CHAPTER 1

INTRODUCTION

1.1 Background of Study

Nanoparticles are the core elements of nanotechnology. Nanomaterials have emerged as a highly
active and promising field of research with their unique properties and potential for various
applications. Nanomaterials can be defined as materials with at least one external dimension that
have at least one dimension in the nanometers scale which is typically between 1 to 100
nanometers. These materials extremely small sizes, as a result they possess high surface area that
can exhibit unique physical, chemical, biological properties, high reactivity and stability that are
significantly different from their bulk counterparts. These properties can be adjusted by changing
their size and shape by adding various functional groups or coating. Reduced size allows
nanoparticles to have a higher surface to volume ratio and more atoms or molecules per volume,
using less material to display the same characteristics and achieve the same activity (Álvarez-
Chimal & Ángel Arenas-Alatorre, 2023).Due to their adaptable characteristics and enchanced
performance over their parent material, nanoparticles play a crucial role in technological
advancements(Altammar, 2023). Figure 1.1 shows comparison of surface to volume ratio between
nanoparticles and bulk materials.

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Figure 1.1 Surface to volume ratio between nanoparticles and bulk materials (Álvarez-Chimal &
Ángel Arenas-Alatorre, 2023)

Zinc oxide nanoparticles (ZnO-NPs) have recently attracted intensive research in various sectors
such as catalysis, medicine, electronics, chemical sensors and ultraviolet (UV) light emitters due
to their distinct characteristics like large surface area that lead to increasing in rate of reactivity.
ZnO-NPs contribute a lot to various societal challenges from healthcare to environmental
sustainability to continue growing. To synthesis nanoparticles, generally, there are two major
processes which is top down and bottom-up but high temperatures, vacuum conditions, and harsh
toxic chemicals are required in both process (Balasooriya et al., 2017). Hence, different
techniques such as green synthesis is another efficient and friendly way to create nanoparticles.

A medicinal plant called Cleome viscosa, also known as “Asian spider flower” or “tickweed” is a
common weed that grow extensively in a warm and humid habitats over different geographical
areas. The phytochemical and functional groups present in this plant make the plant extract-
mediated synthesis is a practical, economical, and efficient method. Overall, this study
synthesizes ZnO-NPs doped with activated carbon by using the concept of green synthesis to
utilize Cleome viscosa plant extract in nanotechnology and its catalytic activity towards methyl
red dyes.

1.2 Problem Statement

Dye has been extensively used in various industries from pharmaceutical, paper , food and textile
industries. In recent times, the presence of organic dyes in wastewater has became a crucial
environmental issue. To address this issue, photocatalysts from nanoparticles have gained

2
attention as one of the materials for degrading organic pollutants in wastewater. One of dyes that
might cause harms is methyl red dye. Methyl red dye is mutagenic and have high possibility to
give serious impacts on human health and environmental (Takkar et al., 2022). To overcome this
issue, we employ the application of a ZnO-NPs dope with activated carbon as photocatalyst to
degrade the methyl dye into non-toxic compounds.

ZnO-NPs has a wide band gap energy that limit its light absorption to the UV region and requiring
high energy for photoexcitation. However, we can improve the effectiveness of ZnO-NPs as a
photocatalyst by doping with activated carbon. Carbon added to the ZnO lattice will cause the
material’s bandgap to have an intermediate energy level and lower its absorption energy (Zhang
et al., 2015). The doping serves a few purposes such as narrowing the band gap, enchancing ZnO
conductivity, and modifying its conduction and valence band position.

Traditional methods to synthesis nanoparticles have several limitations such as high usage of
hazardous chemicals, high energy consumption, high costs and the worst impact is it can
contribute to environmental pollution and emit greenhouse gases too. The production of high
toxicity by-products also contributes to human health especially. Some chemical synthesis use
heavy metal catalysts that can negatively harm ecosystems and human health due to their potential
toxicity and long-lasting presence in the environment.

