FYP Report (Ver-4)

PHOTOCATALYTIC ADSORPTION PROCESS USING
SYNTHESIZED CELLULOSE BASED QUANTUM-

DOTS ADSORBENT
By
WONG ZHI CHENG
A Report Submitted in Partially Fulfilment of the

Requirement for the Degree of BEng (Hons) Chemical
Engineering
Faculty of Engineering, Technology & Built Environment
UCSI University
May 2018
1
ACKNOWLEDGEMENT
I am greatly indebted to the wonderful people ho have aided me professionally

as well as personally, without whose help this thesis would not have been possible.
First of all, I would like to take this opportunity to express my utmost

gratitude to my supervisor, Asst. Prof. Dr, Ng Ching Yin for her patience, valuable
guidance and advice throughout the whole project. Her encouragement, support, and
inspiring knowledge was much appreciated. I am grateful to be under her
supervision and would like to acknowledge her contribution during my final year
project.
“Furthermore, special thanks to my university, UCSI University for providing

me with a comfortable environment and instruments needed to carry out my final year
project. I also would like to take this opportunity to express uncountable thanks to the
lab officers for their help throughout the experimental work in indicating the equipment
and devices that I required and in making the setup for the process.”
Apart from that, I would also like to thank my friends who supporting,
motivating, giving advices and encourage me throughout my whole research period. I
am greatly appreciative for their help with experimental and studies.
Last but not least, I would like to thank to my parents for their sincere supports
and constant encouragement they have given to me in the completion of the project.
This project would not been carried out smoothly without the help, guidance and
support from all of them. My family has been my greatest strength and I cannot thank
them enough.
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DECLARATION OF ORIGINALITY & EXCLUSIVENESS
I hereby declare that the dissertation is based on my original work except for
quotations and citations which have been duly acknowledged. I also declare
that it has not been previously or concurrently submitted for any other
degree at UCSI or other institutions.
___________________________
WONG ZHI CHENG
1001436835
Date:
Supervised by:
____________________________
ASST. PROF. DR. NG CHING YIN
Date:
ii
ABSTRACT
iii
TABLE OF CONTENT
Page
ACKNOWLEDGEMENT i
ABSTRACT iii
TABLE OF CONTENT iv
LIST OF TABLES viii
LIST OF FIGURES ix
LIST OF EQUATIONS x
CHAPTER I 11
1.1 INTRODUCTION 11
1.2 PROBLEM STATEMENT 13
1.3 RESEARCH OBJECTIVES 15
1.4 SCOPE OF STUDY 15
1.5 ORGANIZATION OF THESIS 16
CHAPTER II 18
2.1 OIL PALM 18
2.1.1 Oil Palm Empty Fruit Bunch (OPEFB) and its structure 19
2.2 CELLULOSE 20
2.2.1 Structure of cellulose 20
2.2.2 Extraction of cellulose 21
2.3 QUANTUM-DOTS 22
2.3.1 Carbon Quantum Dots 24
2.3.2 Sources of Carbon Quantum Dots 25
2.3.3 Application of Carbon Quantum Dots (CQDs) 25
2.4 SYNTHESIS OF CARBON QUANTUM DOTS 26
2.4.1 Microwave Assisted Method 28
2.4.2 Hydrothermal Method 30
2.5 DYE REMOVAL 32
iv
2.5.1 Dye 32
2.5.2 Methylene blue 33
2.5.3 Current technologies for dye removal 34
2.6 ADSORPTION 35
2.6.1 Chemisorption and Physisorption 36
2.6.2 Adsorbent 37
2.6.3 Adsorption in dye removal application 39
2.7 PHOTOCATALYTIC ADSORPTION 39
2.8 FACTOR AFFECTING THE PERFORMANCES OF ADSORPTION 41
2.8.1 Effect of pH 41
2.8.2 Effect of contact time 42
2.8.3 Effect of initial concentration of dye 43
2.9 ADSORPTION ISOTHERM 44
2.9.1 Langmuir Isotherm 44
2.9.2 Freundlich Isotherm 45
2.10 ADSORPTION KINETICS 46
2.10.1 Pseudo-first-order kinetic model 47
2.10.2 Pseudo-second-order kinetic model 47
2.11 RESEARCH SURFACE METHODOLOGY (RSM) 48
2.11.1 Central Composite Design (CCD) 48
2.11.2 Box-Behnken Design 49
2.12 CHARACTERIZATION TECHNIQUES 50
2.12.1 Scanning Electron Microscope (SEM) 50
2.12.2 UV-Vis Spectroscopy 51
CHAPTER III 53
3.1 MATERIALS AND CHEMICALS 53
3.2 EQUIPMENT 54
v
3.3 RESEARCH METHODOLOGY FLOW CHART 54
3.4 EXTRACTION OF α-CELLULOSE FROM AGROWASTE-OIL PALM

EMPTY FRUIT BUNCH (OPEFB) 56
3.4.1 Preparation of Oil Palm Empty Fruit Bunch (OPEFB) 56
3.4.2 Pre-treatment of Oil Palm Empty Fruit Bunch (OPEFB) 56
3.4.3 Bleaching Treatment 57
3.4.4 Extraction of alpha-cellulose 57
3.5 SYNTHESIS OF CARBON QUANTUM DOTS (CQDs) FROM

EXTRACTED ALPHA-CELLULOSE 59
3.5.1 HYDROTHERMAL SYNTHESIS METHOD 59
3.5.2 Characterization of samples 59
3.6 ADSORPTION PERFORMANCE USING RESEARCH SURFACE

METHODOLOGY (RSM) APPROACH 60
3.7 REMOVAL OF METHYLENE BLUE DYE 61
3.7.1 Calibration of Methylene Blue Solutions Standard Curve 61
3.7.2 Batch Adsorption Experiment 62
3.7.3 Photocatalytic Adsorption Experiment 64
3.8 ISOTHERM ANALYSIS OF ADSORPTION 64
3.8.1 Langmuir isotherm model 65
3.8.2 Freundlich isotherm model 66
3.9 KINETICS STUDIES OF ADSORPTION 66
3.9.1 Pseudo-first-order kinetic model 67
3.9.2 Pseudo-second-order kinetic model 67
CHAPTER IV 68
4.1.1 PERCENTAGE YIELD OF CELLULOSE 68
4.2 ADSORPTION PROCESS OF METHYLENE BLUE ON CELLULOSE 68
4.2.1 RSM Modelling 68
4.2.2 Effect of Experimental Parameters 72
vi
4.2.3 RSM Optimization 77
4.3 SYNTHESIS AND CHARACTERIZATION 78
4.3.1 SEM 79
4.3.2 Particle Size Distribution 80
4.3.3 Zeta-Potential 80
4.4 PHOTOCATALYTIC ADSORPTION OF METHYLENE BLUE ON CQDs

82
4.4.1 RSM Modelling 82
4.4.2 Effect of Experimental Parameters 85
4.4.3 RSM Optimization 90
4.5 COMPARISON OF CELLULOSE ADSORBENT AND CQDs ADSORBENT

IN DYE REMOVAL 91
4.6 Isotherm Analysis 91
4.7 Kinetics Analysis 96
CHAPTER V 100
REFERENCES 102
APPENDICES 119
APPENDIX 1 119
APPENDIX 2 121
APPENDIX 3 121
APPENDIX 4 122
APPENDIX 5 123
APPENDIX 6 124
APPENDIX 7 127
APPENDIX 8 130
APPENDIX 9 131
APPENDIX 10 132
vii
LIST OF TABLES
TABLE II.1 Annual Generation of Oil Palm Biomass...............................................18

TABLE II.2 Synthesis CQD from various carbon sources relevant to different
applications. 26
TABLE II.3 The advantages and disadvantages of different synthesis methods
for the preparation of CQDs........................................................................................27
TABLE II.4 Classification of dyes...............................................................................33
TABLE II.5 Dye removal technology with respect to their advantages and
disadvantages 34
TABLE II.6 Previous research on the removal of different dyes by agricultural
sorbent 37
TABLE II.7 Number of experiments for different factors (Otto, 2007)...............50
TABLE 0.1 List of materials and chemicals used.......................................................53
TABLE 0.2 Experimental range and factor level of process variables applied.......60
TABLE 0.3 Design matrix for experimental factors at different factor levels........60
TABLE 0.1 Box-Behnken design matrix of three factors along with
experimental and predicted responses for methylene blue dye removal..................69
TABLE 0.2 ANOVA for the response surface quadratic model...............................70
TABLE 0.3 RSM Optimization for adsorption of methylene blue on cellulose......78
TABLE 0.4 Box-Behnken design matrix of three factors along with
experimental and predicted responses for removal of methylene blue by CQDs....82
TABLE 0.5 ANOVA for the response surface quadratic model for removal of
methylene blue by CQDs..............................................................................................83
TABLE 0.6 RSM Optimization for adsorption of methylene blue on cellulose......90
Table 0.7 Comparison of cellulose adsorbent and CQDs adsorbent in removal
of methylene blue dye....................................................................................................91
TABLE 0.8 Comparison of Langmuir and Freundlich isotherm constants for
removal of methylene blue by Cellulose and CQDs adsorbents...............................93
TABLE 0.9 Comparison of pseudo-first and pseudo-second order for removal
of methylene blue by cellulose and cellulose-based CQDs.........................................97
viii
ix
LIST OF FIGURE
FIGURE 2.II.1 Schematic drawing of cell wall hierarchical structure of OPEFB

[Adapted from Kolakovic et al., 2012].........................................................................22
FIGURE 2.II.2 Structure of cellulose [Adapted from Kontturi et al., 2006]..................24
FIGURE 2.II.3 Scheme of quantum dot structure.....................................................25
FIGURE 2.II.4 Colour emission of carbon dots solution under UV radiation
indicated wavelength directly [Adapted from Sun et al, 2006].................................26
FIGURE 2.II.5 Illustration of CDs (a)Elementary CDs; (b)After functionalization
with surface passivation reagents [Adapted from Zuo et al., 2015]..........................27
FIGURE 2.II.6 Scheme representation of microwave assisted method [Adapted
from Zhu et al. (2009)]..................................................................................................32
FIGURE 2.II.7 Schematic representation of the microwave assisted method to
obtain the CQDs from raw cashew gum [Adapted from Pires et al. (2015)]...........32
FIGURE 2.II.8 A typical hydrothermal autoclave.....................................................34
FIGURE 2.II.9 Illustration of CQDs formation from orange juice via
hydrothermal treatment...............................................................................................34
FIGURE 2.II.10 Structure of Methylene Blue................................................................36
FIGURE 2.II.11 Basic process of adsorption [Adapted from Worch, 2012]...........39
FIGURE 2.II.12 Schematic Diagram and Steps involved in Heterogeneous
Photocatalysis [Adapted from Bora and Mewada, 2017]..........................................43
FIGURE 3.0.1 Research Methodology Flow Chart....................................................58
FIGURE 3.0.2 Washed OPEFB in Ethanol/Hexane Mixed Solvent.........................59
FIGURE 3.0.3 OPEFB fibers after bleaching treatment...........................................60
FIGURE 3.0.4 Alkaline treatment of bleached fibers................................................61
FIGURE 3.0.5 Extracted Cellulose..............................................................................61
FIGURE 3.0.6 Teflon-lined stainless steel autoclave..................................................62
FIGURE 3.0.7 Calibration Curve of Methylene Blue Dye........................................65
FIGURE 3.0.8 Adsorption experiment for methylene blue removal (a) Before (b)
After................................................................................................................................66
FIGURE 3.0.9 Photocatalytic adsorption of methylene blue on cellulose-based
CQDs under UV light....................................................................................................67
x
FIGURE 4.0.1 Plot of Correlation between Predicted and Experimental values for
MB Percentage removal by Cellulose Adsorbent.......................................................74
FIGURE 4.0.2 (a) Response surface plots and (b) Contour for MB percentage
removal by cellulose as a function of pH and Contact time [Condition: initial
concentration of MB = 6 mg/L]....................................................................................75
removal by cellulose as a function of initial concentration of MB and Contact time
[Condition: pH = 7].......................................................................................................76
removal by cellulose as a function of initial concentration of MB and pH
[Condition: Contact time = 25 mins]...........................................................................77
FIGURE 4.0.5 CQDs solution under (a) white light; (b) UV light............................81
FIGURE 4.0.6 SEM image of cellulose fibers (a) before adsorption (b) after
adsorption.......................................................................................................................82
FIGURE 4.0.7 Particle Size Distribution of cellulose-based CQDs..........................83
FIGURE 0.8 Zeta Potential distribution of cellulose......................................................84
FIGURE 4.0.9 Zeta Potential distribution of cellulose-based CQDs..............................84
FIGURE 4.0.10 Plot of Correlation between Predicted and Experimental values
for MB Percentage removal by CQDs Adsorbent......................................................87
removal by CQDs as a function of pH and Contact time [Condition: initial
concentration of MB = 6 mg/L]....................................................................................88
removal by CQDs as a function of initial concentration of MB and Contact time
[Condition: pH = 7].......................................................................................................89
removal by CQDs as a function of initial concentration of MB and pH [Condition:
Contact time = 25 mins]................................................................................................90
FIGURE 4.0.14 Langmuir Isotherm Plot for Methylene Blue dye onto Cellulose..95
FIGURE 4.0.15 Freundlich Isotherm Plot for Methylene Blue dye onto Cellulose 95
FIGURE 4.0.16 Langmuir Isotherm Plot for Methylene Blue dye onto cellulose-
based CQDS...................................................................................................................96
xi
FIGURE 4.0.17 Freundlich Isotherm Plot for Methylene Blue dye onto cellulose-
based CQDs....................................................................................................................96
FIGURE 4.0.18 Plot of Separation Factor vs Initial concentration of methylene
blue..................................................................................................................................98
FIGURE 4.0.19 Pseudo-first-order kinetic for adsorption of methylene blue onto
cellulose...........................................................................................................................99
FIGURE 4.0.20 Pseudo-second-order kinetic for adsorption of methylene blue onto
cellulose...........................................................................................................................99
cellulose-based CQDs....................................................................................................99
cellulose-based CQDs..................................................................................................100
xii
LIST OF EQUATIONS
xiii
CHAPTER I
INTRODUCTION
1.1 INTRODUCTION
Nowadays, over thousands of various dyes are widely used in manufacturing,

leather, fabric dying, pharmaceutical, printings, and cosmetics industries. These dyes
will then end up in the industries disposal and is a potential source of rivers and
waterways pollution (Jin et al., 2015). The dyes in water are highly visible, have acute
and chronic toxicities that causes adverse effects to the living organism and it is difficult
to be removed (Jin et al., 2015). In Malaysia, for instance, wastewater treatment is a
vital focus of government. Therefore, an economically viable alternative for the removal
of pollutants by adsorbent that is easily available inexpensive and affordable method
which prefer by industries.
Various methods such as photocatalytic degradation (Sohrabi and Ghavami,

