FYP Report-Finalized PDF

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
April 2019
1
ACKNOWLEDGEMENT
I am greatly indebted to the wonderful people who 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 the

equipment and facilities needed to carry out my final year project. I also would like to
thank to the lab tutors 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.
i
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
Carbon Quantum Dots (CQDs) were synthesized by hydrothermal treatment using

cellulose as carbon sources for photocatalytic adsorption of methylene blue (MB) dye.
The cellulose was firstly extracted from oil palm empty fruit bunch (OPEFB) via alkaline
treatment. Then, CQDs were synthesized from cellulose via hydrothermal method. Both
cellulose and cellulose-based CQDs were employed as adsorbents for MB dye removal
under visible light and UV light respectively. The adsorption process using both
adsorbents were conducted with the help of Box-Behnken design to model and optimize
the effects of the operating conditions such as contact time (10-40 min), pH (3-11) and
initial concentration of MB (2-10 mg/L). Correlation coefficient, R2 obtained for
adsorption by cellulose was 98.09% and 97.34% for photocatalytic adsorption by
cellulose-based CQDs, indicated that the suggested quadratic model successfully
explained the experimental data. The maximum percentage removal for cellulose and
cellulose-based adsorbent were 95.08% and 95.25% respectively. In addition, it was
found that the percentage removal of MB using cellulose-based CQDs (95.97%) was
slightly higher than using cellulose (95.08%), which can be explained by the
photocatalytic activity of CQDs was enhanced under UV light irradiation. The adsorption
studies for cellulose adsorbent were best described by the Langmuir isotherm whereas the
cellulose-based CQDs fitted well in Freundlich isotherm. All adsorption system was to
obey pseudo-second-order kinetic model. The morphological structure and particle size
distribution were characterized using various spectroscopic techniques. The synthesized
CQDs solution portrayed a significant fluorescence property that yellowish-brown colour
can be observed by naked eyes under UV light irradiation. The particle size and zeta
potential were found to be 2170.33 nm and -20.13 mV respectively.
iii
TABLE OF CONTENT
Page
ACKNOWLEDGEMENT i
DECLARATION OF ORIGINALITY & EXCLUSIVENESS ii
ABSTRACT iii
TABLE OF CONTENT iv
LIST OF TABLES viii
LIST OF FIGURES x
LIST OF EQUATIONS xiii
LIST OF ABBREVIATIONS AND SYMBOLS xv
CHAPTER 1 INTRODUCTION 1
1.1 Introduction 1
1.2 Problem Statement 3
1.3 Research Objectives 5
1.4 Scope of Study 5
1.5 Organization of Thesis 6
CHAPTER II LITERATURE REVIEW 8
2.1 Oil Palm 8

2.1.1 Oil Palm Empty Fruit Bunch (OPEFB) and its structure 9
2.2 Cellulose 10
2.2.1Structure of cellulose 10
2.2.2 Extraction of cellulose 11
2.3 Quantum-Dots 12
2.3.1 Carbon Quantum Dots 14
2.3.2 Sources of Carbon Quantum Dots 15
iv
2.3.3 Application of Carbon Quantum Dots (CQDs) 15
2.4 Synthesis of Carbon Quantum Dots 16
2.4.1 Microwave Assisted Method 18
2.4.2 Hydrothermal Method 20
2.5 Dye Removal 22
2.5.1 Dye 22
2.5.2 Methylene blue 23
2.5.3 Current technologies for dye removal 24
2.6 Adsorption 25
2.6.1 Chemisorption and Physisorption 26
2.6.2 Adsorbent 27
2.6.3 Adsorption in dye removal application 29
2.7 Photocatalytic Adsorption 29
2.8 Factor Affecting the Performances of Adsorption 31
2.8.1 Effect of pH 31
2.8.2 Effect of contact time 32
2.8.3 Effect of initial concentration of dye 33
2.9 Adsorption Isotherm 34
2.9.1 Langmuir Isotherm 34
2.9.2 Freundlich Isotherm 35
2.10 Adsorption Kinetics 36
2.10.1 Pseudo-first-order kinetic model 36
2.10.2 Pseudo-second-order kinetic model 37
2.11 Research Surface Methodology (RSM) 38
2.11.1 Central Composite Design (CCD) 38
2.11.2 Box-Behnken Design (BBD) 39
2.12 Characterization Techniques 40
2.12.1 Scanning Electron Microscope (SEM) 40
2.12.2 UV-Vis Spectroscopy 41
2.12.3 Particle size measurement 42
2.12.4 Zeta potential measurement 42
v
CHAPTER III RESEARCH METHODOLOGY 43
3.1 Materials and Chemicals 43

3.2 Equipment 44
3.3 Research Methodology Flow Chart 44
3.4 Extraction of alpha-Cellulose from Agrowaste-Oil Palm Empty 46
Fruit Bunch (OPEFB)
3.4.1 Preparation of Oil Palm Empty Fruit Bunch (OPEFB) 46
3.4.2 Pre-treatment of Oil Palm Empty Fruit Bunch (OPEFB) 46
3.4.3 Bleaching Treatment 47
3.4.4 Extraction of alpha-cellulose 47
3.5 Synthesis of Carbon Quantum Dots (CQDs) From Extracted 49
alpha-Cellulose
3.5.1 Hydrothermal Synthesis Method 49
3.5.2 Characterization of samples 49
3.6 Adsorption Performance Using Research Surface Methodology 50
(RSM) Approach
3.7 Removal of Methylene Blue Dye 51
3.7.1 Calibration of Methylene Blue Solutions Standard Curve 51
3.7.2 Batch Adsorption Experiment 52
3.7.3 Photocatalytic Adsorption Experiment 53
3.8 Isotherm Analysis of Adsorption 54
3.8.1 Langmuir isotherm model 54
3.8.2 Freundlich isotherm model 55
3.9 Kinetics Studies of Adsorption 56
3.9.1 Pseudo-first-order kinetic model 56
3.9.2 Pseudo-second-order kinetic model 57
CHAPTER IV RESULTS AND DISCUSSION 58
4.1 Percentage Yield of Cellulose 58

4.2 Adsorption Process of Methylene Blue on Cellulose 58
4.2.1 RSM Modelling 58
4.2.2 Effect of Experimental Parameters 62
vi
(a) Effect of pH 65
(b) Effect of Contact Time 66
(c) Effect of Initial Concentration of MB 66
4.2.3 RSM Optimization 67
4.3 Synthesis and Characterization 68
4.3.1 SEM 69
4.3.2 Particle Size Distribution 70
4.3.3 Zeta-Potential 71
4.4 Photocatalytic Adsorption of Methylene Blue on cellulose-based 72
CQDs
4.4.1 RSM Modelling 72
4.4.2 Effect of Experimental Parameters 75
(a) Effect of pH 78
(b) Effect of Contact Time 78
(c) Effect of Initial Concentration of MB 79
4.4.3 RSM Optimization 80
4.5 Comparison of Cellulose Adsorbent and Cellulose-based CQDs 81
Adsorbent in Dye Removal
4.6 Isotherm Analysis 82
4.7 Kinetics Analysis 86
CHAPTER V CONCLUSION AND RECOMMENDATIONS 89
5.1 Conclusion 89
5.2 Recommendations 90
REFERENCES 91
APPENDICES 108
vii
LIST OF TABLES
Table No. Page
2.1 Annual Generation of Oil Palm Biomass 8
2.2 Synthesis CQD from various carbon sources relevant to different

16
applications.
2.3 The advantages and disadvantages of different synthesis methods

17
for the preparation of CQDs
2.4 Classification of dyes 23
2.5 Dye removal technology with respect to their advantages and

24
disadvantages
2.6 Previous research on the removal of different dyes by agricultural

27
sorbent
2.7 Number of experiments for different factors 40
3.1 List of materials and chemicals used 43
3.2 List of equipment used 44
3.3 Experimental range and factor level of process variables applied 50
3.4 Design matrix for experimental factors at different factor level 50
4.1 Box-Behnken design matrix of three factors along with

experimental and predicted responses for methylene blue dye 59
removal by cellulose
4.2 ANOVA for the response surface quadratic model for MB

60
Percentage removal by Cellulose Adsorbent
4.3 RSM Optimization for adsorption of methylene blue on cellulose 68
4.4 Box-Behnken design matrix of three factors along with

72
experimental and predicted responses for removal of MB by CQDs
4.5 ANOVA for the response surface quadratic model for removal of
73
MB by CQDs
viii
Table No. Page
4.6 RSM Optimization for adsorption of MB on cellulose 80
4.7 Comparison of cellulose adsorbent and CQDs adsorbent in removal

81
of MB dye
4.8 Comparison of Langmuir and Freundlich isotherm constants for

84
removal of MB by Cellulose and CQDs adsorbents
4.9 Comparison of pseudo-first and pseudo-second order for removal

88
of MB by cellulose and cellulose-based CQDs
ix
LIST OF FIGURES
Figure No. Page
2.1 Schematic drawing of cell wall hierarchical structure of OPEFB 9
2.2 Structure of cellulose 11
2.3 Scheme of quantum dot structure 12
2.4 Colour emission of carbon dots solution under UV radiation 13

indicated wavelength directly
2.5 Illustration of CDs (a)Elementary CDs; (b)After 14

functionalization with surface passivation reagents
2.6 Scheme representation of microwave assisted method 19
2.7 Schematic representation of the microwave assisted method to 19

obtain the CQDs from raw cashew gum
2.8 A typical hydrothermal autoclave 21
2.9 Illustration of CQDs formation from orange juice via 21

hydrothermal treatment
2.10 Structure of MB 23
2.11 Basic process of adsorption 26
2.12 Schematic Diagram and Steps involved in Heterogeneous 30

