A

PROJECT REPORT

on
PHOTOCATALYTIC ACTIVITY OF CERIUM OXIDE
NANO-PARTICLES THROUGH GREEN SYNTHESIS
ROUTES

Submitted by

Chandan Kumar (20BCH8008)

Shashwat Gupta (19BCH1029)
in partial fulfillment for the award of the degree

of
BACHELOR OF ENGINEERING
in

DEPARTMENT OF CHEMICAL ENGINEERING

Chandigarh University

November, 2022
 BONAFIDE CERTIFICATE

Certified that this project report “Photocatalytic activity of cerium oxide Nano-particles
through green synthesis routes” is the bonafide work of “Shashwat Gupta, Chandan
Kumar” who carried out the project work under the supervision of Dr. Srinu Nagireddi.

Dr. Srinu Nagireddi Dr. Deepak Tiwari

Supervisor Head of The Department

Submitted for the project viva-voce examination held on November, 2022

Prof (Dr.). Manish Khodwe

Internal Examiner External Examiner

i
 ACKNOWLEDGEMENT

The world is changing, the cycle of competition grows further, and those who are willing to
come forward are working hard for it. A project is like a bridge between theoretical and practical
knowledge. With these thoughts in mind, we have done this project wholeheartedly till this point.
Foremost, we would like to thank the almighty God who gave us strength and guided us
throughout the journey.
My sincere thanks to our guide Dr. Srinu Nagireddi for his continuous support, patience,
motivation, immense knowledge, and enthusiasm who helped us in every aspect of the project.
His guidance helped us all time during the project work. We could not have imagined a better
mentor than he is. Thanks to our Dr. Manish Khodwe for providing guidance in the project,
special thanks to faculty and our Head of the Department for always helping in the time of need.
Besides our mentor and faculty, we would like to thank our classmates for their continuous
support and for helping us throughout the way and with things that we did not understand. Last
but not least, we would like to thank our parents for always supporting and always making our
selfish wishes their priorities. Their continuous effort has made this moment possible and it’s all
thanks to them that we are here today doing our best in every step of our life.

Chandan Kumar (20BCH8008)

Shashwat Gupta (19BCH1029)

ii
 CONTENTS

BONAFIDE CERTIFICATE ......................................................................................................................... i

ACKNOWLEDGEMENT ............................................................................................................................ ii
LIST OF FIGURES ...................................................................................................................................... v
LIST OF TABLES ....................................................................................................................................... vi
ABSTRACT................................................................................................................................................ vii
सार.............................................................................................................................................................. viii
LIST OF SYMBOLS/ABBREVATIONS ................................................................................................... ix
CHAPTER 1 – INTRODUCTION ............................................................................................................... 1
1.1 Need Identification ........................................................................................................................ 1
1.2 Identification of Problem .............................................................................................................. 1
1.3 Identification of Tasks .................................................................................................................. 2
1.3.1 Why cerium is considered ? ......................................................................................................... 2
1.3.2 Why Green Synthesis method is considered for developing metal oxide nanoparticle ? ............ 2
1.3.3 Plants considered for Green Synthesis. ........................................................................................ 4
1.3.4 Photocatalytic activity for removal of organic dye. ..................................................................... 4
1.4 Organization of the Report ............................................................................................................ 5
CHAPTER 2 - LITERATURE REVIEW ..................................................................................................... 6
2.1 Timeline of the reported problem ....................................................................................................... 6
2.2 Proposed solutions .............................................................................................................................. 6
2.3 Bibliometric analysis ........................................................................................................................ 11
2.4 Review Summary ............................................................................................................................. 11
2.5 Problem Definition........................................................................................................................... 12
2.6 Objectives :- ..................................................................................................................................... 12
CHAPTER 3 -MATERIALS AND METHODS ........................................................................................ 14
3.1 Materials Used .................................................................................................................................. 14
3.2 Evaluation & Selection of Specifications/Features ........................................................................... 14
3.3 Design Flow : .................................................................................................................................... 15
3.4 Methodology ..................................................................................................................................... 15
CHAPTER-4 RESULTS ANALYSIS AND VALIDATION .................................................................... 20
4.1 Implementation of Solution: ............................................................................................................. 20
4.1.1 Photocatalytic activity of MI:CeO2-NPs. ................................................................................... 20
4.1.2. X-Ray Diffraction Analysis ...................................................................................................... 22
4.1.3 FT-IR Analysis........................................................................................................................... 23
4.1.4. UV–Visible spectra Analysis .................................................................................................... 24
4.1.5 Photocatalytic Activity ............................................................................................................... 24

iii
CHAPTER-5 CONCLUSION AND FUTURE WORK ............................................................................ 27
5.1 Conclusion ........................................................................................................................................ 27
5.2 Future Recommendations ................................................................................................................. 28
REFRENCES: ............................................................................................................................................. 29

iv
 LIST OF FIGURES

Figure 1 Applications of cerium oxide ( CeO2) nanoparticles ....................................................... 2

Figure 2 Key merits of green synthesis method.............................................................................. 3
Figure 3 Synthesis of cerium oxide Nano-particles ...................................................................... 15
Figure 4 Mango plant leaves ......................................................................................................... 15
Figure 5 Boiling of Plant leaves.................................................................................................... 16
Figure 6 Filtration of Plant extract ................................................................................................ 16
Figure 7 Weighing 6.48 gram (i.e 0.05 M of cerium Nitrate in 300 ml distilled water) .............. 17
Figure 8 Various Plant Extract ...................................................................................................... 17
Figure 9 Composition of Tulsi plant extract ................................................................................. 17
Figure 10 Composition of Neem plant extract .............................................................................. 18
Figure 11 Stirring plant extract with cerium solution ................................................................... 18
Figure 12 Composition received after heating .............................................................................. 19
Figure 13 Muffle Furnace ............................................................................................................. 19
Figure 14 Obtained Cerium Oxide Nano-particles ....................................................................... 19
Figure 15 Mechanism of photodegradation of dyes using CeO2-NPs ......................................... 21
Figure 16 XRD patterns of CeO2 nanoparticles. .......................................................................... 22
Figure 17 The FTIR spectra CeO2-NPs from Mangifera indica (mango) leaf extract. ................ 23
Figure 18 a UV–Vis spectra of MI:CeO2NPs, b Tauc plot for determination of optical energy
band gap of MI:CeO2NPs ............................................................................................................. 24
Figure 19 UV–Vis spectra of MB dye with MI:CeO2NPs as a catalyst at different irradiation
time ............................................................................................................................................... 25
Figure 20 Linear fitting of degradation (%) versus irradiation time. ............................................ 26

v
 LIST OF TABLES

Table 1: Comparative assessment of various plant along with results and applications……6