2008), coagulation/flocculation (Fosso-Kankeu et al., 2017), membrane filtration
(Melbiah et al., 2017), advanced oxidation (Miodrag, 2014), electrolysis (Shen et al.,
2001) and adsorption (Pang and Abdullah, 2013) have been used in treating dye
containing water. Photocatalytic adsorption, which is also known as advanced oxidation
processes (AOPs), is one of the modern methods widely employed for the dye removal
(Pandit, V.K. et al., 2015). Therefore, it is a great challenge to develop new adsorbents
with good adsorption efficiency for treatment of dyes pollution. However, over the past
few years, cellulose is being known as a new type of versatile adsorbents to be applied
in dye removal application (Li et al., 2014). Several researches have demonstrated that
the cellulose can be extracted from different biomass such as wood pulp, rice husk,
wheat, sugar cane, pineapple, bananas, and coconut crops (Song et al., 2016). However,
in Malaysia, Oil Palm biomass is considered as the most abundant renewable resources,
14
thus, oil palm empty fruit brunch (OPEFB) agro-waste will be used as a source for α-
cellulose extraction in this study.
Cellulose is an important element of plant’s main cell wall. It is an organic

compound which possesses structural formula of (C 6H10O5)n. As a long-
polysaccharides, cellulose is consist of linear homopolymer of β-D-glucopyranose units
and multiple hydroxyl groups, which offer abundant active adsorption sites and provide
high possibility of functionalization in order to improve its adsorption capacity (Qiao et
al., 2015). Cellulose can be easily obtained from natural sources such as plants, banana
peels, coconut husk, sugar canes and many more. In addition, these are considered as
renewable thus ensuring cellulose to be obtained at low cost too. Low cost might be one
of the factors that encourage the cellulose to be utilized. For the extraction or isolation
of cellulose, there are many different methods that can be used. These methods include
acid hydrolysis, alkali treatment, ultrasound treatment and many more.
Quantum dots are referred as a high-quality colloidal semiconductor

nanocrystals, which have gained crucial attentiveness due to their size-tunable
properties and flexibility throughout the past several decades (Qian et al., 2006). The
number of atoms range from 1000 to 10000 in a quantum dot, causes it to be neither a
solid substance nor a single molecular entity. Recently, several methods have been
introduced to produce quantum dots and several factors can be controlled such as the
size of the QD particle, solubility and emission properties. (Njuguna et al., 2014)
The successful of producing quantum dots will definitely bring the cellulose
application to a higher level in cellulose study. To date, quantum dots are recognized as
a useful tool in monitoring the cancer cells, produces inexpensive white LEDs,
photovoltaic solar cells (Karmakar, 2015). In this study, dye is chosen as a first waste
element in determining the effectiveness of using quantum dots synthesized from
cellulose. This study can act as a first and primarily in nanotechnology research.
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1.2 PROBLEM STATEMENT
The contamination of water due to dye pollution has aroused the concern of the
global community. Hence, efficient dye removal application is a growing concern in
water resources management around the world. Adsorption on activated carbon can be
known as one of the best and widely used method for dye removal. However, it is very
costly. Therefore, there is a need to extract low-cost adsorbent from local biomass
resources that can be obtained readily. New inexpensive, easily obtainable and highly
effective adsorbents are still needed.
In order to synthesis adsorbent that is more cost-effective, environmentally

friendly, and sustainable to be used in dye removal application, it is important to
produce adsorbent from inexpensive agriculture, agro-wastes, or wood. To date,
researchers have reported that oil palm empty fruit bunch (OPEFB) can be used as an
effective adsorbent for removal of dyes. According to Hameed and El-Khaiary (2008),
OPEFB has been successfully utilized as a low-cost adsorbent for the removal of
malachite green, and the adsorption results were investigated by adsorption isotherm.
Ofomaja and Ho (2007), also discovered the potential of OPEFB as a good adsorbent
for the removal of anionic dyes. Besides, several modification techniques on OPEFB
have been studied as an effective adsorbent for dyes removal from wastewater. For
example, Shanmugarajah et al. (2019) isolated nanocrystalline cellulose from OPEFB to
study its methylene blue adsorption behaviour, and the modification was successful
where 144.93 mg/g of maximum monolayer adsorption capacity was determined.
Large specific surface area and high number of adsorption sites are absolutely
necessary for adsorption treatments in order to remove dyes impurities from
wastewater. Over the past decades, scientists have reported that nanosized adsorbents
are being used progressively in dye removal due to their greater active sites, higher
surface area and good adsorption efficiency (Savage and Diallo, 2005). Quantum dots
(QD) which was first discovered in glass crystals in 1980 by a Russian physicist,
16
Ekimov whose has brought the promotion in nanotechnology research (Ekimov and
Onoshchenko, 1982). According to Bajorowicz et al. (2018), QDs are the new category
of nano-dimension materials which have high functionalization possibility. QDs have
fascinated significant interest for their large surface to volume ratio and the quantum
confinement effects which resulting in extraordinary structural, optical and electronic
properties. Due to these properties, QD have been used commonly as an adsorbent to
remove organic dyes (Bajorowicz et al., 2018). Several researches have been reported
that carbon sources can be used to prepare carbon quantum dots (CQDs). Hence,
cellulose molecule that contains a large amount of hydroxyl and ether groups provide
the fundamental and structural basis for the formation of CQDs (Wu et al., 2017). The
existence of the great number of oxygen-containing functional groups such as -OH,
C=O, -NH2 and -COOH on the surface of CQD has caused high solubility in water and
functionalization ability with various substances (Zuo et al., 2015).
To date, various methods to synthesis QDs from natural resources have been
developed, For example, Pires et al. (2015) have reported that raw cashew gum is used
as precursor to obtain CQDs via microwave assisted method. Besides, Sahu et al.
(2012) synthesised CQDs using orange juice with ethanol via hydrothermal technique.
Grass was also used as precursor to synthesis quantum dots through hydrothermal
treatment (Liu, et al., 2012) However, no studies have been reported on the use of
OPEFB for the synthesis of QDs and to be used in the application on dye removal.
Thus, this study was undertaken to investigate the adsorption efficiency using cellulose-
based quantum dots adsorbent for dye removal. The effects of pH, contact time and
initial dye concentration were evaluated by batch process with Research Surface
Methodology Approach. Investigation on adsorption isotherms and kinetics were also
carried out.
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1.3 RESEARCH OBJECTIVES
The principal objective of this research is to investigate the possibility of

synthesising cellulose into quantum dots to be used as an adsorbent in dye removal
application. The objectives of this study are:
i. To extract the cellulose from agro-waste Oil Palm empty fruit bunch
(OPEFB).
ii. To synthesis quantum dots adsorbent from extracted cellulose.
iii. To investigate the performance of cellulose-based quantum dots in dye

removal application using RSM approach.
1.4 SCOPE OF STUDY
This study was firstly focus on the extraction of cellulose from agriculture wastes
which are oil palm empty fruit bunch (OPEFB) that were discharged as biomass from
oil palm production. Pre-treatments of OPEFB such as size reducing, removal of
impurities, and bleaching treatment were carried out to enhance the extraction of
cellulose. Then, alkaline treatment was performed using 17.5 % NaOH to extract the
cellulose from treated OPEFB.
The second part of this research was then proceeded to synthesis quantum dots
adsorbent from extracted cellulose. Hydrothermal method was conducted by adding
cellulose fibers and distilled water into Teflon stainless steel autoclave and heated in an
18
oven at high temperature for overnight. The physiochemical characteristics of the CQDs
were studied using Scanning Electron Microscope (SEM) and zetasizer.
At the end of the research, batch photocatalytic adsorption experiment was

conducted to investigate the performances of quantum dots adsorbents in dye removal
application. In this experiment, methylene blue dye was used as adsorbate. The
percentage removal of the methylene blue dye was determined and compared between
cellulose adsorbent and CQDs adsorbent. In adsorption studies, there were several
factors taken into consideration that will affect the adsorption efficiency in dye removal,
for example, the effect of pH, contact time, and initial concentration of dye. Best
parameters for better controlling of the adsorption process in dye removal were
determined. Besides, best fitting of adsorption isotherms was determined to identify the
kind of interaction between the adsorbate and adsorbent in dye removal application. The
adsorption kinetics which demonstrates the rate of transport of the dye particles from
solution to the surface of adsorbent were also investigated by pseudo-first order and
pseudo-second-order kinetic models.
1.5 ORGANIZATION OF THESIS
There are five chapters in this thesis and each of the chapter is focusing on
specific discussion on different aspects throughout the research project.
Chapter I describes the overview of this study “Photocatalytic Adsorption Process

Using Synthesized Cellulose Based Quantum-Dots Adsorbent”. An introduction about
the current water pollution resulted from dye was presented. The problem statement
further describes the needs to synthesis cellulose into quantum dots which will be able
to produce a more efficient adsorbent for dye removal from wastewater. Besides, the
objectives of this research are also stated clearly in this chapter. Lastly, the scope of
study is elaborated to describe the overall procedures for this research.
19
Chapter II presents the literature review of this research project in detail manner.
This chapter starts with explanation of OPEFB and cellulose. The details and types of
quantum dots, properties and preparation methods of quantum dots, as well as further
reviews on the application of quantum dots are also illustrated. Other methods of dye
removal are briefly elaborated, and the mechanism of adsorption and photocatalytic
adsorption are explained. Isotherm and kinetics studies of adsorption are well described
with equations. Lastly, the process parameters that will affect the adsorption efficiency
are described.
Chapter III provides the details of all the chemicals, equipment and methodology
in this research. Firstly, chemicals and equipment required in this study are listed down
and explained along with their respective purpose. A process flow chart is also
performed. The subsequent sections described the procedures to conduct the
experiment, including extraction of cellulose from OPEFB using bleaching followed by
alkaline treatment, synthesis of carbon quantum dots (CQDs) using hydrothermal
synthesis method and analysis using SEM and Zetasizer. Lastly, the procedures in
adsorption and photocatalytic adsorption experiment using RSM approach are explained
including the isotherm and kinetic studies.
Chapter IV describes in detail the experimental results of extraction of cellulose

and cellulose based CQDs. Particle size, zeta-potential and surface morphology of
synthesized CQDs are shown. The experimental results obtained from adsorption and
photocatalytic adsorption experiment are discussed using RSM approaches,
optimization of experimental results is presented, experimental terminologies are
explained, and the adsorption isotherm and kinetic studies are discussed as well.
Chapter V lay outs the conclusion or overall experiment.
20
CHAPTER II
LITERATURE REVIEW
2.1 OIL PALM
Oil palm tree, species of Elaeis guineensis belongs to the Palmacea family,
originated from West Africa tropical forests is one of the most valuable and important
commercial crops for worldwide mostly in Malaysia, Thailand and Indonesia country.
Malaysia was acknowledged as the first country in terms of processing and large-scale
planting (Abdul Khalil et al., 2012). Approximately 50% of the world’s production
were came from Malaysia. Around 70.21 million metric tons yield of crude oil palm
produced in 2017, and the biomass generated from the oil palm processing are shown in
Table 2.1 (Kushairi, A. et al., 2018). As such, the huge production of oil palm biomass
has generated large amount of waste, creating environmental concern. Therefore, the
biomass consumption towards proper economic utilization will be beneficial in creating
value added products and solving the disposal problem.
TABLE II.1 Annual Generation of Oil Palm Biomass
Oil Palm Biomass Annual Generation (million tonnes)

Empty Fruit Bunch (EFB) 7.34
Palm Kernel Shell (PKS) 4.46
Pressed Fruit Fiber (PFF) 7.1
Oil Palm Frond (OPF) 37.7
Oil Palm Trunk (OPT) 13.0
MF 7.72
Palm Oil Mill Effluent (POME) 3.0
2.1.1 Oil Palm Empty Fruit Bunch (OPEFB) and its structure
21
Oil palm empty fruit bunch (OPEFB) is one of the main solid wastes from oil
palm mill processing. It is an abundant agricultural biomass where the source comes
from oil palm tree by-product. The EFB is the empty bunch that is left behind and
obtained after the oil palm fruit had been removed in the oil extraction process during
harvesting. Fresh EFB accumulates around 12.4 million tons per year are regularly
discharged from oil palm refineries where some quantity of this is used as fuel, while
the rest is left unexploited (Abdul et al., 2012).
OPEFB is composed mainly of cellulose (41.3–46.5%), hemicellulose (25.3–

33.8%) and lignin (27.6–32.5%) (Ariffin et al., 2008; Hamzah et al., 2011; Han et al.,
2011; Piarpuzán et al., 2011). The OPEFB fibers also known as lignocellulosic fibers
consist of high cellulose content and certain amount of organic compound such as
hemicellulose and lignin. The schematic drawing of cell wall ultrastructure and
cellulose organization hierarchical structure of oil palm tree are shown in Figure 2.1.
FIGURE 2.II.1 Schematic drawing of cell wall hierarchical structure of OPEFB

[Adapted from Kolakovic et al., 2012]
The existence of amorphous and crystalline regions is shown in lateral fiber

structure. This high in cellulose content properties of OPEFB represents quality as
potential natural fiber resource. Moreover, OPEFB consists of 42% C, 0.8% N, 0.06%
22
P, and 2.4% K and 0.2% Mg (Krause, 1994). Thus, exploring the beneficial and
practical oil palm biomass utilization as reinforcement in natural fiber based composites
will help to reduce the environmental problems issue as associated with the oil palm
wastes disposal in industry (Abdul Khalil et al., 2012a,b)
2.2 CELLULOSE
Cellulose is a natural occurring linear polymer of anhydroglucose that is found

abundantly on earth (Kester and Fennema, 1986). Elemental composition of cellulose
was first determined by Payen in 1838 to have the empirical formula of C 6H10O5
whereby he found the composition of 44.4 % C and 6.2 % H in an elemental analysis of
cellulose (Payen, 1842; Krassig and Schurz, 1986). Cellulose is usually a type of cheap,
biodegradable and renewable polymer which is fibrous, tough and water insoluble and
helps in sustaining the structure of the cell walls of plants, oomycetes and algae. (Suhas
et al. 2016). Furthermore, cellulose was described as a material which is resistant to the
extraction with water, ether or ethanol (Payen, 1842).
2.2.1 Structure of cellulose
Cellulose is actually a polysaccharides which these carbohydrate polymers

literally has approximately ten to hundreds to several thousand monosaccharide units
bonded by covalent bond (Lavanya et al. 2011). It is the main lignocellulosic
component of cell wall in plants along with hemicellulose, lignin, pectin, wax and
constitutes 25 -50% of the plants (Abraham et al. 2013). The structure of cellulose is
shown in Figure 2.2.
23
FIGURE 2.II.2 Structure of cellulose [Adapted from Kontturi et al., 2006]
These cellulose molecules form a long straight, almost fully extended chain,
where cellobiose are rotated 180° relative to each other along 19 the main axis. Long
cellulose chain is known as α-cellulose where the β-1, 4 glucan chains length depends
on the cellulose source. The quality of celluloid substance has connection with the
degree of polymerization cellulose molecules (Maya Jacob and Sabu, 2008).
2.2.2 Extraction of cellulose
Various efficient methods have been developed by researchers in order to extract

cellulose from cellulosic materials. The cellulose isolation requires the removal of other
substances such as hemicelluloses and lignin from OPEFB. Alkali treatment is
considered as most commonly used method for delignification of lignocellulosic
materials (Thomas et al., 2011). This treatment is applied to disrupt the lignin structure
and to allow the separation of the structural linkages between lignin and carbohydrates.
Chieng et al. (2017) has successfully extracted cellulose fibers from Oil Palm Mesocarp
Fiber (OPMF), where the OPMF was treated in reflux condition with 4 wt% NaOH
solution at 80℃. Then, the alkali-treated fibers were bleached three times to whitening
the products. According to Sun et al. (1998), cellulose was isolated from dewaxed
wheat straw after alkali extraction using sodium hydroxide solution.
24
Besides, Bhattacharya et al. (2008) isolated cellulose microfibers from
sugarcane bagasse (SCB) using a conventional pulping process to remove lignin and
hemicelluloses. Besides, it is found that acid hydrolysis of the cellulose fibers with 60%
(v/v) sulfuric acid for 2.5 hour at 60 ºC was optimum and resulted in the removal of
most of the amorphous domains without any significant damage to the crystal structure.
Furthermore, biological treatment was also used by Kikuchi et al. (2002) with
molecular-genetically bred Coprinus Cinereus monokaryotic strains to isolate cellulose
efficiently from rice straw.
2.3 QUANTUM-DOTS
Quantum dots (QDs) is first discovered by a Russian physicist named Ekimov in

1980s (Ekimov and Onoshchenko, 1982). QDs also referred as inorganic semiconductor
nanomaterials (Lovingood, 2017). As shown in figure 2.2, they are nano-sized particles
composed of a core and a shell that cover the core. Moreover, it can be doped with
metal ions to improve photoluminescence and attached with organic linker on surface to
maintain stability (Centre and Electrochemistry, 2013).
FIGURE 2.II.3 Scheme of quantum dot structure