Photocatalysis
2.13 Geometric view of Central Composite Design for three factors 39
3.1 Research Methodology Flow Chart 45
3.2 Washed OPEFB in ethanol/hexane mixed solvent 46
3.3 OPEFB fibers after bleaching treatment 47
x
Figure No. Page
3.4 Alkaline treatment of bleached fibers 48
3.5 Extracted cellulose 48
3.6 Teflon-lined stainless steel autoclave 49
3.7 Calibration curve of MB dye 52
3.8 Adsorption experiment for MB removal (a) Before (b) After. 53
3.9 Photocatalytic adsorption of MB on cellulose-based CQDs 54

under UV light
4.1 Plot of correlation between predicted and experimental values 61

for mb percentage removal by cellulose adsorbent
4.2 (a) Response surface and (b) Contour for MB percentage 62

removal vs pH and Contact time [Condition: initial
concentration of MB = 6 mg/L]
4.3 (a) Response surface plots and (b) Contour for MB percentage 63
removal by cellulose vs initial concentration of MB and Contact
time [Condition: pH = 7]
removal by cellulose vs initial concentration of MB and pH
[Condition: Contact time = 25 mins]
4.5 CQDs solution under (a) white light; (b) UV light 68
4.6 SEM image of cellulose fibers (a) before adsorption (b) after 69
adsorption
4.7 SEM image of cellulose-based CQDs 69
4.8 Particle size distribution of cellulose-based CQDs 70
4.9 Zeta Potential distribution of cellulose 71
4.10 Zeta Potential distribution of cellulose-based CQDs 71
4.11 Plot of correlation between predicted and experimental values 74

for mb percentage removal by CQDs adsorbent
xi
Figure No. Page
removal by CQDs vs pH and Contact time [Condition: initial
concentration of MB = 6 mg/L]
removal by CQDs vs initial concentration of MB and Contact
time [Condition: pH = 7]
removal by CQDs vs initial concentration of MB and pH
[Condition: Contact time = 25 mins]
4.15 Langmuir isotherm plot for MB dye onto cellulose 83
4.16 Freundlich isotherm plot for MB dye onto cellulose 83
4.17 Langmuir isotherm plot for MB dye onto cellulose-based CQDS 83
4.18 Freundlich isotherm plot for MB dye onto cellulose-based 84

CQDs
4.19 Plot of separation factor vs initial concentration of MB 85
4.20 Pseudo-first-order kinetic for adsorption of MB onto cellulose 86
4.21 Pseudo-second-order kinetic for adsorption of MB onto 87

cellulose
4.22 Pseudo-first-order kinetic for adsorption of MB onto cellulose- 87

based CQDs
4.23 Pseudo-second-order kinetic for adsorption of MB onto 87

cellulose-based CQDs
xii
LIST OF EQUATIONS
Equation No. Page
2.1 1 1 1
= + 34
𝑄𝑄𝑒𝑒 𝑄𝑄0 𝑄𝑄0 𝐾𝐾𝐿𝐿 𝐶𝐶𝑒𝑒
2.2 1
𝑅𝑅𝐿𝐿 = 35
1 + 𝐾𝐾𝐿𝐿 𝐶𝐶𝑜𝑜
2.3 𝑄𝑄𝑒𝑒 = 𝐾𝐾𝐹𝐹 𝐶𝐶𝑒𝑒 1/𝑛𝑛 35
2.4 1
ln 𝑄𝑄𝑒𝑒 = 𝑙𝑙𝑙𝑙𝐾𝐾𝐹𝐹 + 𝑙𝑙𝑙𝑙𝐶𝐶𝑒𝑒 36
𝑛𝑛
2.5 𝑑𝑑𝑄𝑄𝑡𝑡
= 𝑘𝑘1 (𝑄𝑄𝑒𝑒 − 𝑄𝑄𝑡𝑡 ) 37
𝑑𝑑𝑑𝑑
2.6 𝐾𝐾1
log(𝑄𝑄𝑒𝑒 − 𝑄𝑄𝑡𝑡 ) = 𝑙𝑙𝑙𝑙𝑙𝑙 𝑄𝑄𝑒𝑒 − 𝑡𝑡 37
2.303
2.7 𝑑𝑑𝑄𝑄𝑡𝑡
= 𝑘𝑘2 (𝑄𝑄𝑒𝑒 − 𝑄𝑄𝑡𝑡 )2 37
𝑑𝑑𝑑𝑑
2.8 𝑡𝑡 1 1
= 2 + 𝑡𝑡 37
𝑄𝑄𝑡𝑡 𝐾𝐾2 𝑄𝑄𝑒𝑒 𝑄𝑄𝑒𝑒
3.1 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤ℎ𝑡𝑡 (𝑔𝑔)

𝑌𝑌𝑌𝑌𝑌𝑌𝑌𝑌𝑌𝑌(%) = 𝑥𝑥 100% 48
𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤ℎ𝑡𝑡 (𝑔𝑔)
3.2 𝑌𝑌 = 𝛽𝛽0 + 𝛽𝛽1 𝑋𝑋1 + 𝛽𝛽2 𝑋𝑋2 + 𝛽𝛽3 𝑋𝑋3 + 𝛽𝛽12 𝑋𝑋1 𝑋𝑋2 + 𝛽𝛽13 𝑋𝑋1 𝑋𝑋3
51
+ 𝛽𝛽23 𝑋𝑋2 𝑋𝑋3 + 𝛽𝛽11 𝑋𝑋12 + 𝛽𝛽22 𝑋𝑋22 + 𝛽𝛽33 𝑋𝑋32
mg 𝐴𝐴𝐴𝐴𝐴𝐴
3.3 Concentration of unadsorbed MB in solution ( )= 52
L 0.2667
3.4 𝐶𝐶𝑜𝑜 − 𝐶𝐶𝑒𝑒

𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 (%) = × 100% 53
𝐶𝐶𝑜𝑜
3.5 Qe = (Co – Ce) x V/m 53
3.6 1 1 1
= + 55
xiii
Equation No. Page
3.7 1
𝑅𝑅𝐿𝐿 = 55
3.8 1
ln 𝑄𝑄𝑒𝑒 = 𝑙𝑙𝑙𝑙𝐾𝐾𝐹𝐹 + 𝑙𝑙𝑙𝑙𝐶𝐶𝑒𝑒 55
𝑛𝑛
3.9 𝑘𝑘1
log(𝑄𝑄𝑒𝑒 − 𝑄𝑄𝑡𝑡 ) = log 𝑄𝑄𝑒𝑒 − (𝑡𝑡) 56
2.303
3.10 𝑡𝑡 1 𝑡𝑡
= 2 + 57
𝑄𝑄𝑡𝑡 𝐾𝐾2 𝑄𝑄𝑒𝑒 𝑄𝑄𝑒𝑒
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 59
X1X2 – 0.0003 X2X3 + 0.0459 X2X3
4.2 MB Removal % (coded) = 21.8961 + 0.0831X1 + 8.9329 X2 +

8.2434 X3 + 0.0037 X12 – 0.4276 X22 – 0.3212 X32 - 0.0068 73
X1X2 – 0.0202 X2X3 - 0.2224 X2X3
xiv
LIST OF ABBREVIATIONS AND SYMBOLS
℃ Degree Celsius
•OH Hydroxyl Radical
ζ Zeta potential
λ Wavelength
2D Two dimensional
3D Three dimensional
A
ANOVA Analysis of Variance
AOP Advanced Oxidation Process
atm Atmospheric pressure
B
BBD Box-Behnken Design
C
C Carbon
C0 Initial concentration
C0 Highest concentration of solution
CB Conduction Band
CCD Central Composite Design
CDs Carbon Dots
Ce Equilibrium concentration
cm Centimetre
CNCs Cellulose Nanocrystals
CO2 Carbon dioxide
CQDs Carbon Quantum Dots
D
DLS Dynamic Light Scattering
E
e- Electrons
EFB Empty Fruit Bunch
G
xv
g Gram
GHz GigaHertz
GQDs Graphene Quantum Dots
H
h Hour
h+ Holes
H2O Water
HCL Hydrochloric Acid
K
K1 Langmuir constant
K1 Pseudo-first-order constant
K2 Pseudo-second-order constant
KF Freundlich constant
KL Langmuir constant
L
L Litre
LED Light Emitting Diode
LoF Lack of Fit
M
M Molar
m Mass
MB Methylene blue
MF Mesocarp Fiber
mg/g Milligram per gram
mg/L Milligram per litre
min Minute
mL Millilitre
mV Millivolts
N
n Freundlich exponent
NaOH Sodium hydroxide
nm Nanometre
O
xvi
O2•- Superoxide Radical
OPEFB Oil Palm Empty Fruit Bunch
OPF Oil Palm Frond
OPT Il Palm Trunk
P
PFF Pressed Fruit Fiber
PKS Palm Kernel Shell
PL Photoluminescence
PLP Pineapple Leaf Powder
POME Palm Oil Mill Effluent
Q
QDs Quantum Dots
Qe Adsorption capacity
Qt Adsorption capacity at t
R
R2 Correlation coefficient
RL Separation factor
RSM Research Surface Methodology
S
SEM Scanning Electron Microscopy
T
t Time
TiO2 Titanium dioxide
U
UPCL Up-conversion Photoluminescence
UV Ultraviolet
UV-Vis Ultraviolet-visible spectroscopy
V
V Volume
v/v Volume/volume percent
VB Valance Band
W
W Watt
xvii
wt% Weight percent
X
X-rays X-radiations
xviii
CHAPTER 1
INTRODUCTION
1.1 INTRODUCTION
Nowadays, various dyes are commonly 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 feasible alternative for the elimination of pollutants by
adsorbent that is easily available inexpensive and affordable method which prefer by
industries.
Various methods such as photocatalytic degradation (Houas, 2001),

coagulation/flocculation (Fosso-Kankeu et al., 2017), membrane filtration (Melbiah et al.,
2017), advanced oxidation (Narayanasamy et al., 2013), 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 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, thus,
1
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 (C6H10O5)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 extracted 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,
alkaline 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.
2
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 broadly used method for dye elimination. 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 sources to produce adsorbent for
removal of dyes. Thus, there is opportunity to study the potential of OPEFB as a good
adsorbent for the removal dyes. Besides, several modification techniques on OPEFB have
been studied as a natural adsorbent for dyes removal from industrial wastewater.
Large specific surface area indicating the huge amount of adsorption sites, which
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. Quantum dots (QD) which was first
discovered in glass crystals in 1980 by a Russian physicist, Ekimov whose has brought
the promotion in nanotechnology research (Ekimov and Onoshchenko, 1982). 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 dyes. Several researches have been reported that carbon sources can be used to
prepare carbon quantum dots (CQDs). Hence, cellulose molecule that contains a large
3
amount of hydroxyl and ether groups provide the fundamental and structural basis for the
formation of CQDs. 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.
To date, various methods to synthesis QDs from natural resources have been
progressed, such as synthesis of CQDs from raw cashew gum via microwave synthesis
method, synthesis of CQDs from orange juice via hydrothermal technique, and synthesis
of QDs via hydrothermal technique. 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.
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.
4
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
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 using RSM approaches. In this experiment, methylene blue (MB) dye was
used as adsorbate. The percentage removal of the MB dye was determined and compared
between cellulose adsorbent and cellulose-based 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
5
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.
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.
6
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 of overall experiment with summary of the
results and discussion.
7
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 2.1 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
Mesocarp Fiber (MF) 7.72
Palm Oil Mill Effluent (POME) 3.0
8
2.1.1 Oil Palm Empty Fruit Bunch (OPEFB) and its structure
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 proportion and certain amount of organic compound such as hemicellulose
and lignin (Fahma et al., 2010). The schematic drawing of cell wall ultrastructure and
cellulose organization hierarchical structure of oil palm tree are shown in Figure 2.1.
FIGURE 2.1 Schematic drawing of cell wall hierarchical structure of OPEFB.

