytic oxidation,
wet-air oxidation.

9
1.2 Semiconductor

1.2.1 Semiconductor Nano particles

Semiconductors are basic structural molecular portion for a Nano particle .Natural behavior of
semiconductor is react with photons. That leads to formulating end solutions. It has two bands.
They are valance band(VB) and conducting band(CB).These bands are consist electron ,holes
that may act to provide material for degradation of dyestuff. moreover semiconductor material
contain between metallic and nonmetal properties and so they found varied applications in the
world because of this property.(Ali et al., 2017).

Semiconductor Nano particles possess wide bandgap and so showed important alteration in
their properties with bandgap calibration .Therefore, they are important materials in
photocatalysis, sonocatalysis, photo optics and electronic devices(Sun, Murray, Weller, Folks,
& Moser, 2000).

1.2.2 Heterojunction
A heterojunction, is the interface between two different semiconductors with unequal band
structure, which can result in band alignments.Typically, there are three varieties of typical
heterojunction photocatalyst, those with a straddling gap (type-I), those with a staggered gap
(type-II), and those with a broken gap (type-III).

Among them type-II heterojunction is that the most effective typical heterojunction to be used
for improving catalytic activity because of its appropriate structure for spatial separation of
electron–hole pairs. In the past many decades, huge efforts are created to prepare different
type-II heterojunction photocatalyst, like CuBi2O4/ TiO2, BiVO4/WO3, g-C3N4–WO3, g-C3N4–
BiPO4, and so on, for enhancing the photocatalytic activity. Generally, type-II heterojunction
photocatalyst exhibit smart electron–hole separation potency, wide light-absorption range, and
quick mass transfer(W. Chen et al., 2015).

1.2.3 Photocatalysis
Photocatalysis can be defined as the acceleration of a chemical reaction by irradiation of a
catalyst that select the pathway with lower activation energy for the primary reaction to occur
(Serpone & Emeline, 2002).Among the numerous environmental remediation methods, the
degradation of pollutants by means of photocatalytic semiconductor materials and renewable
solar energy has been considered as a promising green technique for the environmental
remediation(Liang, Yan, Rtimi, & Bandara, 2019).

Here photocatalytic material is semiconductor, it ought to have appropriate properties like a

energy positions and gap, wonderful photostabilty,low recombination of electron-hole pairs,
low cost and nontoxic nature(Mamba, Pulgarin, Kiwi, Bensimon, & Rtimi, 2017).

10
The photocatalytic reactions concerned in separation of electron-hole pairs. When radiation,
charge carriers are triggered and separated well. Their efficient separation is important to
participate in the reduction and oxidation reactions(Bagheri, TermehYousefi, & Do, 2017).
Even though several strategies are projected to boost the photocatalytic activities however it’s
still a difficult task to attain an efficient charge separation methods in photocatalytic systems.

In the recent past, there’s a great interest on the utilization of ferroelectric and piezoelectric
materials in photocatalysis to attain higher charge separation.(Liang et al., 2019).

Type of photocatalysis

Photocatalysis can either be homogeneous or heterogeneous.

1.2.3.1 Homogeneous photocatalysis

It is type of photocatalysis. In homogeneous photocatalysis, the reactant and photocatalysts
exist in the same phase. Destruction of atmospheric ozone is the good example for
homogeneous photocatalysis, where everything is present as gas.

1.2.3.2 Heterogeneous photocatalysis

Heterogeneous photocatalysis is a distinguished technology for the removal of water
pollutants. Photocatalysis occurring at the interfacial boundary between two phases as a solid-
liquid; solid-gas or liquid-gas.
Most common heterogeneous photocatalysts are transition metal oxides and semiconductors,
which have distinctive properties(Li & Yu, 2016). Unlike the metals that have a continuum of
electronic states, semiconductors possess a bandgap. The bandgap exist between the top of the
filled valence band and also the bottom of the vacant conduction band.
Once a semiconductor absorbs a photon with enough energy or greater than the material band
gap, the electron is excited from the valence band to the conduction band,
which results in a positive hole in the valence band. Such a photogenerated electron-hole pair
is called an exciton.The excited electron and hole will recombine and release the energy gained
from the excitation of the electron as heat.

Moreover, once the semiconductor is activated by light, an extremely reactive electron–hole

pair is made. However, this reactive pair will simply recombine. In order to delay this
recombination, different approaches are investigated, like catalyst doping or surface
modifications by the addition of varied anionic and cationic elements. The introduction of
doping elements in the catalyst structure may result in the successful reduction of activating
light frequencies from ultraviolet illumination to the visible region. This can be a really positive
facet because it permits the use of dye degradation to activate the photocatalyst (chen 2009).

11
1.3 Piezoelectric effect

In 1880 the curie brothers first observed this phenomenon of piezoelectricity or the production
of electricity by applying mechanical stress to a variety of different materials. When
piezoelectric substances are deformed, that creates the electricity it is referred to as
piezoelectricity.

Hence, the Molecular phenomenon of the piezoelectric effect can be observed at the
macroscopic level (Dahiya & Valle, 2013). Both inorganic and organic piezoelectric materials
have the capabilities to convert mechanical stress into electrical charge and vice versa. The
non-centrosymmetric nature of materials can create the piezoelectricity, which means their
structure has not centered of symmetry, which leads to forming electric dipoles within the
materials.

Most of the crystals have a symmetrical unit cell but the unit cell of piezoelectric crystal is
asymmetrical. Even though the neighboring negative charges are canceling the positive
charges due to their asymmetric arrangement of atoms in the lattice, therefore piezoelectric
crystals are electrically neutral.

However, if squeezing or stretching can create stress on the piezoelectric material,

consequently, the atoms are displaced from their original position to another position to acquire
a net electrical charge in the entire crystal. Hence, piezoelectric materials appear the net
positive and negative charges on the opposite and outer face of their crystal structure. Hence,
the collective induced polarization of charges in whole unit cells in the crystal leads to produce
the piezoelectric potential in the crystal structure. It is called piezoelectric
potential(piezopotental) The materials that possess piezoelectric properties are subcategorized
into ferroelectrics, pyroelectrics, and piezoelectric.

Furthermore, knowing the symmetry of the crystalline structure is a vital component for
understanding the origin of piezoelectricity.

Among the thirty-two point groups in the crystal structure, twenty-one of them are non-
centrosymmetric. However, concerning the piezoelectric effects, twenty point groups are
exhibit piezoelectric effects, except one. Again, among these twenty non-centrosymmetric
point groups, ten belong to polar crystals i.e. crystals that have a unique polar axis. (S.-P. Chen
et al., 2018; Kholkin, Pertsev, & Goltsev, 2008) Further, to create spontaneous polarization,
the materials must possess a unique polar axis.

There are three classification on materials possessing piezoelectric properties, which are
ferroelectrics, pyroelectrics and piezoelectric.(Kao, 2004)

12
1.3.1 Types of piezoelectric materials
1.3.1.1 Pyroelectrics
The pyroelectric crystal is formed when a change in temperature on crystals, the electric
charges can develop on the faces of the crystal perpendicular to the polar axis only. e.g., ZnO

1.3.1.2 Ferroelectrics
The ferroelectric crystal is formed when the polarization along the polar axis of the polar
crystal can be reversing the polarity of the electric field. e.g., BaTiO3

1.3.1.3 Piezoelectric
Piezoelectric materials are materials that generate an electric current during they are placed
under mechanical stress. The process of piezoelectric is also reversible since applying an
electric current to these materials, which caused the shape to change slightly in a ratio of a
maximum of 4%.

Meantime, concerning the formation of the electric field, ferroelectric materials automatically
create electric fields, whereas pyroelectric and piezoelectric materials create the electric field
by a trigger of thermal and mechanical energy respectively. Figure 1.6 below explains the
comprehensive relationship between all three classification materials.

