RESEARCH PROPOSAL

Fabrication and Characterization of CuBi2O4/TiO2

Heterojunction Photocatalyst for Effective Photo-Degradation of
Textile Dye

M.M.F RUMANA
SEU/IS/14/BS/026
SPECIAL DEGREE IN CHEMISTRY
SOUTH EASTERN UNIVERSITY OF SRI LANKA

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RESEARCH TITLE :

Fabrication and characterization of CuBi2O4/TiO2 heterojunction photocatalyst for

effective Photo-degradation of textile dye

NAME OF THE STUDENT :

Mohamed Mawjoodh Fathima Rumana

REGISTRATION NUMBER :

SEU/IS/14/BS/026

NAME OF THE SUPERVISOR :

Dr. Mr. A. Manjceevan

(Lecturer(prob) in Chemistry, Department of chemical sciences, Faculty of Applied

Sciences, South Eastern University of Sri Lanka)

………………………………………. …………………………………
Date Signature of the supervisor

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Table of Contents

Introduction .......................................................................................................................... 4

Research problems ................................................................................................................ 6

Objective............................................................................................................................... 7

Materials and Method............................................................................................................ 7

Project delivery-output .......................................................................................................... 8

Project completion date ......................................................................................................... 9

Work plan time line ............................................................................................................... 9

References ............................................................................................................................ 9

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 Fabrication and Characterization of CuBi2O4/TiO2
Heterojunction Photocatalyst for Effective Photo-Degradation of
Textile Dye

Introduction

Objective of this proposal is degradation of Azo dye in stable method.

To accomplish the objective following sections will give detailed elaboration of key
components of formulating Heterogeneous photocatalyst material and step by step
methodology for preparing stable Heterogeneous photocatalyst material.
Further, this proposal will talk about major problems in existing solutions and how proposed
solution will eliminate those problems.

Nano Particles

Nano particles are tiny materials. Its size ranges from 1 to 100 nm which have one
dimension less than 100 nm at least (Laurent et al., 2010). Depending on the overall shape these
materials can be 0D, 1D, 2D or 3D (Tiwari et al., 2012).They can be classified into different
classes based on their properties, shapes or sizes. Such as fullerenes, Metal nano particles,
semiconductor nano particles, ceramic nano particles and polymeric nano particles. It consist
unique physical and chemical properties due to their high surface area and nano scale size.

Semiconductor Nano particles

Semiconductors act as insulator at low temperature and conduct electricity at elevated

temperature. The Highest Occupied Molecular Orbital in valance band(VB) is call HOMO and
the lowest unoccupied molecular orbital conduction band(CB) is referred as LUMO. The gap
between HOMO and LUMO stated as bandgap of material. The excitation of electron under
irradiation under illumination and it could produce electron hole pair. Semiconductor Nano
particles possess tunable bandgap and it could be performed by synthesize of materials with
different sizes. Tunable bandgap of semiconductor facilitates to manipulate the properties of
semiconductor. Therefore, they can be used for various applications include photocatalysis,
photo optics and electronic devices (Sun, 2000).

Heterojunctions

A heterojunction, is the interface between two different semiconductors with unequal

band structure, which can result in band alignments (K. Vinodgopal, P. V. Kamat,1995).
Typically, there are three types of conventional heterojunction photocatalysts, those with a

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straddling gap (type-I), those with a staggered gap (type-II), and those with a broken gap (type-
III) (Shown in figure 1).
Among them type-II heterojunction is the most effective conventional heterojunction to be used
for improving photocatalytic activity because of its suitable structure for spatial separation of
electron–hole pairs. In the past several decades, enormous efforts have been made to prepare
different type-II heterojunction photocatalysts, such as TiO2/CuBi2O4, BiVO4/WO3, g-C3N4–
WO3, g-C3N4– BiPO4, and so on, for enhancing the photocatalytic activity(REF). Generally,
type-II heterojunction photocatalysts exhibit good electron–hole separation efficiency, wide
light-absorption range, and suppress the recombination of excited electron (W. Chen,,2015).

Figure-1: Types of heterojunctons (W. Chen,,2015)

Heterogeneous photocatalysis

Heterogeneous photocatalysis could be used as photocatalyst to degradation of

pollutants in aqueous environment. With referenced to research article by Huang TiO2 is highly
usable photocatalysis, due to its high stability, chemical inertness, non-toxicity, and low cost
(huang, 2006). TiO2 is characterized by a band gap energy value of 3.2 ev, which corresponds
to a prevalent photocatalyst activation under UV light (whang, 2009). Moreover, when the
TiO2 semiconductor is activated by UV light, an extremely reactive electron–hole pair is
created. However, this reactive pair can easily recombine. In order to delay this recombination,
different approaches have been investigated, such as catalyst doping or surface modifications
by the addition of various anionic and cationic elements. The introduction of doping elements
in the catalyst structure can result in the successful reduction of activating light frequencies