It is important to discuss how the nanoparticles produced from traditional methods also can affect
the environment. Depending on a number of variable, including concentration, size, and duration
of exposure, nanoparticles may be harmful to humans, animals, and plants (Wilson, 2018). It is
simple for nanoparticles to be released into the environment through a variety of sources,
including medical procedures, and industrial emmisions. There is a chance for nanoparticles
gradual accumulation. Nanoparticles have the potential to persist for extended periods of time and
can accumulate in the environment and the possibility that nanoparticles could negatively impact
human health and the environment in a long time (Wilson, 2018).

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Health considerations, environmental issues, energy efficiency and costing in traditional methods
are factors that drive the desire to synthesize nanoparticles in more eco-friendly and sustainable
ways. By applying green synthesis techniques, we can reduce the potential for ecological harm,
high energy usage and cost while guarantee the safety of researchers, employees, and users since
it is less hazardous synthesis method. Figure 1.2 shows the comparison between traditional and
and green synthesis methods.

Figure 1.2 Comparison between traditional and green synthesis methods (Dadkhah & Tulliani,
2022)

Hence, green synthesis using Cleome viscosa is one of the way to overcome the cons of traditional
method to synthesis ZnO-NPs. Cleome viscosa extracts can be the a precursor to produce
nanoparticles in more sustainable way and lessen the environmental and health effect of
traditional methods. Furthermore, it is important to study the photocatalytic activity of methyl red
dye using ZnO-NPs since study found that photocatalysis with nanomaterials one of the most
effective technique for breaking down dye contaminants because it breaks down the dye
constituents into CO2, H2O, and safe by products preventing pollution (Anjali et al., 2022).

1.3 Significance of Study

The importance of this study is to fully utilize Cleome viscosa plant extract for the green synthesis
of zinc oxide nanoparticles (ZnO-NPs) doped with activated carbon and its catalytic activity
towards methyl red dye. Plant extract acts as a reducing and stabilizing agent to form ZnO-NPs
since they consist various phytochemicals. It is important to select a synthesis path that tendency

4
produce a high yield of pure nanoparticles with least amount of negative impacts on the
environment and human health (Vishwanath & Negi, 2021). Green synthesis technique is better
for the environment than conventional synthesis since less dangerous and less toxicity chemicals
will be use. The study broadens the range of green synthesis by proving that plant extracts can be
use to synthesis nanoparticles.

Other than that, ZnO-NPs is one of the most popular photocatalysts due to its photocataytic
activity, high photosensitivity and stability, simple, and low cost of manufacturing (Hassan et al.,
2015). ZnO-NPs are excellent for degrading dyes since they have high ability to absorb light and
generate reactive oxygen species that lead to the degradation of organic pollutants (Gaur et al.,
2024). The research findings for the environmentally friendly synthesis of ZnO-NPs and their
catalytic activity towards methyl red dye.

This study will evaluate catalytic activity of ZnO-NPs doped with activated carbon towards
methyl red dye over specific time interval, and quantifying the percentage of degradation.
Morphological analysis of the synthesized materials will be conducted. This research aimed to
expand our understanding of the properties of pure ZnO-NPs and ZnO-NPs doped with activated
carbon through a green synthesis route using Cleome viscosa plant extracts.

1.4 Research Objectives

The main objectives of this research are:

i. To synthesis zinc oxide nanoparticles (ZnO-NPs) doped with activated carbon via green
synthesis route using Cleome viscosa plant extract .
ii. To characterize the ZnO-NPs doped with activated carbon using Thermogravimetric
Analysis (TGA), Fourier Transform Infra-Red Spectroscopy (FTIR), Ultraviolet-Visible
Spectroscopy (UV-Vis), Scanning Electron Microscopy (SEM), Accelerated Surface
Area and Porosimetry (ASAP), and X-Ray Diffraction (XRD).
iii. To investigate ZnO-NPs catalytic activity towards methyl red dye

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 CHAPTER 2

LITERATURE REVIEW

2.1 Zinc Oxide Nanoparticles (ZnO-NPs)

ZnO-NPs are nanoscale particles composed of zinc oxide, a compound made up from zinc and
oxygen atoms. These nanoparticles have gained attention in various field since they can exhibit
unique sizes and properties. ZnO-NPs are among the metal oxide semiconductors that have drawn
the most interest because of their special qualities and range of applications, especially in
photocatalysis.

