RECENT ADVANCE IN PHOTOCATALYTIC APPLICATIONS OF

TERNARY NANOCOMPOSITES

COLLEGE NATURAL SCIENCE

DEPARTMENT: CHEMISTRY
SENIOR SEMINAR PROJECT FOR 3rd YEAR CHEMISTRY STUDENTS

Name Id Number
1.TENNET ABITEW RCHE/1707/10

2.AGERIE NIBRET RCHE/1477/10

3.SUFIYA HISA RCHE/1699/10

4.HABTE LAMESSA RCHE/1601/10

5.SHAMSADIN ABDELA RCHE/1689/10

Advisor: Belay Minase (Msc)

December ,2020

Fiche, Ethiopia

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Table of Contents
list Of Abbreviation....................................................................................................................................i
ACKNOWLEDGEMENT.........................................................................................................................ii
Abstract.....................................................................................................................................................iii
INTRODUCTION.....................................................................................................................................1
1.1 BACKGROUND INFORMATION..................................................................................................1
1.2. Statement of problem........................................................................................................................2
1.3.Objective of the study........................................................................................................................2
1.3.1. General Objective......................................................................................................................2
1.3 .2.Specific Objective......................................................................................................................3
2. LITERATURE REVIW........................................................................................................................4
2.1. Dyes in Industrial Effluents..............................................................................................................4
2.2. Principles of Photocatalytic Degradation..........................................................................................5
3. CONCLUSION......................................................................................................................................9
4. RECOMMENDATION.......................................................................................................................10
5. REFERENCE......................................................................................................................................11

List of figure
Figure 1. Comparison of photocatalytic activities of the as-synthesized single, binary and ternary
Photocatalysts. 6
Figure 2: Photocatalytic degradation and kinetic plots of Reactive Blue160 over various photocatalysts. 7
Figure 3. photocatalytic degradation of Reactive Blue160 over various photocatalysts 8

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 list Of Abbreviation
UV LIGHT Ultra Violet Light

AOP Advanced Oxidation process

VB Valanc Band

MO Metyl Orange

RB Reactive Blue

MB Metyl Blue

CB Conduction Band

LED Light Emitting Diode

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 ACKNOWLEDGEMENT
Above all, we give our heartfelt gratefulness before the supreme power of God Almighty For
guiding us through the stages in our life.we would like to express our sincere feelings of
gratitude and appreciation to our advisor, Belay Minase(MSc), for her genuine follow up,
advices, , valuable Suggestions, continuous and devoted support during the entire period of this
work.we would like to express or deepest gratitude for our family for their finical Support,
motivation, encouragement, care and love.Our warm thanks goes to all individuals who give us
moral support, Motivation and comments at all times.

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Abstract
This review seeks to explore the literature pertaining to the applicability of nano-photocatalysts
in fine chemical synthesis of organic compounds. The current methods of preparation of organic
compounds in laboratories and industries are highly demanding on the non-renewable sources
of energy. These conventional methods also generally require extreme conditions of temperature
and pressure. Owing to deeper global awareness toward conservation of non-renewable sources
of energy, there has been a shift of focus toward photocatalysis in the recent years.
Photocatalysts are long known to catalyze various organic reactions such as oxidation,
reduction, addition, cyclization and decomposition. The advent of nanotechnology made it
possible to scale down these photocatalytic materials from bulk- to nano-scale and thereby
further widen their scope and efficiency. Advances in material chemistry and nanotechnology
have also made it possible to synthesize nano photocatalysts of new genres, properties of which
can be controlled and designed at molecular level. In this review, an attempt has been made to
classify these diverse nano photocatalysts into different groups, based on their composition and
mechanism. Since the literature survey revealed that the chemo selectivity and efficiency of the
nano photocatalysts depend on their method of preparation, an overview of their common
synthesis protocols is included. The review also highlights the various organic conversions for
which these nanomaterials can be used under UV/visible irradiation. Nano photocatalysts hold a
great promise for environmentally-benign synthesis of highly useful organic compounds. We
believe that this review can provide insights into research done in this field so far, which can
pave way for further progress in this topic of far-fetched social significance.