Table 2: Green synthesis of metallic NPs from several plant extracts………………………7

vi
 ABSTRACT

Nanomaterials have been widely used in a variety of scientific and technical applications as an
active component. This study focuses on a method for producing green cerium oxide (CeO2)
nanoparticles from a cerium nitrate hexahydrate solution by Green synthesis that commonly
include the production of cerium oxide helped by organic extracts obtained from leaves, plants,
food, fruits etc. Phytochemicals and metabolites present in the plant extracts were used to
stabilizing and reduce the nanoparticles. XRD, SEM-EDS, FTIR, and UV-Vis spectroscopy were
used to analyze the produced CeO2 nanoparticles. The prepared Nano-particles has the capacity
to deteriorate Methylene blue solution under UV light. Photocatalytic activities were studied by
the use of organic dye i.e methylene blue under UV-radiation. Several applications have been
estimated, collated and discussed like cancer therapy, antimicrobial, antioxidant, cytotoxicity,
photocatalytic degradation of pollutants, cancer therapy and UV ray’s absorption. Future
prospects are also suggested.

Keywords: Green synthesis; Reduction; Nano-particles; Photocatalysis; Degradation.

vii
 सार

एक सक्रिय घटक के रूप में क्रिक्रिन्न प्रकार के िैज्ञाक्रिक और तकिीकी अिुप्रयोगोों में िैिोमैटेररयल्स का
व्यापक रूप से उपयोग क्रकया गया है । यह अध्ययि ग्रीि सोंश्लेषण द्वारा एक सेररयम िाइटर े ट हे क्साहाइड्रेट

समाधाि से ग्रीि सेररयम ऑक्साइड् (CeO2) िैिोकणोों के उत्पादि के क्रिए एक क्रिक्रध पर केंक्रित है क्रिसमें
आमतौर पर पक्रियोों, पौधोों, िोिि, फिोों आक्रद से प्राप्त कार्बक्रिक अकब द्वारा मदद से सेररयम ऑक्साइड् का

उत्पादि शाक्रमि होता है । फाइटोकेक्रमकल्स और मेटार्ोिाइट् स िैिोकणोों को स्थिर करिे और कम करिे

के क्रिए पौधे के अकब में मौिूद अकब का उपयोग क्रकया गया िा। उत्पाक्रदत CeO2 िैिोकणोों का क्रिश्लेषण
करिे के क्रिए XRD, SEM-EDS, FTIR और UV-Vis स्पेक्ट्रोस्कोपी का उपयोग क्रकया गया। तैयार िैिो-
कणोों में यूिी प्रकाश के तहत मेक्रििीि िीिे घोि को खरार् करिे की क्षमता होती है । यूिी-क्रिक्रकरण के

तहत कार्बक्रिक ड्ाई यािी मेक्रििीि ब्लू के उपयोग से फोटोकैटक्रिक्रटक गक्रतक्रिक्रधयोों का अध्ययि क्रकया
गया। कैंसर क्रिक्रकत्सा, रोगाणुरोधी, एों टीऑस्क्सड्ें ट, साइटोटॉस्क्सक्रसटी, प्रदू षकोों की फोटोकैटक्रिक्रटक

क्रगरािट, कैंसर क्रिक्रकत्सा और यूिी क्रकरण के अिशोषण िैसे कई अिुप्रयोगोों का अिुमाि, क्रमिाि और ििाब
की गई है । िक्रिष्य की सोंिाििाएों िी सुझाई िाती हैं ।

कीवर्ड : हररत संश्लेषण; कमी; नैनो-कण; फोटोकैटलिलसस; पतन।

viii
 LIST OF SYMBOLS/ABBREVATIONS

MILE = mangifera indica leaf extract

MB = methylene blue

NPs = nanoparticles
CeO2 = cerium dioxide

UV = ultraviolet

Cin = initial concentration of MB dye

Cf = final concentration of MB dye

Ct = concentration of MB dye after time ‘t’

ix
 CHAPTER 1 – INTRODUCTION

1.1 Need Identification

Richard Feynman, a well-known scientist, won the Nobel Prize for popularizing the idea of
nanotechnology in 1959. A physical entity with at least one exterior dimension in the
nanoscale (one billionth of a meter), between 1 and 100 nm, is referred to as a nanoparticle
(NP). Nanotechnology is the branch of technology that focuses on creating, modifying, and
designing nanoparticles with a specific use in mind. Nanomaterials are created utilizing
nanotechnology from nanoparticles and come in a variety of sizes, shapes, and orientations 1.
Based on their exterior dimensions, nanomaterials can be divided into four categories: zero-
dimensional (0-D), one-dimensional (1-D), two-dimensional (2-D), and three-dimensional (3-
D) (3-D). Nanospheres and nanoclusters are examples of 0-D nanomaterials, which have all
dimensions that are 100 nm or smaller in size. One-dimensional (1-D) nanomaterials, such as
nanofibers, nanotubes, nanorods, and nanowires, have two dimensions at the nanoscale (one
dimension is larger than 100nm). 2-D nanomaterials, such as nanofilms, nanocoating, and
nanolayers with a thickness of 100 nm, contain just one dimension at the nanoscale (two
dimensions above 100 nm). 3-D nanomaterials (beyond 100 nm) contain three arbitrary
dimensions, and the majority Nanoparticles of different sorts and orientations make up 3-D
nanomaterials2. Nanomaterials can be divided into four categories based on their underlying
material: carbon-based, metal-based, dendrimer- or polymer-based, and composite-based.
Carbon and silicon atoms make up the majority of carbon-based or non-metallic
nanomaterials. Metals of all types and their compounds, typically oxides, are used to create
metallic nanomaterials. Dendrimers are nanomaterials formed of polymer chains and feature
repeated networks of basic materials. Nanoparticles can be combined with other
nanomaterials or with bulk materials to create composite-type nanomaterials.