[Adapted from Bajorowicz et al., 2018]
25
The small size composition of QDs which range from 2-10 nm gives them
unique optical properties that are readily tuneable by altering their size (Pathak et al.,
2006). This size dependent confinement properties provide an advantage for QDs over
bulk semiconductors. As the semiconductor becomes smaller, it begins to approach the
size of the Bohr Radius. Once the size of the semiconductor becomes smaller than the
Exciton Bohr radius, the band gap energy levels are no longer continuous and become
discrete. This is when the semiconductor no longer has bulk semiconductor properties
and is referred to as QDs. Moreover, the small size of QDs particle results in large but
specific energy jumps between energy band gaps of excited electron-hole pairs in the
quantum dot core. Hence, QDs tend to adsorb more energy , and thus emits at shorter
wavelength (Arya et al., 2005). QDs can be commonly studied by UV-Vis absorbance
which characterizes the amount of light that a QD can absorb within a specific size
range. As shown in figure 2.3, colour changes as the wavelength increases, indicate the
size of QD also increases (Sun et al, 2006). Therefore, the physical properties of a QD
can be easily changed by only changing its size.
FIGURE 2.II.4 Colour emission of carbon dots solution under UV radiation

indicated wavelength directly [Adapted from Sun et al, 2006]
Traditionally, cadmium is the main element for the core of the quantum dots
according to the first discovery. However, with the demand of more application
researches such as bioimaging (Ji et al., 2014), biosensing (Wang et al., 2013), solar
cells for energy conversion (Fabregat-santiago and Omez, 2009) and sensor for drug
detection (Gao et al., 2009), several types of QDs have been reported, for example,
26
silicon QDs, carbon quantum dots (CQDs), graphene QDs (GQDs), Ag2Se, Ag2S, InP,
CuInS2/ZnS (Zhu et al., 2013). Among these QDs, carbon quantum dots are the most
popular QDs due to their properties of non-toxic, excellent solubility in water, lower
cost and sustainable sources (Bajorowicz et al., 2018).
2.3.1 Carbon Quantum Dots
Carbon quantum dots (CQDs), which are also recognized as carbon dots (CDs),
are firstly introduced in 2004 during the purification of single walled carbon nanotubes
(Xu et al., 2004). The CQDs can be extracted from natural carbon sources (Pires et al.,
2015). Therefore, CQDs can be synthesised from natural resources which are cost-
effective and environmentally friendly. It has a spherical shape with the diameter less
than 10nm, and consisting numerous oxygen-containing functional groups such as -OH,
-COOH and -NH2 on the surfaces (Cao et al., 2007). The occurrence of functional
groups has provided the potential for further functionalization via surface passivation
agent compared to other carbon materials, which endowing different functional
properties (R. Wang et al., 2017).
FIGURE 2.II.5 Illustration of CDs (a)Elementary CDs; (b)After functionalization

with surface passivation reagents [Adapted from Zuo et al., 2015]
To date, several researches have shown the success application of carbon

quantum dots used in dye removal application. For example, Tadesse et al. (2018) has
27
successfully synthesised “nitrogen doped carbon quantum dots for efficient removal of
methylene blue dye pollutant from contaminated water”, and Mallakpour and
Behranvand (2018) has proven the “synthesis of carbon quantum dots from sustainable
materials using ultrasonic waves in application for methylene blue removal”. This is due
to their high specific surface area, low toxicity, great water solubility, good
biocompatibility (Guo et al., 2017), low cost (Mallakpour and Behranvand, 2018) and
easy functionalization (Pires et al., 2015). Based on the extraordinary properties of
CQDs mentioned, they can be considered as a favourable material for removal of a
diversity of inorganic and organic pollutant.
2.3.2 Sources of Carbon Quantum Dots
Carbohydrate-based resources such as glucose, cellulose, starch and other raw

materials can be used as precursor to synthesis low-cost CQDs (Pires et al., 2015). For
example, citric acid, glucose, raw cashew gum, orange juice, watermelon, lemon juice,
red pepper, carbon powder, starch, glucose and biomass can be the carbon sources to
synthesis CQDs (Paulo et al. 2016). Furthermore, Souza et al. (2016) have
demonstrated that CNCs can be used as versatile precursor for the synthesis of different
species of CQDs. In addition, water has been used as a solvent in the synthesis of CQDs
(Zhao, Zuo and Miao, 2017).
2.3.3 Application of Carbon Quantum Dots (CQDs)
Research on CQDs are mostly focused on synthesis and characterization since

its discovery. Plenty of synthesis methods are reported, and hypotheses on the origin of
photoluminescence are propsed. Besides studying the synthesis and mechanism and
exploring more synthetic methods, the application of CQDs are important topics as
well. Practical application can drive the research f CQDs further and longer.
28
Since CQDs have many hydrophilic surface functional groups, e.g., hydroxyl
groups and carboxyl groups, CQDs have great potential for surface modification,
especially when CQDs also have large surface to volume ratio. The surface
functionalization of CQDs and their application have become the centre of CQDs
related researches since 2013. Table 2.2 has shown the synthesis of CQDs by using
different type precursors that perform different application. More insights and
experiments are expected. To commercialize these CQDs application for daily life or in
the scientific lab, it will take tremendous effort and time. This would be the next focus
point for CQDs in the next decade.
TABLE II.2 Synthesis CQD from various carbon sources relevant to different
applications.
Precursors Application References

Sucrose Drug delivery and biosensing (Chandra et al., 2011)
Starch Photoluminescence properties (PL) (Chandra et al., 2012)
Orange pericarp Nano-biotechnology (Du et al., 2015)
Red pepper Methylene blue removal (Mallakpour and
Behranvand, 2018)
3+
Papaya Detection of Fe (Wu et al., 2012)
Carbon powder Photocatalyst for carbon dioxide (Cao et al., 2011)
conversion
Lemon juice Methylene blue removal (Tadesse et al., 2018)
2.4 SYNTHESIS OF CARBON QUANTUM DOTS
The CQDs which can be obtained from different carbon sources are synthesised
via ‘top-down’ and ‘bottom-up’ strategies. Top-down strategies state that where the
carbon sources were broken down using different methodologies such as
electrochemical oxidation, laser ablation, arch discharge and ultrasonic synthesis (D. da
Silva Souza et al., 2018). Whereas for bottom-up strategy, the CQDs can be obtained
from small precursor molecules such as biomass sources chitosan or lignocellulosic
materials by different heat treatments, for example, hydrothermal treatment or
29
microwave-assisted methods. (D. da Silva Souza et al., 2018). Most of the CQDs were
synthesised through the bottom-up strategies due to the availability of natural carbon
sources as the precursor molecules, easy operation of the techniques used and only few
reaction parameters such as temperature and pressure have to be controlled. Table 2.3
shows the methods for CQD synthesis with comparison of advantages and
disadvantages.
TABLE II.3 The advantages and disadvantages of different synthesis methods for
the preparation of CQDs
Methods Advantages Disadvantages References

Top-down strategy
Laser ablation Adjustable Difficult operation; Sun et al. (2006);
morphology and Expensive; Yang et al.(2009);
size; Low quantum yield; Cao et al.(2007)
Rapid synthesis Harsh condition
Electrochemical High purity; Complicated Li et al. (2014);

oxidation Large scale operation Activity et al.
production; (2013)
Adjustable size;
Good reproducibility
Chemical Easy operation; Non-uniform size X. Yu et al (2013)

oxidation Large scale distribution.
production;
No elaborate
equipment.
Ultrasonic Easy operation Instrument wastage; Zhuo et al. (2012)

treatment High energy cost;
Undesirable changes
caused.
Bottom-up strategy
Microwave Short reaction time; High energy cost. Qi Wang, Xing Liu
synthesis Uniform size (2012);
distribution; Xiao et al. (2013)
Adjustable size.
TABLE 2.3 – Continued

Thermal Easy operation; Non-uniform size Martindale et al.
decomposition No solvent is distribution. (2015)
30
needed:
Cheap;
Large scale
production.
Hydrothermal High quantum Poor control over Bian et al. (2014)

treatment efficiency; size. Tadesse et al.,
Inexpensive; (2018)
Non-toxicity.
2.4.1 Microwave Assisted Method
Microwave is a technique that utilizes electromagnetic waves with a broad

wavelength range of 1mm to 1m, corresponding to the frequency of 30GHz to 0.3 GHz,
which induces heat energy to breakdown the chemical bonds of a molecule (R. Wang et
al., 2017). Traditionally, a conventional hydrothermal synthesis which used water bath
or oil bath takes much longer time for transferring energy into the compound (Kappe,
2004). Thus, the synthesis of CQDs by microwave assisted methods is more preferable
due to higher reaction rate, lower energy usage as compared to conventional
hydrothermal synthesis. This has shown its advantages which allows quicker reactions
by heating the precursors on the molecular level through absorption of microwave
energy (Lovingood, 2010).
Zhu et al. (2009) have firstly reported an efficient and simplified microwave
assisted method to synthesis CQDs with outstanding water solubility using only few
minutes. Carbohydrate was used as the carbon source and PEG200 as the passivating
agent, both were mixed with the water which acts as solvent and gradually changed
from colourless to dark brown under 500 W of microwave power for 2 – 10 minutes.
Figure 2.6 has shown the synthesis of CQDs from carbohydrate and polyethylene glycol
via microwave assisted method.
31
FIGURE 2.II.6 Scheme representation of microwave assisted method [Adapted
from Zhu et al. (2009)]
Nevertheless, Pires et al. (2015) have reported that raw cashew gum is used as
precursor to obtain CQDs via microwave assisted method. Raw cashew gum was
dissolved in water, filtered and then heated in microwave with 800 W for 40 minutes.
Thus, producing a dark brownish solid. After cooling, the solid was dissolved in water
and centrifuged to remove impurities, then freeze dried to obtain brown solid which
considered to be CQDs.
FIGURE 2.II.7 Schematic representation of the microwave assisted method to

obtain the CQDs from raw cashew gum [Adapted from Pires et al. (2015)]
The principle behind the microwave assisted method is due to the interaction
between electric charged particles with electromagnetic wavelength, which caused by
collision or conduction. As the wave energy alters its polarity between positive charge
to negative charge with each cycle of the wave, energy is transferred rapidly into the
carbon molecule, which causes heating by collision (Samaj and City, 2017). The
absorption of microwave energy causes internal heating via mechanisms, which are
ionic conduction mechanism and dipolar polarisation. Both produce heat by disturbance
of weak hydrogen bonds enhanced by the dipole rotation of the molecules without
altering the molecular structure (Christen, 2002). The greater the dielectric constant and
polarity of the solution, the better the absorption of microwave energy, hence the more
optimal the heating (Christen, 2002). Therefore, water which is polar, is an excellent
32
solvent for microwave-assisted with dielectric constant of 78.5 (Leadbeater, 2005).
Moreover, water is inexpensive, readily accessible, non-hazardous and safe to use in
microwave. The aqueous sources will be hastily heated until it exceeds the boiling point
of water by microwave energy. Thus, the reaction rate will be enhanced, and some
reactions that cannot occur at ambient temperature will rapidly take place (Leadbeater,
2005). Hence, water is a good candidate as solvent in microwave assisted method as an
effective heating source, provide an extremely useful way to make the production of
CQDs easier and more environment-friendly.
2.4.2 Hydrothermal Method
The convenient hydrothermal method has been used in most of these cases to
synthesise CQDs. It was first proposed by the British geologist, Sir Roderick
Murchison, to explain the formation of rocks and minerals in the earth’s crust by the
changes resulting from water at elevated temperature and pressure. Generally,
hydrothermal method is a chemical reaction in the presence of aqueous solvents above
100˚C and at pressures greater than 1 atm in a closed system in order to dissolve and
recrystallize materials which are relatively insoluble under normal conditions
(Nadimpalli et al., 2018). It is also interesting scientifically because using high pressure
provides an additional parameter for obtaining fundamental information on the
structures, behaviour and properties of solids.
The hydrothermal reaction is generally performed in the autoclave as illustrated

in Figure 2.8. A Teflon cup is used to avoid contamination with steel. In a typical
synthesis, selected precursors, mineralizer and additives together with the solvent
(normally water) are sealed in the inner Teflon cup. After the heat treatment, one can
collect the final product from the solution. In such a closed reaction environment, many
properties of water change with the increase of temperature and pressure, including
density, ionic product, viscosity, and dielectric constant.
33
FIGURE 2.II.8 A typical hydrothermal autoclave
To date, several researches had reported the use of hydrothermal method to

synthesis CQDs. According to Sahu et al. (2012), orange juice was used as carbon
source for the green method of synthesis of CQDs as shown in Figure 2.9. The orange
juice was mixed with ethanol and then heated at 120°C for 150 min until a dark brown
solution formed in an autoclave.
FIGURE 2.II.9 Illustration of CQDs formation from orange juice via

hydrothermal treatment.
On the other hand, Lu et al. (2012) reported the hydrothermal synthesis of low
cost, water soluble fluorescent CQD from pomelo peel. In this process, the peels were
added to water and then heated in an autoclave at 200°C for 3 hours. Huang et al.
34
(2013) also successfully produced nitrogen-doped carbon nanoparticles (FNCPs) from
strawberry juice using hydrotreatment at 180°C for 12 hours.
In comparison with other methods, the hydrothermal strategy has many

advantages. For example, it is environmentally benign because only water is used as the
reaction solvent. The reactions are generally carried out below 250 °C, which avoid
some problems encountered with high temperature processes such as high energy cost,
stress-induced defects caused by phase transformations that occur as the sample is
cooled to room temperature (Adschiri et al., 2013). Another main advantage of this
method is the easy combination with other techniques such as ultrasound, microwave,
and optical radiation, which can significantly improve the reaction kinetics and favour
the formation of new phase structures.
2.5 DYE REMOVAL
2.5.1 Dye
Dyes are basically organic compounds that contain colours and widely used in
industries to colour their products results in generating a large amount of coloured
wastewater (Kandisa et al., 2016). They can be obtained from animals, vegetables or
mineral origin, with no or very little processing. It consists of chromophore that
provides the colour and the functional groups which bonds dye onto the materials (M,
Stephenson and Judd, 1994). Dyes are difficult to be eliminated through conventional
methods of anaerobic digestion due to their chemical structure which are unaffected to
aerobic digestion and not biologically degradable (Robinson et al., 2001). If the dyes
are not removed from wastewater effluent and release to the environment, it will cause
pollution as they are highly toxic, mutagenic and carcinogenic. These toxic properties
has brought severe effects to humans, such as malfunction of the body system (Amran
et al., 2011; Kandisa et al., 2016). Dyes can be categorized into cationic, anionic, and
non-ionic dyes. Table 2.4 has shown the dyes classification.
35
TABLE II.4 Classification of dyes
Type of charges Dye class Example

Cationic Basic dyes Methylene blue, Basic blue,
Basic yellow, Crystal violet
Anionic Acid dyes Methyl orange, methyl red,
Reactive dyes Congo red, Direct red,
Direct dyes Reactive yellow, Acid black
Non-ionic Disperse dyes Disperse red, Disperse orange,
Sulphur dyes Sulphur black
Vat dyes
[Adapted from Amran et al., 2011]
2.5.2 Methylene blue
The IUPAC name of methylene blue (MB) is 3,7-bis(Dimethylamino)-

phenothiazin-5-ium chloride.“Methylene blue is a basic aniline dye with a chemical
formula of CH18N3SCI. The cation C16H18N3S+ is present in the methylene blue structure.
It is a cationic thiazine dye which shows deep blue colour”in oxidized state but
colourless in reduced form, leukomethylene blue (LMB) (Cragan, 1999). Methylene
blue can be used as dye, which is commonly used in colouring paper, dyeing cotton and
wools (Han, 2007). The serious consequences from methylene blue contamination to
human and the environment urge the need to remove methylene blue from any
wastewater (Altaher and E1Qada., 2011). Figure 2.10 shows the structure of methylene
blue.
FIGURE 2.II.10 Structure of Methylene Blue
36
2.5.3 Current technologies for dye removal
There are various treatment technologies ranging from physical, chemical, and
biological methods that can be applied to remove dye before wastewater are allowed to
be discharged into the environment without causing any harms. However, not all
processes work for all coloured wastewaters. Some studies have shown the successful
decolorization using different treatment method despite the fact that the treated
wastewater still has low colour intensity. Only a few cases have been reported when
they succeed in decolorization. As a whole, each of the technique has its own
advantages and disadvantages that need to be considered as shown in Table 2.5.
TABLE II.5 Dye removal technology with respect to their advantages and
disadvantages
Technology Advantages Disadvantages

Chemical treatments
Coagulation and Different types of dyes can Expensive chemicals reagent;
flocculation be removed effectively pH modification is needed
Sludge is produced;
Difficult in handling
Chemical oxidation Simplicity of application Agents need to be activated

Ozonation Less wastewater and sludge Shorter half-life of 20 mins
produced
Photochemical Sludge free; Formation of by-products
odours can be reduced
Photocatalytic Different kinds of dyes can By-products are produced;
be eliminated effectively Difficult to penetrate UV light
in the water
Radiolysis High efficiency; Not suitable for dispersed
Sludge free dyes;
Shorter half-life
Electrochemical No consumption of High flow rates
destruction chemical
TABLE 2.5 - Continued
37
Technology Advantages Disadvantages
Biological treatments
Fungi Enzyme is used Enzyme production is
decolourization inconstant
Other microbial Bacteria is used Dyes are difficult to be
cultures (mixed removed under aerobic
bacterial) condition
Microbial adsorption Specific microbial species Cannot applied to all dyes
can be used for certain dyes
Anaerobic textile– Azo dyes can be removed Methane and hydrogen
dye bioremediation efficiently sulphide are produced
systems
Physical treatments
Adsorption Most efficient method to Regeneration of adsorbent is
remove most dyes required
Adsorption by Efficient to remove most Costly
activated carbon dyes
Ion exchange Adsorbent can be reused Not effective for all dyes
Irradiation High efficiency of dye Requires a lot of dissolved O2
removal at lab scale
Electro kinetic Inexpensive Sludge is produced
coagulation
[Adapted from (Amran et al. (2011); Pang and Abdullah (2013)]
2.6 ADSORPTION
Adsorption techniques gained most interest among all other techniques in dye
removal application (Ong et al., 2010). This is due to many disadvantages are
performed by other technologies except adsorption which has possessed most
advantages. The term adsorption is a process referred to the deposition of a dye
substance onto the surface on which adsorption occurred through chemical or physical
bonding. Basic terms of adsorption theory are illustrated in Figure 2.11. In simple, an
adsorbent is actually the porous solid adsorbing phase used to attach solute molecules
onto its surface either in liquid or gas form. An adsorbate is the substance which is to be
absorbed on the surface.
38
FIGURE 2.II.11 Basic process of adsorption [Adapted from Worch, 2012]
2.6.1 Chemisorption and Physisorption
Most adsorption processes in wastewater treatment are usually consist of the

combination of neither purely physical nor purely chemical processes (Lowell et al.,
2004). Adsorption processes occurs in both conditions whether steady or unsteady state.
The primary force driving the interaction between the adsorbate and adsorbent is the
electrostatic attraction and also repulsion between molecules of the adsorbate and
adsorbent. This driving force can be either physical or chemical. Adsorption can be
further classified into 2 types which are physical adsorption and chemical adsorption.
Chemisorption is defined as the results of strong chemical reactions between the

ions of adsorbate molecule and the surface of adsorbent, which involves the ions
exchange of electrons and caused it an irreversible reaction. The adsorbed molecules
make a layer over the surface that is only one molecule thick and are relatively not free
to move from one surface site to another surface. Foul (2007) cited that this type of
adsorption is thought to occur on the sides and corners of the micro-crystallites that
compromise the activated carbon. Meanwhile, physical adsorption or better known as
physisorption is occurred as the results of electrostatic forces, Van der Waals force,
hydrogen bonds and dipole-dipole interaction between the adsorbent and the adsorbate
which cause it reversible in most cases (Yagub et al., 2014). The adsorbed molecule is
not affixed to the adsorbent during physical adsorption, but it is free to move about the
surface of the adsorbent. Physical adsorption is a readily reversible reaction and
39
includes both mono and multilayer coverage of adsorbate molecular on the adsorbent’s
surface (Zohra et al. 2014).
2.6.2 Adsorbent
Adsorbent can be used to define the changes between molecules in a mixture

through analysis of adsorption equilibrium and kinetics (Sharifah, 2006). The size of the
pores determines the availability of adsorbate molecules into the internal adsorption
surface of adsorbent, therefore the pore sizes distribution is an important property for
characterizing adsorptivity of the adsorbents. Hence, a good adsorbent should have the
properties of high porous structure with liquid-solid intermolecular forces of attraction
(Kandisa et al., 2016). Thus, activated carbon can be considered as the most effective
adsorbent due to the high porosity and can be regenerated by thermal desorption.
However, the activated carbon is expensive, and this had led many researchers to search
for alternative inexpensive adsorbent (Yagub et al., 2014). Table 2.6 tabulated the list of
researched conducted in search of cheap and effective sorbent especially from
agriculture or industries’ wastes as replacement for activated carbon in removal of dye
compounds.
TABLE II.6 Previous research on the removal of different dyes by agricultural

sorbent
Sorption Capacity
Dyes Adsorbent References
(mg/g)
2,4-dinitrophenylhydrazine Bamboo waste; 884.96 Nwabanne and Mordi,
activated carbon 2009
Acid Red 114 Sesame seed shell; 102.04 Thinakaran et al., 2008
Cotton seed shell; 153.85
Pongam seed shell 204.08
Astrazon yellow Apricot stone; 221.23 Demirbas et al., 2008
activated carbon
Basic Blue 3 Hevea brasiliensis; 227.27 Maneed and Daud,
seed coat 2008
TABLE 2.6 - Continued