[Adapted from Kolakovic et al., 2012]
9
The fiber structure consists of amorphous and crystalline region. 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% 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 can be found plentifully on earth, and is a natural occurring linear

polymer (Kester and Fennema, 1986). Payen firstly examined elemental composition of
cellulose in 1838, and it was found to have the empirical formula of C6H10O5. 6.2 % H
and 44.4 % C are found in the composition of cellulose (Payen, 1842). 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). Moreover, cellulose is unaffected by the extraction with ether,
ethanol and water (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.
10
FIGURE 2.2 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. Alkaline 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 reflux experiment was conducted to OPMF with 4 wt% NaOH
solution at 80℃. Then, the alkaline-treated fibers were bleached three times to whitening
the products. According to Sun et al. (1998), cellulose was isolated from dewaxed wheat
straw after alkaline extraction using sodium hydroxide solution.
11
Besides, Bhattacharya et al. (2008) extracted cellulose microfibers from
sugarcane bagasse (SCB) via conventional pulping process, where the lignin and
hemicellulose were removed. 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 most
amorphous regions were removed without any notable damage to the crystalline region .
Furthermore, biological treatment was also used by Kikuchi et al. (2002) with molecular-
genetically bred Coprinus Cinereus monokaryotic strains to extract cellulose successfully
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 2.3, 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 2.3 Scheme of quantum dot structure

[Adapted from Bajorowicz et al., 2018]
12
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
2.4, colour changes as the wavelength increases, indicate the size of QD also increases
(Sun et al, 2006)(Lovingood, 2017). Therefore, the physical properties of a QD can be
easily changed by only changing its size.
FIGURE 2.4 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, silicon QDs,
13
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
(Wang et al., 2017).
FIGURE 2.5 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 successfully
14
synthesised nitrogen doped carbon quantum dots to be used in removal of methylene blue,
and Mallakpour and Behranvand (2018) has reported the synthesis of quantum via
ultrasound treatment in removal of methylene blue. 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 proposed. 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 of CQDs further and longer.
15
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 2.2 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 MB removal Mallakpour and
Behranvand, 2018
Papaya Detection of Fe3+ Wu et al., 2012
Carbon powder Photocatalyst for carbon dioxide Cao et al., 2011
conversion
Lemon juice MB 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 (Ferreira et al., 2017).
Whereas for bottom-up strategy, the CQDs can be obtained from small precursor
16
molecules such as biomass sources chitosan or lignocellulosic materials by different heat
treatments, for example, hydrothermal treatment or microwave-assisted methods.
(Ferreira et al., 2017). 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 2.3 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 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. Wang and Liu
synthesis Uniform size (2012);
distribution; Xiao et al. (2013)
Adjustable size.
17
TABLE 2.3 – Continued
Thermal Easy operation; Non-uniform size Martindale et al.
decomposition No solvent is distribution. (2015)
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 1 mm to 1 m, corresponding to the frequency of 30 GHz to 0.3 GHz,
which induces heat energy to breakdown the chemical bonds of a molecule (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 PEG 200 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.
18
FIGURE 2.6 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 2.7 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,
19
the better the absorption of microwave energy, hence the more optimal the heating
(Christen, 2002). Therefore, water which is polar, is an excellent 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.
20
FIGURE 2.8 A typical hydrothermal autoclave
To date, several researches had reported the use of hydrothermal method to

synthesis CQDs. According to Sahu et al. (2012), CQDs were successfully synthesized
from orange juice as a carbon source, as shown in Figure 2.9. The mixture of orange juice
and ethanol were heated at 120°C for 150 min until a dark brown solution formed in an
autoclave.
FIGURE 2.9 Illustration of CQDs formation from orange juice via hydrothermal
treatment. [Adapted from Sahu et al., 2012]
On the other hand, Lu et al. (2012) reported that pomelo peel can be used to
synthesis hydrophilic fluorescent CQDs via hydrothermal method. Water is added to the
pomelo peels and then heated in an autoclave at 200°C for 3 hours. Huang et al. (2013)
21
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 Correia et al.,
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.
22
TABLE 2.4 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
Methylene blue (MB) has the IUPAC name of [7-(dimethylamino)phenothiazin-

3-ylidene]-dimethylazanium-chloride. MB possess a chemical formula of CH18N3SCI.
The C16H18N3S+ which is a cation is presented in MB, indicated the MB is an aniline
cationic dye. It displays blue colour in oxidized state but colourless in reduced form
(Cragan, 1999). MB can be used as dye, which is commonly used in colouring paper,
dyeing cotton and wools (Han, 2007). However, MB can cause unpleasant pollution to
the living organism and environment, thus it is important to eliminate MB from any
industrial effluent. (Altaher and E1Qada., 2011). Figure 2.10 shows the structure of MB.
FIGURE 2.10 Structure of Methylene Blue [Adapted from Cragan, 1999]
23
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 get rid of dye before wastewater are allowed to
be discharged into the environment without causing any harms. However, not all
technologies work for all dye pollutant. Studies have shown the successful dye removal
using different technologies despite the fact that low colour intensity wastewater was used
for treatment. Only a few studies 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 2.5 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
24
TABLE 2.5 - Continued
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.
25
FIGURE 2.11 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 two 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 includes
26
both mono and multilayer coverage of adsorbate molecular on the adsorbent’s surface
(Zohra et al. 2014).
2.6.2 Adsorbent
Changes between adsorbent and adsorbate molecules can be defined through

analysis through adsorption mechanism, thus adsorbent is crucial for effective adsorption.
The size of the pores regulates the availability of adsorbate molecule occur on the internal
diffusion into adsorbent molecule, 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 2.6 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
27
TABLE 2.6 - Continued
Sorption Capacity
Dyes Sorbent References
(mg/g)
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
28
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 (Wang et al., 2017a). 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 (Suzuki, 1990).
2.7 PHOTOCATALYTIC ADSORPTION
Photocatalytic adsorption shows a remarkable result in dye removal application due

to its potential to convert various organic pollutants into non-toxic substances (Hoffmann
et al., 1995; Klabunde, 2010), where hydrogen is produced in 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 2.12 illustrated the heterogeneous photocatalysis processes from
the transport of pollutant to the surface of photocatalyst.
29
FIGURE 2.12 Schematic Diagram and Steps involved in Heterogeneous
Photocatalysis [Adapted from Bora and Mewed, 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 photogenerated holes
30
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 have wide intrinsic band gap, and thus
only be excited by UV light. 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.,
2017b). 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 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
31
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 elimination of basic and
reactive dyes using rice hull modifies with ethylenediamine, 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 crucial parameters which shows a great consequence in
adsorption process. 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 adsorbent 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).
According to Rathod et al. (2016), the mechanism of dye removal can be

explained where the dye is transferred from the bulk solution onto the surface of the
adsorbent, and diffused through the boundary layer to the adsorbent surface, and intra-
32
particle diffusion of dye into the internal pores of adsorbent molecules. The boundary
layer resistance affected by the rate of adsorption and with increasing time, resistance will
be reduced, and the mobility of the dye will be increased during the adsorption process.
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 MB adsorption increased as the initial concentration of MB dye
increased, where pineapple leaf powder (PLP) is used as adsorbent to remove MB. The
driving force of the concentration was stronger as the MB concentration was higher, thus
increased the adsorption capacity. From the intra-particle diffusion study, it was also
observed that the adsorption process was 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 dye tends to decrease at higher initial
dye concentration. This might be ascribed 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). Boumediene et al. (2014) also reported
the removal of MB by orange peel. The percentage removal of dye decreased with
increasing initial concentration of MB, and this can be explained by the agglomeration of
adsorbent where less surface area involved in the adsorption process (Khatod, 2013).
33
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 (R2) 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 stated that only homogenous adsorbent surface exists
or in other words, monolayer type of adsorption occurs. (Droste, 1997; Seader and Henley,
2003). When the adsorption reaches equilibrium, the saturation point has been achieved,
and there is no further adsorption process is carried out. As a result, it can be assumed
that only one adsorbate molecule can be occupied on one single site of adsorbent.
Linearized form of Langmuir equation is stated in Equation (2.1).
Equation (2.1):
1 1 1
= +
Where Qe is the amount of dye adsorbed at equilibrium per unit mass of sorbent (mg/g),
𝐶𝐶𝑒𝑒 is the equilibrium concentrations of dye, Q0 is the maximum adsorption capacity (mg/g)
and KL is the Langmuir constant (L/mg).
34
Linear plot of 1/Qe vs 1/Ce will be plotted in order to determine the best fit
isotherm data for the adsorption system. In addition, RL can be derived from Langmuir
isotherm which is expressed in Equation (2.2).
Equation (2.2):
1
𝑅𝑅𝐿𝐿 =
where 𝐶𝐶𝑜𝑜 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 RL > 1, linear if RL = 1, favourable if 0 < RL<1,
and irreversible if RL = 0 (Mahida and Patel, 2016).
2.9.2 Freundlich Isotherm
Freundlich isotherm is another popular isotherm applied in most adsorption