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INTRODUCTION

1.1 BACKGROUND INFORMATION

Due to the development of various industries in modern society, water pollution has become one
of the most serious environmental problems. Polluted water not only affects the ecological
system, causing damages to the livings in water and those relying on the aquatic animals and
plants, but also threatens human beings. One of the most common contaminants in wastewater is
organic substances, most of which are very stable in natural environment (Han et al., 2009).
Hence, they can aggregate in waste water and are therefore harmful to the aquatic ecosystem.
Unfortunately, many industries are producing organic pollutants containing wastewater, which
aggravates the water pollution problems (Go gate and Panda, 2004). Dye wastes represent one of
the most problematic groups of pollutants because they can be easily identified by the human eye
and are not easily biodegradable. Generally, dyes are very stable to light and oxidation due to the
complex aromatic molecular structures, but this causes damage to the environment and
dramatically threatens human health (Chen and Zhao, 2009; Ong et al., 2011; Hue and Yan,
2012). Therefore, how to treat wastewater, especially removing organic pollutants in wastewater
is one of the most crucial problems for sustainable development (Brown and De Vito, 1993).
Various conventional treatment methods for dye removal from wastewater include physical,
chemical and biological processes such as, anaerobic treatment, trickling filters, flotation,
chemical coagulation, electrochemical coagulation, membrane separation, have been studied so
far (Koraris and Liberates, 2006). However, the main disadvantages of these methods include the
production of toxic sludge, high operational cost, technical limitations, lack of effective color
reduction and sensitivity to a variable wastewater input. It is also a problem because these dye
compounds in wastewater ordinarily contain one or several benzene ring and cannot be
decomposed easily in chemical and biological processes. Moreover, most of the dyes are found
to be resistant to normal treatment process. The use of solar energy and semiconductor catalysts
for photocatalytic degradation of organic dyes in water has been intensively investigated as an
emerging renewable technology (Chen et al., 2010; Kubica et al., 2011; Dulbecco et al., 2012;
Fan et al., 2013). Photocatalysis is one of the advanced oxidation processes (AOP) considered as
an efficient, stable, and environmentally friendly method in the field of environmental pollution
control (Ananda et al., 2007). It is known that the photocatalysis process can proceed under UV-

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light or/and visible-light irradiation. Under light irradiation, active species are generated on the
catalyst surface to react with the organic contaminants in the wastewater. During this process, the
organic contaminants can be partially degraded to smaller molecules or even completely
mineralized to CO2 and H2O (Hoffmann et al., 1995). Since visible-light occupies much higher
spectral power within solar spectrum than UV-light, visible-light prompted photocatalysis is
more advantageous for its efficient utilization of the solar irradiation (Asahi et al., 2001).
Therefore, developing a photocatalyst that can efficaciously degrade organic contaminants under
visible-light irradiation is a highly promising direction in the application of wastewater
treatment. TiO2, ZnO, WO3, CDs, ZnS, SrTiO3, SnO2, WSe2, Fe2O3, etc. can be used as
photocatalyst. The anatase phase of titanium dioxide is the material with the highest
photocatalytic detoxification (Zhang et al., 2014). This semiconductor provides the best
compromise between stability and catalytic performance. Binary metal sulphone semiconductors
such as CDs, CDs or PBS are regarded as insufficiently stable for catalysis, at least in aqueous
media as they readily undergo photo anodic corrosion hose materials are also known to be
toxic. The iron oxides are not suitable semiconductors as they readily undergo photocathodic
corrosion . The band gap for ZnO (3.2 eV) is equal to that of anatase.

1.2. Statement of problem

The study of this project focused on application of ternary nano composite.

Generally,the study attempts to answer the folioing basic question concerned to the topic;

What is the application of ternary nano composite?

How to evaluate different ternary nano composite?

How to exhibit photocatalytical performance for dye degradation

1.3.Objective of the study

1.3.1. General Objective
To review the photo catalytic application of ternary nanocomposite for degradation of organic
dyes and textile waste water treatment

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1.3 .2.Specific Objective
To compare the photo catalytical performance different ternary nanocomposite

To know the factor affecting photocatalytic degradation of organic dyes

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 2. LITERATURE REVIW

2.1. Dyes in Industrial Effluents

Dyes are among the most common industrial pollutants and water coloration can be regarded as an
effective and immediate indication of water pollution Synthetic organic dyes have been widely used for
dying textile fibers such as cotton and polyesters (Adeyemo et al., 2012). Recently, considerable amount
of wastewater with color has been generated from many industries including textile, leather, paper,
printing, and dyestuffs, plastic and so on (Crini, 2006). Textile industries consume large volumes of water
and chemicals during wet processing stages (Pelizzetti, 1985) . It is difficult to degrade dye materials
because they are very stable to light and oxidation reactions. For the removal of dye materials from
contaminated water, several methods such as physical, chemical and biological methods have been
investigated. However, the main disadvantages of these methods include the production of toxic sludge,
technical limitations, lack of effective color reduction and sensitivity to a variable wastewater input. The
removal of dye materials from water is very important because water quality is highly influenced by color
and even a small amount of dye is highly visible and considered to be toxic and extremely hazardous to
aquatic living organisms (Khan et al., 2012). Moreover, many dyes are considered to be toxic and even
carcinogenic (Mohanty, 2012). Photocatalysis is a proven, useful approach to solve environmental issues
such as air and water pollution. In general, the methods used for dye wastewater treatments are described
as follows.