Sorption Capacity
Dyes Sorbent References
(mg/g)
40
Basic Red 46, Bentonite 256.40 Turabik, 2008
Basic Yellow 26 333.30
Basic Yellow 28 Boron waste 75.00 Olgun and Atar, 2009
Basic Red 46 74.73
Crystal violet Kaolin 31.94 Nandi et al., 2009
Brilliant green 30.59
Direct blue 86 Orange peel 33.78 Nemr et al., 2009
Indigo carmine dye Rice husk ash 65.90 Lakhmi et al., 2009
Malachite green Oil palm trunk fibre 149.35 Hameed and
ElKhaiary, 2008a
Methyl violet Sunflower (Helianthus 92.59 Hameed, 2008
annuus L.) seed hull
Mansonia wood 23.80 Ofomaja and Ho, 2008
sawdust
Methylene Blue Indian Rosewood 56.40 Garg et al., 2004
sawdust
Pineapple stem 119.05 Hameed et al., 2009
Beer brewery waste 4.92 Tsai et al., 2008
Banana stalk waste 243.90 Hameed et al., 2008b
Broad been peels 192.70 Hameed and
ElKhaiary, 2008b
Pomelo (Citrus gandis) 344.83 Hameed et al., 2008a
Coconut husk activated 434.78 Tan et al., 2008b
carbon
Tea waste 85.16 Uddin et al., 2009
Papaya seed 555.56 Hameed, 2009a
Rattan sawdust 294.14 Hameed, et al., 2007
Guava (Psidium 295.00 Ponnusami et al., 2008
guajava) leaf powder
Procion Yellow MX Poly 250.00 Singh et al., 2009
Remozol Brilliant Violet (methylmethacrylate) 357.00
Reactive Blue H5G grafted chitosan 178.00
Reactive Blue 19, Reactive Modified basic oxygen 76.00 Xue et al., 2009
Black 5, Reactive Red 120 furnace slag 60.00
55.00
Reactive Brilliant Blue Aspergillus fumigatus 190.50 Wang and Hu, 2008
2.6.3 Adsorption in dye removal application
The removal capacity of dyes through the adsorption is depends on the surface
chemistry of the adsorbent and properties of the dye adsorbate (Noroozi et al., 2007).
For example, higher adsorption efficiency will be obtained by the adsorption between
negatively charged adsorbent and the positively charged dye adsorbate due to the
interaction of electrostatic forces (G. Wang et al., 2017). Moreover, surface area and
polarity are the surface properties to characterize adsorbents. High adsorption efficiency
can be obtained by using adsorbent of high specific surface area, but the formation of a
large internal surface area in a limited volume unavoidably gives rise to large numbers
of small sized pores between adsorption surfaces (Suzukl, 1990).
41
2.7 PHOTOCATALYTIC ADSORPTION
Photocatalytic adsorption has been accorded great significance in recent times due
to its potential to mineralize a wide range of organic pollutants into harmless substances
at ambient temperature and pressure (Hoffmann et al., 1995; Klabunde, K.J., 2010), to
produce hydrogen in a photocatalytic water splitting process (Kudo and Miseki, 2009),
to inactive microorganisms (Bonetta et al., 2013) and to be used in dye removal (Liu et
al., 2019). It is the complete removal or mineralize of pollutants with the help of highly
oxidizing the free radicals (∙OH and ∙O2-) to convert them into carbon dioxide and water
which is non-toxic to the environment. In order to produce these radicals, heterogeneous
photocatalysis was developed, which defined as the increase of rate of chemical reaction
under the condition of light such as ultraviolet (UV), visible light or infrared radiation
with the presence of photocatalyst or semiconductor. Figure 2.13 illustrated the
heterogeneous photocatalysis processes from the transport of pollutant to the surface of
photocatalyst.
42
FIGURE 2.II.12 Schematic Diagram and Steps involved in Heterogeneous
Photocatalysis [Adapted from Bora and Mewada, 2017]
The mechanism of photocatalyst activation involve the photocatalytic adsorption

of photons (hv) which having the energy greater than the band gap energy. This will be
resulting in the transfer of electrons (e -) from valence band (VB) to conduction band
(CB) and causing the formation of positive hole (h +) at VB. Band gap energy is the
different between VB and CB of the catalyst. During the reaction, recombination of
separated e- and h+ might occur and resulting in the release of heat energy. At the same
time, the photogenerated e- and h+ will undergo reaction with the available oxidants and
reductants to form ∙OH and ∙O2- radicals which then react with pollutants and
mineralized it into CO2 and H2O. Therefore, the dye pollutants can be oxidized by the
43
photogenerated holes directly through the valence band hole before it is captured either
within particle, and the photogenerated electrons can trigger the reductive
decolourization of dyes (Chun, 2010).
Titanium dioxide (TiO2) has been widely used as a photocatalyst due to its strong,
light-based oxidizing abilities (Nakata and Fujishima, 2012). However, due to great
interest on the application of quantum dots which can only be excited by UV light as a
result of their wide intrinsic band gap, it has been reported that CQDs can be known as
the most reliable and green approach to promoting effective energy conversion. CQDs
are found to possess an incredible property which is up conversion photoluminescence
(UPCL) that enables CQDs to act as a photocatalyst. It is a phenomenon where the
fluorescence emission wavelength has lower energy than excitation wavelength, which
shows that the emission wavelength has lower energy than the excitation wavelength
(Wang et al., 2017). This phenomenon was observed by Sun et al. (2012), where the
CQDs were produced through laser ablation exhibit strong luminescence with two photo
excitations in 800 nm. Furthermore, CQDs inhibited the recombination of the electron-
hole pairs generated during photocatalysis, which will enhance the adsorption
efficiency.
2.8 FACTOR AFFECTING THE PERFORMANCES OF ADSORPTION
2.8.1 Effect of pH
The degree of electrostatic charges is an important factor in adsorption

efficiency, which will be affected by the pH value of the solution. This is due to
different dyes has different kind of functional groups on the surface, which gives
different type of charges where it is cationic or anionic. Basically, a low pH solution
will decrease the removal efficiency for cationic dye removal and increase for anionic
dye removal. This is due to the positive charge on the surface of adsorbent which
44
consequences in a higher removal efficiency in negatively charged dye and a lower
removal efficiency in positively charged dye. On the other hand, a high pH solution will
increase removal efficiency for cationic dye adsorption due to the negative charge ions
on the adsorbent surface (Amran et al., 2011). Different interaction of adsorption
between adsorbent and adsorbate implies different optimum pH value. Therefore, pH is
a significant factor which plays an important role in determining the efficiency of the
whole adsorption process.
In a previous work done by Ong et al. (2007) in the removal of basic and
reactive dyes using ethylenediamine modified rice hull, they proposed that at low pH of
dye solution, the carboxyl groups on the biosorbent surface which are responsible for
binding the dye cations are predominantly protonated, therefore lead to a lower uptake
of the dyes. As the pH of the dye increased, sorption became favourable due to the
deprotonation of the carboxyl groups, resulted in an increase of available binding sites.
2.8.2 Effect of contact time
Contact time is one of the physical parameters for cost-effective wastewater

treatment plant application. The removal efficiency will increase as time increase but
remains constant after reaching the equilibrium time. The amount of dye adsorbed at the
equilibrium time indicates the maximum adsorption capacity of the
adsorbents”(Hameed et al. 2007). Dye compounds initially reacts with the boundary
layer of sorbent which give rise to rapid uptake and eventually slowed down when it
diffuses into the porous structure of sorbent (Hameed and Chiha, 2007; Nemr et al.
2009). In addition, slower rate of dye uptake during adsorption process might be
contributed by the electrostatic encumbrance or repulsion of positively charged
adsorbed seaweeds with the remaining dye compounds in the solutions, which
contributes to longer contact time required for the system to reach equilibrium (Nemr et
al. 2009).
45
According to Rathod et al. (2016), the mechanism for the removal of dye by
adsorption may be ascribed to the transferring of dye from bulk of the solution to the
surface of the adsorbent, diffusion of dye through the boundary layer to the surface of
the adsorbent and intra-particle diffusion of dye into the interior pored of the adsorbent
particles. The boundary layer resistance affected by the rate of adsorption and with
increasing contact time, resistance will be reduced, and the mobility of the dye will be
increased during adsorption.
2.8.3 Effect of initial concentration of dye
Based on Aravindhan et al. (2007), higher initial dye concentration provides

higher driving force to overcome mass transfer resistance between sorbent and dye
compounds, thus, enhances the uptake of dye compounds by unit of adsorbent. In
addition, higher chances of collision between adsorbent and adsorbate at higher initial
dye concentrations augmented uptake of dye compounds by seaweeds and therefore,
lead to improvement of adsorption capacity (Aravindhan et al. 2007). Weng et al.
(2009) also reported that the methylene blue adsorption increased as the initial
methylene blue dye increased, on the removal of methylene blue from aqueous solution
by adsorption onto pineapple leaf powder (PLP). The driving force of the concentration
was stronger as the methylene blue concentration was higher, thus increased the
adsorption capacity. from the intra-particle diffusion study, it was also observed that the
adsorption process wasa controlled by multi-steps process which involved adsorption on
the external surface and diffusion into the internal prose of PLP.
On the other hand, percentage removal of BB3 and BY11 dye tends to decrease
at higher initial dye concentration. This might be attributed by overwhelming in
numbers of dye compounds at higher dye concentrations against the available binding
sites. Unoccupied binding sites become lesser at higher initial dye concentration and
contribute to reduction in percentage removal of dye (Tunc et al., 2009). It was also
46
studied by Boumediene et al. (2014) on the ability of orange peel to remove methylene
blue. Due to the agglomeration of biosorbent, the dye adsorption process decreased with
increasing dye concentration resulted by less surface area involved in adsorption
process (Khatod, 2013).
2.9 ADSORPTION ISOTHERM
The isotherms of adsorption process are important to identify the adsorption

capacity between adsorbent and adsorbate interaction. Mechanism of adsorption can
also be explained using adsorption isotherm. The surface phase can be characterized
into monolayer or multilayer (Yagub et al., 2014). The uptake behaviour of adsorbate is
described by isotherm model such as Langmuir or Freundlich isotherm analysis in batch
adsorption process. Linear regression analysis can be applied to determine the
parameters of each isotherm and the square of the correlation coefficients (R 2) can be
generated. The value of R2 gives an indication of best fitting isotherm model. The
acceptable range of R2 is 0.95 < R2 < 1.00 and the highest R2 value gives the best-fitting.
2.9.1 Langmuir Isotherm
Langmuir isotherm model was the first isotherm model derived. Langmuir
isotherm model assumes that only homogenous adsorbent surface exists or in other
words, monolayer type of adsorption occurs which is probably reasonable for the
assumption in gas adsorption process (Droste, 1997; Seader and Henley, 2003). At
equilibrium, saturation point was been achieved with no further adsorption process to be
taken place, therefore, it is assumed that only one molecule will be occupied one single
site. Linearized form of Langmuir equation is stated in Equation 2.1.
Equation (2.1):
1 1 1
= +
Qe Q0 Q0 K L C e
47
Where Qe is the amount of dye adsorbed at equilibrium ove unit mass of sorbent (mg/g),
C eis the equilibrium concentrations of dye, Q0 is the maximum adsorption capacity
(mg/g) and KL is the Langmuir constant (L/mg).
Linear plot of 1/Qe vs 1/Ce will be plotted in order to determine the best fit
isotherm data for the adsorption system. Crucial characteristic of Langmuir adsorption
model was expressed as dimensionless separation factor, RL which can be derived from
Equation 2.2.
Equation (2.2):
1
R L=
1+ K L Co
where C o is highest concentration of solution (mg/L); RL is favourable condition of

adsorption; and KL is the Langmuir constant (L/mg). Overall, RL values indicate the
adsorption process to be unfavourable if R L > 1, linear if RL = 1, favourable if 0 < RL<1,
and irreversible if RL = 0 (Mahida and Patel, 2016).
2.9.2 Freundlich Isotherm
Another popular isotherm model applied to the adsorption process was

Freundlich adsorption isotherm. Freundlich model suggested that sorption process
involved heterogeneous sorption with different classes of adsorption sites (Hameed et
al., 2007). It gives a representation of the adsorption equilibrium between an adsorbent
in solution and the surface of the adsorbent, using a multi-site adsorption isotherm for
heterogeneous surfaces which occurs with non-uniform distribution of heat over the
surface of the adsorbent (Brunauer, 1943). Freundlich isotherm is expressed as in
Equation 2.3 and linearized equation is shown in Equation 2.4.
48
Equation (2.3):
Q e =K F C e1 /n
Equation (2.4):
1
ln Q e =ln K F + ln Ce
n
where C eis equilibrium concentrations of dye (mg/L); Qe is adsorption capacity at

equilibrium (mg/g); KF is Freundlich constant (mg/g(L/mg)1/n); and n is Freundlich
exponent which calculated from the slopes of plot.
KF (mg/g(L/mg)1/n) and n were Freundlich constants derived from the linear

slope of ln Qe versus ln Ce. Freundlich magnitude of exponent, 1/n indicates favourable
condition of adsorption with value of n> 1. Freundlich constant, n, gives indication on
how favourable the adsorption process occurs. If n < 1, this means poor adsorption.
Value of n in the range of 1 to 10 represents favourable adsorption condition. In general,
as the KF increases the adsorption capacity of the adsorbent increases. Linear plot of ln
Qe versus ln Ce is employed in the system in order to determine the favourable isotherm
model.
2.10 ADSORPTION KINETICS
The dynamics of the adsorption, for example, chemical reaction, diffusion

control or mass transfer can be investigated by using the kinetics of adsorption in terms
of the order of the rate constant (Larrechi et al. 2007). The adsorbent should have large
adsorption capacities and a faster rate of adsorption, therefore adsorption kinetic is a
significant aspect to improve the adsorbent. Most of adsorption kinetic studies used
Pseudo-first-order and Pseudo-second-order models to determine the adsorption kinetics
49
(Amran et al., 2011). Similar to adsorption isotherm, the best fitting kinetic model is
determined by highest R2 value.
2.10.1 Pseudo-first-order kinetic model
Pseudo-first-order was theorised by Lageegran as shown in Equation 2.5 which

is further integrated as linearized form shown in Equation 2.6 (Azizian, 2004).
Equation (2.5):
d Qt
=k 1 (Q e −Q t )
dt
Equation (2.6):
K1
log(Q e −¿ Q t )=log Q e − t¿
2.303
where K1 is the pseudo-first-order rate constant (min-1); Qe is the adsorption capacity at

equilibrium (mg/g); Qt is the adsorption capacity at t (mg/g); and t is contact time (min).
Linear plot of log (Qe – Qt) versus t can be used in determination of K1 constant (min-1)
and R2 values which indicates the best fitted kinetic model.
2.10.2 Pseudo-second-order kinetic model
The differential equation of pseudo-second-order kinetics is given as shown in