process. Freundlich isotherm stated that heterogeneous adsorbent surface exists where the
adsorption process is carried out with different classes of adsorption sites (Hameed et al.,
2007). When the adsorption reaches equilibrium between an adsorbent and surface of
adsorbent in a solution, multi-site adsorption occurred between adsorbent and adsorbate
with non-uniform heat distribution over the surface of adsorbent (Brunauer, 1943).
Freundlich isotherm is expressed as in Equation (2.3) and linearized equation is shown in
Equation (2.4).
Equation (2.3):
𝑄𝑄𝑒𝑒 = 𝐾𝐾𝐹𝐹 𝐶𝐶𝑒𝑒 1/𝑛𝑛
Equation (2.4):
1
ln 𝑄𝑄𝑒𝑒 = 𝑙𝑙𝑙𝑙𝐾𝐾𝐹𝐹 + 𝑙𝑙𝑙𝑙𝐶𝐶𝑒𝑒
𝑛𝑛
35
where 𝐶𝐶𝑒𝑒 is 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
(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).
36
Equation (2.5):
𝑑𝑑𝑄𝑄𝑡𝑡
= 𝐾𝐾1 (𝑄𝑄𝑒𝑒 − 𝑄𝑄𝑡𝑡 )
𝑑𝑑𝑑𝑑
Equation (2.6):
𝐾𝐾1
log(𝑄𝑄𝑒𝑒 − 𝑄𝑄𝑡𝑡 ) = 𝑙𝑙𝑙𝑙𝑙𝑙 𝑄𝑄𝑒𝑒 − 𝑡𝑡
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):
𝑑𝑑𝑄𝑄𝑡𝑡
= 𝑘𝑘2 (𝑄𝑄𝑒𝑒 − 𝑄𝑄𝑡𝑡 )2
𝑑𝑑𝑑𝑑
Equation (2.8):
𝑡𝑡 1 1
= + 𝑡𝑡
𝑄𝑄𝑡𝑡 𝐾𝐾2 𝑄𝑄𝑒𝑒 2 𝑄𝑄𝑒𝑒
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 K2 and equilibrium
adsorption capacity, Qe can be derived from the intercept and slope of the linear plot.
37
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)
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 centre point (α, centre 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 2.13.
38
FIGURE 2.13 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 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 2.7 shows the
number of experiments for different factors with three replications.
39
TABLE 2.7 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)
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
40
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). 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).
41
2.12.3 Particle size measurement
The particle size can be measured using the Dynamic Light Scattering method
(DLS) at 25 °C. This technique relies on the effect of time-dependent light scattering of
the random motion of suspended particles (Brownian motion) that depends on particle
size. The particles in a liquid move randomly, and their speed of movement was used to
determine the size of the particle (Malvern 2013). Particle size measurements were done
using a Zetasizer while particle size distributions were calculated by software. Then, it
reports both an average size for the particle population (z-average) as well as sizes
corresponding to peak intensity for the case of multiple particle populations.
2.12.4 Zeta potential measurement
Zeta potential, ζ is the electrostatic potential that exists at the boundary between
two layers of ions, namely, the compact and the diffuse layers, which surround a particle
in solution. This is an important property for understanding colloidal and interfacial
behaviours. Zeta potential was measured using a combination of the measurement
techniques, namely, Electrophoresis and Laser Doppler Velocimetry. This method
measures the speed at which a particle moves in a liquid when an electrical field is applied.
If all particles of the suspension mixture have a large positive or negative charge, they
will repel each other, and there will be no tendency to fluctuate. On the other hand, low
zeta potential values of the particles mean there is no force to prevent the particles from
coming together, therefore resulting in fluctuation. Practically, particles with zeta
potential more positive than +30 mV or more negative than -30 mV are considered to be
stable (Wissing et al. 2004). Similar to particle size measurements, zeta potential
measurements can be done using a Zetasizer whereas zeta potential distributions were
calculated by software.
42
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) from cellulose via 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 3.1 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
43
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.
44
FIGURE 3.1 Research Methodology Flow Chart.
45
3.4 EXTRACTION OF 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 sun to remove moisture.
FIGURE 3.2 Washed OPEFB in Ethanol/Hexane Mixed Solvent.
46
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 3.3 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 OPEFB fibers
47
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 3.4 Alkaline treatment of bleached fibers.
FIGURE 3.5 Extracted Cellulose.
The percentage of cellulose yield can be obtained by applying the Equation (3.1):
Equation (3.1):
𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤ℎ𝑡𝑡 (𝑔𝑔)
𝑌𝑌𝑌𝑌𝑌𝑌𝑌𝑌𝑌𝑌(%) = 𝑥𝑥 100%
𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤ℎ𝑡𝑡 (𝑔𝑔)
48
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 mixed with distilled water and transferred into a Teflon-lined
stainless steel autoclave shown in Figure 3.6 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 3.6 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.
49
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 3.3 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 3.4 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
50
(Ferreira et al., 2007) has proven that whenever a system of study that
involves 3 significant factors to be as the variables X1, 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 (3.2):
Equation (3.2):
𝑌𝑌 = 𝛽𝛽0 + 𝛽𝛽1 𝑋𝑋1 + 𝛽𝛽2 𝑋𝑋2 + 𝛽𝛽3 𝑋𝑋3 + 𝛽𝛽12 𝑋𝑋1 𝑋𝑋2 + 𝛽𝛽13 𝑋𝑋1 𝑋𝑋3 + 𝛽𝛽23 𝑋𝑋2 𝑋𝑋3 + 𝛽𝛽11 𝑋𝑋12 + 𝛽𝛽22 𝑋𝑋22 +
𝛽𝛽33 𝑋𝑋32
Where 𝑌𝑌 is predicted response; 𝛽𝛽0 is constant; 𝛽𝛽1 , 𝛽𝛽2 , 𝛽𝛽3 are linear coefficients;
𝛽𝛽11 , 𝛽𝛽22 , 𝛽𝛽33 are quadratic coefficients; 𝛽𝛽12 , 𝛽𝛽13 , 𝛽𝛽23 are interaction coefficients; and
𝑋𝑋1 , 𝑋𝑋2 , 𝑋𝑋3 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 (3.3) used to determine the concentrations of dye
solutions during adsorption process.
51
3.00
y = 0.2667x
2.50
R² = 0.9874
2.00
ABS
1.50
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 3.7 Calibration Curve of Methylene Blue Dye
Equation (3.3):
mg 𝐴𝐴𝐴𝐴𝐴𝐴
Concentration of unadsorbed MB in 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 3.4. 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 MB dye solution. The residual concentration of the dye in the filtrate was determined
using a UV-Vis spectrophotometer at 𝜆𝜆max of 668 nm (Nsami and Mbadcam, 2013).
52
(a) (b)
FIGURE 3.8 Adsorption experiment for MB removal (a) Before (b) After.
The percentage removal of dye was calculated using the Equation (3.4):
Equation (3.4):
𝐶𝐶𝑜𝑜 − 𝐶𝐶𝑒𝑒
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 (%) = × 100%
𝐶𝐶𝑜𝑜
and the adsorption capacity (Qe) was calculated using Equation (3.4):
Equation (3.4):
Qe = (Co – Ce) x V/m
where Qe is the amount of MB dye adsorbed per unit mass of adsorbent at equilibrium
(mg/g); Co is the initial concentration of MB dye (mg/L); Ce is the equilibrium
concentration of MB dye (mg/L); V is the volume of MB solution (L); and m is the mass
of adsorbent (g).
3.7.3 Photocatalytic Adsorption Experiment
The photocatalytic adsorption 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 MB solutions at various combination of different factors as
listed in Table 3.4. The mixture was allowed to agitate using magnetic stirrer. The residual
53
concentration of the dye in the filtrate was determined using a UV-Vis spectrophotometer
at 𝜆𝜆max of 668 nm (Nsami and Mbadcam, 2013).
FIGURE 3.9 Photocatalytic adsorption of MB 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 MB dye vary from 2 mg/L to 10 mg/L at pH 11 and 25
minutes.
3.8.1 Langmuir isotherm model
Langmuir stated that adsorbate is attached to the homogenous surface of adsorbent

which has similar binding sites, and there is no transmigration between the adsorbed
molecules (Xing et al. 2010). Linearized form of Langmuir equation is stated in Equation
(3.6).
54
Equation (3.6):
1 1 1
= +
where Qe is the amount of dye adsorbed at equilibrium of unit mass of sorbent (mg/g),
𝐶𝐶𝑒𝑒 is 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. In addition, RL can be derived from Langmuir isotherm
which is expressed in Equation (3.6).
Equation (3.7):
1
𝑅𝑅𝐿𝐿 =
where 𝐶𝐶𝑜𝑜 is the highest concentration of solution (mg/L), RL 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).
3.8.2 Freundlich isotherm model
Freundlich assumes that heterogeneous type of adsorption occurs with non-

uniform heat distribution over the surface of the adsorbent (Brunauer, 1943). Linearized
Freundlich isotherm was expressed in Equation (3.8).
Equation (3.8):
1
ln 𝑄𝑄𝑒𝑒 = 𝑙𝑙𝑙𝑙𝐾𝐾𝐹𝐹 + 𝑙𝑙𝑙𝑙𝐶𝐶𝑒𝑒
𝑛𝑛
55
where 𝐶𝐶𝑒𝑒 is 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.
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):
𝑘𝑘1
log(𝑄𝑄𝑒𝑒 − 𝑄𝑄𝑡𝑡 ) = log 𝑄𝑄𝑒𝑒 − (𝑡𝑡)
2.303
56
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); Qt 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):
𝑡𝑡 1 𝑡𝑡
= +
𝑄𝑄𝑡𝑡 𝐾𝐾2 𝑄𝑄𝑒𝑒 2 𝑄𝑄𝑒𝑒
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 K2 and equilibrium
adsorption capacity, Qe can be derived from the intercept and slope of the linear plot of
t/Qt versus t.
57
CHAPTER IV
RESULTS AND DISCUSSION
4.1 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 suggestive
as the loss of materials might occurred in this process during preparation and filtration,
thus affected the actual yield of cellulose.
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

statistical model from 15 experiment design runs with one centre point. The levels and
ranges of experimental factors such as contact time (min), pH and initial concentration of
MB (mg/L) were investigated as shown in Table 3.4. 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 4.1.
58
TABLE 4.1 Box-Behnken design matrix of three factors along with experimental
and predicted responses for MB dye removal by cellulose
Experimental Factors Response (MB Percentage removal) Error