Furthermore, when concerning drawbacks of photocatalysis, one of the major problems in

photocatalysis is their recombination of excited carriers which leads to degradation efficiency.
Therefore, effectively separated excited carriers via internal polarization of combined electric
field in a piezo / pyro / ferroelectric semiconductor offers a useful tactic to optimizing the
catalytic activity(Liang et al., 2019).

Figure 6: The relationship between the piezoelectric, pyroelectric, ferroelectric

13
In the following section, the piezoelectric field and its influence on catalytic environmental
remediation are discussed.

1.3.2 Applications of the piezoelectric materials / piezoelectric effect.

 Piezoelectric nanogenerators
 Optoelectronics
 Sensors
 Piezoelectric transducers
 Transparent conductor
 Nanogenerators
 Catalytic /photocatalytic environmental remediation.
 Piezocatalytic production of H2 by water splitting.

1.3.3 Piezoelectric in chemical catalysis (PZEC)

In 2010, First-time Hong reported the direct conversion of mechanical energy into chemical
energy or piezoelectric in chemical catalysis. (Hong, Xu, Konishi, & Li, 2010)

In PZEC, localized polarization charges are induced by mechanical stress can be used
effectively to control carrier generation, separation, transfer, and recombination by altering the
local electric field distribution near the interface of metallic semiconductor that depends on the
electronic states of the piezoelectric material and the reaction medium (German, Starr, &
Wang, 2018).

If induced voltage by the strain in the piezoelectric material is more than 3 Volts, (as opposed
to the standard hydrogen electrode (SHE)), the charge carriers in the piezoelectric material can
participate in the reduction or oxidation reactions.

The due to the piezoelectric effect, FEM (finite element method) has simulated the high
piezoelectric voltage and consequently, the charges are accumulated at the CB and VB of the
semiconductor materials, which leads to the alteration in the positions of conduction and
valence band. (Jiang Wu, Qin, & Bao, 2018). To show the high electrochemical activity of
piezoelectric semiconductor, should have a high piezoelectric coefficient and a low electrical
conductivity, and also the electrical permittivity should be improved (Starr & Wang, 2013).

Following are examples of piezoelectric catalytic materials:

 BaTiO3  MoS2 and MoSe2

 ZnO nanorods  CeO2/TiO2

 Pb(Zr0.52Ti0.48)O3 fibers  SnO2/TiO2

 BiFeO3  ZrO2/TiO2

14
1.3.4 Piezocatalytic degradation of organic pollutants
Piezoelectric materials can be used in the degradation of organic pollutants. This can be
conducted by generating a charge due to stress. Hong et al were reported that organic dye
degradation on piezoelectric catalysts by using mechanical energy. When stress is applied to
the piezoelectric materials, a non-zero dipole moment is observed in the crystal lattice, which
is caused by the variation of atomic positions, as a result, generating a charge due to stress on
the surface of the piezoelectric materials.

Further, the primary concern is that the generated free charges must have higher potential than
the standard redox potential of any redox reaction, that is to say in the case of water splitting
must have more than 1.23 eV. Besides, any charging voltage below the redox potential, will
not lead to the redox reaction.

When the strong piezoelectric effect of materials are subjected to mechanical vibration, as a
consequence, positive and negative charges generated on the surface, and also the reaction of
these negative (OH-) and positive (H+) charged ions producing strongly oxidative OH radicals,
which leads to decomposition of dyestuff.

Despite that, the generated charges are usually not in free-state and potentially cannot migrate
since they are created by the relative displacement of positive and negative charges under the
mechanical stress (still under bound state) and would not participate in the degradation process.

Besides that, if free charge carriers, needed to participate in the redox reaction, which must be
effectively separated under the influence of piezoelectric potential generated by mechanical
stress otherwise they could not participate in the redox reaction. Consequently, the
piezoelectric material holds free carrier charges due to the defect formation during their
synthesis, and although the free carrier charges significantly separate and involves in redox
reactions, under the piezoelectric potential exerted by mechanical stress (Liang et al., 2019).

The generation of free charges and their participation in redox reactions in piezocatalytic
process are given in reactions below:

Piezoelectric catalyst + Vibration Piezoelectric catalyst (e- + h+ )

Anode

4𝑒 − + 4𝐻2 𝑂 4𝑂𝐻− + 4𝑂𝐻 .

4𝑂𝐻. 2H2

Overall:

4𝑒 − + 4H2O 4𝑂𝐻− + 2H2

Cathode:

4𝑂𝐻− 4𝑒 − + 4𝑂𝐻 .

2(𝑂𝐻. + 𝑂𝐻 . ) 2H2O + 2𝑂.

15
2𝑂. O2
Overall:
4OH- 4e- + 2H2O +O2
Net reaction of water decomposition:

4𝑒 − + 4H2O 4𝑂𝐻 − + 2H2

4𝑂𝐻− 4𝑒 − + 2H2O +O2

2H2O 2H2 + O2
Dye decomposition:

𝑂𝐻 . + Dye Degradation products of dye

𝑒− + Dye Degradation products of dye

ℎ+ + Dye Degradation products of dye

According to Feng et al, the higher Piezocatalytic performances are generally expected with
one dimension or two dimensions of piezoelectric materials due to their flexed nature under
mechanical stress.

In a later period, Wu et al subsequently reported, 3D piezoelectric materials also show strong

piezoelectric properties and Piezocatalytic activity.

Finally concluded that the piezoelectric potential is caused by polarized charges. It cannot be
directly involved in the redox process. Moreover, the materials must have a Piezoelectric free
charge to be Piezocatalytic active and these free charges are separated under the influence of
Piezoelectric potential which is generated under the mechanical stress.

Figure 7: Piezocatalytic degradation of Rhodamine-B

16
1.3.5 Copper bismuth oxide as a semiconductor
The use of bismuth-containing nanoparticles for application in various advanced technological
areas rather than using the traditional bismuth-containing bulk materials has received greater
attention recently. This widespread interest in bismuth-based nanoparticles is a result of the
very fact that the nanoparticles possess distinct properties that are absent in the bulk solid
materials. These distinctive aspects as well as high optical, electrical, thermal, photocatalytic
and magnetic properties are in the main rely upon nanoparticle's massive area and tiny sizes
(Kargin et al., 2006). CuBi2O4 is one of the bismuth-containing nanoparticles. It is a ternary p-
type metal oxide with bandgap energy of 1.6-1.9 eV.

Many multi-component metal oxide systems are being explored for solar fuel production,
optoelectronic and photoelectrochemical (PEC) applications. Very few have been investigated
thus far with optimum control over morphology and phase. In that way, CuBi2O4 has been used
for its conductivity (Lyskov, Metlin, Belousov, & Tretyakov, 2004), dielectric property
(Yoshii et al., 2011), optical property (Abdulkarem et al., 2011) and magnetic property (Janson
& Rosner, 2007). CuBi2O4 with high activity through doping, modification or combination has
been used for the degradation of organic pollutants under irradiation in the presence of H2O2
(Anandan, Lee, Yang, Ashokkumar, & Wu, 2012) and also used for PEC water splitting (Hahn,
Holmberg, Korgel, & Mullins, 2012).CuBi2O4 has been prepared using solid-state reaction,
electrodeposition and hydrothermal process (Patil, Kelkar, Naphade, & Ogale, 2014).

1.3.6 Titanium dioxide as a semiconductor

Titanium (Ti) is the ninth most abundant element in the earth’s crust. The most common
oxidation number of Ti is +4, however, the +3 and +2 states of Ti also exist. Metallic Ti, TiO2
and TiCl4 are the compound most generally employed in the industry. TiO2 is a white fire-
resistant and inodorous powder with a molecular weight of 79.9 g/mol, a boiling point of
2972oC, a melting point of 1843 oC and a density of 4.26 g/cm3 at 25°C.TiO2 may be a poorly
soluble particulate that has been widely used as a white pigment. Anatase and Rutile are two
crystal structure of TiO2, Where Anatase has being considered highly chemically reactive.