Equation 2.7 and linearized form is expressed in Equation 2.8 (Azizian, 2004).
Equation (2.7):
50
d Qt 2
=k 2 ( Q e −Q t )
dt
Equation (2.8):
t 1 1
= + t
Qt K 2 Qe Qe
2
where K2 is the pseudo-second-order rate constant (gmg-1min-1); Qe is the adsorption

capacity at equilibrium (mg/g); Qt is the adsorption capacity at t (mg/g); and t is contact
time (min). Plot of t/Qt versus t shows a linear relationship. Values of K 2 and
equilibrium adsorption capacity, Qe can be derived from the intercept and slope of the
linear plot.
2.11 RESEARCH SURFACE METHODOLOGY (RSM)
In the approach of the adsorption process, Research Surface Methodology (RSM)

is used. RSM is known to collect mathematical and statistical techniques for modelling
and analysing problems as well as process optimization. The process of optimization is
important in obtaining the value of parameter or process variable in which the response
is at optimum value. Research Surface Methodology has many classes of design which
includes central composite design, Box-Behnken design and three-level factorial design.
Central composite design is commonly used for building second order model for
response variable. Box-Behnken design is used for experimental designs in statistic
while three-level factorial is used for investigating quadratic effects (Dijkstra, 2012).
The approach of the RSM usually will be on the process variable of the production or
the batch adsorption process.
2.11.1 Central Composite Design (CCD)
51
The Central Composite Design (CCD) is the design which included both the full
or fractional factorial design that is often used to estimate the second order response
surface (Otto, 2007). According to Park et al. (2008), the resulting regression coefficient
of the second order polynomial equation is very useful for the linear, interaction and
quadratic terms. There are three points present in a CCD namely: axial point (2. n), cube
point (2n from full factorial design) and center point (α, center point created by nominal
design). CCD is very important in providing information on the experimental variable
effects and the overall experimental error in a minimum number of runs. However, the
adjustments of level are sometimes difficult to achieve due to the present of star points,
α outside design (Morgan, 1997). The design for CCD with three factors and α star
point were illustrated in Figure 2.8.
FIGURE 2.8 Geometric view of Central Composite Design for three factors
(Ferdosian et al., 2007)
2.11.2 Box-Behnken Design
Box-Behnken design (BBD) is known as the one-step response surface design

which requires only three levels (-1, 0, +1) to run an experiment. As suggested by
Ferreira et al. (2007), it was a good design because it enables estimation of parameters
for the quadratic model, detection of lack-of-fit of the model as well as building of a
52
sequential design. However, the BBD might only include the responses in correlation
with only a single factor. BBD is beneficial as the design is not presented in order where
all the factors are at their highest or lowest levels and this type of order inhibits errors in
the resulting responses. BBD method is also considered a good choice in RSM study
compared to CCD method (Ferreira, 2007). This method is more economical and
efficient compared to their corresponding full factorial designs, mainly for many
variables. Table 2 shows the number of experiments for different factors with three
replications.
TABLE II.7 Number of experiments for different factors (Otto, 2007)

Number of factors Number of experiments
3 15
4 27
5 46
6 54
7 62
This analytical method reduced the number of experiments, minimized overall

retention time and enhanced statistical interpretations (Ragonese, 2002). Besides, BBD
does not have combinations for which all factors are simultaneously at their lowest or
highest levels. Therefore, it is useful to prevent experiments perform under extreme
conditions. BBD is more efficient than CCD three-level full factorial designs where the
efficiency of one experimental design is expressed as the number of coefficients in the
estimated model divided by the number of experiments (Ferrreira, 2007).
2.12 CHARACTERIZATION TECHNIQUES
2.12.1 Scanning Electron Microscope (SEM)
53
One of the most common techniques for surface morphology studies is scanning
electron microscope (SEM), which can give information about the chemical
composition, morphology and different structures in the sample. Instead of a light–beam
which is used as an ordinary light–microscope, SEM produces an electron beam which
is focused by going through both lenses and magnetic fields before it strikes the sample.
Some electrons, but also X-rays, are ejected from the sample. These X-rays and
electrons are collected by a detector which produces an 2D image (Schweitzer, 2010). It
allows for magnification at higher levels, since it has much higher resolution, and it is
easier to have a wider focus for that this type of microscope has a large depth of field
(Schweitzer, 2010). SEM works under vacuum conditions to prevent dust to interfere.
An electron gun generates an electron beam which is focused by condenser lenses and
passed through deflection coils. When the sample is hit by the high intensity electron
beam, information is available from the secondary electrons, X-rays, light and back–
scattered electrons (Swapp, 2010). Depending on which detector is used, different data
is collected and used for gaining information about the sample. Such information is
usually surface topography, morphology, chemical composition, conductivity etc. The
resolution can be as good as down to 1 nm. However, in order to get a perfect image,
some adjustments need to be done including the voltage, spot size, vapor pressure,
working distance etc. and such adjustments need time and experience.
2.12.2 UV-Vis Spectroscopy
UV-VIS spectroscopy is a sensitive method which falls under the category of

molecular spectroscopy. This instrument utilizes the UV and visible light in terms of
wavelength which ranges between 200 to 780 nm. For the analysis of dye concentration,
UV-VIS would usually be the preferred method. UV-VIS spectroscopy is one of the
most suitable type of instrument to be used in order to study the aggregation properties
of dyes in relation to their concentration. The concentration of dye would be ranging
around 10-3 – 10-6 M (Antonov et al. 1999).
54
Besides, the UV-VIS can also function as an analytical instrument for the
determination of heavy metals. This method is usually used in order to determine
quantitative and structural information of a specific solution. However, the drawback of
using UV-VIS is due to the time-consuming to prepare sample to be tested and also the
procedure step such as binding to complexes, adjustment on pH-value and special
extraction procedures to obtain coloured metal complexes. In fact, the usage of UV-VIS
can also be interrupted by coloured substances that was present in the specific sample
(Zeiner et al. 2016).
55
CHAPTER III
RESEARCH METHODOLOGY
This chapter describes the methodologies of the study “Photocatalytic Adsorption

Process Using Synthesized Cellulose Based Quantum-Dots Adsorbent”. It involves the
synthesis of carbon quantum dots (CQDs) form cellulose with hydrothermal synthesis
methods. Experimental design software was used to optimize the experimental
parameters and several analyses. Comparison of percentage removal of dye using
cellulose and cellulose-based quantum dots are also presented in detail.
3.1 MATERIALS AND CHEMICALS
There are several materials and chemicals that are necessary to carry out the
experiments. All chemicals used for the experiments were AR grade or equivalent. The
sources of all materials and chemicals used are listed in Table 3.1.
TABLE 0.8 List of materials and chemicals used
Materials/Chemicals Sources/Supplier
Oil Palm empty fruit bunch (OPEFB) Ulu Langat Palm Oil Mill Sdn. Bhd.
Sodium Hydroxide (NaOH) Pellets Friendemann Schmide
Methylene Blue Friendemann Schmide
Ethanol J-Kollin Chemicals
Hexane Friendemann Schmide
Glacial Acetic Acid Friendemann Schmide
Sodium Hypochlorite J-Kollin Chemicals
Hydrochloric Acid Friendemann Schmide
56
3.2 EQUIPMENT
The equipment and facilities used in this research are listed in Table 3.2. The
usage of the equipment is also described.
TABLE 3.2 List of equipment used

Type of Equipment Purpose
Electrical Blender Blending
Siever Sieving into smaller size
Centrifugal machine Centrifugation
Oven Drying and Reaction
pH Meter pH adjustment
Beaker As container
Electrical Weighing Balance Weighing
Hot Plate with magnetic stirrer Heating and stirring
Measuring cylinder Measuring
Micropipette Measuring
UV-Vis spectrophotometer Analysis of adsorption
Scanning Electron Microscope (SEM) Analysis of adsorbent
Surface ζ –Potential Analyser Analysis of adsorbent
3.3 RESEARCH METHODOLOGY FLOW CHART
The overall research methodology for this research presented in Figure 3.1.
57
FIGURE 3.0.13 Research Methodology Flow Chart
58
3.4 EXTRACTION OF α-CELLULOSE FROM AGROWASTE-OIL PALM
EMPTY FRUIT BUNCH (OPEFB)
3.4.1 Preparation of Oil Palm Empty Fruit Bunch (OPEFB)
OPEFB were collected from an oil palm mill company which located at Ulu
Langat, Selangor, in Malaysia. OPEFB samples were blended into smaller pieces to
enhance the extraction and application of chemical treatments.
3.4.2 Pre-treatment of Oil Palm Empty Fruit Bunch (OPEFB)
The blended OPEFB samples were washed and soaked in distilled water for 24
hours to remove dust and dirt. Then, the samples were added into ethanol/hexane
solvent at 1:2 v/v ratio for 24 hours to remove impurities such as wax, resins, fats and
oils. The OPEFB samples were then rinsed five times with distilled water to remove
solvent traces and dried under the sun until constant weight.
FIGURE 3.0.14 Washed OPEFB in Ethanol/Hexane Mixed Solvent
59
3.4.3 Bleaching Treatment
The purpose of this bleaching treatment was to break down phenolic compounds
or molecules with chromophoric groups presented in lignin as well as whitening the
fibers. The bleaching solution was made up of buffer solution, sodium hypochlorite
solution and distilled water. The buffer solution was prepared by mixing 8.1 g of NaOH
pellet and 22.5 mL of glacial acetic acid into 300 mL of distilled water. The volume of
buffer solution, sodium hypochlorite and distilled water used were at a ratio of 1:1:1.
The treated OPEFB fibers were added into the bleaching solution with respect to 1:10
g/mL samples to bleaching solution ratio, and the bleaching treatment was carried out at
80℃ for one hour. Bleaching treatment was repeated four times until brown colour was
completely removed. The bleached fibers were then filtered, rinsed with distilled water
until a pH 7 was obtained and dried in the oven until constant weight was obtained.
FIGURE 3.0.15 OPEFB fibers after bleaching treatment
3.4.4 Extraction of alpha-cellulose
Alpha-cellulose indicates high quality cellulose and cannot be dissolved in the

17.5 wt% NaOH. Therefore, alkaline treatment was performed to remove alkaline-
soluble components such as lignin and hemicellulose. 17.5 wt% NaOH solution was
prepared by dissolving 17.5 g of NaOH pellet in 100 mL of distilled water. Bleached
60
OPEFB fibers were treated with 17.5 wt% NaOH solution at 1:10 g/mL ratio of
bleached fibers to NaOH solution to prevent degradation of cellulose due to severe
condition. The alkaline treatment was carried out at 80℃ for 30 minutes. The treated
fibers were then filtered and washed using distilled water until pH 7 was obtained. The
extracted cellulose was dried under the sun until constant weight.
FIGURE 3.0.16 Alkaline treatment of bleached fibers
FIGURE 3.0.17 Extracted Cellulose
The percentage of cellulose yield can be obtained by applying the Equation (3.1):
Equation (3.1):
Cellulose weight ( g )
Yield ( % )= x 100 %
Sample weight(g)
61
3.5 SYNTHESIS OF CARBON QUANTUM DOTS (CQDs) FROM
EXTRACTED ALPHA-CELLULOSE
3.5.1 HYDROTHERMAL SYNTHESIS METHOD
The carbon quantum dots (CQDs) were synthesized by hydrothermal method.

Cellulose fibers were dissolved in distilled water and sealed in a Teflon-lined stainless
steel autoclave shown in Figure 3.2 and treated at 180℃ for reactions to occurred. After
the reaction, the autoclave was placed overnight to cool down to room temperature. A
yellow coloured solution was obtained which was filtered to remove the remaining
cellulose fibers.
FIGURE 3.0.18 Teflon-lined stainless steel autoclave
3.5.2 Characterization of samples
The surface morphology of cellulose and cellulose-based CQDs were studied

using Scanning Electron Microscopy (SEM). The particle size distribution and zeta
potentials were measured by using a Zetasizer Nano instrument from Malvern.
62
3.6 ADSORPTION PERFORMANCE USING RESEARCH SURFACE
METHODOLOGY (RSM) APPROACH
A statistical software called Minitab (version 16) was used to design the
experiment. This is to model and analyse the process where the response is influenced
by several factors and thus to optimize the response. The Box-Behnken Design (BBD)
with three factors and three levels were used for optimization of all the variables. The
independent variables were contact time (X1), pH (X2), and initial concentration of dye
(X3) and the three levels of the design were low (-1), medium (0) and high (+1)
respectively as shown in Table 3.3. Then, 15 sets with different parameters was
generated as shown in Table 3.4.
TABLE 0.9 Experimental range and factor level of process variables applied
Box-Behnken Levels
Factors
Low (-1) Medium (0) High (+1)
Contact time (min) 10 25 40
pH 3 7 11
Initial concentration of dye (mg/L) 2 6 10
TABLE 0.10 Design matrix for experimental factors at different factor levels
Run Contact Time (mins) pH Initial Conc. Of dye (mg/L)

1 10 3 6
2 25 7 6
3 10 7 10
4 40 3 6
5 40 7 2
6 25 7 6
7 25 7 6
8 10 11 6
9 25 3 10
10 25 3 2
11 10 7 2
12 25 11 10
13 40 11 6
14 40 7 10
15 25 11 2
63
(Khajeh 2009) has proven that whenever a system of study that involves 3
significant factors to be as the variables X 1, X2 and X3, the mathematical relationship of
response relating the 3 variables will be represented by the following second -order
polynomial model expressed as in Equation (3.3):
Equation (3.5):
Y = β0 + β 1 X 1 + β 2 X 2 + β 3 X 3 + β 12 X 1 X 2 + β 13 X 1 X 3 + β 23 X 2 X 3 + β 11 X 21 + β 22 X 22+ β33 X 23
Where Y is predicted response; β 0 is constant; β 1 , β 2 , β 3 are linear coefficients;

β 11 , β22 , β 33 are quadratic coefficients; β 12 , β 13 , β 23 are interaction coefficients; and
X 1 , X 2 , X 3 are independent variables.
A positive sign in the equation represents a significant effect of the factor, while
a negative sign indicates an insignificant effect of the factor. The predicted values were
calculated by using the regression equation, analysing the contour plots and response
surface plots.
3.7 REMOVAL OF METHYLENE BLUE DYE
3.7.1 Calibration of Methylene Blue Solutions Standard Curve
Series of dye concentrations were prepared by diluting 10 mg/L of dye stock

solution and analysed by using UV-Vis spectrophotometer at maximum wavelength of
668 nm (Nsami and Mbadcam, 2013). Calibration graphs of methylene blue was plotted
as shown in Figure 3.7 and Equation 3.2 used to determine the concentrations of dye
solutions during adsorption process.
64
3.00
2.50 f(x) = 0.27 x

R² = 0.99
2.00 f(x) = 0.75 ln(x) + 0.4

R² = 0.9
1.50
ABS
1.00
0.50
0.00
0.00 2.00 4.00 6.00 8.00 10.00 12.00
Conc. of dye (mg/L)
FIGURE 3.0.19 Calibration Curve of Methylene Blue Dye
Equation (3.2):
mg
)= ¿ ¿
||
Concentration of unadsorbed MB∈solution (
L 0.2667
3.7.2 Batch Adsorption Experiment
The batch adsorption experiments were carried out with the various
combinations of different conditions listed in Table 3.3. 50 mL of methylene blue (MB)
solution at different concentration were prepared in a beaker. Prior to mixing with 50
mg of cellulose adsorbent, a few drops of 0.1 M HCL or 0.1 M NaOH were added for
adjusting the pH to the methylene blue dye solution. The residual concentration of the
dye in the filtrate was determined using a UV-Vis spectrophotometer at λmax of 668
nm (Nsami and Mbadcam, 2013).
65
(a) (b)
FIGURE 3.0.20 Adsorption experiment for methylene blue removal (a) Before (b)
After
The percentage removal of dye was calculated using the Equation 3.3:
Equation (3.3):
C o −Ce
Removal ( % )= ×100 %
Co
and the adsorption capacity (Qe) was calculated using Equation 3.2:
Equation (3.4):
Qe = (Co – Ce) x V/m
where Qe is the amount of methylene blue dye adsorbed per unit mass of adsorbent at
equilibrium (mg/g); Co is the initial concentration of methylene blue dye (mg/L); C e is
the equilibrium concentration of methylene blue dye (mg/L); V is the volume of
methylene blue solution (L); and m is the mass of adsorbent (g).
66
3.7.3 Photocatalytic Adsorption Experiment
The photocatalytic experiments were conducted under UV light irradiation using

UV lamp in the dark. 2 mL of liquid CQDs and 50 mg of cellulose fibers were added
into 50 mL of methylene blue solutions at various combination of different factors as
listed in Table 3.3. The mixture was allowed to agitate using magnetic stirrer. The
residual concentration of the dye in the filtrate was determined using a UV-Vis
spectrophotometer at λmax of 668 nm (Nsami and Mbadcam, 2013).
FIGURE 3.0.21 Photocatalytic adsorption of methylene blue on cellulose-based