1.2 Identification of Problem

Cerium oxide nanoparticles (CeO2NPs, nanoceria) are widely employed in fuel oxidation
catalysis, solar cells, chemical mechanical polishing/planarization, corrosion protection, and
automobile exhaust treatment. Relevant to this review, CeO2NPs also exhibit a variety of bio-
relevant activities, including imitating catalase, peroxidase, nitric oxide radicals, and

1
peroxynitrite as well as superoxide dismutase (SOD), catalase, peroxidase, oxidase, and
phosphatase. CeO2NPs are suitable for application in prospective pharmacological agents 3,
drug transport, and bio scaffolding due to their bio-relevant capabilities. The thermodynamic
efficiency of redox-cycling between 3+ and 4+ states on CeO2NP’s surface and their
extraordinary capacity to take in and release oxygen serve as the foundation for these
activities4. It was once believed that the antioxidant properties of CeO2NPs were a result of
both oxygen vacancies and the redox-cycling between cerium in the 3+ and 4+ states;
however, this is no longer the case. Redox-cycling is now recognised as being the only
mechanism responsible for all antioxidant properties.

1.3 Identification of Tasks

1.3.1 Why cerium is considered ?

There are numerous uses for cerium and its derivatives in various sectors. Cerium oxide is
used to polish glass surfaces, in the mantles of incandescent lanterns, in the walls of self-
cleaning ovens, and as a decolorizer for glass5. Cerium is a good conductor of heat and
electricity as well as having the ability to block UV light 6. Cerium differs between cerium
dioxide (CeO2) and dicerium trioxide due to its unique electrical structure (Ce2O3). Ce2O3, on
the other hand, is an unstable state that radially transforms into CeO27. Figure 1 illustrates the
applications of cerium oxide nanoparticles in various domain.

Figure 1 Applications of cerium oxide ( CeO2) nanoparticles 8

1.3.2 Why Green Synthesis method is considered for developing metal oxide nanoparticle ?

American physicist Dr. Richard Feynman, a pioneer in the subject of nanotechnology,

2
successfully created metallic salt nanoparticles. Nanotechnology is a young field of research.
For the synthesis of CeO2 NPs, a wide range of procedures, equipment, and methodologies are
available. NPs have several uses in a variety of industries, including the pharmaceutical,
medical, cosmetic, agricultural, and engineering sectors due to their small size and high
surface-to-volume ratio9. A material with effective photocatalytic characteristics is cerium
oxide. In comparison, Ceria has a band gap of roughly 3.2 eV and is a direct semiconductor
with a face-centered cubic (fcc) crystal structure that includes the Fm3m space group [10, 11, 12].
Since they can be used for drug delivery13, biocatalysts [14, 15], photocatalysts [16, 17, 18], optical
devices19, oxygen sensors20, fuel cells, and UV absorbers, CeO2-NPs have drawn a lot of
attention in the field of nanotechnology. These nanoparticles have been produced using a
variety of techniques, including hydrothermal, solvothermal, co-precipitation21, sol-gel [22, 23],
and microwave. CeO2-NPs are now largely made using two techniques: physical and chemical
[24, 25]
. However, these techniques use hazardous reducing solvents, which pose a number of
risks to the ecology and biodiversity. Furthermore, the NPs produced using such methods are
poisonous and unstable, which reduces their effectiveness [26, 27
]. As a result, scientists have
recently employed a risk-free, less harmful technique called "Green Synthesis." This technique
makes use of a variety of biological resources, including plants, microorganisms, and any other
biological byproduct[28, 29]
. These biological extracts contain a variety of phytochemicals,
including phenols, amines, enzymes, and as ketones, which are thought to be responsible for
the stability and reduction of bulk salts into their corresponding nanoparticles NPs [30, 31]. Figure
2 displays key merits of green synthesis method.

Figure 2 Key merits of green synthesis method32

3
1.3.3 Plants considered for Green Synthesis.

In this study, we have exerted Mangifera indica(mango), Ocimum tenuiflorum(neem),

Azadirachta indica(tulsi) plant extract to function as the stabilizing agent through the
synthesis of CeO2-NPs. The Mangifera and Anacardiaceae families of plants include the
luscious mango33. Although it is widely grown in tropical places throughout the world, India
is where its many variants originated. Traditional uses include antidiarrheal, antiemetic,
acidity, and renal problems medications. Mango leaves also possess antibacterial, anti-
diabetic, and antimicrobial properties34. The Meliaceae plant Azadirachta indica, sometimes
known as neem, is employed for the environmentally friendly manufacture of cerium oxide
nanoparticles. Since ancient times, this plant has been used as medicine to treat bacterial,
fungal, viral, and numerous other skin conditions. The creation of several nanoparticles,
including gold, zinc oxide, silver, and others, uses the aqueous neem extract. Terpenoids and
flavanones are the two major phytochemicals present in neem which play a important role in
stabilizing the nanoparticle and also act as capping and reducing agent 35. All tropical nations,
including India, have a lot of the wild herbaceous plant Ocimum sanctuma, often known as
tulsi. The stems are thin, frequently reddish in color, and coated with bristly golden hairs,
especially in the younger sections36. The herb has received widespread recognition in
traditional medicine for the treatment of cough, coryza, hay fever, asthma, bronchial
infections, intestinal problems, worm infestations, and kidney stones[37, 38].