TiO2 NPs typically possess dramatically completely different physiochemical properties

compared to FPs of an equivalent composition. TiO2 NPs are widely employed in industrial
and consumer products because of their strong catalytic activity compared to TiO2 FPs.
Catalytic activities of TiO2 NPs are increased due to their smaller size. Which has allowed for
a larger surface area per unit mass. TiO2 NPs consist 80:20 = Anatase: Rutile ratio and their
size is 21 nm, but TiO2 FPs consist 100% rutile, their Size is 1μm. (Shi, Magaye, Castranova,
& Zhao, 2013).

Among semiconductor materials, titanium dioxide (TiO2) is commonly used as a catalyst due
to its low cost, excellent chemical durability, good oxidation and hydrophilic properties

17
(Nakata & Fujishima, 2012). However, TiO2 can only be activated by ultraviolet (UV) light (λ
< 380 nm) due to its wide bandgap (3.0–3.2 eV)(H. Liu, Zhang, Yang, Xiao, & Sun, 2016).
Some transition metal oxides were introduced into TiO2, to improve the catalytic performance
of TiO2 such as FeOx , CuOx, NiO , CeO2 and ZnO . Metal doping can leads to easier, to
excite the electrons and reduce the recombination of electron-hole pairs of TiO2 (Khairy &
Zakaria, 2014).

When doping metal oxide defects generated on the surface of TiO2 can effectively hinder the
recombination of photogenerated electron-hole pairs (Sonobe et al., 2011).

1.3.7 p-CuBi2O4/n-TiO2 nancomposites

The p–n heterojunction of p-CuBi2O4/n-TiO2 nanocomposite was prepared by the sol-gel
method. TiO2 has been widely used as a photocatalyst but some problems remain such as fast
recombination of electron-hole pairs. Accordingly, doping with metal oxides would improving
the photocatalytic activity of TiO2 (Hu, Lan, Qu, Hu, & Wang, 2006; Wei, Shifu, Huaye, &
Xiaoling, 2011). CuBi2O4 is p-type semiconductor(Puzikova, Dergacheva, & Khusurova,
2020). TiO2 is n-type semiconductor(Sonobe et al., 2011). P-n junction is formed by the
combination of p-type semiconductor and n-type semiconductor, the inner electric field will
be formed in the interface and will effectively separate the generated electron-hole pairs, and
the catalytic activity is enhanced (Lin et al., 2007).

In this study, we synthesized p-CuBi2O4/n-TiO2 nanostructures using only water as the solvent
and analyzed its optical, morphological and electrical properties.

18
 CHAPTER-02

EXPERIMENTAL DETAILS

2.1 Materials

CuBi2 𝑂4 /𝑇𝑖𝑂2 nanocomposite was synthesized using sol-gel method in-situ process. Titanium (IV)
isopropoxide was purchased and used without further purification.
Copper (ll) nitrate trihydrate (Cu(NO3)2.3H2O), Bismuth nitrate pentahydrate (Bi(NO 3)3.5H2O) and
sodium hydroxide (NaOH) were used as precursor to prepare CuBi2O4 nanoparticle.
Distilled water, ethanol (EtOH), small amount of nitric acid (HNO3) and acetic acid (AcOH) were used
as solvents. Rhodamine B dye ( C28H31ClN2O3 (aq), λmax = 568 nm) is the dye used to test the ultrasonic
degradation efficiency.

2.2 Apparatus

CuBi2 𝑂4 /𝑇𝑖𝑂2 nancomposites were dried using an oven and sintered using HD-230 electrical
muffle furnace. Sound was irradiated with sonicator. Absorption of the nanoparticles was
measured using Genesys 10S UV-Vis spectrophotometer using 1.0 cm quartz cuvettes.

2.3 Sample preparation

2.3.1 Preparation of CuBi2O4 nanoparticle

Bismuth nitrate pentahydrate (3 mmol) was dissolved in con nitric acid (2.42M, 6 ml). The
solution was stirred for 1 hours at RT for complete dissolution of bismuth precursor. At the
same time Copper (ll) nitrate trihydrate Cu(NO3)2·3H2O (1.5 mmol) was dissolved in distilled
water (4 ml) and solution was stirred at RT for complete dissolution. Copper precursor solution
was added to the bismuth solution. The resulting solution was slowly heated to 80℃. Then 10
M NaOH solution was added to precipitate the salt until the pH of the solution reached 10. The
reaction mixture turned into green color. The solution was stirred for 2.5 hours at 80℃. After
2.5 hours of stirring the reaction mixture changed its color to dark brown. After that Solution
was allowed to cool RT and remove the supernatant and powder obtained was washed several
times with mixture of ethanol and distilled water (1:1) and dried in an oven at 120℃ for about
2 hours and was calcined at 500℃ for 1h using muffle furnace.

19
 .

Solution A Solution B
Cupper nitrate Distilled water Bismuth nitrate pentahydrate Nitric acid
pentahydrate
Stir at RT for 30 mins Stir at RT for 30 mins

Add A slowly to solution B

Stir at 80 C for 1 hour

Add sodium hydroxide

Stir at 80 °C for 2.5 hour

Cool to RT

Remove supernatant

Wash with ethanol

& d.water

Dry precipitate at
120C for 2 hour

Calcinate at 500C for 1

hour

Figure 8: Scheme of the pure CuBi2O4 nanoparticle preparation method

2.3.2 Preparation of CuBi2O4/TiO2 nanocomposite materials

muffle furnace. Using these same procedure CuBi2O4/TiO2 nancomposites were CuBi2O4/TiO2
nanocomposite were synthesized by using a modified single step sol-gel method in insitu-
process. Firstly, prepared CuBi2O4 (100 mg) was dissolved with distilled water (25 ml) and
stirred for 10 minutes at RT. Particular amount of titanium isopropoxide was added into that
solution. Resulting solution was stirred for 1 hour at room temperature. After that solution was
20
dried using an oven at 100℃ for 1 hour. Finally resultant powder was calcined at 500℃ for 1
hour using electrical synthesized in different molar ratio such as, Cu: Ti-1:1, Cu: Ti-1:2, Cu:
Ti-1:3, Cu: Ti-1:4, Cu: Ti-1:5 and Cu: Ti-1:10.

Table 1: Molar ratios and amount of reactants used for synthesis of nancomposites

Sample I.D Cu :Ti (mole CuBi2O4 TIP H2O

ratio)
Cu: Ti-1:0 0.0001 : 0.0000 - - -
Cu: Ti-1:1 0.0001 : 0.0003 100 mg 0.1 ml 25 ml
Cu: Ti-1:2 0.0001 : 0.0006 100 mg 0.2 ml 25 ml
Cu: Ti-1:3 0.0001 : 0.001 100 mg 0.3 ml 25 ml
Cu: Ti-1:4 0.0001 : 0.0013 100 mg 0.4 ml 25 ml
Cu: Ti-1:5 0.0001 : 0.0016 100 mg 0.5 ml 25 ml
Cu: Ti-1:10 0.0001 : 0.003 100mg 1.0 ml 25 ml
Cu: Ti-0:10 0.0000 : 0.003 - 1.0 ml 25 ml

Copper bismuth oxide Distilled water

CuBi2O4

Stirring at RT, 10 mins

Add Titanium isopropoxide

Asolution A

Stirring at RT,1 hour

Oven drying 100℃, 1 hour

Calcination 500℃, 1 hour

21
2.3.3 Preparation of TiO2 bare nanomaterial
For the preparation of TiO2 bare nanoparticles titanium isopropoxide was used as a precursor
and glacial acetic acid used as a chelating agent for control the hydrolysis of titania precursor
and efficient stabilizer. Both solutions were stirred using magnetic stirrer for 30 minutes.
Mixture of distilled water and ethanol was added into the above solution under ice-water bath.
The resultant sol was vigorously stirred for one hour and dried in an oven at 100℃ 3hours.
Finally the resultant was calcined at 500℃ 4 hours and was synthesized TiO2 bare nanoparticle.