fFigure

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2.2. Principles of Photocatalytic Degradation
In the photocatalytic degradation process, organic pollutants are destroyed in the presence of
semiconductor photocatalyst, an energetic light source and oxidizing agent such as oxygen or air.
Only photons with energies equal or greater than the band gap energy can result in excitation of
valence band (VB) electrons which then promote the possible reactions with organic pollutants.
The absorptions of photon with energies lower than the band gap energy usually cause
dissipation in the form of heat. The illumination of the photocatalyst with sufficient energy leads
to the formation of positive hole (h +) in the valence band and an electron (e -) in the conduction
band (CB). The positive hole oxidizes either the pollutants directly or water to produce hydroxyl
radical: •HO, whereas the electron in the conduction band reduce the oxygen adsorbed on the
photocatalyst (Ahmed et al., 2010).

In general photocatalysis degradation of organic effluents are described briefly as follows:-

Bandgap energies and corresponding threshold wavelengths of various semiconductors.

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It is known that photocatalytic redox reaction mainly takes place on the surface of the
photocatalysts and the improved surface properties significantly influence the efficiency of the
photocatalysts (Yang et al., 2008).

The photocatalytic activities of as-synthesized nano-materials were evaluated and compared

using water soluble model dye, methyl orange (MO) solution. The MO photodegradation curves
via the as-prepared rGO/UiO-66/Ag3PO4 hybrids were evaluated under visible-light irradiation
(= 464 nm). The binary nanocomposites such as rGO/Ag3PO4, rGO/UiO-66,and Ag3PO4/UiO-
66 systems show higher degradation efficiency of methyl orange (MO) under visible light
irradiation than the single photocatalyst UiO-66 because of the retardation of back reaction
between rGO and Ag3PO4 with UiO-66 which produces more number of charge carriers that
would increase the degradation efficiency (Figure 2). Thus, the efficiency of photo generated
electron–hole in the binary system rGO/Ag3PO4, rGO/UiO-66, and Ag3PO4/UiO-66 was higher
than that of the pure UiO-66. The highest percentage degradation of the photo catalysts for U, A,
AU, RA, RU, RUA1, RUA2 and RUA3 were 25.44, 43.86, 46.09, 54.09, 59.69, 69.80, 81.57,
and 88.80% respectively .

Fig
ure 1. Comparison of photocatalytic activities of the as-synthesized single, binary and ternary
Photocatalysts.

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Similarly, the photocatalytic activity of the TiO2, FeTiO3, WO3, FeTiO3/TiO2, WO3/TiO2 and
WO3/TiO2/FeTiO3 photocatalyst has been evaluated on reactive blue 160 (RB 160) in the
presence of UV-visible light irradiation. This dye has been chosen for the studies since it has a
strong light absorption in UV-visible region. The UV-visible transmittance spectrum of the RB
160 solution show that more than 80% of incident light in the wavelength range 200-450 nm was
absorbed by 50 mg/l dye solution in a path length of 1 cm. Hence, the degradation of the RB 160
solution with concentration above 50 mg/l in a simple photocatalytic process over a UV active
photocatalyst like TiO2 is difficult and will take more treatment time for complete degradation.
The photocatalytic activity TiO2 and FeTiO3/TiO2 photocatalyst were shown below.

Figure 2: Photocatalytic degradation and kinetic plots of Reactive Blue160 over various
photocatalysts.
Photocatalytic activity of FeTiO3/TiO2 photocatalyst with different mass ratios exhibits better
photocatalytic activity than that

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of bare TiO2. It could be clearly seen that the photocatalytic degradation rate of RB 160 was
gradually increased with increase of FeTiO3 content, which indicated that RB 160 could be
degraded more efficiently by FeTiO3 coupled with TiO2 than that of TiO2. It was interesting to
note that the 3 wt% FeTiO3/TiO2 exhibited the highest photocatalytic degradation efficiency.

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 Figure 3. photocatalytic degradation of Reactive Blue160 over various photocatalysts

3. CONCLUSION
In conclusion, we have synthesized a series of MoO3/ Fe2O3/rGO ternary nanocomposites using
an in situ hydrothermal method for the photocatalytic degradation of MB dye under visible light
illumination. In a hybrid structure, the enormous surface area of rGO sheets not only inhibits the
aggregation of Fe2O3 in MoO3/Fe2O3 binary composite but also assists in enhancing the
degradation of MB dye molecules, which eventually offer more photocatalytic reaction sites.
Moreover, the as-synthesized MoO3/Fe2O3/rGO5% ternary nanocomposite exhibited excellent
performances in the complete photocatalytic degradation of MB in aqueous solution under
visible light ilumination. After incorporation with different rGO loads, they displayed enhanced
photocatalytic activity up to the saturation level and enhanced light-harvesting efficiency.