They offer unique electrical, optical, and chemical properties at the nanoscale make them suitable
for various applications in materials science and nanotechnology. Moreover, ZnO-NPs several
unique properties such as wide band gap, strong room temperature luminescence, high electron
mobility, and good transparency (Junaid et al., 2023). ZnO-NPs have various shapes such as rod-
like, and isometric and a broad size distribution ranges from a few nanomaters to hundred
nanometers. The synthesis of ZnO-NPs can be achieved using either chemical, physical or green
synthesis. Figure 2.1 shows the synthesis approach of nanoparticles.

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 Figure 2.1 : Method to synthesis nanoparticles (Junaid et al., 2023)

2.1.1 Doped ZnO-NPs

The deliberate insertion of impurities into ZnO-NPs to modify its structural, optical, and electrical
characteristics is known as doping. A doped substance is referred to as an extrinsic
semiconductor. Doping would improve ZnO shape and increase its adaptability for better
applications (Bharat et al., 2019). Various metals like silver, copper, manganese and transition
elements used as dopant materials.

The synthesis of doped ZnO-NPs can be achieved by chemical or green synthesis. The specific
doping and preparation methods may vary depending on the desired properties and targeted
applications. Table 2.1 shows the dopant used to dope ZnO-NPs in previous study.

Table 2.1 Dopant used to dope ZnO-NPs (Shenoy et al., 2022)

Materials synthesized Dopant References

Ag-ZnO NPs Silver (Rajendran & Mani, 2020)
Ga-ZnO NPs Gallium (Sathish et al., 2021)
Al-ZnO NPs Aluminium (Khashan et al., 2020)
Cu-ZnO NPs Copper (Khan et al., 2020)
Ni-ZnO NPs Nickel (Naik et al., 2019)

2.2 Synthesis Route of Zinc Oxide Nanoparticles (ZnO-NPs)

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ZnO-NPs can be synthesis using either chemical or green synthesis.

2.2.1 Chemical Synthesis of ZnO-NPs

ZnO-NPs have been synthesized by using sol-gel method. In the study conducted by Hasnidawani
et al., (2016), a ZnO-NPs was synthesized using a single step sol gel process and the host
precursor used is zinc acetate. Controlling several reaction parameters such as the precursor
concentration, reaction temperature, and pH can impact the nanoparticles’ size and structure. The
characteristics of ZnO-NPs was analyzed using Field Emission Scanning Electron Microscopy
(FE-SEM), X-Ray Diffractometer (XRD), and Differenial Scanning Calorimetry (DSC).

2.2.2 Green Synthesis of ZnO-NPs

Green synthesis is easier, less expensive, more reproducible, and frequently yields more stable
materials for creating nanoparticles. ZnO-NPs can be produced with an eco-friendly process that
uses non-toxic, renewable, and natural resources. By using less potential harmful chemicals, this
method seeks to lessen the cons of chemical synthesis techniques towards human health and
enviromental. In this study, green synthesis technique will be conducted using plant extract and
its photodegradation activity. Several green synthesis approaches exist for nanoparticles synthesis
such as combustion, co-precipitation, and UV-light radiation. These environmentally friendly
methods have gained attention due to their high sustainability. Table 2.2 shows the plant used in
the previous study of ZnO-NPs green synthesis.