Run
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 MB (mg/L). All terms regardless of their significance are included in the
following Equation (4.1):
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.
59
TABLE 4.2 ANOVA for the response surface quadratic model for MB
Percentage removal by Cellulose Adsorbent
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
X12 0.13 0.132 0.03 0.877
X22 135.89 135.89 27.39 0.003
X32 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
60
terms of contact time. Hence, the contact time did not give an effect to remove the MB
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
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
MB 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.
100.00
95.00 R² = 0.9809
Predicted (%)
90.00
85.00
80.00
75.00
75.00 80.00 85.00 90.00 95.00 100.00
Experimental (%)
FIGURE 4.1 Plot of Correlation between Predicted and Experimental values for
MB Percentage removal by Cellulose Adsorbent
61
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)
FIGURE 4.2 (a) Response surface plots and (b) Contour for MB percentage
removal by cellulose vs pH and Contact time [Condition: initial concentration of
MB = 6 mg/L]
62
(a)
(b)
removal by cellulose vs initial concentration of MB and Contact time [Condition:
pH = 7]
63
(a)
(b)
removal by cellulose vs initial concentration of MB and pH [Condition: Contact
time = 25 mins]
64
(a) Effect of pH
The effect of pH was analysed using RSM and the results of response surface plots
and contour and are presented in Figure 4.2 with initial concentration of MB 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 MB 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 MB was

considerable with P-value > F equal to 0.003. The percentage removal of MB increased
with increasing pH can be supported by the coded Equation (4.1) in which positive (+)
sign was observed in this effect of pH (X2). Therefore, it is evident that pH is crucial in
the removal of MB dye by cellulose adsorbent.
According to Nonviho (2015), cellulose contains hydroxyl groups or carboxyl

groups, hence it is negatively charged in solution. This trend can be supported by the zeta
potential of -41.37 mV in section 4.3.3. 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 MB which is
a cationic dye. Therefore, electrostatic attraction between positively charged MB and
negatively charged cellulose resulted increases in dye adsorption (Khatrri et al. 2009). On
the other hand, when pH is lower, 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 MB (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 MB solution for the adsorption experiment.
65
(b) Effect of Contact Time
The results of response surface plots and contour shown in Figure 4.2 and 4.3
presented the effect of contact time at constant initial concentration of MB 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 MB decreased with increasing contact time. The reduction can be
supported from the model Equation (4.1) where negative (-) sign was presented for
contact time (X1). 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 MB molecules were held with weak bond on the cellulose adsorbent. The
MB molecules might leach from the cellulose adsorbent after some time. Enenekeaku
(2017) also stated that there is the formation of secondary adsorption layer caused the MB
molecule to be adsorbed weakly, rather than the primary adsorption layer which having a
stronger attachment. The uneven of energy also occurred between primary and secondary
adsorption layers, hence, facilitate the dislodging of MB dye with increasing of contact
time.
(c) Effect of Initial Concentration of MB
From the response surface plots and contour shown in Figure 4.3 and 4.4, effect
of the initial concentration of MB at constant pH at pH 7 and contact time at 25 mins were
shown respectively. From the findings, the percentage removal of MB by cellulose
increased with increasing initial concentration of MB. This can be explained by the model
Equation (4.1) in which positive (+) sign was observed for effect of initial concentration
of MB (X3). Moreover, this effect is significant with the P-value > F lower than 0.05.
66
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 MB between the aqueous and the solid phases (Ouasif
et al, 2013).Thus, the permeation of MB molecules into the pores of cellulose adsorbent
could be facilitated as the initial concentration of MB dye increased. Hence, a higher
initial concentration of MB increased the percentage removal of MB.
Similar trend was noticed by Amel et al. (2012), the adsorption process can be
improved with increasing the initial concentration of MB, as this will increase the number
of collisions between dye molecules and adsorbent molecules.
4.2.3 RSM Optimization
Percentage removal of MB was set at maximum as special goal to be achieved.

Table 4.3 showed the results of the predicted responses for percentage removal of MB by
cellulose after optimization. The optimum conditions were found at contact time of 10
minutes, pH 8.81 and initial concentration of MB at 8.303 mg/L. The predicted percentage
removal of MB using cellulose adsorbent was 96.79 %. In order to verify the predicted
values from the model, experiment was carried out at the optimum conditions. The
experimental result of percentage removal of MB 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.
67
TABLE 4.3 RSM Optimization for adsorption of MB 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 photocatalytic adsorption (Guo et al., 2016).
(a) (b)
FIGURE 4.5 CQDs solution under (a) white light; (b) UV light
68
4.3.1 SEM
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 MB,
the cellulose surface becomes rougher. It can be seen that the MB molecule attached on
the cellulose adsorbents, indicated the adsorption of MB dye from solution. Besides, the
SEM image of cellulose-based CQDs presented in Figure 4.7 showed the porous and
crystalline structure, which consistent with the results reported by He et al. (2018), where
the CQDs were synthesised from lemon juice via hydrothermal reaction. However, the
CQDs obtained did not showed uniform morphology as expected, thus further studies are
needed.
(a) (b)
FIGURE 4.6 SEM image of cellulose fibers (a) before adsorption (b) after
adsorption
FIGURE 4.7 SEM image of cellulose-based CQDs
69
4.3.2 Particle Size Distribution
FIGURE 4.8 Particle Size Distribution of cellulose-based CQDs
Particle size of CQDs were found to be ranged from 200 nm to 700 m with the
highest intensity at 400 nm. The size of CQDs produced was relatively large compared
to other research reports. CQDs should have nano-sized particles, which is typically
below 10 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 typically below 10 nm. This might due
to the reaction temperature which is low and inconsistent in the oven. For the synthesis
of CQDs from mangosteen peel, Aji et al (2017) found that the size of CQDs were greatly
affected by the temperature, where the size of CQDs decreased as the temperature
increased. Thus, further studies were needed on the optimum reaction conditions of
hydrothermal synthesis method such as reaction time, reaction temperature and pH in the
formation of CQDs from cellulose.
70
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. The negative value of zeta potential indicated
negative surface charge of the CQDs. Therefore, CQDs was easily dispersible in basic
medium, but quite unstable in acidic medium. This is because of the availability of
hydrophilic carboxyl group in both adsorbents which contributed to the solubility in water.
Based on Ucun et al. (2013), the negative charge on the particle surface increased with
increasing pH, therefore more cationic MB dye adsorption takes place at higher pH due
to electrostatic force of attraction.
FIGURE 4.9 Zeta Potential distribution of cellulose
FIGURE 4.10 Zeta Potential distribution of cellulose-based CQDs
71
4.4 PHOTOCATALYTIC ADSORPTION OF METHYLENE BLUE ON
CELLULOSE-BASED 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 4.4 Box-Behnken design matrix of three factors along with experimental
and predicted responses for removal of MB 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 MB as a function of the coefficient of

independent variables of the full quadratic model was obtained as shown in Equation (4.2).
72
Equation (4.2):
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 4.5 ANOVA for the response surface quadratic model for removal of MB
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
X22 167.993 167.933 24.36 0.004
X32 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 MB (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 MB by CQDs. However,
73
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 less than P-value at the 95% confidence limit,
verified that the model terms were significant for removal of MB by CQDs.
The Lack-of-Fit (LoF) values for removal of MB 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, R2 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 MB by CQDs were clustered along a diagonal line, indicating that the
predicted values matched well with the observed ones.
100.00
95.00
y = 0.973x + 2.291
Predicted (%)
90.00 R² = 0.9734
85.00
80.00
75.00
70.00
70.00 75.00 80.00 85.00 90.00 95.00 100.00
Experimental (%)
FIGURE 4.11 Plot of Correlation between Predicted and Experimental values for
MB Percentage removal by CQDs Adsorbent
74
4.4.2 Effect of Experimental Parameters
removal by CQDs vs pH and Contact time [Condition: initial concentration of MB
= 6 mg/L]
75
removal by CQDs vs initial concentration of MB and Contact time [Condition: pH
= 7]
76
removal by CQDs vs initial concentration of MB and pH [Condition: Contact time
= 25 mins]
77
(a) Effect of pH
The effect of pH on photocatalytic adsorption of MB on cellulose-based CQDs

was analysed using RSM and the results of response surface plots and contour were
shown in Figure 4.12 and 4.14 with constant initial concentration of MB at 6mg/L and
constant time at 25 mins respectively. From the results, it was observed that the
percentage removal of MB increased with increasing pH up to pH 9.8, thereafter, it
decreased. 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 MB
by CQDs was significant with P-value > F less than 0.05. Thus, it is evident that pH
showed significance in the photocatalytic adsorption of MB by cellulose-based CQDs
adsorbent.
According to Tadesse et al. (2018), lower adsorption of MB was observed due to

the presence of negatively charged ions acid competing with the MB cations for the
available adsorption sites which reduce the adsorbed amount. Therefore, higher pH was
preferable for the adsorption of MB dye solution on cellulose-based CQDs, considering
the electrostatic attraction that exists between the negatively charged surfaces of
adsorbent mainly due to the MB dyes (Khatrri et al. 2009).
(b) Effect of Contact Time
Based on the response surface plots and contour as shown in Figure 4.13 and 4.14,
the effect of contact time to photo-catalytically adsorb MB by cellulosed-based CQDs
was analysed at constant initial concentration of MB dye at 6 mg/L and constant pH at
pH 7, respectively. It was noted that the percentage removal of MB increased with
increasing contact time. This trend can be supported by the coded Equation (4.2) in which
positive (+) sign was observed in this effect of contact time (X1). However, as observed
78
in Table 4.5, the effect of contact time on percentage removal of MB 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 MB on cellulose fibers which showed the