1.3.4 Photocatalytic activity for removal of organic dye.

As is common knowledge, harmful organic dyes are regarded as serious impurities that are
frequently present in a variety of textiles and industries. In this regard, CeO 2, an n-type
semiconductor with a gap band of approximately 3.2 eV, can serve as a useful material for
decolorizing the organic dyes produced by industrial wastewaters39. CeO2-NPs have a rather
high band gap energy, hence UV light must be present in order to carry out the necessary
photocatalytic activity40. In a photocatalytic process, e- is transferred from the valence band
towards the conductive band while a hole (h+) is also produced within the valence band when
the semiconductor (CeO2-NPs) band gap energy is greater than the photon energy of the
irradiation light41. Consequently, the composed e‾-h+ pairs lead to the liberation of hydroxyl
OH and superoxide anion O2- radicals, which react with dye molecules and result in their
annihilation42. Pollutants from industrial and municipal effluent are currently overwhelming
the environment. Industrial items must therefore be created using non-polluting techniques

4
and even have the ability to remove some of the impurities. In this study, we examined the
photocatalytic activity of produced CeO2-NPs in light of this fact43. The synthesized pure
cerium oxide nanoparticle was further characterized by XRD, SEM, EDX, FT-IR and UV-Vis
analysis.

1.4 Organization of the Report

There are 5 chapters in this report.

Chapter 1: Introduction chapter, which covers the definition of the issue, the assignment, and
the suggested fix.

Chapter 2: A review of the relevant literature and the project's objectives. This chapter
discusses a thorough timeline of the stated issue as well as earlier studies in the area of
nanoparticles. Key attributes, efficacy, and disadvantages are examined.

Chapter 3: flowchart for the synthesis of cerium oxide nanoparticles. Concept generation,
consideration and selection of features and specifications, design constraints, design flow, and
a strategy for implementation.

Chapter 4: In this chapter Characterization has been done for example X-Ray Diffraction
Analysis, Photocatalytic activity of MI:CeO2-NPs, FT-IR Analysis, UV–Visible spectra
Analysis and its results is discussed.

Chapter 5: Conclusion

5
 CHAPTER 2 - LITERATURE REVIEW

2.1 Timeline of the reported problem

In 1959, Nobel Prize-winning American physicist Richard Feynman introduced the idea of
nanotechnology. Different physio-chemical processes used to create nanoparticles which were
time consuming ,less-biocompatible and used harmful chemicals eventually creating threat to the
environment. An effective method of Green synthesis was developed in the late 90s to minimize
the negative affects on ecology and vegetation.44

2.2 Proposed solutions

Metal nanoparticles were made using a variety of plant extracts, and they were investigated using
a range of techniques. Green synthesis studies have exploded in recent years as a result of the
utilization of plants to produce metal nanoparticles. This review's objectives are to provide a
succinct account of the most recent research on the environmentally friendly synthesis of metal
oxide nanoparticles and to describe how different synthesis methods can change the size and
morphologies of the metal oxide nanoparticles. According to regional availability, various
components of numerous different plant species were employed to create plant extract, which
was then used for the synthesis process. Moreover, functional group obtained by the use of
characterization studies have been discussed and listed in Table 1.

Table 1: Comparative assessment of various plant along with results and applications

Functional
Characterization Size Application
S.No Plant Name Part Groups Ref
Studies (nm) Studies
Available

SEM, XRD, FT- C-O, O-H & 45

1 Olive Leaf 6 Antimicrobial
IR, TGA H-H

FT-IR, XPS, HR- Drug Delivery

2 Aloe vera Leaf 2–3 –C-H, –C-C 46
TEM & Antioxidant

6
 XRD, PL, TEM & 10– -OH, -COO- UV-rays 47
3 Lemon grass Grass
SAED 40 and C-H Absorption

Ce-O, C=O, Antibacterial

Fruit PXRD, FT-IR, 48
4 Watermelon 36 C-O, C-H & &
juice UV-Vis & SEM
O-H Photocatalytic
-OH, C-H,
Jatropha XRD, TEM & C=O, N=O, Pollution
5 Leaf 3 −5 49
curcus UV-Vis C=C, C-O & Degradation
C-N-C

XRD, TEM, FT- 20– C-O-H or C- Cytotoxicity & 50

6 Orange Peel
IR & UV-vis 25 O-R Antioxidant

Annona XRD, FT-IR, UV- 51

7 Fruit _ _Ce-O _
muricata DRS, FESEM
-OH, C-H,
XRD, SEM, -Anti-bacterial
Justicia 20- C=O, N=O, 52
8 Leaf TEM, FT-IR & and Anti-
adhatoda 25 C=C, C-O &
UV-DRS oxidant
C-N-C
Anti-oxidant
Origanum TEM, FESEM, O-H, C-H & 53
9 Leaf 20 and
majorana XRD & FT-IR C=O
Cytotoxicity
O-H, C-H,
Pedalium XRD, FT-IR, UV- C-O, C=O, 54
10 Leaf 5-55 Anti-bacterial
murex Vis DRS, SEM C=N, C-N &
Ce-O
Elaeagnus XRD, SEM, 30- 55
11 Leaf C-H & C=O Antioxidant
angustifolia TEM, FT-IR 75
Euphorbia TEM, SEM, XRD
12 42 -OH, -COO- Cytotoxicity 56
amygdaloides & UV-vis and C-H
XRD, FT-IR,
N-H, N-O & Photocatalytic
13 Piper betle Leaf SEM, EDS, XPS – 57
C-N efficiency
& TEM

Potential applications of different metal oxides extracted from various plant species along with
size and morphology have been listed in the table 2