Table 2.2 Plants used in the previous studies green synthesis of ZnO-NPs
Biological Used plant Method Particle Applications Reference
source parts size (nm)
Noni berry Leaf Co- 43 Antioxidant (Shreema et
(Morinda precipitation al., 2021)
citrifolia)
Java plum Fruit exract Combustion 26 Photocatalytic (R et al., 2024)
(Syzgium degradation
cumini)
Breadfruit Fruit Combustion >20 Photocatalytic (Suresh et al.,
(Artocarpus extract degradation 2015)
gomezianus)

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2.2.3 Green Synthesis of Doped ZnO-NPs
Green synthesis is a method that provides a sustainable approach to produce compounds with
intention to reduce energy consumption, eliminate toxic waste, and to use ecological starting
materials. The production of metal oxide nanoparticles using plant extracts has greatly improved
since this technique is safe for the environment and produces particles with a higher dynamic
reaction rather than those mare with conventional methods.

Pure ZnO-NPs is a wide band gap semiconductor with a very low carrier concentration in its
intrinsic form and its photocatalytic performance is limited to the UV region due to its wide band
gap. Doping can modify the characteristics of ZnO-NPs and enhance its suitability in various
fields such as optoelectronics, gas sensing, and photocatalysis (Bharat et al., 2019). Table 2.3
shows dopant have been used in previous study to synthesis doped ZnO-NPs via green synthesis.

Table 2.3 Doped ZnO-NPs

Biological Dopant Method Particle size Applications References
source (nm)
Noni berry Silver Co- 43 Antioxidant (Shreema et al.,
(Morinda precipitation 2021)
citrofolia)
Java plum Tb3+ Combustion 26 Photocatalytic (R et al., 2024)
(Syzygium degradation
cumini)
Milk bush Cu Thermal 30 Photocatalytic (Karthik et al., 2022)
(Synadium decomposition degradation
grantii)

2.3 Characterization ZnO-NPs and Doped ZnO-NPs

ZnO-NPs especially doped ZnO-NPs have drawn interest in various field especially in thermal
fields such as photocatalytic reaction and they differ significantly from bulk in terms of physical
and chemical properties. The factors like synthesis method, particle morphology and size, and,

9
surface modifications such as doping and compositing with other materials affect both physical
and chemical properties of ZnO-NPs. Doping play important role to achieve high % degradation
of dye to form non-volatile organic compounds since it can improve bandgap and stability of
ZnO-NPs as photocatalyst. The characterization was done through Thermogravimetric Analysis
(TGA), Fourier Transform Infra-Red Spectroscopy (FTIR), Ultraviolet-Visible Spectroscopy
(UV-Vis), Scanning Electron Microscopy (SEM), Accelerated Surface Area and Porosimetry
(ASAP), and X-Ray Diffraction (XRD).

2.3.1 Thermogravimetric Analysis (TGA)

Figure 2.2 shows TGA curves of ZnO-NPs and silver doped zinc oxide (Ag/ZnO-NPs). TGA
curves of Ag/ZnO-NPs shows a continuous weight loss heating due to removal of water from
samples. Beyond 700 °C, ZnO-NPs showed a net weight loss of 22% and Ag/ZnO-NPs weight
loss 12% beyond 400 °C.

Figure 2.2 TGA curves ZnO-NPs and Ag/ZnO-NPs (A & M, 2022)

2.3.2 Ultraviolet Visible Spectroscopy (UV-Vis)

Figure 2.3 shows the UV Visible spectrum obtained in the range of 200-800 nm of ZnO-NPs and
Cu/ZnO-NPs synthesized with Citrus limetta pulp. It is clear that between 300 nm and 400 nm
are the λmax for ZnO-NPs and Cu/ZnO-NPs. Previous studies also confirmed that λmax between
330 and 380 nm (Lu et al., 2019).

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Figure 2.3 UV-Vis absorbance spectrum of ZnO-NPs and Cu/ZnO-NPs with λmax value (Fazil et
al., 2021)

2.3.3 Scanning Electron Microscope (SEM)

SEM analysis is done by Budianto et al., (2021) to determine the shape, size, and morphology of
ZnO-NPs and Au-doped ZnO-NPs synthesized from Imperata cylindrica leaf extract. The
presence of gold, Au gave impact towards the morphology of ZnO and it transformed from
hexagonal shaped to oval shaped. Figure 2.4 shows SEM image of ZnO-NPs and Au/ZnO-NPs.