CQDs under UV light
3.8 ISOTHERM ANALYSIS OF ADSORPTION
The adsorption data were analysed by fitting to isotherm models which are
Langmuir and Freundlich models. This is to reveal the interactive behaviour between
the adsorbent and adsorbate molecules. The isotherm experiments were carried out at
different initial concentrations of methylene blue dye vary from 2 mg/L to 10 mg/L at
pH 11 and 25 minutes.
67
3.8.1 Langmuir isotherm model
Langmuir stated that adsorption took place on the homogeneous surface of

adsorbent with identical binding sites and there is no transmigration between the
adsorbed species occurs (Xing et al. 2010). Linearized form of Langmuir equation is
stated in Equation 3.6.
Equation (3.6):
1 1 1
= +
Qe Q0 Q0 K L C e
where Qe is the amount of dye adsorbed at equilibrium of unit mass of sorbent (mg/g),
C eis the equilibrium concentrations of dye, Q0 is the maximum adsorption capacity
(mg/g) and KL is the Langmuir constant (L/mg).
Linear plot of 1/Qe vs 1/Ce was plotted in order to determine the best fit isotherm
data for the adsorption system. Crucial characteristic of Langmuir adsorption model was
expressed as dimensionless separation factor, RL which can be derived from Equation
3.7.
Equation (3.7):
1
R L=
1+ K L Co
where C o is the highest concentration of solution (mg/L), R L is the favourable condition

of adsorption and KL is the Langmuir constant (L/mg). Overall, RL values indicate the
adsorption process to be unfavourable if RL > 1, linear if RL = 1, favourable if 0 < RL <
1, and irreversible if RL = 0 (Mahida and Patel, 2016).
68
3.8.2 Freundlich isotherm model
Freundlich assumes that heterogeneous type of adsorption occurs with non-

uniform distribution of heat over the surface of the adsorbent (Brunauer, 1943).
Linearized Freundlich isotherm was expressed in Equation 3.8.
Equation (3.8):
1
ln Q e =ln K F + ln Ce
n
where C eis equilibrium concentrations of dye (mg/L); Qe is adsorption capacity at

equilibrium (mg/g); KF is Freundlich constant (mg/g(L/mg)1/n); and n is Freundlich
exponent which calculated from the slopes of plot.
KF (mg/g(L/mg)1/n) and n were Freundlich constants derived from the linear

slope of ln Qe versus ln Ce. Freundlich magnitude of exponent, 1/n indicates favourable
condition of adsorption with value of n> 1. Freundlich constant, n, gives indication on
how favourable the adsorption process occurs. Value of n in the range of 1 to 10
represents favourable adsorption condition. Linear plot of ln Qe versus ln Ce were
employed in the system in order to determine the favourable isotherm model.
3.9 KINETICS STUDIES OF ADSORPTION
The kinetics of adsorption indicate the rate of transport of the dye from solution
to the surface of adsorbent and is investigated by pseudo-first-order and pseudo-second
order kinetic models. These two models differ in the type of uptake mechanism by
adsorbent. The correlation coefficient, R2 values was used to determine he
appropriateness of kinetic models that best fitted to the adsorption kinetic system.
69
3.9.1 Pseudo-first-order kinetic model
The linearized mathematical form of pseudo-first-order model is expressed in

equation 3.9.
Equation (3.9):
k1
log ( Q e −Q t )=logQ e − (t)
2.303
where, K1 is pseudo-first-order rate constant (min-1); Qe is amount of dye adsorbed onto

unit mass of adsorbent at equilibrium (mg/g); Q t is the amount of adsorbate on the
adsorbent surface at time, t(mg/g); and t is the contact time for adsorption process
(min). Plot of log (Qe - Qt ) versus t were plotted to obtain the R2 value.
3.9.2 Pseudo-second-order kinetic model
The linearized mathematical form of pseudo-second-order model is expressed in

equation 3.10.
Equation (3.10):
t 1 t
= +
Qt K 2 Qe Qe
2
where K2 is the pseudo-second-order rate constant (gmg-1min-1); Qe is the adsorption

capacity at equilibrium (mg/g); Qt is the adsorption capacity at t (mg/g); and t is contact
time (min). Plot of t/Qt versus t shows a linear relationship. Values of K 2 and
equilibrium adsorption capacity, Qe can be derived from the intercept and slope of the
linear plot of t/Qt versus t.
70
71
CHAPTER IV
RESULTS AND DISCUSSION
4.1.1 PERCENTAGE YIELD OF CELLULOSE
The yield of cellulose extracted from the bleached OPEFB was measured after
the alkaline treatment. The average percentage yield of cellulose was ranged from 48%
to 62%, which the average yield percentage of 53%. However, this value is only
indicative since the actual yield strongly depends on the preparation conditions and pre-
treatment such as filtration, which inevitably induces loss of material inherent to this
process.
4.2 ADSORPTION PROCESS OF METHYLENE BLUE ON CELLULOSE
4.2.1 RSM Modelling
The Box-Behnken model of RSM was employed in these experiments to obtain

a polynomial model from 13 experiment design runs with one centre point. The ranges
and levels of the three independent variables such as contact time (min), pH and initial
concentration of methylene blue (mg/L) were investigated as shown in TABLE 0 .10.
The variables design matrix of not coded and coded units by the Box-Behnken model
along with the values of the response which are experimental and predicted is presented
in TABLE 0 .11.
72
TABLE 0.11 Box-Behnken design matrix of three factors along with experimental
and predicted responses for methylene blue dye removal
Error
Run Experimental Factors Response (MB Percentage removal) (%)
X1 X2 X3 Experimental (%) Predicted (%)
1 10 3 6 83.04 81.64 1.70
2 25 7 6 92.25 92.10 0.16
3 10 7 10 94.45 93.92 0.56
4 40 3 6 79.61 79.95 0.43
5 40 7 2 73.94 74.38 0.60
6 25 7 6 92.08 92.10 0.02
7 25 7 6 92.08 92.10 0.02
8 10 11 6 92.46 92.03 0.46
9 25 3 10 79.00 80.88 2.38
10 25 3 2 65.00 64.04 1.48
11 10 7 2 73.25 75.58 3.17
12 25 11 10 92.31 93.20 0.96
13 40 11 6 89.94 91.25 1.46
14 40 7 10 95.08 92.65 2.55
15 25 11 2 75.38 73.42 2.59
Note. X1: Contact Time (min), X2: pH, and X3: Initial concentration of MB (mg/L)
The regression equation obtained after analysis of variance gives the level of
adsorption of dye as a function of different contact time (min), pH, and initial
concentration of methylene blue (mg/L). All terms regardless of their significance are
included in the following equation:
Equation (4.1):
MB Removal % (coded) = 36.037 – 0.1059X1 + 6.2947 X2 + 8.0863 X3 + 0.0008 X12 –

0.3792 X22 – 0.5093 X32 + 0.0038 X1X2 – 0.0003 X2X3 + 0.0459 X2X3
where X1, X2 and X3 are the coded values for the three variables, i.e. contact time (min),
pH, and initial concentration of MB (mg/L), respectively.
TABLE 0.12 ANOVA for the response surface quadratic model
73
Mean P-Value
Model Terms Sum of Square F-value
Square Prob>F
Regression 1272.34 141.371 28.5 0.001

X1 0.56 0.565 0.11 0.749
X2 134.9 134.898 27.19 0.003
X3 260.09 260.085 52.43 0.001
2
X1 0.13 0.132 0.03 0.877
X22 135.89 135.89 27.39 0.003
2
X3 245.17 245.17 49.42 0.001
X1X2 0.21 0.21 0.04 0.845
X1X3 0 0.001 0 0.989
X2X3 2.16 2.157 0.43 0.539

Residual Error 24.8 4.961
Lack of fit 24.78 8.262 892.48 0.001
Pure Error 0.02 0.009
Total 1297.14
2
R 0.9809
2
R (adjusted) 0.9465
Table 4.2 showed the ANOVA parameters of the produced model. It also
showed the parameters which are based on statistics and are related to the suggested
correlation which are quadratic. F-value can be calculated by dividing the mean square
of the factor by the residual mean square. In most cases, the P-value and F-value can be
applied in order to realise the configuration of interactions among the variables as the
criteria. The factors being more significant is shown by a higher F-value and a lower P-
value and if the factor with P-value is lower than 0.05, it is regarded as significant
(Aravind et al., 2015). From the results as depicted in Table 4.2, the model F-value was
28.5, and the low probability value (0.001), which was less than P-value at the 95%
confidence limit, verified that the model terms were significant, and all the coefficients
were highly important for removal of MB. It shows that the linear effects and quadratic
effects of pH (X2, X22) and initial concentration of MB (X3, X32) were significant except
the interaction terms of contact time. Hence, the contact time did not give an effect to
remove the methylene blue by cellulose adsorbent.
The ANOVA analysis also shows the Lack-of-Fit (LOF) of the results, which
can be used to investigate the model’s adequacy. The hypothesis is, if the LoF is not
74
significant, then the model is adequate and if there is a significant LoF then the model is
unfit to represent the data (Elmoubarki et al., 2017). The LoF P-value of 0.001 implies
the lack-of-fit is significant indicating the model did not fit the data. As shown in Table
4.2, the coefficient of determination, R2 and adjusted R2 of this model were 0.9809 and
0.9465 respectively indicated that 1.91% and 5.32% of variability in percentage
removal cannot be explained by this model. For a model with good prediction
efficiency, the value of R2 should be close to 1 (Sarabia L.A. and Ortiz M.C. 2009). The
difference between values of R2 (0.9809) and adjusted R2 (0.9465) are small, therefore
the similarity between R2 and adjusted R2 showed the adequacy of the model to predict
the response. Figure 4.1 shows the relationship between the predicted and experimental
values for adsorption of methylene blue by using the cellulose adsorbent. The parity
plot shows the satisfactory correlation between the values of experimental and predicted
values, wherein, the points clustered around the diagonal line which indicates the good
fit of the model.
95.00
R² = 0.98
90.00
Predicted (%)
85.00
80.00
75.00
75.00 80.00 85.00 90.00 95.00 100.00
Experimental (%)

for MB Percentage removal by Cellulose Adsorbent
75
4.2.2 Effect of Experimental Parameters
3D response surface plots for the measured responses have been constructed in
order to reach the better understanding of the independent variable effects and their
interactions on the dependent variables.
(a)
(b)
removal by cellulose as a function of pH and Contact time [Condition: initial
concentration of MB = 6 mg/L]
76
(a)
(b)
removal by cellulose as a function of initial concentration of MB and Contact time
[Condition: pH = 7]
77
(a)
(b)
removal by cellulose as a function of initial concentration of MB and pH
[Condition: Contact time = 25 mins]
78
(a) Effect of pH
The effect of pH was analysed using RSM and the results of contour and
response surface plots and are presented in Figure 4.2 with initial concentration of
methylene blue at 6 mg/L and Figure 4.4 with constant contact time at 25 minutes. From
Figure 4.2 and 4.4, it can be inferred from the plots that the percentage removal of
methylene blue dye from solution onto cellulose adsorbent increased with increasing pH
up to pH 10.5, thereafter, it decreases.
As observed in Table 4.2, the effect of pH on percentage removal of methylene

blue was considerable with P-value > F equal to 0.003. The percentage removal of
methylene blue increased with increasing pH can be supported by the coded Equation
(4.1) in which positive (+) sign was observed in this effect of pH (X 2). Therefore, it is
evident that pH plays a vital role in the removal of methylene blue dye by cellulose
adsorbent.
According to Nonviho (2015), cellulose contains hydroxyl groups or carboxyl

groups, hence it is negatively charged in solution. Moreover, the negative charge of the
adsorbent surface will increase with increasing pH, resulted in an increase of available
binding sites. This negative charge exhibits an electrostatic attraction with respect to the
methylene blue which is a cationic dye. Therefore, electrostatic attraction between
positively charged methylene blue and negatively charged cellulose resulted increases in
dye adsorption (Khatrri et al. 2009). On the other hand, the hydrogen ions that were
positively charged were attached to the surface area of adsorbent. This caused the
surface charge became positive charge and electrostatic repulsion happened because of
the positively charged methylene blue (Nurul et al. 2016). Similar results were also
reported by Abkenar et al. (2015), where pH 10.5 is chosen as the optimum pH value of
methylene blue solution for the adsorption experiment.
79
(b) Effect of Contact Time
The results of contour and response surface plots shown in Figure 4.2 and 4.3
presented the effect of contact time at constant initial concentration of methylene blue at
6 mg/L and constant pH at 7 respectively. It can be observed from Figure 4.2 and 4.3
that, the percentage removal of methylene blue decreased with increasing contact time.
The reduction can be supported from the model Equation (4.1) where negative (-) sign
was presented for contact time (X 1). However, the P-value > F for effect of contact time
is more than 0.05, indicated that this effect is not significant.
Most researches stated that the percentage removal of dye should increase with
increasing contact time (Njoku et al., 2014; Rathod et al., 2016; Hameed et al., 2017),
but explanation can be made in this case. According to Enenebeaku (2017), this is due
to the adsorbed methylene blue molecules were weakly held on adsorbent during
saturation. This is feasible for the formation a secondary adsorption layer (held with
weak bond) on a primarily adsorbed methylene blue layer (having stronger attachment
with the adsorbent substrate). Assuming the methylene blue molecules absorb on
heterogeneous sites on the adsorbent surface, such could also provide an uneven spread
of energy between the primary and secondary adsorption layers and, hence, facilitate the
dislodging of methylene blue dye with increasing of contact time.
(c) Effect of Initial Concentration of Methylene Blue
From the contour and response surface plots shown in Figure 4.3 and 4.4, effect
of the initial concentration of methylene blue at constant pH at pH 7 and contact time at
25 mins were shown respectively. From the findings, the percentage removal of
methylene blue by cellulose increased with increasing initial concentration of methylene
blue. This can be explained by the model Equation (4.1) in which positive (+) sign was
80
observed for effect of initial concentration of methylene blue (X3). Moreover, this effect
is significant with the P-value > F lower than 0.05.
This phenomenon can be attributed to the fact that the initial concentration of
dye plays an important role which provided the necessary driving force to overcome the
resistances to the mass transfer of methylene blue between the aqueous and the solid
phases (Ouasif et al, 2013). Thus, the adsorption of methylene blue and subsequent
permeation into the pores of the adsorbent, are both facilitated with increasing dye
concentration. Hence, a higher initial concentration of methylene blue increased the
percentage removal of methylene blue.
Similar trend was noticed by Amel et al. (2012), an increase in the initial ions
concentrations of methylene blue will enhance the number of collisions resulted
between the dye ions and the adsorbent, thus, improves the adsorption process. Based
on Enenebeaku (2017), assuming the formation of weak bonds between primary and
secondary adsorption layers or between methylene blue and heterogeneous sites on
cellulose, such effects could conveniently be overcome by increasing initial dye
concentration. This is the reason that the percentage removal of methylene blue
continued to increase as initial concentration of methylene blue increased.
4.2.3 RSM Optimization
Percentage removal of methylene blue was set at maximum as special goal to be

achieved. Table 4.3 showed the results of the predicted responses for percentage
removal of methylene blue by cellulose after optimization. The optimum conditions
were found at contact time of 10 minutes, pH 8.8182 and initial concentration of
methylene blue at 8.303 mg/L. The predicted percentage removal of methylene blue
using cellulose adsorbent was 96.7924 %. In order to verify the predicted values from
the model, experiment was carried out at the optimum conditions. The experimental
81
result of percentage removal of methylene blue was 93.38%, and the error was only
3.53%. therefore, this substantiates that the predicted model was valid since the
predicted value was not differ much from the experimental value.
TABLE 0.13 RSM Optimization for adsorption of methylene blue on cellulose
Optimized Factors Percentage removal of MB

Error
Contact Initial concentration
pH Predicted Experimental (%)
time (min) of MB (mg/L)
10 8.82 8.30 96.79% 93.38% 3.53%
4.3 SYNTHESIS AND CHARACTERIZATION
The CQDs solution synthesized from cellulose was observed under daylight, and
yellowish-brown colour was shown in the inset of Figure 4.5 (a). Besides, from Figure
4.5 (b), Yellow fluorescence emissions colour was observed under the irradiation of UV
light, indicates the formation of CQDs. The yellow fluorescence of CQDs that can be
observed by naked eyes visually confirmed its fluorescence characteristics that renders
it a promising candidate in broad range of applications (Guo et al., 2016).
(a) (b)
FIGURE 4.0.26 CQDs solution under (a) white light; (b) UV light
82
4.3.1 SEM
(a) Cellulose Fibers
SEM was used to investigate the surface morphology of the cellulose. Figure 4.6
presented the SEM images of cellulose isolated from OPEFB with rod-like shaped. The
smooth surface of cellulose fibre is shown in Figure 4.6 (a). After the adsorption of
methylene blue, the cellulose surface becomes rougher. It can be seen that the
methylene blue molecule attached on the cellulose adsorbents, indicated the adsorption
of methylene blue dye from solution.
(a) (b)
FIGURE 4.0.27 SEM image of cellulose fibers (a) before adsorption (b) after
adsorption
83
4.3.2 Particle Size Distribution
FIGURE 4.0.28 Particle Size Distribution of cellulose-based CQDs
An average particle size of CQDs were found to be 2170.33 nm ranged from