2.3.4 Characterization of the CuBi2O4/TiO2 nanocomposite materials

Prepared CuBi2O4/TiO2 nanocomposite was characterized in detail as follows, Phase and
crystalline structure of composite was investigated using X-ray diffraction (XRD, Model D8
Advance, BRUKER/ AXS, Germany), The surface morphology was observed using scanning
electron microscope (SEM Carl zeiss EVO LS 15), the elemental analysis of composite was
performed using Energy-dispersive X-ray spectroscopy (EDS), and optical properties of
prepared sample absorbance spectra were recorded by using GENESYS 10S UV–Visible
spectrophotometer.

2.3.5 Piezocatalytic degradation of dye

To evaluate and compare the piezocatalytic activity of CuBi2O4/TiO2 nanocomposite,
degradation of Rhodamine B was performed under Ultrasonic vibration with (Bandelin,
Sonorex Digitec model; 860 W, 30 kHz) (as seen in Figure 9).

Under the experimental condition, initial Rh-B concentration was equal to 25 ppm, 25ml
sample of Rhodamine B was taken into two beakers. One is loaded with the 0.025 g of
CuBi2O4/TiO2 nanocomposite and other one is without catalyst used as a reference. Prior to
irradiation, loaded sample was maintained in the dark for 30 minutes for obtain homogeneous
solution and determine an adsorption-desorption equilibrium of the system. Afterwards, H2O2
(0.05 ml) was added into both dye solutions and these suspensions were placed in an ultrasound
apparatus.

The mixture of Rh-B and nanocomposite were then irradiated with ultrasound while stirring
the solutions using a magnetic stirrer. During the sonocatalytic reaction, the suspension was
sampled with 30 minutes regular interval upto 3 hours and was centrifuged immediately at
5000 rpm for 10 minutes to remove catalyst and finally absorbance of supernant solution was
measured using UV spectrophotometer (Genesys 10s) at 568nm over the wavelength range of
380-850 nm. All absorbance readings were compared with blank as a reference. Similarly using
this same procedure piezocatalytic activity of seven nanocomposites were measured.

22
Figure 9: Sonicator, Homemade reaction system to maintain dark condition and Genesys 10S UV-Visible
spectrophotometer

Calibration based on the Beer-Lambert law was used to quantify the dye concentration.

There is a relationship between concentration and absorbance. Lambert-Beer law shows the
relationship between concentration of solution and absorbance. This law states that the
absorbance of a light is proportional to its concentration in solution.

𝑨 = 𝜺𝒄𝒍 (2.1)

Where,

ε- The extinction coefficient of the substance (mol-1 dm3 cm-1 )

c- Concentration (moldm-3)

l- Sample path length (cm)

The piezocatalytic degradation efficiency (%) for CuBi2O4/TiO2 nanocomposite was

calculated using the Equation.

(𝑨𝟎 −𝑨𝒕 )
𝑫= ×100% (2.2)
𝑨𝟎

Where,

D- Percent of degradation

𝐴0- Initial absorbance of Methylene Blue

𝐴t- Absorbance of solution at time t after irradiation

23
That piezocatalytic degradation of most dyes well fits in the pseudo-first-order kinetics
model. According to first order kinetics reaction, rate constant ‘k’ was determined by using
the Equation (2.3). A plot of ln(𝐴t/𝐴0) versus t will yield a slope of k.

As a result, the evaluation of the piezocatalytic activity of the nancomposites could be

achieved.
𝑨
𝒍𝒏( 𝒕 ) = kt (2.3)
𝑨𝟎

Where, k- Apparent reaction rate constant

t- Reaction time

24
 CHAPTER-03

RESULTS AND DISCUSSIONS

3.1 Prepared CuBi2O4/TiO2 nanocomposite materials

Prepared various molar ratio nanocomposite CuBi2O4/TiO2 precursor powders are Cu: Ti-
1:1, Cu: Ti-1:2, Cu: Ti-1:3, Cu: Ti-1:4, Cu: Ti-1:5 and Cu: Ti-1:10, CuBi2O4 bare and TiO2
bare respectively. Those are shown in Figure 10.

G H
Figure 10: Prepared CuBi2O4/TiO2 nanocomposite, pure Cubi2O4 and pure TiO2

25
 3.2 Piezocatalytic activities of CuBi2O4/TiO2 nanocomposite materials

The CuBi2O4/TiO2 nancomposites were used a piezocatalyst for the degradation of Rhodamine
B dye, taken as test case Figure 11. Those are A- Cu:Ti-1:1, B- Cu:Ti-1:2, C- Cu:Ti-1:3 , D-
Cu:Ti -1:4, E- Cu:Ti-1:5, F- Cu:Ti-1:10 G- CuBi2 O4 bare and H-TiO2 bare. Those Figures 10
(A–H) shows the UV-Vis absorption spectra of the dye solution with time. The maximum
absorption wavelength is 568 nm for Rhodamine B.Absorbance against wavelength for all
different sizes of CuBi2O4/TiO2 nancomposites were measured every 30 minutes up to 3 hours.

The observed rate of degradation was high with CuBi2O4 and TiO2 in 1:10 ratio. (as shown in
Figure 11 (f)).In the dark, absorbance is high due to more dye molecules are present in the
solution. So photocatalytic degradation is low. More amount of the Rhodamine B was degraded
after 120min of exposure to the ultrasonic irradiation.

Absorbance
Absorbance

Wavelength (nm) Wavelength (nm)

A B
Absorbance
Absorbance

Wavelength (nm) Wavelength (nm)

D
C

26
 Absorbance
Absorbance

Wavelength (nm) Wavelength (nm)

E F
Absorbance

Absorbance

Wavelength (nm) Wavelength (nm)

G H

Figure 11: Absorption spectra showing piezocatalytic degradation of Rhodamine-B dye

In order to evaluate the effect of amount of doped n-TiO2 on the piezocatalytic activity of the p–n
heterojunction piezocatalyst p-CuBi2O4/n-TiO2 under Ultrasonic irradiation, it is necessary to consider
how much of the piezocatalytic conversion in the absence of TiO2 or in the presence of TiO2. The
experimental results showed the conversions were so small that the absence of TiO2 under the ultrasonic
irradiation. The considerable result can only be achieved when TiO2 catalyst are present.

The experiments were carried out using different concentrations of TiO2 varying from 0% to 72.30
wt%. From above graphs we can be seen that the amount of doped TiO2 shows an important role in the
piezocatalytic reduction of Rh-B. The piezocatalytic activity of the p-CuBi2O4/n-TiO2 is much higher
than that of TiO2 under ultrasonic irradiation. The piezocatalytic activity increases remarkably
with the increase in concentration of doped TiO2 from 0% to 72.30 wt%.

27
Under ultrasonic irradiation, when the amount of doped TiO2 increases from 0% to 72.30 wt%,
the piezocatalytic degradation efficiency of Rh-B- increases rapidly from 25.60% to 70.4 wt%

However, the CuBi2O4 bare and TiO2 bare show, small piezocatalytic activity.

When compare the different ratio of CuBi2O4/TiO2 nanocomposite and its piezocatalytic
activity. Logarithmic values of At/A0 varying with time are shown in Figure 12 (b) which
represents a straight line. Here they get slightly deviated from the first order derivative. The
slope of this graph is equal to the rate constant according to the equation (3.1).
𝑨
-𝒍𝒏( 𝒕 ) = kt (3.1)
𝑨𝟎

Calculated rate constants and the percentage of degradation efficiencies of CuBi2O4/TiO2

nanocomposite are shown in the Figure 13 (a) and (b) respectively. Among them, mixture of
CuBi2O4/TiO2 nanocomposite of ratio 1:10 shows the highest rate constant and higher
degradation efficiency than others. After 180 min of ultrasonic irradiation, almost 70.4% of
Rhodamine-B dye solution was degraded.