Figure 2.4 SEM image of (a) ZnO-NPs and (b) Au/ZnO-NPs (Budianto et al., 2021)

2.3.4 X-Ray Diffraction (XRD)

Study conducted by Nguyen-Hong et al., (2021), they prepared Ce-doped ZnO via green synthesis
using Hedyotis capitellata leaf extract with various weight of Ce doping concentrations from 0 to
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5%. They found out that the 1% Ce/ZnO-NPs sample is likely to be most promising photocatalyst
for methyl orange degradation. Figure 2.5 shows the XRD patterns of ZnO-NPs with various Ce
doping.

Figure 2.5 XRD patterns of ZnO-NPs with various Ce doping (Nguyen-Hong et al., 2021)

2.4 Cleome viscosa Plant

Cleome viscosa, known as tickweed or Asian spider flower, is a member of Cleomaceae family
found in plains of India, Africa, and Pakistan and the height is about 30 to 90 cm. the flowers are
yellow in colour and the seeds are brown in black in colour when ripe (Singh et al., 2015). It is
widely distributed in waste lands, crop fields, wet, and grassy places. This plants have many
numerous traditional applications including analgesic, anti inflammatory, and antipyretic due to
presence of various phytoconstituents such as alkaloids, amino acids, phenolic compounds and
tannins. Researchers have also investigated its potential to be one of the main reagents to produce
nanoparticles in green synthesis way. In past study by Singh et al., (2015), fruit extract of Cleome
viscosa had been used to synthesis silver nanoparticles to study its antibacterial and anticancer
activities. Figure 2.6 shows the physical looks of the Cleome viscosa plant

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 Figure 2.6 Cleome viscosa (Lakshmanan et al., 2018)

2.4.1 Phytochemical Study of Cleome viscosa

Phytochemicals are organic substances naturally present in plants, giving them scent, flavour,
and colour. Phytochemicals are not necessary for human survival, but they have been discovered
to have several positive benefits on human health and nanotechnology advancements especially.
They may have antioxidant, anti-inflammatory, anticancer activities and also can act as reducing
agents and stabilizers due to presence of various secondary metabolites.

Phytochemical screening is scientific and qualitative process of analyzing, examining, and

extracting different classes of phytoconstituents present in various parts of plants. Table 2.4 shows
the presence of phytochemicals in Cleome viscosa by using different solvent plant extract.

Table 2.4 Phytochemical analysis of Cleome viscosa plant extract (Yarrappagaari et al., 2022)
Phytochemicals Test MeCV AqCV EaCV NhCV
Flavonoids Shinoda’s test + + + -
Phenols Salkowski test + + + +
Steroids Libermann-burchard + + + +
Alkaloids Wagner’s test + + + +
Terpenoids (coumarins) Trim-hill reagent test + + + +
Tannins Lead acetate test + + - -
+ =Presence; - = Absence

2.5 Activated Carbon (AC)

Activated carbon (AC) is a rough, imperfectly structured kind of graphite sometimes referred to
as activated charcoal. It is a solid carbonaceous material with an amorphous structure, high
13
porosity, and a well developed surface area with numerous oxygenated functional groups.
Activated carbon exist in three forms: mesopores, micropores, and macropores. Due to these
uniques properties, AC may be employed as a catalyst or co-catalyst for the removal of pollutants
from gases and liquids as well as the recovery of chemicals (Afif et al., 2019).

AC usually produced from finite resources such as coal, petroleum residue and ignite that are
expensive and required intensive regeneration. According to reports by Maneerung et al., (2016),
by 2018, there would be a 2.1 million metric ton increase in the demand for AC. The high demand
led to discovery of sustainable and cheaper resources for production of AC like biochar from
thermal treatment of biomass. Figure 2.7 shows the methods of the activation process.