1931 nm to 2445 nm. According to Alam et al. (2015), the CQDs derived from cabbage
by hydrothermal treatment were found to be 2–6 nm in diameter with a narrow size
distribution. Lu et al., (2012) also reported that pomelo was used to synthesis CQDs,
and the size obtained was found to be 2-4 nm. Furthermore, CQDs was extracted
successfully from strawberry juice with the size of 5.2 nm (Huang et al., 2013). This
showed that the CQDs should have nano-sized particles, which is normally below 10
nm. However, the size of CQDs produced from cellulose by hydrothermal synthesis
could not be supported, and the reasons were unknown.
4.3.3 Zeta-Potential
Zeta-potential can be known as surface charge, which measured by tracking the

moving rate of negatively or positively charged particles across an electric field. The
average zeta potential of CQD solution was calculated as -20.13 mV, which ranged
from -19.1 mV to -21.1 mV. Meanwhile, the average zeta potential of cellulose was
-41.37 mV which ranged from -41.1 mV and -41.9 mV. It was found that the zeta
potential of cellulose has the higher negative value compared to CQDs, which can be
84
supported by Gheorghe et al. (2013), where the zeta potential becomes more negative as
the pH increases. This might due to the higher pH value of cellulose after alkaline
treatment. Besides, these finding was ascribed to the presence of a large amount of
negatively charged carboxyl groups on the surface of the cellulose and cellulose-based
CQDs, and induced increase in the surface charges of particles (Bondeson et al. 2006).
This indicated that the CQDs was easily dispersible in basic medium, but quite unstable
in acidic medium. Based on Ucun et al. (2013), the negative charge on the particle
surface increased with increasing pH, therefore more cationic methylene blue dye
adsorption takes place due to electrostatic force of attraction.
FIGURE 0.29 Zeta Potential distribution of cellulose
FIGURE 4.0.30 Zeta Potential distribution of cellulose-based CQDs
85
4.4 PHOTOCATALYTIC ADSORPTION OF METHYLENE BLUE ON CQDs
4.4.1 RSM Modelling
The variables design matrix of not coded and coded units by the Box-Behnken
model along with the values of responses which are experimental and predicted were
shown in Table 4.4.
TABLE 0.14 Box-Behnken design matrix of three factors along with experimental
and predicted responses for removal of methylene blue by CQDs
Experimental Factors Response (Percentage Removal of MB) Error

Run X1 X2 X3 Experimental (%) Predicted (%) (%)
1 10 3 6 77.65 78.53 1.13
2 25 7 6 92.23 92.20 0.03
3 10 7 10 95.23 96.93 1.78
4 40 3 6 82.11 82.32 0.26
5 40 7 2 83.06 81.29 2.14
6 25 7 6 92.23 92.20 0.03
7 25 7 6 92.23 92.20 0.03
8 10 11 6 91.17 90.88 0.32
9 25 3 10 89.93 87.32 2.90
10 25 3 2 60.19 61.58 2.31
11 10 7 2 78.19 75.88 2.95
12 25 11 10 93.19 91.74 1.56
13 40 11 6 94.00 93.04 1.02
14 40 7 10 95.25 97.48 2.34
15 25 11 2 77.69 80.24 3.28
The response for percentage removal of methylene blue as a function of the

coefficient of independent variables of the full quadratic model was obtained as shown
in Equation 4.2.
Equation (4.2):
86
MB Removal % (coded) = 21.8961 + 0.0831X1 + 8.9329 X2 + 8.2434 X3 + 0.0037 X12 –
0.4276 X22 – 0.3212 X32 - 0.0068 X1X2 – 0.0202 X2X3 - 0.2224 X2X3
where X1, X2 and X3 are the coded values for the three variables, i.e. contact time (min),
pH, and initial concentration of MB (mg/L), respectively.
TABLE 0.15 ANOVA for the response surface quadratic model for removal of
methylene blue by CQDs
P-value
Model Terms Sum of Square Mean Square F-value
Prob>F
Regression 620.508 68.945 10.0 0.002

X1 0.338 0.338 0.05 0.833
X2 264.091 264.091 38.3 0.002
X3 64.233 64.233 9.32 0.002
X12 2.545 2.545 0.37 0.57
2
X2 167.993 167.933 24.36 0.004
2
X3 7.39 7.39 1.07 0.014
X1X2 0.642 0.642 0.09 0.773
X1X3 5.715 5.715 0.83 0.404
X2X3 49.25 49.25 7.14 0.044

Residual Error 34.474 6.895
Lack of fit 34.474 11.491
Pure Error 0 0
Total 654.983
2
R 0.9734
2
R (adjusted) 0.9255
Table 4.5 showed the parameters which are based on statistics and are related to
the suggested correlation which are quadratic. From the findings, only pH (X2) and
initial concentration of methylene blue (X3) were significant since P-value > F is less
than 0.05, whereas the effect of contact time (X1) did not give an effect to remove the
methylene blue by CQDs. However, the insignificant terms were kept, despite of the
insignificancy to improve prediction and optimization ability of produced model. The
model F-value, which was calculated by dividing the mean squares of each variable
effect by the mean square, was 10.0, and the low probability value (0.002), which was
87
less than P-value at the 95% confidence limit, verified that the model terms were
significant for removal of methylene blue by CQDs.
The Lack-of-Fit (LoF) values for removal of methylene blue by CQDs was
statistically insignificant since there was no evidence of Lack-of-Fit shown in ANOVA
analysis. As shown in Table 4.5, the coefficient of determination, R 2 and adjusted R2 of
this model were 0.9734 and 0.9255 respectively indicated that only 2.66% and 7.45% of
the variation in the response could not be explained by the model and the model fitted
well with the observed data. For a model with good prediction efficiency, the value of
R2 should be close to 1 (Sarabia L.A. and Ortiz M.C. 2009). The difference between
values of R2 (0.9734) and adjusted R2 (0.9255) are small, therefore the similarity
between R2 and adjusted R2 showed that the terms were required for modelling the data.
Figure 4.7 showed that the points of the predicted vs. experimental values plots for
percentage removal of methylene blue by CQDs were clustered along a diagonal line,
indicating that the predicted values matched well with the observed ones.
100.00
95.00
f(x) = 0.97 x + 2.29
R² = 0.97
90.00
Predicted (%)
85.00
80.00
75.00
70.00
70.00 75.00 80.00 85.00 90.00 95.00 100.00
Experimental (%)

for MB Percentage removal by CQDs Adsorbent
4.4.2 Effect of Experimental Parameters
88
removal by CQDs as a function of pH and Contact time [Condition: initial
concentration of MB = 6 mg/L]
89
removal by CQDs as a function of initial concentration of MB and Contact time
[Condition: pH = 7]
90
removal by CQDs as a function of initial concentration of MB and pH [Condition:
Contact time = 25 mins]
91
(a) Effect of pH
The effect of pH on photocatalytic adsorption of methylene blue on cellulose-

based CQDs was analysed using RSM and the results of contour and response surface
plots were shown in Figure 4.11 and 4.13 with constant initial concentration of
methylene blue at 6mg/L and constant time at 25 mins respectively. From the results, it
was observed that the percentage removal of methylene blue increased with increasing
pH up to pH 9.8, thereafter, it decreases. This can be explained by the coded Equation
(4.2) where positive (+) sign was presented for effect of pH (X2). Besides, the effect of
pH on percentage removal of methylene blue by CQDs was significant with P-value > F
less than 0.05. Thus, it is evident that pH plays a vital role in the photocatalytic
adsorption of methylene blue by cellulose-based CQDs adsorbent.
According to Tadesse et al. (2018), lower adsorption of methylene blue was

observed due to the presence of negatively charged ions acid competing with the
methylene blue cations for the available adsorption sites which reduce the adsorbed
amount. Therefore, higher pH was preferable for the adsorption of methylene blue dye
solution on cellulose-based CQDs, considering the electrostatic attraction that exists
between the negatively charged surfaces of adsorbent mainly due to the methylene blue
dyes (Khatrri et al. 2009).
(d) Effect of Contact Time
Based on the contour and response surface plots as shown in Figure 4.12 and
4.13, the effect of contact time to photo-catalytically adsorb methylene blue by
cellulosed-based CQDs was analysed at constant initial concentration of methylene blue
dye at 6 mg/L and constant pH at pH 7, respectively. It was noted that the percentage
removal of methylene blue increased with increasing contact time. This trend can be
supported by the coded Equation (4.2) in which positive (+) sign was observed in this
92
effect of contact time (X1). However, as observed in Table 4.5, the effect of contact time
on percentage removal of methylene blue by cellulose-based CQDs was not significant
with the P-value of 0.833 which is higher than 0.05.
As compared with the adsorption of methylene blue on cellulose fibers which

showed the percentage removal of methylene blue decreased with increasing contact
time, the photocatalytic adsorption of methylene blue with addition of CQDs showed
opposite results. This showed that the removal of methylene blue using cellulose based
CQDs adsorbent was more effective and efficient than cellulose adsorbents. Moreover,
maximum percentage removal of methylene blue dye was observed when contact time
was at maximum point, which can be ascribed to the presence of vacant sites on the
adsorbent surface which are available to the methylene blue dye molecules, in
accordance with that obtained by Tchuifon (2016). This result showed that increasing
contact time favoured the prolonged interaction between the methylene blue molecules
and the cellulose-based CQDs surface and subsequent permeation into the adsorbent
pores (Enenebeaku et al., 2017).
(e) Effect of Initial Concentration of Methylene Blue
The results of contour and response surface plots shown in Figure 4.11 and 4.12
presented the effect of initial concentration of methylene blue at constant pH at pH 7
and constant contact time at 25 mins respectively. It can be observed that the percentage
removal of methylene blue increased with increasing initial concentration of methylene
blue dye, which can be explained by the model Equation (4.2) where positive (+) sign
was presented for the effect of initial concentration of methylene blue (X 3). This effect
was significant with P-value > F (0.002) was lower than 0.05.
In order to overcome the diffusive mass transfer resistance of all molecules

between the adsorbents and adsorbates, initial dye concentration is an important driving
93
force (Khataee et al., 2013). Hence, a higher initial concentration of methylene blue
gives a crucial driving force to overcome all resistance of methylene blue between
aqueous and solid phases thus increased the percentage removal of methylene blue by
cellulose-based CQDs. It also enhanced the number of collisions resulted between the
methylene blue ions and the CQDs, thus, improved the catalytic adsorption process
(Amel et al. 2012). Therefore, an increase in initial concentration od methylene blue
dye leads to increase in the adsorption uptake of methylene blue dye. Similar results
were reported by various researchers for methylene blue adsorption on activated carbon
(Sharma, 2009), on carbon nanotube (Shahryari et al., 2010), and on cashew nut shell
(Kumar et al., 2010).
4.4.3 RSM Optimization
Response surface optimization was performed to maximize the percentage

removal of methylene blue using cellulose-based CQDs. Table 4.6 showed the results of
the predicted responses for percentage removal of methylene blue by cellulose-based
CQDs after optimization. The optimum conditions were found at contact time of 40
minutes, pH 7.8485 and initial concentration of methylene blue at 8.8687 mg/L. The
predicted percentage removal of methylene blue using cellulose adsorbent was 98.0465
%. To determine the validity of obtained optimal parameters, confirmation experiment
was performed using the experimental conditions as reported in Table 4.6. The
experimental result of percentage removal of methylene blue was 95.97 %, and the
percentage of error value calculated was only 2.12%, which was within ±10 %.
Therefore, this substantiates that the predicted model was valid since the predicted value
was not differ much from the experimental value.
TABLE 0.16 RSM Optimization for adsorption of methylene blue on cellulose
Optimized Factors Percentage removal of MB Error

Contact pH Initial concentration Predicted Experimental (%)
time (min) of MB (mg/L)
40 7.8485 8.8687 98.0465% 95.97% 2.12%
94
4.5 COMPARISON OF CELLULOSE ADSORBENT AND CQDs
ADSORBENT IN DYE REMOVAL
The adsorption capacity obtained from optimized RSM parameters of newly

synthesized cellulose-based CQDs with cellulose fibers were presented in Table 4.6.
From the comparable data of the adsorption capacity, it is clear that the newly
synthesized cellulose-based CQDs possess better adsorption capacity with respect to the
cellulose fibers adsorbents. The percentage removal of methylene blue using cellulose-
based CQDs 95.97%. which was slightly higher than that of using cellulose fibers
adsorbents via batch adsorption, with percentage removal of 93.38%. When the
cellulose-based CQDs were illuminated by UV light, it absorbs the light, where
photocatalytic adsorption process was conducted.
According to Hossein and Masoud, (2017) in removal of methylene blue dye

pollutant under UV-light with N-doped graphene quantum dots/titanium dioxide
nanocomposite, the N-GQDs were attached on the surface of TiO 2 nanoparticles. This
phenomenon causes that excited electrons of N-GQDs transfer to TiO 2, which facilitated
the formation of active oxygen and hydroxyl radicals and these radicals oxidize
methylene blue. On the other hand, the surface area is increased, and this improved the
performance of adsorption. Due to the up-conversion properties and electron
withdrawing property of CQDs, the photocatalytic activity of the composite material
was largely enhanced under UV-light irradiation (Miao et al., 2016). Hence, this trend
can be applied in photocatalytic adsorption of methylene blue using cellulose-based
CQDs.
Table 0.17 Comparison of cellulose adsorbent and CQDs adsorbent in removal

of methylene blue dye
Adsorbent Adsorption capacity (mg/g) Percentage Removal (%)
Cellulose fibers 0.7753 93.38
Cellulose-based CQDs 0.8511 95.97
95
4.6 Isotherm Analysis
The distribution of methylene blue molecule between the liquid phase and the
adsorbent is a measure of the position of equilibrium in the adsorption process and can
generally be expressed by one or more series of isotherm models. Adsorption isotherms
are critical in optimizing the use of adsorbents, and the analysis of the isotherm data by
fitting them to different isotherm models is an important step to find the suitable model
that can be used for design purposes (Dawood and Sen, 2012). The Langmuir isotherm
and Freundlich isotherm studies were conducted using various initial concentration of
methylene blue from 2 mg/L to 10 mg/L in the presence of 0.5 g adsorbents. The
applicability of the isotherm equation was compared by the linear correlation
coefficients, R2.
7.00
6.00 f(x) = 6.42 x − 7.66
5.00 R² = 0.98
4.00
1/Qe
3.00
2.00
1.00
0.00
1.20 1.40 1.60 1.80 2.00 2.20 2.40
1/Ce
FIGURE 4.0.35 Langmuir Isotherm Plot for Methylene Blue dye onto Cellulose
0.00
-0.20 f(x) = 3.53 x + 0.85
-0.40 R² = 0.98
-0.60
-0.80
-1.00
ln Qe
-1.20
-1.40
-1.60
-1.80
-2.00
-0.90 -0.80 -0.70 -0.60 -0.50 -0.40 -0.30 -0.20
ln Ce
FIGURE 4.0.36 Freundlich Isotherm Plot for Methylene Blue dye onto Cellulose
96
7.00
6.00
f(x) = 3.77 x − 4.54
5.00 R² = 0.98
4.00
1/Qe
3.00
2.00
1.00
0.00
1.20 1.40 1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00
1/Ce
FIGURE 4.0.37 Langmuir Isotherm Plot for Methylene Blue dye onto cellulose-
based CQDS
0.00
f(x) = 2.57 x + 0.81
-0.50 R² = 0.99
-1.00
ln Qe
-1.50
-2.00
-1.10 -1.00 -0.90 -0.80 -0.70 -0.60 -0.50 -0.40 -0.30
ln Ce
FIGURE 4.0.38 Freundlich Isotherm Plot for Methylene Blue dye onto cellulose-
based CQDs
TABLE 0.18 Comparison of Langmuir and Freundlich isotherm constants for

removal of methylene blue by Cellulose and CQDs adsorbents
Langmuir Isotherm Freundlich Isotherm