Table 2 Green synthesis of metallic NPs from several plant extracts

7
Sr Species Nanoparticl Size Morpholog application Referenc
. es (nm y es
no )
.

1 Bacillus cereus Silver 20– Spherical Antibacterial

activity
40
against
Escherichia
coli,
Pseudomonas
aeruginosa, 58
Staphylococc
us aureus,
Salmonella
typhi, and
Klebsiella
pneumonia
bacteria

2 Pseudomonas Silver 6-13 Spherical Antibacterial

proteolytica, activity
Bacillus cecembensis against A.
kerguelensis,
A. 59

gangotriensis,
B. indicus, P.
antarctica, P.
proteolytica,
and E. coli

60
3 Lactobacillus casei Silver 20– Spherical Drug
delivery,
50
cancer
treatments,
bio-labeling

61
4 Bacillus subtilis 168 Gold 5– Hexagonal- Antimicrobial
50 octahedral , catalysis

62
5 Desulfovvibriodesulfuric Gold 20– Spherical Catalysis
ans 50

8
 63
6 Shewanellaoneidensis Uranium 1–5 Octahedral Handle
oxide prism shaped cluster

64
7 Fusarium solani Silver 5– Spherical Biolabeling,
sensors, drug
35
delivery

65
8 Verticillium luteoalbum Gold < 10 Triangular, Optics,
hexagonal sensor,
coatings

66
9 Fusarium oxysporum Gold-silver 8– Spherical Biomedical
alloy 14 field

67
10 Aspergillus terreus Zinc oxide 8 Spherical Catalysis,
biosensing,
drug
delivery,
molecular
diagnostics,
solar cell,
optoelectronic
s,
cell labeling,
and
imaging

Dutta et al used Aloe Vera extract as an oxidizing and stabilizing agent during the production of
biocompatible cerium oxide nanoparticles from cerium nitrate at room temperature. CeO2NPs
included a significant amount of cerium that was in the Ce(III) oxidation state. When CeO2NPs
was incubated with H2O2, Ce(III) was immediately transformed into Ce(IV) on a time scale of
minutes, whereas Ce(IV) was slowly transformed back into Ce(III) on a time scale of days,
illustrating the cyclical ongoing antioxidant property of CeO2NPs against ROS. The NPs were
nearly spherical, 2-3 nm in size, and lowly crystalline in character. Aloe Vera extract was used to
coat the surface of CeO2NPs throughout the production process. CeO2NPs was more likely to
interface with biological cell surfaces and be internalized into the cell because it has a variety of
biomolecules (components of Aloe Vera extract) on its surface.

9
Utilizing cerium (III) acetate hydrate and lemongrass plant extract, Maensir et al successfully
created CeO2 nanoparticles using a straightforward, economical, and environmentally friendly
process. The CeO2 samples calcined at 400, 500, and 600 °C appear to have formed the cubic
fluorite structure, according to the XRD patterns, Raman spectra, and electron diffraction data.
According to TEM, the synthetic CeO2 samples are polycrystalline and have 310–40 nm-sized
particles.

Reddy et al used watermelon juice as a combustible fuel to create CeO2 nanoparticles using the
solution combustion method. The product's cubic-phase CeO2 nanoparticle composition is
confirmed by the XRD pattern. The Ce-O vibration is present, as evidenced by the FTIR and
Raman spectra of the CeO2 nanoparticles. The photocatalytic and antibacterial properties of the
CeO2 nanoparticles are excellent. This fuel is used to create nanoparticles of MgO, ZnO, CuO,
and NiO metal oxides.

Magudieswaran et al used CeO2 nanoparticles for the photocatalytic destruction of acetaldehyde.

The comparative photocatalysis performance of green-synthesized CeO2 nanoparticles strongly
urges reconsidering the use of the green-synthesis pathway in place of the chemical-synthesis
route for applications based on indoor photocatalysis-based pollutant degradation. Greenly
manufactured CeO2, which is low dimensional and nanoscale in size, will be a valuable addition
to diesel engines to increase the efficiency of fuel conversion. Overall, power-free photocatalysis
technology using environmentally friendly nanoparticles will be effective at removing indoor
gaseous contaminants in energy-efficient buildings.

Sebastiamma et al used the green synthesis method to create CeO2-NPs from Annona Muricata
fruit extracts This method can be a superior option to chemical synthesis because it does not
involve the use of any dangerous chemicals, reducing agents, or capping agents. The creation of
a face-centered cubic phase structure in CeO2 NPs was confirmed by the XRD results. The
generated CeO2 NPs displayed a fiber-like shape in FESEM images. The blue shift detected by
the UV-DRS analysis may be a result of the quantum confinement phenomenon

Nithya et al report the effective synthesis of the Justicia adhatoda leaf extract with an ionic liquid
(IL) medium to produce CeO2/ZrO2 core metal oxide nanoparticles. In this, IL is synthesised to
act as a capping agent and to align the structure of NPs without changing the surroundings. In
bio-medical activities like antioxidant, antibacterial, and antibiofilm investigations, the

10
CeO2/ZrO2 core metal oxide nanoparticles performed well. The high oxygen site vacancies, ROS
production, smallest particle size, and larger surface area of core metal oxides are the causes of
this beneficial bio-medical activity.

Saynaz et al used O. majorana L. leaf extract in green technique to create cerium nanoparticles.
The findings of the present investigation supported CeO-cytotoxic NP's and antioxidant
characteristics. Additionally, this NP had the ability to raise the gene expression levels of the
principal antioxidant-related enzymes, CAT and SOD. Compared to normal cells, the CeO-NP
demonstrated more cytotoxicity against breast cancer. In light of this, CeO-NP appeared to be a
viable therapeutic agent for the treatment of breast cancer cells while shielding healthy cells from
oxidative stress and inflammation brought on by free radicals. These biological characteristics
make the CeO-NP created from O. majorana L. leaf extract a potential NP that may be exploited
in nanomedicine to treat various diseases.