Figure 2.7 Methods of the activation process (Reza et al., 2020)

In this study, we will utilize Areca catechu or commonly known as areca palm as a main source
to obtain activated carbon as a dopant for ZnO-NPs. The purpose of using AC as a dopant ZnO-
NPs is to improve its morphology. Also, there has been no report on the synthesis of areca palm
activated carbon doped ZnO-NPs in study of photodegradation towards methyl red dye.

2.6 Methyl Red Dye (MR)

Lately, dyes have been used widely for various industrial colouring process like textile, leather,
cosmetics, plastics and dyestuffs. MR is a dark-red, single charged basic dye that turns a deep red
in low pH solutions. Among various dyes, methyl red (MR) is a non-polar, monoazo textile dye
that have ability to undergo reductive cleavage to produce aromatic amines that have high ability

14
to cause carcinogenic and mutagenic effect (Ahmad et al., 2019). In its pure form, MR appears as
a dark red crystalline powder with the chemical formula C15H15N3O2.

2.7 Photodegradation Study

The objective of this study was to investigate the photodegradation activity of the synthesized
nanoparticles acting as a photocatalyst for the degradation of methyl red dye under solar
radiation specifically sunlight. The photocatalyst can generate potent oxidizing agents that can
break down organic substances and convert it into less pollutant compounds such as carbon
dioxide and water. The photocatalytic mechanism of ZnO-NPs towards dye pollutant can be
illustrated based on Figure 2.8.

Figure 2.8 Photocatalytic Mechanism Of ZnO-NPs Towards Dye Pollutant (Yaqoob et al., 2020)

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 CHAPTER 3

METHODOLOGY

3.1 Chemicals and Apparatus

Zinc nitrate will be used for this synthesis is purchased from Sigma Aldrich same with methyl red
dye. Activated carbon as a dopant of ZnO-NPs obtain from Arecha catechu and Cleome viscosa
plant from residential area and roadsides around Kuala Nerus district.

The apparatus used are beakers, Erlenmeyer flasks, volumetric flasks, hot plate, electronic
balance, magnetic bar stirrer, dropper, measuring cylinder and Buchner funnel. The apparatus will
be provided by laboratory assistant of Organic Lab, cleaned with tap water, rinsed with acetone,
and dried using the oven.

3.2 Plant Extract Preparation

Firstly, Cleome viscosa plants will be collected near Kampung Pak Tuyu at Kuala Nerus district
and the plant is washed thoroughly with tap water and rinsed using deionized water. Then, dry the
plants in an oven at 100 °C for 4 hours to eliminate moisture. Grind the plants and sieve until
obtain fine powders. Next, add 100 mL of deionized water into 250 mL beaker contain 2g of dry
plant powder. Heat the mixture for 15 minutes at 100 °C and stir contionously using magnetic
stirrer. The crude is then filtered using Whatman No. 1 filter paper, and the filtrate is collected.

16
3.2.1 Phytochemical Test

To identify the phytoconstituents presence in the Cleome viscosa (CV) plant extract, several test
will be done for alkaloids, flavonoids, saponins, steroids, phenolic and tannin. Table 3.1 shows
the methods for the test that will be conducted.

Table 3.1 Methods for Phytochemical Tests

Tests Methods
Alkaloids 2 mL CV extract will be added with three drops of 1% HCl and a few
drops of Mayer Wagner reagent (I2 in KI). The appearance of brown-red
precipitates indicates the resence of alkaloids.
Flavonoids 2 mL CV extract will be added with a few drops of concentrated HCl, and
Mg ribbon. The formation of pink or red colour indicates the presence of
flavonoids.
Saponins 2 mL of CV extract will be added with 2 mL distilled water. The formation
of foam indicates the presence of saponins.
Steroids 2 mL of CV extract will be added with 15 mL of chloroform and 15 mL
of H2SO4. Bilayer (red top layer and greenish top layer) will form reveals
the presence of steroids.
Phenolic 2 mL of CV extract will be added with 6 drops of FeCl3 and 2 mL of
K2Fe(CN)6 and greenish blue will form to indicate presence of phenols.
Tannins 2 mL of CV extract will be added with 0.1 % Ferric chloride and observe
for blue-black colouration indicating the presence of tannins.