A B

Figure 12: (A) Piezocatalytic degradation of Rhodamine-B dye with respect to initial dye concentration
with the increasing time in the presence of different ratio of CuBi2O4/TiO2 nancomposite under Ultrasonic
irradiation (B) Graph of –ln(At/A0) vs irradiation time for different CuBi2O4/TiO2 nancomposite under
Ultrasonic irradiation

28
 A B
Figure 13: (A) Rate constants of different ratio of CuBi2O4/TiO2 nanocomposite under Ultrasonic irradiation (B)
Comparison of Comparison of degradation efficiency of different CuBi2O4/TiO2 nancomposite after irradiation for
3 hours

When consider the piezocatalytic degradation mechanism under the ultrasonic irradiation
produced the cavitation bubbles in the reaction solution. Within the very short time the bubbles
continue to absorb the sound energy, after that the bubbles collapse and release the energy to
cause the ultrasonic cavitation phenomenon. The heat produced by ultrasonic cavitation could
be excited on the surface of nanocomposite. At the time electron-hole pairs can constantly
formed. On the other hand the electrons on the surface of the catalyst are obtained by oxygen
molecules and produced active molecules such as OH., O2. radicals and H2O2.Finally lot of
electrons are trapped by the metal cations doped in titanium dioxide. While decomposition
process of water molecules produced ·OH and ·H radicals, most of which occur on the surface
of the catalyst.

Generation of free radical under the ultrasonic vibration.

H2O HO. + H. (Thermolysis)

HO. + HO. H2O2

H. + O2 HO2.

2HO2. H2O2 + O2

H2O2 + HO. HO2. + H2O

DYE + HO. Degradation product of dye

29
When consider the reaction of dye degradation at p-n junction, the p-n junction is formed by
combination of p-type semiconductor and n-type semiconductor, the inner electric field will
be formed in the interface. At the equilibrium, negative charge created at region of p-type
CuBi2O4 and positive charge created at region of n-type TiO2 by the inner electric fled.

When ultrasonic irradiation, electron-hole pairs will be created. Meanwhile, the holes flow into
the negative field and electrons move to the positive field under influence of inner electric
field. Therefore Inner electric field will effectively separate the electron-hole pairs and
enhanced the catalytic activity.

Figure 14: p–n junction formation model

and the schematic

Under the ultrasonic irradiation, the energy of the excitation is large enough to excite both the
p- CuBi2O4 and n-TiO2. The holes produced in the TiO2 valence band will transfer to the
valence band of the p- CuBi2O4 particle, meanwhile the electrons generated in the p- CuBi2O4
particle conduction band will transfer to the conduction band of the TiO2 particle.
Simultaneously, the generated electrons of TiO2 will persist in the conduction band of the TiO2.
Which make charge separation more effective. The separated electrons and holes are then free
to subjected to reaction with adsorbates on the catalyst surface. Therefore, the piezocatalytic
degradation of Rh-B can be enhanced.

Piezoelectric catalyst + Vibration Piezoelectric catalyst (e - + h+ )

H2O + h+ HO. + H+

e- + Dye Degradation product of dye

h+ + Dye Degradation product of dye

3.3 The influencing factors in piezocatalytic degradation process

To optimize the degradation condition, this experiment was done using CuBi2 O4 / TiO2
(1:10) nancomposite and control as a CuBi2O4 bare, TiO2 bear with different parameters.

30
3.3.1 Effect of ultrasonic catalyst dosage
Figure 16(A) shows a series of experimentations was done by varying the loaded of
nanocomposite, CuBi2O4 bare and TiO2 bare from 25mg to 250mg in order to gain the best
loading. . During the degradation process (initial Rh-B concentration = 25 mg/L; ultrasonic
irradiation time =150 min; pH = 6.5 ±0.1; room temperature) was maintained.

The rate of degradation was increased linearly with nanocomposite loading up to particular
limit. Once nanocomposite loaded higher than this limit, rate of degradation not changed that
much. The degradation rate of pure TiO2 powder firstly increased and then decreased.
Likewise, rate of degradation of pure CuBi2O4 initially increased with loaded amount and after
that increasing rate was reduced.

The rise in the quantity of catalyst enhanced the number of active sites on the photocatalyst
surface, that successively, increased the quantity of hydroxyl radical, and superoxide radicals.
Once the concentration of catalyst increased higher than the limiting value, the degradation
rate decreases or constant. This happens due to the rise in the turbidness of the suspension and
a decrease in ultrasound penetration as a result of increased scattering effect. The optimum
catalyst loading is found to be based on the initial solute concentration(B. Chen, Wang, Wang,
Jiang, & Li, 2011)

3.3.2 Effect of ultrasonic irradiation time

The effect of irradiation time on the degradation rate of Rh-B dye was explored. . During the
degradation process (initial Rh-B concentration = 25 mg/L; catalyst dosage = 200 mg; pH =
6.5 ±0.1; room temperature) was maintained. As can be seen that the degradation rate increased
with time from figure 15(A, B).During the reaction time 150 minutes, the color of dye was
changed from reddish violet to colorless.

It is found that the degradation rate of Rh-B increase with time in three cases, such as
ultrasound combined with TiO2 doped modified CuBi2O4 powder, ultrasonic combined with
pure TiO2 and pure CuBi2O4 powder. After 150 minutes, the degradation rate of TiO2 doped
modified CuBi2O4 powder was more than 98 % .Therefore, the ultrasonic irradiation of 150
minutes is selected to continue the experiment. Based on figure 13 (B) as can be seen the
degradation rate of CuBi2O4/ TiO2 was increased with every 30 minutes, the rate of
degradation was observed 3.7%,45.40%,59.47%,70.85%,78.94% and 95.24% respectively
Here additionally found that the ultrasonic catalytic activity of CuBi2O4/TiO2 nanocomposite
is greater than that of pure CuBi2O4 and TiO2.While keeping all other factors as a
constant.(Song, Hao, Zhang, Zhang, & Sun, 2018)

3.3.3 Effect of Initial pH

The effect of changing the initial PH of Rh-B solution on piezocatalytic degradation was shown
in figure 16(B).During the degradation process (initial Rh-B concentration = 25 mg/L; catalyst

31
dosage = 200 mg; ultrasonic irradiation time =150 min; room temperature) was maintained. In
order to investigate the effect of pH value of Rh-B solution, three different pH values
(pH=3,6.5,8) of Rh-B were selected. As can be seen, the piezocatalytic degradation efficiency
is faster in an acid PH than in alkaline and higher degradation rate was observed at
pH=3.During the reaction, the color of dye solution was changed from reddish violet to
colorless within 40 minutes in an acidic media than in alkaline media. Based on above figure
the extent of degradation follows this order: pH 3 > pH 6.5 > pH 8

According to this statement the piezocatalytic degradation of Rh-B is principally dependent on

the pH value because of its impact on the catalyst charge, aggregates’ size, and valance and
conductance bonds position. The surface charge of catalyst particles could be change with
changing of solution PH and it is leads to shifts the potentials of catalytic reactions(Azad
Kumar, 2017). As a result, the adsorption of dye on the surface is changed thereby inflicting
an amendment in the reaction rate. Underneath acidic or alkaline condition the surface of
catalyst is protonated or deprotonated. When pH value is greater than 4.4, the azo bond is
strong and difficult to break(Song et al., 2018).

3.3.4 Effect of initial dye concentration

The effect of initial concentration (25, 40, 60 and 100 mg/L) of the simulated organic dye of
Rh-B on the degradation efficiency was studied. . During the degradation process (ultrasonic
irradiation time =150 min; catalyst dosage = 200 mg; pH = 6.5 ±0.1; room temperature) was
maintained. From Figure 16(D), it could be found that the best degradation concentration of
simulated organic dye of Rh-B was 25 mg/L .When the initial concentration of dye was
increased from 25mg/L to 100mg/L the rate of degradation of dye was decreased considerably,
while keeping a fixed amount of catalyst. The study was used 25mg/L as a initial concentration,
the decoloration was observed within 45 minutes.At the same time further increased,
Consequently, it took the time too much. Because the rate of catalytic degradation of dye is
depends on the adsorption of dyes on the surface of ultrasonic catalyst. As well as the
adsorption of dye depends on the initial concentration of dye.