Pinheiro et al founded that Piper beetle leaf extract is efficient for the catalytic reduction of 4-
nitrophenol, the CeO2/g-C3N4/Ag system, as a result of the analysis, it was determined that the
percentage reduction of 4-NP in the presence of NaBH4 at room temperature could be confirmed
by the established BBD model. This relationship between predicted and actual values for the
reduction of 4-NP using our catalyst is strong and linear, according to the results.

2.3 Bibliometric analysis

Drawbacks Found:-
➢ Unavailability of Comparative study on different plant leaves varying in order to
concentration with different medicinal values
➢ Analysis of degradation of organic dyes by photocatalytic activity by varying
concentration of plant extract and cerium salt
➢ As particle size, shape and morphology determines the percentage of degradation of
organic dye. It is supposed to increase the efficiency by varying plant extracts
concentrations and to obtain the Optimum feasible condition.

2.4 Review Summary

11
Past research has been done on the many ways that cerium nanoparticles can be synthesised and
used for photocatalysis. According to regional availability, various components of numerous
different plant species were employed to create plant extract, which was then used for the
synthesis process. The discovered nanoparticle had a number of anti-microbial, anti-bacterial,
anti-cancer, and anti-fungal property indicators that point the research in the direction of
numerous practical uses for cerium nanoparticles. It is still unclear exactly how plant extracts
used in green synthesis processes produce nanoparticles. According to the available research,
water-soluble plant metabolites make excellent reducing agents, and a variety of biomolecules
found in plant extracts, including ascorbic acids, sterols, saponins, flavonoids, polyphenols,
polysaccharides, alkaloids, alcoholic compounds, triterpenes, b-phenylethylamines, phenolic
compounds, glucose/fructose, proteins/enzymes, and vitamin-based intermediate.

2.5 Problem Definition

There has been various advantage of nano particles like Drug delivery, Diagnosis, Antimicrobial,
Bioimaging. Cerium nano particles has been proved effective in dealing these types of problems.
The leaves of Mango(Mangifera indica), Neem (Azadirachta indica), Tulsi (Ocimum
tenuiflorum) are obtained and prepared for extract production. After that, extract is made using
the boiling technique in the heating gauze. Drug nanoparticles have increased bioavailability due
to their tiny size and huge surface area, and they have the added capacity to pass the blood-brain
barrier (BBB), enter the pulmonary system, and be absorbed through the skin's tight connections.

2.6 Objectives :-

1. Identification of Mango(Mangifera indica), Neem (Azadirachta indica), Tulsi (Ocimum

tenuiflorum) plant extracts with medicinal values.
2. Synthesis of Cerium oxide Nano-particle through green synthesis routs by varying cerium
concentrations.

12
3. Carrying out of Characterization studies to identify the physicochemical properties.
4. Evolution of photocatalytic activity of synthesized nanoparticles by increasing
degradation percentage.

13
 CHAPTER 3 -MATERIALS AND METHODS

3.1 Materials Used

1. Cerium nitrate hexahydrate (Ce(NO3)3·6H2O), (from Central drug house Pvt. Ltd..)
2. Plant leaves (Mango/Neem/ Tulsi) freshly collected from university campus.

3.2 Evaluation & Selection of Specifications/Features

In this study, cerium oxide nanoparticles (CeO2- NPs) were synthesized through green synthesis
method from cerium nitrate salt, the extract of Neem, Mango and Tulsi were taken.
Mango(Mangifera indica), Neem (Azadirachta indica), Tulsi (Ocimum tenuiflorum) leaves are
acquired and prepared for extract formation by breaking the leaves into smaller pieces and
washing with tap water followed by distilled water to remove the dirt and dust on the surface of
the leaves. The following leaves was then crushed, mixed with 200 ml distilled water and boiled
in the heating gauze at 90 degree until the level reaches half of the initial value i.e 100 ml. The
plant extract was filtered using Whatman filter paper after being allowed to cool at room
temperature.

To perform the synthesis, 0.05 M of cerium i.e. 6.48 g of cerium nitrate hexahydrate
(Ce(NO3)3·6H2O) was dissolved in 300 mL of distilled water to have the obtained mixture
stirred at room temperature for 20 min. 50 ml of above prepared plant leaf extract and 50 ml of
prepared cerium nitrate hexahydrate solution (blue) were mixed resulting in a green solution. A
100 ml solution of cerium nitrate hexahydrate along with plant extract was prepared. The
mixture solution was stirred at 80°C for 6 h to acquire a highly viscous gel. Once the stirred had
been completed, the obtained gel was put aside for 1h at a temperature of 110°C to be dried. The
remaining residue was further transferred to a crucible and put in the muffle furnace for
calcination at 400 degree Celsius for 2 h. After calcination, dry powdered form of Cerium Oxide
nanoparticles (yellow colored) were obtained.

14
3.3 Design Flow :

Figure 3 Synthesis of cerium oxide Nano-particles

3.4 Methodology
The schematic of CeO2-NPs, which were synthesized through the usage of Mango(Mangifera
indica), Neem (Azadirachta indica), Tulsi (Ocimum tenuiflorum) leaves, extract, is displayed in
below steps :-
Step-1 Collect three different plant leaves(Mangifera indica, Ocimum tenuiflorum, Azadirachta
indica) wash with distilled water properly. Grind it well to get the maximum concentration.

Figure 4 Mango plant leaves

15
Step-2 Boil with 150ml water in heater at 90°C until the level reaches half of the initial value,
then filter the constituents with filter paper.

Figure 5 Boiling of Plant leaves

Figure 6 Filtration of Plant extract

Step -3 Take 0.05 mol solution of CeO2 along with plant extract in composition of 50 ml in
distilled water.

16
Figure 7 Weighing 6.48 gram (i.e 0.05 M of cerium Nitrate in 300 ml distilled water)

Figure 8 Various Plant Extract

Figure 9 Composition of Tulsi plant extract

17
 Figure 10 Composition of Neem plant extract

Step -4 Using stirrer at 80°C for 6 hours to acquire a highly viscous gel.