percentage removal of MB decreased with increasing contact time, the photocatalytic
adsorption of MB with addition of CQDs showed opposite results. This showed that the
removal of MB using cellulose based CQDs adsorbent was more effective and efficient
than cellulose adsorbents. Moreover, maximum percentage removal of MB 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 MB dye molecules, in
accordance with that obtained by Tchuifon (2016). This result showed that increasing
contact time favoured the prolonged interaction between the MB molecules and the
cellulose-based CQDs surface and subsequent permeation into the adsorbent pores
(Enenebeaku et al., 2017).
(c) Effect of Initial Concentration of MB
The results of response surface plots and contour shown in Figure 4.12 and 4.13
presented the effect of initial concentration of MB at constant pH at pH 7 and constant
contact time at 25 mins respectively. It can be observed that the percentage removal of
MB increased with increasing initial concentration of MB dye, which can be explained
by the model Equation (4.2) where positive (+) sign was presented for the effect of initial
concentration of MB (X3). 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
force (Khataee et al., 2013). Hence, a higher initial concentration of MB gives a crucial
driving force to overcome all resistance of MB between aqueous and solid phases thus
79
increased the percentage removal of MB by cellulose-based CQDs. It also enhanced the
number of collisions resulted between the MB ions and the CQDs, thus, improved the
catalytic adsorption process (Amel et al. 2012). Therefore, the removal of MB dye
increased with the increasing initial concentration of MB. Similar results were also
reported by several researchers om the removal of MB by (Sharma, 2009), by carbon
nanotube (Shahryari et al., 2010), and by cashew nut shell (Kumar et al., 2010).
4.4.3 RSM Optimization
Response surface optimization was performed to maximize the percentage

removal of MB using cellulose-based CQDs. Table 4.6 showed the results of the predicted
responses for percentage removal of MB by cellulose-based CQDs after optimization.
The optimum conditions were found at contact time of 40 minutes, pH 7.85 and initial
concentration of MB at 8.87 mg/L. The predicted percentage removal of MB using
cellulose-based CQDs adsorbent was 98.05 %. 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 MB
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 4.6 RSM Optimization for adsorption of MB on cellulose
Optimized Factors Percentage removal of MB

Error
Contact pH Initial concentration
Predicted Experimental (%)
time (min) of MB (mg/L)
40 7.85 8.87 98.05% 95.97% 2.12%
4.5 COMPARISON OF CELLULOSE ADSORBENT AND CELLULOSE-

BASED CQDs ADSORBENT IN DYE REMOVAL
80
The adsorption capacity obtained from optimized RSM parameters of newly
synthesized cellulose-based CQDs with cellulose fibers were presented in Table 4.7.
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 highest percentage removal of MB using cellulose-based CQDs
was 95.97%, which was just slightly higher than that of using cellulose fibers adsorbents
via batch adsorption, with percentage removal of 95.08%. When the cellulose-based
CQDs were illuminated by UV light, it absorbs the light, where photocatalytic adsorption
process was conducted.
TABLE 4.7 Comparison of cellulose adsorbent and CQDs adsorbent in removal

of MB dye
Adsorbent Adsorption capacity (mg/g) Percentage Removal (%)

Cellulose fibers 0.7753 95.08
Cellulose-based CQDs 0.8511 95.97
Based on Tadesse et al. (2018), nitrogen doped CQDs/magnetic nanocomposites

obtained from lemon juice and ethylenediamine via hydrothermal method showed rapid
removal of MB dye within 20 minutes with percentage removal of about 90.84 % in batch
adsorption at optimum conditions. Additionally, Gnanasekaran et al. (2015) reported that
the synthesized TiO2 QDs effectively remove MB dye under UV light, and the percentage
removal was found to be 97.9% in 80 minutes. Therefore, the results of using cellulose-
based CQDs to adsorb MB dye via photocatalytic adsorption were comparative
acceptable.
According to Hossein and Masoud (2017) in removal of MB dye pollutant under

UV-light with N-GQDs / TiO2 nanocomposite, the N-GQDs were attached on the surface
of TiO2 nanoparticles. This phenomenon causes that excited electrons of N-GQDs
transfer to TiO2, which facilitated the formation of active oxygen and hydroxyl radicals
81
and thus oxidize MB. 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). On the other hand, the SEM
image of CQDs showed the porous structure, promoting the formation of relatively higher
surface area than cellulose, which facilitated the diffusion of MB molecule, provided a
large number of readily accessible active sites and fostered the light transfer into the inner
surface of the CQDs. Hence, this trend can be applied in photocatalytic adsorption of MB
using cellulose-based CQDs.
4.6 Isotherm Analysis
The isotherm model can used to explain the distribution of MB on the adsorbent,
which is a measure of the position of equilibrium in the adsorption process, and can be
expressed by one or more series of isotherm models. The use of adsorbents can be
analysed and optimized by the adsorption isotherms by fitting them into different kind
of isotherm models (Dawood and Sen, 2012). Therefore, it is an important step to figure
out the most suitable isotherm model for the adsorption of MB using different adsorbents.
The Langmuir isotherm and Freundlich isotherm studies were conducted using various
initial concentration of MB 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.
82
7.00
6.00
5.00 y = 6.42x - 7.6633
4.00 R² = 0.982
1/Qe
3.00
2.00
1.00
0.00
0.00 0.50 1.00 1.50 2.00 2.50
1/Ce
FIGURE 4.15 Langmuir Isotherm Plot for MB dye onto Cellulose
0.00
-0.50
y = 3.526x + 0.8497
-1.00 R² = 0.9778
ln Qe
-1.50
-2.00
-2.50
-1.00 -0.80 -0.60 -0.40 -0.20 0.00
ln Ce
FIGURE 4.16 Freundlich Isotherm Plot for MB dye onto Cellulose
7.00
6.00 y = 3.7696x - 4.5358
R² = 0.9835
5.00
4.00
1/Qe
3.00
2.00
1.00
0.00
0.00 0.50 1.00 1.50 2.00 2.50 3.00
1/Ce
FIGURE 4.17 Langmuir Isotherm Plot for MB dye onto cellulose-based CQDS
83
0.00
-0.50 y = 2.5738x + 0.8104

R² = 0.9924
ln Qe
-1.00
-1.50
-2.00
-1.20 -1.00 -0.80 -0.60 -0.40 -0.20 0.00
ln Ce
FIGURE 4.18 Freundlich Isotherm Plot for MB dye onto cellulose-based CQDs
TABLE 4.8 Comparison of Langmuir and Freundlich isotherm constants for

removal of MB 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 4.15 and 4.16 showed the linear plot of linearized Langmuir and Freundlich
isotherm analysis for batch adsorption of MB using cellulose adsorbent respectively. The
calculated constants and regression values of these isotherm models are listed in Table
4.8. Based on the data obtained, both isotherm models exhibited high correlation
coefficient, R2 values (>0.95). However, Langmuir isotherm 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 MB 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).
84
In addition, Langmuir and Freundlich plots for photocatalytic adsorption of MB
dye on cellulose-based CQDs were shown in Figure 4.17 and 4.18. The calculated
constants and regression values of these isotherm models were listed in Table 4.8. Based
on the data obtained, it was found that the adsorption equilibrium data fit both Langmuir
and Freundlich equations with a correlation coefficient value, R2 of 0.9835 and 0.9924
respectively. However, Freundlich isotherm appeared to better describe the catalytically
adsorption of MB 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 RL values lie between 0 and
1 at different initial concentration of MB suggesting the isotherm to be favourable at the
concentrations studied. Besides, cellulose adsorbents with lower RL values at higher
initial MB concentrations showed that adsorption was more favourable at higher
concentrations.
0.4
0.35
0.3
0.25
0.2
RL
Cellulose
0.15
CQDs
0.1
0.05
0
0 2 4 6 8 10 12
Co (mg/L)
FIGURE 4.19 Plot of Separation Factor vs Initial concentration of MB
85
Freundlich constant (KF) values derived from Freundlich isotherm models served
as an indication of adsorption capacity of cellulose fibers and cellulose-based CQDs for
MB 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
MB adsorption on cellulose and cellulose-based adsorbent were examined using pseudo-
first and pseudo-second order equation, as presented in Figure 4.20 to 4.23.
-0.5
-1 y = 0.0239x - 2.8322
R² = 0.3492
log(qe-qt)
-1.5
-2
-2.5
-3
-3.5
0 10 20 30 40 50
t
FIGURE 4.20 Pseudo-first-order kinetic for adsorption of MB onto cellulose
86
70
60 y = 1.0902x + 0.1999
R² = 0.9999
50
40
t/qt
30
20
10
0
0 10 20 30 40 50 60 70
t
FIGURE 4.21 Pseudo-second-order kinetic for adsorption of MB onto cellulose
-0.5
log(qe-qt)
-1
-1.5
y = -0.0271x - 0.9831
-2
R² = 0.8515
-2.5
0 10 20 30 40 50
t
FIGURE 4.22 Pseudo-first-order kinetic for adsorption of MB onto cellulose-based

CQDs
70
60 y = 1.0293x + 0.8518
50 R² = 0.9999
40
t/qt
30
20
10
0
0 10 20 30 40 50 60 70
t
FIGURE 4.23 Pseudo-second-order kinetic for adsorption of MB onto cellulose-

based CQDs
87
TABLE 4.9 Comparison of pseudo-first and pseudo-second order for removal of
MB by cellulose and cellulose-based CQDs
Adsorbent pseudo-first-order kinetic model pseudo-second-order kinetic model