3.3 Preparation of Activated Carbon

The raw materials of Arecha catechu nut husk (AH) waste will be collected around campus of
Universiti Malaysia Terengganu (UMT). The raw materials will be washed and dried at 105 °C
for 24 h to remove moisture content. To get raw carbon, a silica crucible contain 10g of of AHs
will be kept in furnace at 350 °C and the activation step will be carried out after the carbonization
step at 720 °C for 1 h under purified CO2 at flowrate of 300 mL/min for 1 h. Figure 3.1 shows the
steps to prepare activated carbon.

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 Figure 3.1 Preparation of Activated Carbon

3.4 Green Synthesis of Zinc Oxide Nanoparticles (ZnO-NPs)

This study will involve the synthesis of zinc oxide nanoparticles (ZnO-NPs) via green synthesis
to utilize Cleome viscosa plant extract. Stoichiomteric amount of zinc nitrate will be added to 10
mL of Cleome viscosa plant extract 10 mL of deionized in a beaker. The solution will be stirred
continuously to achieve a homogenous mixture. Then, the solution will be transferred to a crucible
and heated in furnace at 400 °C for 1 hours to obtain the ZnO precursor. Before doping process,
ZnO precursor will undergo the analysis using thermalgravimetric analysis (TGA) and Fourier
Transform Infra Red Spectroscopy (FTIR). TGA will be used to determine their stability and
identify the calcine temperature while FTIR to identify functional group presence in the precursor
coming from plant extract. The calcination process will be conducted at two different
temperatures from TGA data to form ZnO-NPs. The process is outlined in Figure 3.2.

Figure 3.2 Green Synthesis of ZnO-NPs

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3.4.1 Synthesis of Activated Carbon Doped Zinc Oxide Nanoparticles (AC/ZnO-NPs)

For synthesis of zinc oxide doped with activated carbon (AC/ZnO-NPs), ZnO-NPs will be added
to activated carbon prepared from Arecha catechu with various concentrations of 1%, 3% and
5%. The mass of each starting material used will be determined using a weight percentage
calculation. Then, the materials will be dissolved in deionized water and will be stirred until both
ZnO-NPs and activated carbon dissolved completely. The solutions will be placed in crucible and
put it in oven then will be heated at 150 °C for 24 hours to get final products which is AC/ZnO-
NPs. Figure 3.3 shows the flow chart the synthesis AC/ZnO-NPs.

Figure 3.3 Flow Chart to Synthesis of AC/ZnO-NPs

3.5 Material Characterization

The evaluation and analysis of the study on ZnO-NPs doped with activated carbon will be
conducted using the following instruments.

3.5.1 Thermogravimetric Analysis (TGA)

Thermogravimetric analysis (TGA) is a method used to study materials by observing the weight
changes when exposed to different temperatures. TGA provides information about heat resistance,
how much they break down, and weight lose during photodegradation process. For instance, in
the case of synthesizing ZnO-NPs doped with activated carbon using the green synthesis, TGA
was used.

3.5.2 Fourier Transform Infra Red Spectroscopy (FTIR)

Fourier Transform Infra Red (FTIR) is a quick, easy, and economical technique compared to other
characterization techniques used to identify characteristics of functional groups exist in ZnO-NPs
synthesized via green synthesis. Figure 3.4 shows the FTIR (Perkin Elmer Spectrum BX) that
will be used to identify presence of functional groups in ZnO-NPs and AC/ZnO-NPs produced
from green synthesis method using Cleome viscosa.

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 Figure 3.4 Fourier Transform Infra Red Spectroscopy

3.5.3 Scanning Electron Microscopy (SEM)

Scanning Electron Microscopy (SEM) is technique used to characterize surface morphology,

microstructure of materials and particle size. Single nanoparticles (NPs) with diameters below 10
nm may be imaged in great resolution due to developments in SEM (Hodoroaba et al., 2016).