Figure 11 Stirring plant extract with cerium solution

Step -5 The obtained viscous gel must be put aside universal oven for 1 hour at a temperature of
110°C to be dried and remove left over moisture.

18
 Figure 12 Composition received after heating

Step -6 Calcinate thoroughly inside muffle furnace at 400°C for 2 hours

Figure 13 Muffle Furnace

Step -7 Fine nanoparticles are collected in Cruisible.

Figure 14 Obtained Cerium Oxide Nano-particles

19
 CHAPTER-4 RESULTS, ANALYSIS AND VALIDATION

4.1 Implementation of Solution:

Generally, to investigate the surface features of CeO2-NPs, such as morphology, phase

determination, and chemical structure, different methods have been used including FTIR, UV-
Vis, XRD analyses. Furthermore, their photocatalytic activity has been assessed for the
degradation of MB dye. A UV-Vis spectrophotometer was used to confirm the successful
formation of CeO2-NPs during the biosynthesis method and also to determine the optical
properties of the CeO2-NPs. Fourier-transform infrared spectroscopy (FTIR) was used to
determine the functional groups present in the synthesized CeO2-NPs within the wavenumber
range of 4000–400 cm−1. In order to determine the phase and the crystal structure of the
synthesized CeO2-NPs, a separate XRD with Cu Ka radiation X-ray source was used.

4.1.1 Photocatalytic activity of MI:CeO2-NPs.

The photocatalytic activity of Cerium Oxide NPs utilizing the organic dye Methylene Blue (MB)
was investigated. A chain of widely used pigments that are mostly used in industry has been
narrowed down to methylene blue (MB), which has been chosen as an easy kind. Based on the
breakdown of methylene blue (MB) dyes in the presence of a UV light source, the photocatalytic
activity of constructed CeO2-NPs was evaluated. Figures 15 shows the photocatalytic activity
graphs of CeO2-NPs in relation to the degradation of MB dye. A UVA lamp tuned to 365 nm
was used as the photocatalytic process light source in addition to being carried out at room
temperature. The test was conducted using a 16 W UV lamp and a 500 mL container. A beaker
was filled with the aqueous dye (50 mL, 0.00007837M, 25 ppm) and photocatalyst (25 mg of
CeO2-NPs) solutions. The suspension was then magnetically agitated for 45 minutes in the dark
to demonstrate the creation of an adsorption or desorption equilibrium. The radiation was then
turned on to begin the photocatalytic reaction at the prescribed intervals (30 min), while the
absorbance of the solutions was determined using a UV-Vis spectrophotometer at wavelengths of
663 nm (for MB) with distilled water as the solvent. Application of Equation (1) yielded the

20
degradation % of dyes that had been accomplished by using CeO2-NPs68.

Degradation (%): [(Cin-Ct)/Cin] *100 (1)

where Cin is the initial concentration of the MB dye and Ct is the concentration of dye after time
‘t’

Equation (1) estimated that 79.69 % of the MB dye would have degraded after 100 minutes. We
also proposed a photodegradation process using CeO2-NPs for MB organic dye, which had been
collected from industrial waste water. It appears that excitation can be induced by applying light
energy (hv) that is equal to or greater than the semiconductor's bandgap energy (Eg). The valence
band's (VB) electrons are photoexcited under lighting, which encourages them to migrate toward
the conduction band (CB). The subsequent observation of the electron vacancy or holes
remaining in the VB leads to the formation of e-h+ pairs. These e-h+ couples are transported to the
photocatalyst surface as O2- and OH radicals, respectively, are generated over the reaction
between e- and h+ via O2 and H2O molecules69. The degradation of the dye molecules by the
combined O2- and OH radicals completes this process.

Figure 15 Mechanism of photodegradation of dyes using CeO2-NPs

21
4.1.2. X-Ray Diffraction Analysis

Figure 16 displays the XRD results of green produced CeO2 nanoparticles from Mangifera
indica (mango) plant extract. The crystalline form of CeO2 nanoparticles was shown by a strong
and distinct diffraction peak. The crystal planes (111), (200), (220), (311), (222), (400), (331),
and (420) correspond to the indexed diffraction peaks at the 2 position of 28.43, 33.62, 48.38,
57.74, 59.03, 76.69, and 79.09, respectively. According to the XRD planes, cerium dioxide
nanoparticles have a cubic structure with a lattice constant (a) value of 5.435. Mango (Mangifera
indica) is used to facilitate the green synthesis of CeO2, and the unit volume for this process is
calculated to be 160.543. The crystallite size of the synthesized nanoparticles is calculated the
Debye–Scherrer formula:

Average Crystallite Size (

In the formula, λ is the wavelength of the used X-ray for the analysis, β is the angular peak width
at half maxima with units in radian, and θ represents the Bragg’s diffraction angle. The average
crystallite size was approximately 30 nm using the above-mentioned mathematical relation70.

Figure 16 XRD patterns of CeO2 nanoparticles.

22
4.1.3 FT-IR Analysis

To identify the functional groups of plant extract derivatives involved in the stabilization,
reduction, and capping of CeO2NPs, the FTIR spectra of Mangifera indica (mango) CeO2NPs
was examined. The MI:CeO2NPs FTIR spectra are shown in Figure 17. Due to the presence of
polyphenols in MILE, FTIR spectra showed large hump at 3415 cm-1, 3425 cm-1, 1638 cm-1,
and 1627 cm-1 that belonged to the hydroxyl - OH group, revealing the secondary metabolites of
MILE71. Alkane -CH stretching was indicated by the peak seen at 2916 cm-1 and 2929 cm-1. A
tiny hump that demonstrated the presence of the C=C conjugated group at 2552 cm-1 and 2341
cm-1. A minor hump at 1400 cm-1 was attributed to the -C=O group, and peaks at 739 cm-1 and
719 cm-1 were given to the N=O nitro group, respectively. The peaks that occurred at 1638 cm-1
and 1627 cm-1 corresponded to the C-O ester group72. The presence of phytochemicals like
polyphenols, flavonoids, alkaloids, proteins, and amino acids which are involved in the creation
of CeO2NPs and also act as reducing and capping agents was confirmed by the FTIR spectrum.
Additionally, it is possible to attribute the different bands seen at the ranges of 552 and 1424 cm1
to the stretching vibration of the respective Ce-O and O-Ce-O links73.