K1 qe K2 qe
-1 R2 R2
(min ) (mg/g) (g/mg.min) (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 MB by both adsorbents fitted well to pseudo-second-order model where the
correlation coefficient, R2 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 MB on cellulose can be explained appropriately by the pseudo-second-
order, where the chemisorption was occurred which involving the valency forces via
sharing or exchange of electron between the adsorbent and MB dye (Ho and Mc Kay,
2000). The occurrence of chemisorption is controlled by strong intraparticle bonding,
such as ionic and covalent bonding, contributes to the irreversible adsorption process
(Allen and Koumanova, 2005).
88
CHAPTER V
CONCLUSION AND RECOMMENDATIONS
5.1 CONCLUSION
In this study, cellulose was successfully extracted from OPEFB using alkaline
treatment, with the average yield percentage of 53%. Additionally, response surface
methodology was used to investigate the interactive effect of the operating parameters in
adsorption such as contact time, pH and initial concentration of MB dye. MB was
adsorbed on cellulose fibers with highest percentage removal of 95.08 %, where the
percentage removal of MB increased with increasing pH, decreasing contact time and
increasing initial concentration of MB solution. The optimum conditions on the
adsorption by cellulose at initial concentration of 8.30 mg/L, pH 8.82 at 10 minutes,
possessed the experimental value of 93.38%. On the other hand, the photocatalytic
adsorption using cellulose-based CQDs under UV light showed the highest percentage
removal of 95.25%, where the percentage removal of MB increased with increasing pH,
increasing contact time and increasing initial concentration of MB solution. From the
predicted optimum conditions obtained from Minitab at contact time of 40 minutes, pH
7.85, and initial concentration of MB at 8.87 mg/L, the experimental results showed that
the percentage removal of MB was 95.97%. It was found that the adsorption by cellulose
followed Langmuir isotherm and pseudo-second-order kinetics model, where the
photocatalytic adsorption by cellulose-based CQDs possessed Freundlich isotherm and
pseudo-second-order kinetics model. The results of this study indicated that the
photocatalytic adsorption using cellulose-based CQDs as photocatalyst was effective in
MB dye removal in the presence of UV light (95.97%), but surprisingly there was not
great difference with the adsorption using cellulose fibers (95.08%). The CQDs solution
synthesized from cellulose by hydrothermal treatment showed yellowish-brown colour,
and yellow fluorescence emission colour was observed under irradiation of UV light,
indicates the formation of CQDs. Further, the surface morphology, size distribution and
89
zeta potential for both adsorbents were studied. cellulose showed the rod-like shaped and
zeta-potential of -41.37 mV whereas cellulose-based CQDs showed porous and
crystalline structure, size of 2170.33 nm and zeta-potential of -20.13 mV.
5.2 RECOMMENDATION
Several uncertainties are yet to be confirmed and some improvements are needed
to achieve a more comprehensive work on the synthesis and application of CQDs. Firstly,
the optimum condition to synthesis CQDs from cellulose via hydrothermal can be studied
at various parameters such as temperature, reaction time and pH of the solvent used to
obtain the smallest size of CQDs. Another method such as microwave synthesis which
takes shorter time can be performed in producing CQDs as hydrothermal synthesis took
around one day to synthesis a small amount of CQDs.
Moreover, UV-vis adsorption spectrum can be studied to determine the wavelength

of the CQDs produced, which can further explain the photocatalytic activity of the CQDS.
The quantum yield (QY) of CQDs can be determined also to study the efficiency of
photon emission which is an important role in photocatalytic adsorption.
Instead of using the MB dye which prepared by own for the studies of adsorption,
textile wastewater can be used as the model pollutant to study the photocatalytic
adsorption using cellulose-based CQDs. Besides, since cellulose-based CQDs synthesis
from cellulose could absorb dye efficiently, heavy metal ions can be adopted as pollutant
in further studies.
90
REFERENCES
Abdelmouleh, M., Boufi, S., Belgacem, M., Dufresne, A. and Gandini, A., 2005.
Modification of cellulose fibers with functionalized silanes: Effect of the fiber treatment on
the mechanical performances of cellulose-thermoset composites. Journal of Applied
Polymer Science, 98(3), 974-984.
Abdul, H., Jawaid, M., Hassan, A., Paridah, M., and Zaido, A., 2012. Oil Palm Biomass
Fibres and Recent Advancement in Oil Palm Biomass Fibres Based Hybrid
Biocomposites. Composites and Their Applications.
Abitbol, T., Rivkin, A., Cao, Y., Nevo, Y., Abraham, E., Ben-Shalom, T., Lapidot, S. and
Shoseyov, O., 2016. Nanocellulose, a tiny fiber with huge applications. Current Opinion in
Biotechnology, 39, 76-88.
Abkenar, S. D., Khoobi, M., Tarasi, R., Hosseini, M., Shafiee, A., and Ganjali, M. R., 2015.
Fast Removal of Methylene Blue from Aqueous Solution Using Magnetic-Modified Fe3O4
Nanoparticles. Journal of Environmental Engineering, 141(1), 0401-4049.
Adschiri, T., Takami, S., Arita, T., Hojo, D., Minami, K., Aoki, N., and Togashi, T., 2013.
Supercritical Hydrothermal Synthesis. Handbook of Advanced Ceramics, 949–978.
Alam, A.-M., Park, B.-Y., Ghouri, Z. K., Park, M., and Kim, H.-Y., 2015. Synthesis of
carbon quantum dots from cabbage with down- and up-conversion photoluminescence
properties: excellent imaging agent for biomedical applications. Green Chemistry, 17(7),
3791–3797.
Aljebori, A.M., Alshirifi, AmN., and Alkaim, A.F., 2014. Kinetics and equilibrium study for
the adsorption of textile dyes onto coconut shell activated carbon. Arabian Journal of
Chemistry, S1878-5352, 23-29.
Altaher, H. and ElQada, E., 2011. Investigation of the treatment of colored water using
efficient locally available adsorbent. International Journal of Energy and Environment, 2(6),
1113-1124.
Amel, K., Hassena, M.A., and Kerroum, D., 2012. Isotherm and Kinetics study of
biosorption of cationic dyes onto banana peel. Energy Procedia, 19, 286-295.
Aravind, J., Lenin, C., Nancyflavia, C., Rashika, P., and Saravanan, S., 2015. Response
surface methodology optimization of nickel (II) removal using pigeon pea pod biosorbent.
International Journal of Environmental Science and Technology, 12, 105-114.
Aravindhan, R., Rao, J.R., and Nair, B.U., 2007. Removal of basic yeloow from aqueous
solution by sorption on green alga Caulerpa scalpelliformis. Journal of Hazardous
Materials, 142, 68-76.
91
Arya, H., Kaul, Z., Wadhwa, R., Taira, K., Hirano, T. and Kaul, S., 2005. Quantum dots in
bio-imaging: Revolution by the small. Biochemical and Biophysical Research
Communications, 329(4), 1173-1177.
Ayawei, N., Ekubo, A., Wankasi, D. and Dikio, E., 2019. Adsorption of Congo Red by
Ni/Al-CO3: Equilibrium, Thermodynamic and Kinetic Studies. Oriental Journal of
Chemistry, 31(3), 1307-1318.
Azizian, S., 2004. Kinetic models of sorption: a theoretical analysis. Journal of Colloid and
Interface Science, 276(1), 47-52.
Bajorowicz, B., Kobylański, M., Gołąbiewska, A., Nadolna, J., Zaleska-Medynska, A. and
Malankowska, A., 2018. Quantum dot-decorated semiconductor micro- and nanoparticles:
A review of their synthesis, characterization and application in photocatalysis. Advances in
Colloid and Interface Science, 256, 352-372.
Batmaz, R., Mohammed, N., Zaman, M., Minhas, G., Berry, R. and Tam, K., 2014. Cellulose
nanocrystals as promising adsorbents for the removal of cationic dyes. Cellulose, 21(3),
1655-1665.
Bhattacharya, D., Germinario, L. T., and Winter, W.T., 2008. Isolation preparation and
characterization of cellulose microfibers obtained from bagasse. Carbohydr. Polym., 73,
371-377.
Bian, J., Huang, C., Wang, L., Hung, T., Daoud, W. and Zhang, R., 2014. Carbon Dot
Loading and TiO2 Nanorod Length Dependence of Photoelectrochemical Properties in
Carbon Dot/TiO2 Nanorod Array Nanocomposites. ACS Applied Materials & Interfaces,
6(7), 4883-4890.
Bondeson, D., Mathew, A., and Oksman, K., 2006. Optimization of the isolation of
nanocrystal from microcrystalline cellulose by acid hydrolysis. Cellulose, 13, 171-180.
Bonetta, S., Motta, F., Strini, A., and Carraro, E., 2013. Photocatalytic bacterial inactivation
by TiO2-coated surfaces. AMB Express, 3, 59.
Boumediene, M., Benaissa, H., George, B., Molina, S., and Merlin, A., 2014.
Characterization of two cellulosic waste materials (orange and almond peels) and their 4 use
for the removal of methylene blue from aqueous solutions. Maderas-Cienc. Technology, 17.
Bragd, P., Bekkum, H.V. and Besemer, A., 2004. TEMPO-Mediated Oxidation of
Polysaccharides: Survey of Methods and Applications. Topics in Catalysis, 27(1-4), 49–66.
Camarero Espinosa, S., Kuhnt, T., Foster, E. and Weder, C., 2013. Isolation of Thermally
Stable Cellulose Nanocrystals by Phosphoric Acid Hydrolysis. Biomacromolecules, 14(4),
1223-1230.
Cao, L., Sahu, S., Anilkumar, P., Bunker, C. E., Xu, J., Fernando, K. A. S., and Sun, Y.P.,
2011. Carbon Nanoparticles as Visible-Light Photocatalysts for Efficient CO2 Conversion
and Beyond. Journal of the American Chemical Society, 133(13), 4754-4757.
92
Cao, L., Wang, X., Meziani, M. J., Lu, F., Wang, H., Luo, P. G., and Sun, Y.-P., 2007.
Carbon Dots for Multiphoton Bioimaging. Journal of the American Chemical
Society, 129(37), 11318-11319.
Chandra, S., Das, P., Bag, S., Laha, D., and Pramanik, P., 2011. Synthesis, functionalization
and bioimaging applications of highly fluorescent carbon nanoparticles. Nanoscale, 3(4),
1533-1540.
Chandra, S., Pathan, S. H., Mitra, S., Modha, B. H., Goswami, A., and Pramanik, P., 2012.
Tuning of photoluminescence on different surface functionalized carbon quantum dots. RSC
Advances, 2(9), 3602-3606.
Chang, S. H., 2014. An overview of empty fruit bunch from oil palm as feedstock for bio-
oil production. Biomass and Bioenergy, 62, 174-181.
Chen, L., Li, Y., Hu, S., Sun, J., Du, Q., Yang, X., and Xia, Y., 2016. Removal of methylene
blue from water by cellulose/graphene oxide fibres. Journal of Experimental
Nanoscience, 11(14), 1156–1170.
Chen, X. L., Liu, W., Zhang, J. C., Pan, Q. S., Huang, D. S., and Dong, L. X., 2014.
Hydrothermal-Based Synthesis of CdS/ZnO Quantum Dots. Advanced Materials Research,
875-877, 362–365.
Chieng, B., Lee, S., Ibrahim, N., Then, Y., and Loo, Y., 2017. Isolation and Characterization
of Cellulose Nanocrystals from Oil Palm Mesocarp Fiber. Polymers, 9(12), 355.
Correa-Duarte, M. A., Giersig, M., Kotov, N. A., and Liz-Marzán, L. M., 1998. Control of
Packing Order of Self-Assembled Monolayers of Magnetite Nanoparticles with and without
SiO2 Coating by Microwave Irradiation. Langmuir, 14(22), 6430-6435.
Correia, V.M., Stephenson, T., & Judd, S.J., 1994. Characterisation of textile wastewaters ‐
a review. Environmental Technology, 15(10), 917–929.
Cragan, J. D., 1999. Teratogen update: Methylene Blue. Teratology, 1, 42-48.
Dabrowski A., 2001. Adsorption-from theory to practice. Advances in Colloid and Interface
Science, 93, 135–224.
Dada, A.O., Olalekan, A.P., Olatunya, A.M., and Dada, O., 2012. Langmuir, Freundlich,
Temkin and Dubinin–Radushkevich Isotherms Studies of Equilibrium Sorption of Zn 2 Unto
Phosphoric Acid Modified Rice Husk. IOSR Journal of Applied Chemistry, 3(1), 38-45.
Das, S.K., Ghosh, P., Ghosh, I., and Guha, A. K., 2008. Adsorption of rhodamine B on
Rhizous oryzae: Role of functional groups and cell wall components. Colloids and Surfaces
B: Biointerfaces, 65, 30-34.
Demirbas, E., Kobya, M., and Sulak, M.T., 2008. Adsorption kinetics of a basic dye from
aqueous solutions onto apricot stone activated carbon. Bioresource Technology, 99, 5368-
5373.
93
Domingues, R. M. A., Gomes, M. E., and Reis, R. L., 2014. The Potential of Cellulose
Nanocrystals in Tissue Engineering Strategies. Biomacromolecules, 15(7), 2327-2346.
Du, W., Xu, X., Hao, H., Liu, R., Zhang, D., Gao, F., and Lu, Q., 2015. Green synthesis of
fluorescent carbon quantum dots and carbon spheres from pericarp. Science China
Chemistry, 58(5), 863–870.
Ekimov, A. I. and Onoshchenko, A. A., 1982. Quantum size effect in three-dimensional