For the sample preparation, double sided carbon adhesive will be applied onto stub and remove
the protective film. Wait until the sample dried, then, load the sample onto the sample stage within
the SEM chamber. Figure 3.5 shows the summary of the preparation of sample using SEM
technique.

Figure 3.5 Preparation of sample for SEM technique

3.5.4 Accelerated Surface Area and Porosimetry (ASAP)

Accelerated surface area and porosimetry (ASAP) used to analyze pore size and pore volume of
ZnO-NPs by using BET (Brunnaeur, Emmett and Teller) theory. The results from ASAP technique
can be used to optimize the properties of AC/ZnO-NPs.

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3.5.5 Ultraviolet Visible Spectroscopy (UV-Vis)

For further characterization, UV-Vis spectroscopy is used to get the information absorbance
spectrum between 200 nm to 800 nm. Both sample ZnO-NPs and AC/ZnO-NPs solution will be
filled in the cuvette and placed into the sample compartment and use suitable solvent as a
reference. The data is then displayed in spectrum where absorbance against concentration. The
summary of the procedure to use UV-Vis is shown in Figure 3.6.

Figure 3.6 Procedure of UV-Vis instrument

3.5.6 X-Ray Diffraction (XRD)

X-Ray Diffraction (XRD) is a useful method for studying the crystal structure, crystallinity, and
phase composition of materials. The size of crystallite correlates with the peak width in XRD.

3.6 Photodegradation of Methyl Red

The degradation of methyl red dye as a model pollutant will be used to investigate the
photocatalytic activity of the ZnO-NPs where sunlight will be used as energy source. A 15 ppm
stock solution of methyl red will be prepared and 40 mg of each ZnO-NPs and AC/ZnO-NPs will
be used in 100 mL of dye stock solution. Before both sample expose to the sunlight, the solution
will be mixed and stirred using a magnetic stirrer in dark environment to get absorption-
desorption equilibrium.

All experiments will be carried out under direct solar radiation, specifically sunny days in
between 10 AM to 4 PM when the light intensity variations will be negligible. Thereafter, for
every 30 minutes, 5 mL of the solutions that will be exposed to sunlight will be taken out using a
syringe. Then, use the filter paper to separate the catalyst before conducting the absorption
measurement. The UV-Vis spectroscopy will be use to identify the photocatalytic activity in
absorbance and the percentage of degradation of methyl red solution will be calculated by using
the following equation

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 Ao - At
% degradation = × 100%
Ao

where Ao and At is initial absorbance of methyl red dye and absorbance of methyl red at each time
interval “t” respectively. Figure 3.7 shows the summary to study photocatalytic activity of both
ZnO-NPs and AC/ZnO-NPs towards methyl red dye.

Figure 3.7 Photodegradation activity of ZnO-NPs and AC/ZnO-NPs towards methyl red dye

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 CHAPTER 4

EXPECTED OUTCOME

It is expected that zinc oxide nanoparticles (ZnO-NPs) and activated carbon doped zinc oxide
nanoparticles (AC/ZnO-NPs) will be successfully synthesized with Cleome viscosa plant extract
using more sustainable route which is green synthesis. The product is expected appear as yellow
powder after undergo a calcination at three different temperatures of 300 °C, 500 °C, and 700 °C.

Both nanoparticles (NPs) will be characterized using Thermogravimetric Analysis (TGA), Fourier
Transform Infra Red Spectroscopy (FTIR), Ultraviolet Visible Spectroscopy (UV-Vis), Scanning
Electron Microscopy (SEM), Accelerated Surface Area and Porosimetry (ASAP), and X-Ray
Diffraction (XRD). Each instruments and techniques will provide different information about
ZnO-NPs and AC/ZnO-NPs.

Lastly, the photodegradation activity of both ZnO-NPs and AC/ZnO-NPs will be evaluated
towards the degradation of methyl red dye. It is expected that AC/ZnO-NPs will show % of
degradation higher than ZnO-NPs.

23