Figure 17 The FTIR spectra CeO2-NPs from Mangifera indica (mango) leaf extract.

23
4.1.4. UV–Visible spectra Analysis

Green synthesis of CeO2NPs using plants as bio-reductants is advantageous over other biological
resources because large-scale synthesis or production plants are more suitable74.The optical
characteristics of MI:CeO2NPs were determined by obtaining UV-Vis absorption spectra. The
MI:CeO2NPs UV-Vis spectra are shown in Figure 18. According to earlier reports, CeO2NPs had
a peak between 400 and 450 nm [75, 76
]. In our case, a sharp peak was seen at * 404 nm that
belonged to CeO2NPs' surface plasmon resonance (SPR) regions, which was indicative of how
the particles formed in solution77 and a hump at * 300 nm that was ascribed to MILE's optical
absorption78. When exposed to visible light, SPRs—localized cooperative charges of electrons
that would change in metal nanoparticles—are activated. As shown in the inset of Fig. 5.3, the
Tauc plot of (ahm) 2 versus photon energy (hm) was used to determine the optical energy band
gap energy of MI:CeO2NPs to be 2.53 eV79.

Figure 18 a UV–Vis spectra of MI:CeO2NPs, b Tauc plot for determination of optical energy band gap of MI:CeO2NPs

4.1.5 Photocatalytic Activity

When MB dye containing MI:CeO2NPs was exposed to UV radiation, it was found that the dye
regularly deteriorated over time. Figure 19 shows the MB dye's absorption spectra when exposed
to UV light. After 100 minutes of UV irradiation, MI:CeO2NPs reduced the toxicity of the MB
dye's aqueous solution. This occurred as a result of CeO2NPs putative photosensitizing

24
properties. (i)Trapping of electron/hole (e=h) for the reduction of electron hole recombination
and (ii) higher absorption capacity are two effects of increased photocatalytic activity80. With
longer exposure times, the MB dye's 663 nm absorption peak deteriorated. The first order rate
formula, which can be written as, was used to simulate the kinetic process underlying the
degradation of MB dye.

ln

where k is the rate constant, t is the irradiation duration, Ci is the initial concentration of the MB
dye, and Cf is the final concentration. The degradation (%) vs time curve is shown in Figure 20.
The rate constant k = 0.2426 min-1 is determined by the linear fitting of the data points. The
degrading impact of plant extract-mediated CeO2NPs was similarly reported by Aravind et al.
and Rabeea et al. The presence of organic components on the surface of CeO2NPs may be the
cause of the acceleration in degradation81. The chromophore structure deteriorates as a result of
the transfer of electrons from the reducing agents (phytochemicals of MILE) to the dye
molecule82. It demonstrates that MI:CeO2NPs function as a possible Nano catalyst for the
degradation of MB dye.

Figure 19 UV–Vis spectra of MB dye with MI:CeO2NPs as a catalyst at different irradiation time

25
Figure 20 Linear fitting of degradation (%) versus irradiation time.

26
 CHAPTER-5 CONCLUSION AND FUTURE WORK

5.1 Conclusion

In summary, The green synthesis of metal nanoparticles and metal oxide is an emerging field of
nanoscience and technology that can help in avoiding the production of unwanted and harmful
substances by introducing safe and environmentally friendly methods. In this study, CeO2-NPs
have been synthesized using three different plants i.e. Mango(Mangifera indica), Neem
(Azadirachta indica), Tulsi (Ocimum tenuiflorum) through the application of a green synthesis
method which is very ecofriendly and cost-effective. The findings of the manuscripts are as
follows:

• X-ray diffraction profile analysis with an aid of Rietveld refinement confirmed that
MI:CeO2NPs exhibited face-centered cubic crystallinity with space group Fm3m with high
purity. It has been indicated by the obtained XRD pattern that the average size of CeO2NPs
decreases as the temperature is heightened. Furthermore, these results have suggested that the
presence of CeO2NPs phase in the final product, along with increasing the temperature of
calcination, can lead to the inducement of higher crystallization that is exhibited by the peak
intensity of XRD pattern.

• Furthermore, the presence of phytochemicals (such as alkaloids, polyphenols, flavonoids etc.)

were perceived in FTIR Spectra. UV–Vis indicated a sharp absorption peak in the UV region of
MILE and a perturbance in the visible region (* 404 nm) for synthesized MI:CeO2NPs. As it can
be perceived in the UV-Vis spectrum of CeO2-NPs, the position of peaks has shifted towards
higher wavelengths as the calcination temperature had been heightened, which is indicative of a
decrease in the optical energy gap of cerium oxide. The outcomes of the performed assessment
on the degradation of MB dyes with CeO2NPs, upon being irradiated with UV light, have
confirmed their satisfying photo-catalytic activity.

• MI:CeO2NPs achieved the best degradation against MB dye reaching 79.69% at 100 min of
irradiation time under UV light.

27
The findings have demonstrated that Mango(Mangifera indica), plant stands as an interesting
substance that can be exerted as a stabilizing agent throughout the green synthesis methods that
are applied for producing nanoparticles.

5.2 Future Recommendations

➢ Analysis of cerium oxide Nano-particle in different salts concentrations.

➢ Application of cerium oxide Nano-particle in medical & bio-medical fields.
➢ Comparative analysis of cerium oxide Nano-particle in different plant extract
concentrations.
➢ Cytotoxicity study of cerium oxide nanoparticles.
➢ Evolution of further Physicochemical properties of cerium NPs through TEM, FESEM,
EDX and HPLC.

28
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