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from UV to the visible region. This is a very positive aspect as it allows the use of dye
degradation to activate the photocatalyst (chen 2009).
When noble metals deposition (sasahara et al. 2006) doping non-metallic elements (Geng et al.
2008; Sathish et al. 2005), doping transition metals (Couselo et al. 2008; Ikeda et al.2001),
surface photosensitization (Mora-Sero et al.2007), and forming composite photocatalysts from
different semiconductors (Bian et al. 2008), and so on to enhance the photocatalytic activity of
TiO2 and to improve the utilization of the visible light.
Azo dye

Azo dyes are the largest class of dyes used in industry (Hunger, 2003).These
compounds are characterized by the presence of one or more azo bonds (–N=N–) in their
molecule in association with one or more aromatic structures (Clark, 2011).In the textile
industry, the use of Azo dyes for coloring cellulosic fibers such as cotton and wool has
increased significantly over the last few decades due to their cost effectiveness, brightness of
color, and good resistance to washing and light exposure.

Following figure illustrate Methylene Blue as a Pollutant (Azo dyes). Methylene blue dye is a
nitrogen- containing, hetero-aromatic cationic dye with the chemical formula: C16H18ClN3S
(tetramethylthionine chloride).

Figure-2: Methylene Blue as a Pollutant

Research problems

Most of the dyes are found to be toxic and carcinogenic to aquatic animals and plants.
The discharge of colored dye effluents into water bodies has been an environment problem of
increasing concern. Dyes are being increasingly used in a number of industries, worldwide.
Including textile, chemicals, pharmaceuticals, foods, cosmetics and laboratories. Discharge of
colored wastewater from such industries creates serious problems to the environment. Among
them Azo dyes are widely used in textile dyeing because of its brightness, ease of application,
and good fastness to washing.
A major drawback of azo dye related to their application on textiles is the low fixation yield of
the dye on the fiber caused by the hydrolysis of the reactive groups in the dye molecule .As a

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result, up to about 30% of the initial amount of dye can be lost in water (Petrucci, 2015).The
presence of azo dyes in textile effluents makes them particularly harmful to the environment
and to human health (Yaseen, 2019).
In fact, their release into aquatic ecosystems may lead to a reduction of sunlight penetration
and dissolved oxygen concentration, with deleterious effects on local flora and fauna (Ventura-
Camargo, 2013). In addition, toxic and potentially carcinogenic compounds such as aromatic
amines can be formed during dye degradation .For these reasons, textile wastewater needs to
be properly treated.
In this topic we investigate the degradation of Azo dye by a photocatalytic treatment with
CuBi2O4-doped TiO2 photocatalysts exposed to visible light. However, its complex aromatic
structure makes it highly resistant to degradation .Accordingly, a first aim of this study was to
evaluate whether the use of the selected photocatalyst in the presence of visible light could be
a suitable method to degrade Azo dyes.
Since conventional water treatments are often ineffective in eliminating azo dyes from textile
effluents, more efficient technologies, such as advanced oxidation processes (AOPs), are used
AOPs are based on the generation of highly reactive radical species, such as hydroxyl radicals
(•OH), by solar, chemical, or other forms of energy. These radicals can attack the target
compounds through different reaction mechanisms, leading to their degradation.

Objective

Main goal for this proposal is to develop more effective Photocatalytic process for the
degradation of the textile dyes (Azo dyes) by using TiO 2/CuBi2O4 heterojunction
photocatalysts.

Materials and Method

Required chemicals

1. Acetic acid (CH3COOH)

2. Ethanol (CH2CH3OH)
3. Titanium oxide (TiO2)- P-25
4. Copper bismuth oxide CuBi2O4
5. Methylene blue (tetramethylthionine chloride) C16H18ClN3S

Preparation of p-n heterojunction photo catalyst p-CuBi2O4/n-TiO2

CuBi2O4/ TiO2 Nano particle is synthesized through the sol-gel method. Prepared
CuBi2O4(50mg )is mixed with TiO2 (50mg ) in 1:1 ratio.6 drops of ethanol and 1 drop of acetic
acid are mixed well and added to motor and pastel. Then above CuBi2O4/TiO2 mixture also
added to motor. After that these mixture is grinded well for 30 minutes. Until to get paste like

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product. Then this product is transferred to crucible and sintered upto 500 oC for 1 hour in
muffle furnace. After this product is cooled upto 50oC .Finally powder like catalyst is formed.

Preparation dye (Methylene blue)

Procedure
Prepare 20 ppm Methylene blue dye solution in 250 ml volumetric flask. Add
methylene blue pigment (5mg) in to the distilled water and diluted upto 250 ml.

Catalytic degradation characterization

UV–Vis diffuse reflectance spectroscopy
Experiment will be carried out in a photoreaction apparatus. Halogen and UV lamp will be
used as the radiation source for all experiments. The start of the experiment, the reaction
solution containing reactants and photocatalyst will be put in the unsealed beakers, and in order
to disperse the photocatalyst powder, the suspensions will be ultrasonically vibrated by using
magnetic stirrer. So, we want to add the catalyst to dye solution and also maintain control one.
Then the concentration changes of dye solution will be measured from its characteristic
absorption at optimum wavelength (350-850nm) by using uv-visible spectrophotometer.
In order to determine the reproducibility of the results, at least duplicated runs will be carried
out. In all cases during the experiment, dye solutions containing an appropriate quantity of the
semiconductor powder will be magnetically stirred before and during the illumination.In this
setup water bath will be used to remove the heat and maintain the constant temperature inside
the apparatus.
Above procedure will be continued using different PH and temperature.And also CuBi2O4/
TiO2 photocatalyst will be characterized by X-ray powder diffraction (XRD)scanning electron
microscopy (SEM), and photoluminescence emission spectra.