When initial concentration of dye increases, catalyst surface adsorbs more and more organic
substances. Therefore, the generation of hydroxyl radicals should be reduced since there are
only a fewer active sites for adsorption of hydroxyl ions and the generation of hydroxyl
radicals.

Further, as the concentration of a dye solution increases, the vibration get interrupted before
they can reach the catalyst surface, hence the absorption of ultrasound by the catalyst decreases,
and consequently, the piezocatalytic degradation efficiency of Rh-B is decreased.

32
3.3.5 Effect of Reaction temperature
The effect of temperature on the piezocatalytic degradation of dye is crucial factor. The effect
of temperature on the piezocatalytic degradation of Rh-B was observed, and the results are
shown in Figure 16(C). During the degradation process (initial Rh-B concentration = 25 mg/L;
ultrasonic irradiation time =150 min; pH = 6.5 ±0.1) was maintained .The raise in temperature
from 270C to 600C resulted of extent of degradation was increased from 74.4% to
88.9%.However, as the temperature contend to increased upto 800C, extent of degradation was
declined to79.7% .The effect of temperature on piezocatalytic degradation rate is complicated.
Because increasing the reaction temperature will enhance the equilibrium vapour pressure and
lead to easier to cavitation. Which will afford increase in catalytic effect. However at the higher
temperature a large number of cavitation bubbles are formed and will act as a barrier to sound
transmission and dampen the effective ultrasonic energy from the source to the solution, which
will leads to a decrease in sonical effect(Lan, Li, & Chen, 2013).

3.3.6 Effect of Formation of Hydrogen Peroxide during Ultrasonic irradiation.

When addition of H2O2 was strongly enhanced the degradation rate. The effect of addition of
H2O2 on the degradation rate was studied by addition of varying amount of H2O2. During the
degradation process (initial Rh-B concentration = 25 mg/L; ultrasonic irradiation time =150
min; catalyst dosage = 200 mg; pH = 6.5 ±0.1; room temperature) was maintained. In order to
degradation of dye was increased upto certain limit of H2O2 dosage.

The sonic degradation of dye, water molecules suffer hemolytic bond breakage to get hydrogen
and hydroxyl radicals, then undergo a series of reactions leading to the production of H2O2.The
speed of H2O2 formed reflects the active hydroxyl radicals generation in the sonic method and
additionally affects the extent of the sonic degradation of dye. Formation of hydrogen peroxide
was found to extend with time of ultrasonic irradiation. However the presence of dye, the
hydrogen peroxide production was lower in the solution. Therefore during the reaction extra
few amount of H2O2was added into solution. Therefore degradation of dye was increased (Lan
et al., 2013).

33
 A B
Figure 15: (A) Changes in the absorbance with time, during the degradation of Rhodamine-B. (B): Effect of
time on sonocatalytic degradation of Rhodamine-B. (Initial dye concentration = 25 mg/L, Catalyst loading
= 200 mg, Ultrasonic frequency = 30 kHz, pH= 6.5

pH
A B

C D

Figure 16: Effect of (A) CuBi2O4/TiO2 nanocomposite added amount, (B) pH, (C) Temperature and (D)
initial concentration on sonocatalytic degradation of Rhodamine-B.

34
 CHAPTER-04

CONCLUTION

In this work, the modified CuBi2O4, pure CuBi2O4 and TiO2 nanoparticles was prepared
successfully by sol-gel methods. The modified CuBi2O4 was synthesized using different molar
ratio of CuBi2O4 and TiO2 nanoparticles. These were calcined at 500oC. A good degradation
rate was tested in this study. Ultrasound radiation has a certain effect on the degradation of
Rhodamine-B dye. At the same time, we concluded that 50% of TiO2 doped modified CuBi2O4
has a higher degradation rate. The best parameters of degradation under the ultrasound by
analysis experimental data was obtained, such as initial added amount of catalyst powder is
200mg, PH = 3, 45 minutes and initial concentration of Rhodamine-B is 25ppm.Meanwhle,UV
and visible light has no significant effect on degradation rate. The all evidences was showed
that the combination of stirred ultrasonic catalysis and TiO2 doped CuBi2O4 nancomposites
can effectively improve the degradation of Rhodamine-B dye.

35
 REFERENCES

Anila Ajmala, Imran Majeedb, Riffat Naseem Malika, H. I. (2014). RSC Advances.

Abdulkarem, A. M., Li, J., Aref, A. A., Ren, L., Elssfah, E. M., Wang, H., . . . Yu, Y. (2011). CuBi2O4
single crystal nanorods prepared by hydrothermal method: Growth mechanism and optical
properties. Materials Research Bulletin, 46(9), 1443-1450. doi:
https://doi.org/10.1016/j.materresbull.2011.05.005
Ali, S., Khan, I., Khan, S. A., Sohail, M., Ahmed, R., ur Rehman, A., . . . Morsy, M. A. (2017).
Electrocatalytic performance of Ni@ Pt core–shell nanoparticles supported on carbon
nanotubes for methanol oxidation reaction. Journal of Electroanalytical Chemistry, 795, 17-
25.
Anandan, S., Lee, G.-J., Yang, C.-K., Ashokkumar, M., & Wu, J. J. (2012). Sonochemical synthesis of
Bi2CuO4 nanoparticles for catalytic degradation of nonylphenol ethoxylate. Chemical
Engineering Journal, 183, 46-52. doi: https://doi.org/10.1016/j.cej.2011.12.018
Bagheri, S., TermehYousefi, A., & Do, T.-O. (2017). Photocatalytic pathway toward degradation of
environmental pharmaceutical pollutants: structure, kinetics and mechanism approach.
Catalysis Science & Technology, 7(20), 4548-4569. doi: 10.1039/C7CY00468K
Benkhaya, S., M' rabet, S., & El Harfi, A. (2020). A review on classifications, recent synthesis and
applications of textile dyes. Inorganic Chemistry Communications, 115, 107891. doi:
https://doi.org/10.1016/j.inoche.2020.107891
Chattopadhyay, D. P. (2011). 4 - Chemistry of dyeing. In M. Clark (Ed.), Handbook of Textile and
Industrial Dyeing (Vol. 1, pp. 150-183): Woodhead Publishing.
Chen, B., Wang, X., Wang, C., Jiang, W., & Li, S. (2011). Degradation of azo dye direct sky blue 5B by
sonication combined with zero-valent iron. Ultrasonics Sonochemistry, 18(5), 1091-1096.
doi: https://doi.org/10.1016/j.ultsonch.2011.03.026
Chen, S.-P., Coco, C., Zhou, H.-T., Tan, Y.-H., Wen, H.-R., & Tang, Y.-Z. (2018). Symmetry Breaking and
Switchable Thermal Dielectric Behaviors Triggered by Order-Disorder Phase Transition in a
Neutral Co-crystallized Organic Adduct. Chemical Physics Letters, 715. doi:
10.1016/j.cplett.2018.11.017
Chen, W., Liu, T.-Y., Huang, T., Liu, X.-H., Duan, G.-R., Yang, X.-J., & Chen, S.-M. (2015). A novel yet
simple strategy to fabricate visible light responsive C,N-TiO2/g-C3N4 heterostructures with
significantly enhanced photocatalytic hydrogen generation. RSC Advances, 5(122), 101214-
101220. doi: 10.1039/c5ra18302b
Christie, R. (2014). Colour chemistry: Royal Society of Chemistry.
Clark, M. (2011). Fundamental principles of dyeing. Handbook of Textile and Industrial Dyeing;
Woodhead Publishing: Cambridge, UK, 1, 1-27.
Dahiya, R. S., & Valle, M. (2013). Tactile Sensing Technologies. In R. S. Dahiya & M. Valle (Eds.),
Robotic Tactile Sensing: Technologies and System (pp. 79-136). Dordrecht: Springer
Netherlands.
Dwivedi, A. (2017). RESEARCHES IN WATER POLLUTION: A REVIEW.
Ferreira, E., Hulme, A., McNab, H., & Quye, A. (2004). The Natural Constituents of Historical Textile
Dyes. Chemical Society reviews, 33, 329-336. doi: 10.1039/b305697j
Forgacs, E., Cserháti, T., & Oros, G. (2004). Removal of synthetic dyes from wastewaters: a review.
Environ Int, 30(7), 953-971. doi: 10.1016/j.envint.2004.02.001