Adsorbent
Qo (mg/g) KL (L/mg) R2 n Kf (mg/g) R2
Cellulose 0.130 1.194 0.9820 0.284 2.339 0.9778
Cellulose-
0.220 0.831 0.9835 0.389 2.249 0.9924
based CQDs
Figure 4.11 and 4.12 showed the linear plot of linearized Langmuir and
Freundlich isotherm analysis for batch adsorption of methylene blue using cellulose
adsorbent respectively. The calculated constants and regression values of these isotherm
models are listed in TABLE 0 .18. Based on the data obtained, both isotherm models
exhibited high correlation coefficient, R2 values (>0.95). However, Langmuir isotherm
97
represented the best fit of experimental data than the Freundlich isotherm due to the
higher correlation coefficient, R2 (0.9820) obtained. The fact that Langmuir isotherm fits
the experimental data very well confirms the monolayer coverage of methylene blue
onto cellulose adsorbents and also the homogeneous distribution of active sites on the
adsorbent, since the Langmuir equation assumed that the surface is homogeneous
(Dakhil, 2013). This model also assumed uniform energies of adsorption onto the
surface and no transmigration of adsorbate in the plane of the surface (Dada et al.
2012).
In addition, Langmuir and Freundlich plots for photocatalytic adsorption of

methylene blue dye on cellulose-based CQDs were shown in Figure 4.13 and 4.14. The
calculated constants and regression values of these isotherm models were listed in Table
4.7. Based on the data obtained, it was found that the adsorption equilibrium data fit
both Langmuir and Freundlich equations with a correlation coefficient value, R 2 of
0.9835 and 0.9924 respectively. However, Freundlich isotherm appeared to better
describe the catalytically adsorption of methylene blue on cellulose-based CQDs with
higher R2 value obtained. This indicated that the photocatalytic adsorption process
involved heterogeneous adsorption with different classes of adsorption sites
(Aravindhan et al., 2007). It also predicted that the dye concentrations on the adsorbent
increased if the concentration of dye solutions increased (Cheung et al., 2009).
In addition, the separation factor, RL which is a dimensionless constant related to

the propitiousness of the adsorption using both adsorbents have been calculated from
Langmuir isotherm plot. It can be found that the calculated R L values lie between 0 and
1 at different initial concentration of methylene blue suggesting the isotherm to be
favourable at the concentrations studied. Besides, cellulose adsorbents with lower R L
values at higher initial methylene blue concentrations showed that adsorption was more
favourable at higher concentrations.
98
0.4
0.35
0.3
0.25
0.2
RL
0.15 Cellulose
0.1 CQDs
0.05
0
1 2 3 4 5 6 7 8 9 10 11
Co (mg/L)
FIGURE 4.0.39 Plot of Separation Factor vs Initial concentration of methylene

blue
Freundlich constant (KF) values derived from Freundlich isotherm models

served as an indication of adsorption capacity of cellulose fibers and cellulose-based
CQDs for methylene blue system where n is the heterogeneity factor representing the
deviation from linearity of adsorption. Freundlich constant, KF for cellulose and
cellulose-based CQDs were 2.339 and 2.249 respectively, with n values of 0.284 and
0.389 respectively. The n value is lower than unity (1), showed that the adsorption
process is chemical (Aljebrori et al., 2014).
4.7 Kinetics Analysis
Kinetics models have been used to investigate the mechanism of adsorption and
potential rate controlling steps, which is helpful for selecting optimum operating
conditions for the full-scale batch process (Santhi and Smitha, 2010). The kinetic of the
methylene blue adsorption on cellulose and cellulose-based adsorbent were examined
using pseudo-first and pseudo-second order equation, as presented in Figure 4.16 to
4.19.
99
12
10
log(qe-qt)
6
0
0 f(x)
10= 0 20 30 40 50 60 70
R² = 0
t

cellulose
70
60 f(x) = 1.09 x + 0.2
R² = 1
50
40
t/qt
30
20
10
0
0 10 20 30 40 50 60 70
t

cellulose
12
10
8
log(qe-qt)
0
0 f(x)
10= 0 20 30 40 50 60 70
R² = 0
t

cellulose-based CQDs
100
70
60 f(x) = 1.03 x + 0.85
50 R² = 1
40
t/qt
30
20
10
0
0 10 20 30 40 50 60 70
t

cellulose-based CQDs
TABLE 0.19 Comparison of pseudo-first and pseudo-second order for removal of

methylene blue by cellulose and cellulose-based CQDs
Adsorbent pseudo-first-order kinetic model pseudo-second-order kinetic model

K2
K1 qe qe
-1
R2 (g/mg.min R2
(min ) (mg/g) (mg/g)
)
Cellulose 0.024 0.059 0.827 5.946 0.917 0.9999
Cellulose-
0.027 0.374 0.8515 1.244 0.972 0.9999
based CQDs
Kinetic parameters obtained from fitting model plots during contact time of 5
mins to 60 mins were listed in Table 4.8. Based on the correlation coefficients with both
models, removal of methylene blue by both adsorbents fitted well to pseudo-second-
order model where the correlation coefficient, R 2 were closer to unity (> 0.99). Pseudo-
first-order kinetic model does not fit well to the whole range of contact time whereas
pseudo-second-order kinetic model correlates well to adsorption study in most cases
(Wan Ngah et al. 2004). Thus, the adsorption of methylene blue on cellulose was more
appropriately described by pseudo-second-order model which is based on the
assumption that the rate limiting step may be chemical sorption or chemisorption
involving valency forces through sharing or exchange of electron between sorbent and
sorbate (Ho and Mc Kay, 2000). The occurrence of chemisorption is controlled by
101
strong intraparticle bonding, such as ionic and covalent bonding, contributes to the
irreversible adsorption process (Allen and Koumanova, 2005).
4.7.1
102
CHAPTER V
CONCLUSION
103
104
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APPENDICES
APPENDIX 1
PICTORIAL FLOW DIAGRAM
i. Extraction of Cellulose
ii. Extraction of cellulose-based CQDs
122
iii. 10 mg/L Methylene blue solution
iv. Adsorption Experiment using cellulose fibers adsorbent
v. Photocatalytic Adsorption Experiment using cellulose-based CQDs adsorbent
123
APPENDIX 2
CELLULOSE YIELD CALCULATION DATA
Sample (g) Cellulose (g) Yield (%)

20.035 9.632 48.08
15.015 7.652 50.96
15.007 9.365 62.40
20.012 10.256 51.25
Average yield (%) 53.17
APPENDIX 3
CALIBRATION CURVE DATA OF METHYLENE BLUE

Concentration of MB Dye (mg/L) ABS Avg ABS
0.00 0 0 0 0.0000
0.50 0.21 0.213 0.224 0.2157
1.00 0.336 0.344 0.316 0.3320
1.50 0.546 0.552 0.482 0.5267
3.00 0.885 0.942 0.921 0.9160
5.00 1.451 1.469 1.463 1.4610
7.00 1.798 1.859 1.895 1.8507
10.00 2.548 2.452 2.648 2.5493
Dye Calibration Curve

3.00
2.50 f(x) = 0.27 x

R² = 0.99
2.00 f(x) = 0.75 ln(x) + 0.4
R² = 0.9
1.50
ABS
1.00
0.50
0.00
0.00 2.00 4.00 6.00 8.00 10.00 12.00
Conc. of dye (mg/L)
124
APPENDIX 4
ADSORPTION OF METHYLENE BLUE ON CELLULOSE FIBERS
Contact Time Initial Conc. of MB ABS Final Conc. Adsorption

Run pH st Avg ABS
(min) (mg/L) 1 2nd rd
3 (mg/L) capacity (mg/g)
1 10 3 6 0.274 0.244 0.296 0.2713 1.0174 0.4983
2 25 7 6 0.124 0.124 0.124 0.1240 0.4649 0.5535
3 10 7 10 0.159 0.144 0.141 0.1480 0.5549 0.9445
4 40 3 6 0.318 0.331 0.330 0.3263 1.2236 0.4776
5 40 7 2 0.139 0.137 0.141 0.1390 0.5212 0.1479
6 25 7 6 0.124 0.128 0.128 0.1267 0.4749 0.5525
7 25 7 6 0.124 0.128 0.128 0.1267 0.4749 0.5525
8 10 11 6 0.123 0.129 0.110 0.1207 0.4524 0.5548
9 25 3 10 0.596 0.536 0.548 0.5600 2.0997 0.7900
10 25 3 2 0.186 0.193 0.181 0.1867 0.6999 0.1300
11 10 7 2 0.156 0.131 0.141 0.1427 0.5349 0.1465
12 25 11 10 0.193 0.215 0.207 0.2050 0.7687 0.9231
13 40 11 6 0.166 0.169 0.148 0.1610 0.6037 0.5396
14 40 7 10 0.136 0.123 0.135 0.1313 0.4924 0.9508
15 25 11 2 0.122 0.136 0.136 0.1313 0.4924 0.1508
125
APPENDIX 5
PHOTOCATALYTIC ADSORPTION OF METHYLENE BLUE ON CELLULOSE-BASED CQDs
Contact Time Initial Conc. of dye ABS Adsorption

Run pH st Avg ABS Conc.
(min) (mg/L) 1 2nd rd
3 capacity (mg/g)
1 10 3 6 0.359 0.346 0.368 0.3577 1.3411 0.4659
2 25 7 6 0.119 0.125 0.129 0.1243 0.4662 0.5534
3 10 7 10 0.149 0.109 0.124 0.1273 0.4774 0.9523
4 40 3 6 0.292 0.276 0.291 0.2863 1.0736 0.4926
5 40 7 2 0.096 0.084 0.091 0.0903 0.3387 0.1661
6 25 7 6 0.119 0.125 0.129 0.1243 0.4662 0.5534
7 25 7 6 0.119 0.125 0.129 0.1243 0.4662 0.5534
8 10 11 6 0.145 0.138 0.141 0.1413 0.5299 0.5470
9 25 3 10 0.265 0.269 0.272 0.2687 1.0074 0.8993
10 25 3 2 0.205 0.220 0.212 0.2123 0.7962 0.1204
11 10 7 2 0.116 0.124 0.109 0.1163 0.4362 0.1564
12 25 11 10 0.180 0.185 0.180 0.1817 0.6812 0.9319
13 40 11 6 0.098 0.091 0.099 0.0960 0.3600 0.5640
14 40 7 10 0.130 0.128 0.122 0.1267 0.4749 0.9525
15 25 11 2 0.120 0.118 0.119 0.1190 0.4462 0.1554
126
APPENDIX 6
SIZE DISTRIBUTION OF CQDS
i. 1st trial analysis
127
ii. 2nd trial analysis
128
iii. 3rd trial analysis
129
APPENDIX 7
ZETA POTENTIAL OF CQDS
i. 1st trial analysis
130
ii. 2nd trial analysis
131
iii. 3rd trial analysis
132
APPENDIX 8
ISOTHERM STUDIES DATA
Co ABS Ce Qe 1/Qe 1/Ce lnQe lnCe RL

0.45744 0.29521
2 0.122 0.153 6.522 2.186 -1.875 -0.782
3 9
0.59242 0.17317
4 0.158 0.333 3.005 1.688 -1.100 -0.524
6 1
0.66741
6 0.178 0.526 1.902 1.498 -0.643 -0.404 0.12252
7
0.68241 0.09479
8 0.182 0.716 1.397 1.465 -0.334 -0.382
5 3
0.76865
10 0.205 0.901 1.109 1.301 -0.104 -0.263 0.0773
4
i. Adsorption of methylene blue on cellulose fibers
[condition: pH=11, time = 25mins, adsorbent = 0.5g, MB = 0.05L]
Co ABS Ce Qe 1/Qe 1/Ce lnQe lnCe RL
2 0.096 0.359955 0.163 6.134 2.778 -1.814 -1.022 0.375636
4 0.129 0.48369 0.343 2.912 2.067 -1.069 -0.726 0.231251
6 0.152 0.569929 0.536 1.867 1.755 -0.625 -0.562 0.167044
8 0.177 0.663667 0.718 1.393 1.507 -0.332 -0.410 0.130743
10 0.182 0.682415 0.910 1.099 1.465 -0.094 -0.382 0.107402

ii. Photocatalytic adsorption of methylene blue on cellulose-based CQDs
[condition: pH=11, time = 25mins, adsorbent = 0.5g, MB = 0.05L]
133
APPENDIX 9
KINECTIC STUDIES DATA
t (min) ABS Ct (mg/L) Qt log qe-qt t/qt

5 0.218 0.817398 0.91826 -2.9489 5.44508
10 0.219 0.821147 0.917885 -3.12499 10.89461
15 0.243 0.911136 0.908886 -2.0836 16.50371
20 0.244 0.914886 0.908511 -2.0643 22.01403
25 0.264 0.989876 0.901012 -1.79255 27.74657
30 0.254 0.952381 0.904762 -1.90751 33.15789
35 0.247 0.926134 0.907387 -2.01105 38.57231
40 0.231 0.866142 0.913386 -2.42602 43.7931
45 0.236 0.884889 0.911511 -2.24993 49.36857
50 0.228 0.854893 0.914511 -2.58092 54.67405
55 0.221 0.828646 0.917135 59.96934
60 0.221 0.828646 0.917135 65.4211
[condition: pH = 11, Co = 10mg/L, adsorbent = 0.05g, MB = 0.05L]
t (min) Abs Ct (mg/L) Qt log qe-qt t/qt

5 0.263 0.986127 0.901387 -1.2385 5.547005
10 0.252 0.944882 0.905512 -1.27069 11.04348
15 0.231 0.866142 0.913386 -1.33966 16.42241
20 0.205 0.768654 0.923135 -1.44375 21.66531
25 0.182 0.682415 0.931759 -1.5627 26.83099
30 0.173 0.648669 0.935133 -1.61984 32.08099
35 0.126 0.472441 0.952756 -2.19557 36.73554
40 0.132 0.494938 0.950506 -2.0643 42.08284
45 0.125 0.468691 0.953131 -2.2219 47.21282
50 0.109 0.408699 0.95913 52.13057
55 0.109 0.408699 0.95913 57.34363
60 0.109 0.408699 0.95913 62.55668
[condition: pH = 11, Co = 10mg/L, adsorbent = 0.05g, MB = 0.05L]
134
APPENDIX 10
RSM OPTIMIZATION PLOT
Optimal Contact pH Initial

D High 40.0 11.0 10.0
Cur [10.0] [8.8182] [8.3030]
0.90835 Low 10.0 3.0 2.0
Composite
Desirability
0.90835
MB Remov
Maximum
y = 96.7924
d = 0.90835
Optimal Contact pH Initial

D High 40.0 11.0 10.0
Cur [40.0] [7.8485] [8.8687]
0.95116 Low 10.0 3.0 2.0
Composite
Desirability
0.95116
MB Remov
Maximum
y = 98.0465
d = 0.95116
135

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PHOTOCATALYTIC ADSORPTION PROCESS USING

SYNTHESIZED CELLULOSE BASED QUANTUM-

WONG ZHI CHENG

A Report Submitted in Partially Fulfilment of the

Faculty of Engineering, Technology & Built Environment

I am greatly indebted to the wonderful people ho have aided me professionally

First of all, I would like to take this opportunity to express my utmost

“Furthermore, special thanks to my university, UCSI University for providing

1.2 PROBLEM STATEMENT 13

1.3 RESEARCH OBJECTIVES 15

1.4 SCOPE OF STUDY 15

1.5 ORGANIZATION OF THESIS 16

2.2.1 Structure of cellulose 20

2.2.2 Extraction of cellulose 21

2.3.1 Carbon Quantum Dots 24

2.3.2 Sources of Carbon Quantum Dots 25

2.3.3 Application of Carbon Quantum Dots (CQDs) 25

2.4 SYNTHESIS OF CARBON QUANTUM DOTS 26

2.4.1 Microwave Assisted Method 28

2.4.2 Hydrothermal Method 30

2.5 DYE REMOVAL 32

2.5.2 Methylene blue 33

2.5.3 Current technologies for dye removal 34

2.6.1 Chemisorption and Physisorption 36

2.6.3 Adsorption in dye removal application 39

2.7 PHOTOCATALYTIC ADSORPTION 39

2.8 FACTOR AFFECTING THE PERFORMANCES OF ADSORPTION 41

2.8.2 Effect of contact time 42

2.8.3 Effect of initial concentration of dye 43

2.9 ADSORPTION ISOTHERM 44

2.9.1 Langmuir Isotherm 44

2.9.2 Freundlich Isotherm 45

2.10 ADSORPTION KINETICS 46

2.10.1 Pseudo-first-order kinetic model 47

2.10.2 Pseudo-second-order kinetic model 47

2.11 RESEARCH SURFACE METHODOLOGY (RSM) 48

2.11.1 Central Composite Design (CCD) 48

2.11.2 Box-Behnken Design 49

2.12 CHARACTERIZATION TECHNIQUES 50

2.12.1 Scanning Electron Microscope (SEM) 50

2.12.2 UV-Vis Spectroscopy 51

3.4 EXTRACTION OF α-CELLULOSE FROM AGROWASTE-OIL PALM

3.4.1 Preparation of Oil Palm Empty Fruit Bunch (OPEFB) 56

3.4.2 Pre-treatment of Oil Palm Empty Fruit Bunch (OPEFB) 56

3.4.3 Bleaching Treatment 57

3.4.4 Extraction of alpha-cellulose 57

3.5 SYNTHESIS OF CARBON QUANTUM DOTS (CQDs) FROM

3.5.1 HYDROTHERMAL SYNTHESIS METHOD 59

3.5.2 Characterization of samples 59

3.6 ADSORPTION PERFORMANCE USING RESEARCH SURFACE

3.7 REMOVAL OF METHYLENE BLUE DYE 61

3.7.1 Calibration of Methylene Blue Solutions Standard Curve 61

3.7.2 Batch Adsorption Experiment 62

3.7.3 Photocatalytic Adsorption Experiment 64

3.8 ISOTHERM ANALYSIS OF ADSORPTION 64

3.8.1 Langmuir isotherm model 65

3.8.2 Freundlich isotherm model 66

3.9 KINETICS STUDIES OF ADSORPTION 66

3.9.1 Pseudo-first-order kinetic model 67

3.9.2 Pseudo-second-order kinetic model 67

4.2 ADSORPTION PROCESS OF METHYLENE BLUE ON CELLULOSE 68

4.2.1 RSM Modelling 68

4.2.2 Effect of Experimental Parameters 72