This review summarizes the recent advances of g-C3N4based structures and applications
including catalyst, chemical and biosensing, imaging, and LEDs. The performances of g-C3N4
are mainly based on their surface state (defects, function groups, and doping) and structures
(porosity, thickness, and morphology). Although a significant advancement has been made for
the development of highly efficient g-C3N4-based photocatalysts, there are still considerable

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problems that require further investigations, including the catalytic rate and design. 2D
polymeric g-C3N4 materials featuring low cost, metal-free, environmental friendly, moderate
bandgap, high chemistry activity, and high stability have only been studied for the past few years
(from fundamental research to practical applications). We believe that more emerging properties
and applications of g-C3N4 are around the corner. Integrations between experimental research
and theoretical approaches will advance the research progress of g-C3N4 to a large extent. As the
exploration of g-C3N4 that is still in its infancy, there are several remaining key challenges that
must be met in near future, including porous nanostructures for the drug loading and delivery,
improvement of electronic conductivity, memory device fabrication, solid-state lighting, energy
conversion, and wearable sensors.

4. RECOMMENDATION
Ternary nano composites is better in photo catalytic application than binary nano
composite to proved photocatalyst potential,synthesis for supe capacitor
application and conducting polymers.

In the next time I will be prepare seminal paper in quaternary nano composite
because,I think the best photocatalytical application than from either binary or
ternary nano composite.

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5. REFERENCE
Abriha Hadush 2018. Synthesis and characterization of rGO/UiO-66/Ag3PO4 for Photocatalytic
degradation of Methyl Orange under visible light irradiation. (Unpublished MSc
Thesis), Haramaya University, Haramaya Ethiopia .

Anandan, S., Vinu, A., Mori, T., Gokulakrishnan, N., Srinivasu, P., Murugesan, V. and Ariga,
K. 2007. Photocatalytic degradation of 2, 4, 6-trichlorophenol using lantha num doped
ZnO in aqueous suspension. Catalysis Communications, 8(9):1377- 1382.

Asahi R, Morikawa T, Ohwaki T, Aoki K, Taga Y. 2001. Visible-Light Photocatalysis in

Nitrogen-15Doped Titanium Oxides. Science, 293: 269-271:

Brown M.A, De Vito S.C. 1993. Predicting azo dye toxicity. Critical Reviews in Environmental
Science and Technology, 23: 249-324.

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 Chen, C., Ma, W. and Zhao, J. 2010. Semiconductor-mediated photodegradation of pollutants
under visible-light irradiation. Chemical Society Reviews, 39(11): 4206- 4219.

Chen, H. and Zhao, J. 2009. Adsorption study for removal of Congo red anionic dye using
organo-attapulgite. Adsorption, 15(4): 381-389.

Dolbecq, A., Mialane, P., Keita, B. and Nadjo, L. 2012. Polyoxometalate-based materials for
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Fan, W., Zhang, Q. and Wang, Y. 2013. Semiconductor-based nanocomposites for

photocatalytic H2 production and CO2 conversion. Physical Chemistry Chemical
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Gogate P.R, Pandit, A.B. 2004. A review of imperative technologies for wastewater treatment I:
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Han F, Kambala V.S.R, Srinivasan M, Rajarathnam D, Naidu R. 2009. Tailored titanium

dioxide photocatalysts for the degradation of organic dyes in wastewater treatment: A
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Hoffmann, M.R., Martin, S.T., Choi, W. and Bahnemann, D.W. 1995. Environmental appli cations of
semiconductor photocatalysis. Chemical reviews, 95(1): 69-96.

Huo S.H and Yan X.P. 2012. Metal–organic framework MIL-100(Fe) for the adsorption of
malachite green from aqueous solution. Journal of Materials Chemistry, 22: 7449– 7455.

Kornaros, M. Lyberatos, G. 2006. Biological treatment of wastewaters from a dye manufacturing

company using a trickling filter. Journal of Hazardous Material, 136: 95–102.

Kubacka, A., Fernandez-Garcia, M. and Colon, G. 2011. Advanced nanoarchitectures for solar
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Ong S.T., Keng P.S., Lee W.N., Ha S.T and Hung Y.T. 2011. Dye waste water treatment. Water review
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