36
German, L., Starr, M., & Wang, X. (2018). Computation of Electronic Energy Band Diagrams for
Piezotronic Semiconductor and Electrochemical Systems. Advanced Electronic Materials,
1700395. doi: 10.1002/aelm.201700395
Ghiyasiyan-Arani, M., Masjedi-Arani, M., & Salavati-Niasari, M. (2016). Facile synthesis,
characterization and optical properties of copper vanadate nanostructures for enhanced
photocatalytic activity. Journal of Materials Science: Materials in Electronics, 27(5), 4871-
4878. doi: 10.1007/s10854-016-4370-3
Golob, V., Vinder, A., & Simonic, M. (2005). Efficiency of the coagulation/flocculation method for the
treatment of dyebath effluents. Dyes and Pigments, 67(2), 93-97. doi:
10.1016/j.dyepig.2004.11.003
Hahn, N. T., Holmberg, V. C., Korgel, B. A., & Mullins, C. B. (2012). Electrochemical Synthesis and
Characterization of p-CuBi2O4 Thin Film Photocathodes. The Journal of Physical Chemistry C,
116(10), 6459-6466. doi: 10.1021/jp210130v
Hassan, S. S. M., Awwad, N. S., & Aboterika, A. H. A. (2009). Removal of synthetic reactive dyes from
textile wastewater by Sorel's cement. Journal of Hazardous Materials, 162(2), 994-999. doi:
https://doi.org/10.1016/j.jhazmat.2008.05.138
Hong, K.-S., Xu, H., Konishi, H., & Li, X. (2010). Direct Water Splitting Through Vibrating Piezoelectric
Microfibers in Water. The Journal of Physical Chemistry Letters, 1(6), 997-1002. doi:
10.1021/jz100027t
Hu, C., Lan, Y., Qu, J., Hu, X., & Wang, A. (2006). Ag/AgBr/TiO2 Visible Light Photocatalyst for
Destruction of Azodyes and Bacteria. The Journal of Physical Chemistry B, 110(9), 4066-4072.
doi: 10.1021/jp0564400
Janson, O., & Rosner, H. (2007). Electronic structure and magnetic properties of Bi2CuO4. Physica C:
Superconductivity and its Applications, 460-462, 458-459. doi:
https://doi.org/10.1016/j.physc.2007.03.430
Jia, T., Wang, W., Long, F., Fu, Z., Wang, H., & Zhang, Q. (2009). Fabrication, characterization and
photocatalytic activity of La-doped ZnO nanowires. Journal of Alloys and Compounds,
484(1), 410-415. doi: https://doi.org/10.1016/j.jallcom.2009.04.153
Kansal, S. K., Singh, M., & Sud, D. (2007). Studies on photodegradation of two commercial dyes in
aqueous phase using different photocatalysts. Journal of Hazardous Materials, 141(3), 581-
590. doi: https://doi.org/10.1016/j.jhazmat.2006.07.035
Kant, R. (2012). Textile dyeing industry an environmental hazard. Natural Science, 04. doi:
10.4236/ns.2012.41004
Kao, K. (2004). Ferroelectrics, Piezoelectrics, and Pyroelectrics (pp. 213-282).
Kargin, Y. F., Ivicheva, S. N., Buslaeva, E. Y., Kuvshinova, T. B., Volodin, V. D., & Yurkov, G. Y. (2006).
Preparation of bismuth nanoparticles in opal matrices through reduction of bismuth
compounds with supercritical isopropanol. Inorganic Materials, 42(5), 487-490. doi:
10.1134/S0020168506050074
Katheresan, V., Kansedo, J., & Lau, S. Y. (2018). Efficiency of various recent wastewater dye removal
methods: A review. Journal of Environmental Chemical Engineering, 6(4), 4676-4697. doi:
https://doi.org/10.1016/j.jece.2018.06.060
Kaur, H., & Kaur, R. (2014). Removal of Rhodamine-B dye from aqueous solution onto Pigeon
Dropping: Adsorption, kinetic, equilibrium and thermodynamic studies. Journal of Materials
and Environmental Science, 5, 1830-1838.

37
Khairy, M., & Zakaria, W. (2014). Effect of metal-doping of TiO2 nanoparticles on their photocatalytic
activities toward removal of organic dyes. Egyptian Journal of Petroleum, 23(4), 419-426.
doi: 10.1016/j.ejpe.2014.09.010
Khatri, M., Ahmed, F., Shaikh, I., Phan, D.-N., Khan, Q., Khatri, Z., . . . Kim, I. S. (2017). Dyeing and
characterization of regenerated cellulose nanofibers with vat dyes. Carbohydrate Polymers,
174, 443-449. doi: https://doi.org/10.1016/j.carbpol.2017.06.125
Kholkin, A., Pertsev, N., & Goltsev, A. (2008). Piezoelectricity and Crystal Symmetry (pp. 17-38).
Křížová, H. (2015). Natural dyes: their past, present, future and sustainability (pp. 59-71).
Kumar, A. (2017). A Review on the Factors Affecting the Photocatalytic Degradation of Hazardous
Materials. Material Science & Engineering International Journal, 1. doi:
10.15406/mseij.2017.01.00018
Kumar, A., & Chowdhury, A. (2018). Eco-friendly dyes and dyeing, You may download the paper
from the following link: http://sciedtech.eu/journals/advmtenvsci/current-issue.
Lan, R.-J., Li, J.-T., & Chen, B.-H. (2013). Ultrasonic Degradation of Fuchsin Basic in Aqueous Solution:
Effects of Operating Parameters and Additives. International Journal of Photoenergy, 2013,
893131. doi: 10.1155/2013/893131
Li, X., & Yu, J. (2016). Water Splitting By Photocatalytic Reduction. In J. C. Colmenares & Y.-J. Xu
(Eds.), Heterogeneous Photocatalysis: From Fundamentals to Green Applications (pp. 175-
210). Berlin, Heidelberg: Springer Berlin Heidelberg.
Liang, Z., Yan, C.-F., Rtimi, S., & Bandara, J. (2019). Piezoelectric materials for
catalytic/photocatalytic removal of pollutants: Recent advances and outlook. Applied
Catalysis B: Environmental, 241, 256-269. doi: https://doi.org/10.1016/j.apcatb.2018.09.028
Lin, X., Xing, J., Wang, W., Shan, Z., Xu, F., & Huang, F. (2007). Photocatalytic Activities of
Heterojunction Semiconductors Bi2O3/BaTiO3:  A Strategy for the Design of Efficient
Combined Photocatalysts. The Journal of Physical Chemistry C, 111(49), 18288-18293. doi:
10.1021/jp073955d
Liu, H., Zhang, Y., Yang, H., Xiao, W., & Sun, L. (2016). Study on Synthesis and Photocatalytic Activity
of Porous Titania Nanotubes. Advances in Materials Science and Engineering, 2016,
3532817. doi: 10.1155/2016/3532817
Liu, R., & Lal, R. (2014). Synthetic apatite nanoparticles as a phosphorus fertilizer for soybean
(Glycine max). Scientific Reports, 4(1), 5686. doi: 10.1038/srep05686
Liu, X., Li, D., Zhang, H., Cai, S., Li, X., & Ao, T. (2015). Research on Nonpoint Source Pollution
Assessment Method in Data Sparse Regions: A Case Study of Xichong River Basin, China.
Advances in Meteorology, 2015, 519671. doi: 10.1155/2015/519671
Lyskov, N. V., Metlin, Y. G., Belousov, V. V., & Tretyakov, Y. D. (2004). Microstructure evolution and
conductivity of Bi2CuO4–Bi2O3 composites nearby the eutectic point. Solid State Ionics,
173(1), 135-139. doi: https://doi.org/10.1016/j.ssi.2004.07.064
Mamba, G., Pulgarin, C., Kiwi, J., Bensimon, M., & Rtimi, S. (2017). Synchronic coupling of
Cu2O(p)/CuO(n) semiconductors leading to Norfloxacin degradation under visible light:
Kinetics, mechanism and film surface properties. Journal of Catalysis, 353, 133-140. doi:
https://doi.org/10.1016/j.jcat.2017.06.036
Marzec, A. (2014). The effect of dyes, pigments and ionic liquids on the properties of elastomer
composites. Université Claude Bernard-Lyon I; Uniwersytet łódzki.