Project delivery-output

Figure-3: Schematic diagram of photoexcited electron-hole separation process: (a)under

visible light irradiation, (b)under UV light irradiation. (Wei et al. (2010))

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The interfacial charge recombination is a big problem for photocatalytic semiconductor. Photo-
generated electrons recombine readily through the surface trap states and hinder the
performance of semiconductor. The recombination could be minimized by effective charge
separation by fabrication of heterojunction of semiconductor material. The photocatalytic
activity of the CuBi2O4/TiO2 could be enhanced by formation of heterojunctions. In the
heterojunction catalyst the photo generated electrons and holes are separated effectively, and
leads to enhance the photocatalytic activity of the photocatalyst.

Project completion date

This proposed research can be completed within 5 months as expected time frame
provided below.

Work plan time line

Activities 2020
Jan Feb Mar Apr May
Literature review

Literature survey

Synthesis of catalyst

Characterization

Research writing/Publication

References

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applications, and challenges of iron oxide nanoparticles- Ali et al., 2016

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Electrocatalytic performance of Ni@Pt core–shell nanoparticles supported on carbon
nanotubes for methanol oxidation reaction- Ali et al., 2017

T. Hisatomi, J. Kubota, K. Domen Recent advances in semiconductors for photocatalytic and

photoelectrochemical water splitting- Hisatomi et al., 2014

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S. Sun Monodisperse Fe Pt nanoparticles and ferromagnetic Fe Pt nanocrystal super attics-
Sun, 2000

S. Laurent, D. Forge, M. Port, A. Roch, C. Robic, L. Vander Elst, R.N. Muller Magnetic iron
oxide nanoparticles: synthesis, stabilization, vectorization, physicochemical characterizations,
and biological applications- Laurent et al., 2010

K. Vinodgopal, P. V. Kamat, Environ. Sci. Technol. 1995, 29, 841.

W. Chen, T.-Y. Liu, T. Huang, X.-H. Liu, G.-R. Duan, X.-J. Yang, S.-M. Chen, RSC Adv.
2015, 5

Huang, D.-G.; Liao, S.-J.; Liu, J.-M.; Dang, Z.; Petrik, L. Preparation of visible-light
responsive N-F-co doped TiO2 photocatalyst by a sol-gel-solvothermal method. J. Photochem.
Photobiol. A-Chem. 2006, 184, 282–288. [CrossRef]

Sathish M, Viswanathan B, Viswanath RP, Gopinath CS(2005) Synthesis, characterization,

electronic structure ,and photocatalytic activity of nitrogen-doped TiO2nano-catalyst.

Ikeda S, Sugiyama N, Pal B, Marcı´G, Palmisano L, NoguchiH, Uosaki K, Ohtani B (2001)

Photocatalytic activity of transition-metal-loaded titanium (IV) oxide powders suspended in
aqueous solutions: correlation with electron-hole recombination kinetics.

Bian Z, Zhu J, Wang S, Cao Y, Qian X, Li H (2008) Self-assembly of active Bi2O3/TiO2visible

photocatalyst with ordered mesoporous structure and highly crystallized anatase.

Arai T, Konishi Y, Iwasaki Y, Sugihara H, Sayama K (2007a)High-throughput screening using

porous photoelectrode for the development of visible-light-responsive semiconductors.

Clark,M.Handbook of Textile and Industrial Dyeing–Volume1: Principles ,Processes and

Types of Dyes ; Wood head Publishing: Cambridge, UK, 2011; pp. 428–438.

Petrucci, E.; Di Palma, L.; Lavecchia, R.; Zuorro, A. Treatment of diazo dye Reactive Green
19 by anodic oxidation on a boron-doped diamond electrode. J. Ind. Eng. Chem. 2015, 26, 116–
121. [CrossRef]

Yaseen, D.A.; Scholz, M. Textile dye wastewater characteristics and constituents of synthetic
effluents: A critical review. Int. J. Environ. Sci. Technol. 2019, 16, 1193–1226. [CrossRef]
Vinodgopal, K., & Kamat, P. V. (1995). Enhanced rates of photocatalytic degradation of an
azo dye using SnO2/TiO2 coupled semiconductor thin films. Environmental science &
technology, 29(3), 841-845.

Wei, L., Shifu, C., Sujuan, Z., Wei, Z., Huaye, Z., & Xiaoling, Y. (2010). Preparation and
characterization of p–n heterojunction photocatalyst p-CuBi2O4/n-TiO2 with high
photocatalytic activity under visible and UV light irradiation. Journal of Nanoparticle
Research, 12, 1355-1366. doi: 10.1007/s11051-009-9672-4

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