38
Merouani, S., Hamdaoui, O., Saoudi, F., & Chiha, M. (2010). Sonochemical degradation of
Rhodamine B in aqueous phase: Effects of additives. Chemical Engineering Journal, 158(3),
550-557. doi: https://doi.org/10.1016/j.cej.2010.01.048
Nakata, K., & Fujishima, A. (2012). TiO2 photocatalysis: Design and applications. Journal of
photochemistry and photobiology C: Photochemistry Reviews, 13(3), 169-189.
Patil, R., Kelkar, S., Naphade, R., & Ogale, S. (2014). Low temperature grown CuBi2O4 with flower
morphology and its composite with CuO nanosheets for photoelectrochemical water
splitting. Journal of Materials Chemistry A, 2(10), 3661-3668. doi: 10.1039/C3TA14906D
Puzikova, D. S., Dergacheva, M. B., & Khusurova, G. (2020). METHOD FOR MANUFACTURING THIN
FILMS OF CUBI2O4 FOR PHOTOELECTROCHEMICAL APPLICATIONS. SERIES CHEMISTRY AND
TECHNOLOGY, 2, 99-106. doi: 10.32014/2020.2518-1491.29
Rauf, M. A., & Hisaindee, S. (2013). Studies on solvatochromic behavior of dyes using spectral
techniques. Journal of Molecular Structure, 1042, 45-56. doi:
https://doi.org/10.1016/j.molstruc.2013.03.050
Saeed, A., Shabir, G., & Shehzadi, S. A. (2015). Synthesis and Characterization of New Xanthene
Derivatives, and Their Electrochemical Study. Journal of the Chinese Chemical Society, 63,
n/a-n/a. doi: 10.1002/jccs.201500345
Shamey, R. (2009). 12 - Improving the colouration/dyeability of polyolefin fibres. In S. C. O. Ugbolue
(Ed.), Polyolefin Fibres (pp. 363-397): Woodhead Publishing.
Shankarling, G. S., Deshmukh, P. P., & Joglekar, A. R. (2017). Process intensification in azo dyes.
Journal of Environmental Chemical Engineering, 5(4), 3302-3308. doi:
https://doi.org/10.1016/j.jece.2017.05.057
Shi, H., Magaye, R., Castranova, V., & Zhao, J. (2013). Titanium dioxide nanoparticles: a review of
current toxicological data. Particle and Fibre Toxicology, 10(1), 15. doi: 10.1186/1743-8977-
10-15
Singh, K., Kumar, P., & Srivastava, R. (2017). An overview of textile dyes and their removal
techniques: Indian perspective. Pollution Research, 36.
Singh, P., Iyengar, L., & Pandey, A. (2012). Bacterial Decolorization and Degradation of Azo Dyes.
101-133. doi: 10.1007/978-3-642-23789-8_4
Song, S., Hao, C., Zhang, X., Zhang, Q., & Sun, R. (2018). Sonocatalytic degradation of methyl orange
in aqueous solution using Fe-doped TiO2 nanoparticles under mechanical agitation. Open
Chemistry, 16(1), 1283-1296. doi: doi:10.1515/chem-2018-0137
Sonobe, T., Yoshida, K., Hachiya, K., Bakr, M., Kii, T., Yoshikawa, S., & Ohgaki, H. (2011). Optical
Studies of the Microwave-Treated TiO2 Photocatalyst by MIR-FEL. Journal of Sustainable
Energy and Environment, 2, 27-29.
Starr, M. B., & Wang, X. (2013). Fundamental Analysis of Piezocatalysis Process on the Surfaces of
Strained Piezoelectric Materials. Scientific Reports, 3(1), 2160. doi: 10.1038/srep02160
Sun, S., Murray, C. B., Weller, D., Folks, L., & Moser, A. (2000). Monodisperse FePt nanoparticles and
ferromagnetic FePt nanocrystal superlattices. Science, 287(5460), 1989-1992. doi:
10.1126/science.287.5460.1989
Tang, C. Y., Chong, T. H., & Fane, A. G. (2011). Colloidal interactions and fouling of NF and RO
membranes: A review. Advances in Colloid and Interface Science, 164(1), 126-143. doi:
https://doi.org/10.1016/j.cis.2010.10.007

39
Thamaraiselvan, C., & Noel, M. (2015). Membrane Processes for Dye Wastewater Treatment: Recent
Progress in Fouling Control. Critical Reviews in Environmental Science and Technology,
45(10), 1007-1040. doi: 10.1080/10643389.2014.900242
Verma, A. K., Dash, R. R., & Bhunia, P. (2012). A review on chemical coagulation/flocculation
technologies for removal of colour from textile wastewaters. J Environ Manage, 93(1), 154-
168. doi: 10.1016/j.jenvman.2011.09.012
Wang, Z. L., & Song, J. (2006). Piezoelectric Nanogenerators Based on Zinc Oxide Nanowire Arrays.
Science, 312(5771), 242. doi: 10.1126/science.1124005
Wei, L., Shifu, C., Huaye, Z., & Xiaoling, Y. (2011). Preparation, characterisation of p–n
heterojunction photocatalyst CuBi2O4/Bi2WO6 and its photocatalytic activities. Journal of
Experimental Nanoscience, 6(2), 102-120. doi: 10.1080/17458081003770295
<wight2000.pdf>.
Wu, J., Li, Q., Li, W., Li, Y., Wang, G., Li, A., & Li, H. (2020). Efficient removal of acid dyes using
permanent magnetic resin and its preliminary investigation for advanced treatment of
dyeing effluents. Journal of Cleaner Production, 251, 119694. doi:
https://doi.org/10.1016/j.jclepro.2019.119694
Wu, J., Qin, N., & Bao, D. (2018). Effective enhancement of piezocatalytic activity of BaTiO3
nanowires under ultrasonic vibration. Nano Energy, 45, 44-51. doi:
https://doi.org/10.1016/j.nanoen.2017.12.034
Yoshii, K., Fukuda, T., Akahama, H., Kano, J., Kambe, T., & Ikeda, N. (2011). Magnetic and dielectric
study of Bi2CuO4. Physica C: Superconductivity and its Applications, 471(21), 766-769. doi:
https://doi.org/10.1016/j.physc.2011.05.049
Zabłocka-Godlewska, E., Przystaś, W., & Grabińska-Sota, E. (2014). Dye Decolourisation Using Two
Klebsiella Strains. Water, Air, & Soil Pollution, 226(1), 2249. doi: 10.1007/s11270-014-2249-6

R.L. Allen, Colour chemistry, Springer Science & Business Media, (2013)

S. Benkhaya, A. El Harfi, Design Of A New Layered Composite Membrane Based On A Physical

Copolymer (PSU/PEI/PPc) Supported By A Tri-Component Support (PA6/Fiberglass/PA6)
Application of Ultrafiltration Baths Based On Azoic and Antraquinonique Dyes, Moroc. J. Chem. 5
(1) (2017) 1–15.

A. Gürses et al., Dyes and Pigments, S. in G. C. for S. (2016). Dyes and Pigments : Their Structure
and Properties. https://doi.org/10.1007/978-3-319-33892-7

P.R. Richards, 17 - Dye types and application methods, in J. Best (Ed.), Colour Des., Woodhead
Publishing, (2012): pp. 471–496.

40