microscopic semiconductor crystals. American Institute of Physics, 34(6), 345-348.
Elmoubarki, R., Taoufik, M., Moufti, A., Tounsadi, H., Mahjoubi, F.Z., and Bouabi, Y.,
2017. Box-Behnken experimental design for the optimization of methylene blue adsorption
onto Aleppo pine cones. Journal of Materials and Environmental Sciences, 8(6), 2184-2191.
El-Naggar, M., Radwan, E., El-Wakeel, S., Kafafy, H., Gad-Allah, T., El-Kalliny, A. and
Shaheen, T., 2018. Synthesis, characterization and adsorption properties of microcrystalline
cellulose based nanogel for dyes and heavy metals removal. International Journal of
Biological Macromolecules, 113, 248-258.
Enenebeaku, C. K., Okorocha, N. J., Enenebeaku, U. E., and Onyeachu, B. I., 2017.
Adsorption of Methylene Blue Dye onto Bush Cane Bark Powder. International Letters of
Chemistry, Physics and Astronomy, 76, 12–26.
Fahma, F., Iwamoto, S., Hori, N., Iwata, T., and Takemura, A., 2010. Isolation, preparation,
and characterization of nanofibers from oil palm empty-fruit-bunch (OPEFB). Cellulose,
17(5), 977–985.
Ferdosian, F., Yuan, Z., Anderson, M., and Xu, C., 2014. Synthesis of lignin-based epoxy
resins: optimization of reaction parameters using response surface methodology. RSC Adv.,
4(60), 31745-31753.
Ferreira, S., Bruns, R., Ferreira, H., Matos, G., David, J., Brandão, G., da Silva, E., Portugal,
L., dos Reis, P., Souza, A. and dos Santos, W., 2007. Box-Behnken design: An alternative
for the optimization of analytical methods. Analytica Chimica Acta, 597(2), 179-186.
Fosso-Kankeu, E., Webster, A., Ntwampe, I. and Waanders, F., 2016.

Coagulation/Flocculation Potential of Polyaluminium Chloride and Bentonite Clay Tested
in the Removal of Methyl Red and Crystal Violet. Arabian Journal for Science and
Engineering, 42(4), 1389-1397.
Gao, J., Gu, H., and Xu, B., 2009. Multifunctional Magnetic Nanoparticles: Design,
Synthesis, and Biomedical Applications. Accounts of Chemical Research, 42(8), 1097-1107.
Garg, V., 2004. Basic dye (methylene blue) removal from simulated wastewater by
adsorption using Indian Rosewood sawdust: a timber industry waste. Dyes and
Pigments, 63(3), 243-250.
Geszke-Moritz, M., and Moritz, M., 2013. Quantum dots as versatile probes in medical
sciences: Synthesis, modification and properties. Materials Science and Engineering:
C, 33(3), 1008–1021.
94
Gheorghe N., Daniela E.P., Mihaela, P, Gina, A.T., Bunaciu, A.A., and Hassan, Y.A., 2013.
Study of adsorption kinetics and zeta potential of phosphate and nitrate ions on a cellulosic
membrane. Rev. Roum. Chim, 58(7), 591-597.
Ghorai, S., Sarkar, A., Raoufi, M., Panda, A.B., Schönherr, H., and Pal, S., 2014. Enhanced
Removal of Methylene Blue and Methyl Violet Dyes from Aqueous Solution Using a
Nanocomposite of Hydrolyzed Polyacrylamide Grafted Xanthan Gum and Incorporated
Nanosilica. ACS Applied Materials & Interfaces, 6(7), 4766-4777.
Gnanasekaran, L., Hemamalini, R., and Ravichandran, K., 2015. Synthesis and characterization
of TiO2 quantum dots for photocatalytic application. Journal of Saudi Chemical Society, 19(5),
589–594.
Gómez, V., Larrechi, M., & Callao, M., 2007. Kinetic and adsorption study of acid dye
removal using activated carbon. Chemosphere, 69(7), 1151–1158.
Gude, V.G., Patil, P., Martinez-Guerra, E., Deng, S., and Nirmalakhandan., N., 2014
Microwave energy potential for biodiesel production. Sustainable Chemical Processes, 1(5),
1-31.
Guo, L., Li, L., Liu, M., Wan, Q., Tian, J., Huang, Q., and Wei, Y., 2018. Bottom-up
preparation of nitrogen doped carbon quantum dots with green emission under microwave-
assisted hydrothermal treatment and their biological imaging. Materials Science and
Engineering: C, 84, 60–66.
Habibi, Y., 2014. Key advances in the chemical modification of nanocelluloses. Chem. Soc.
Rev., 43(5), 1519–1542.
Habibi, Y., Lucia, L.A., & Rojas, O.J., 2010. Cellulose Nanocrystals: Chemistry, Self-
Assembly, and Applications. Chemical Reviews, 110(6), 3479–3500.
Hameed, B., Ahmad, A., and Aziz, N., 2007. Isotherms, kinetics and thermodynamics of
acid dye adsorption on activated palm ash. Chemical Engineering Journal, 133(1-3), 195-
203.
Hameed, B.H. and El-Khaiary, M.I., 2008a. Batch removal of malachite green from aqueous
solution by adsorption on oil palm trunk fibre: Equilibrium isotherms and kinetic studies.
Journal of Hazardous Materials, 154, 237-244.
Hameed, B.H., 2008. Equilibrium and kinetic studies of methyl violet sorption by
agricultural waste. Journal of Hazardous Materials, 154, 204-212.
Hameed, B.H., 2009a. Evaluation of papaya seeds as a novel nonconventional low-cost

adsorbent for removal of methylene blue. Journal of Hazardous Materials, 162, 939-944.
Hameed, B.H., Ahmad, A.L. and Latiff, K.N.A., 2007. Adsorption of basic dye (methylene
blue) onto activated carbon prepared from rattan sawdust. Dyes and Pigments, 75, 143-149.
95
Hameed, B.H., and Daud, F.B.M., 2008. Adsorption studies of basic dye on activated carbon
derived from agricultural waste: Hevea brasiliensis seed coat. Chemical Engineering
Journal, 139, 48-55.
Hameed, B.H., Krishni. R.R., and Sata, S.A., 2009. A Novel Agricultural Waste Adsorbent
for the Removal of Cationic Dye from Aqueous Solutions. Journal of Hazardous Materials,
162, 306-311.
Hameed, B.H., Mahmoud, D.K., and Ahmad, A.L., 2008a. Sorption of basic dye from
aqueous solution by pomelo (Citrus grandis) peel in a batch system. Colloids and Surfaces
A: Physicochemistry Engineering Aspects, 316, 78-84.
Hameed, B.H., Mahmoud, D.K., and Ahmad, A.L., 2008b. Sorption equilibrium and kinetics
of basic dye from aqueous solution using banana stalk waste. Journal of Hazardous
Materials, 158, 499-506.
Hameed, O., and Chiha, M., 2007. Removal of methylene blue from aqueous solution by
wheat bran. Acta Chimica Slovenica, 54, 407-418.
Han, R., Wang, Y., Yu, W., Zou, W., Shi, J. and Liu, H., 2007. Biosorption of methylene
blue from aqueous solution by rice husk in a fixed-bed column. Journal of Hazardous
Materials, 141, 713-718.
He, M., Zhang, J., Wang, H., Kong, Y., Xiao, Y., and Xu, W., 2018. Material and Optical
Properties of Fluorescent Carbon Quantum Dots Fabricated from Lemon Juice via
Hydrothermal Reaction. Nanoscale Research Letters, 13(1).
He, X., Male, K.B., Nesterenko, P.N., Brabazon, D., Paull, B., and Luong, J.H., 2013.
Adsorption and Desorption of Methylene Blue on Porous Carbon Monoliths and
Nanocrystalline Cellulose. ACS Applied Materials & Interfaces, 5(17), 8796-8804.
Henriksson, M., Henriksson, G., Berglund, L., and Lindström, T., 2007. An environmentally
friendly method for enzyme-assisted preparation of microfibrillated cellulose (MFC)
nanofibers. European Polymer Journal, 43(8), 3434-3441.
Henseler, J., Fassott, G., Dijkstra, T. K., and Wilson, B., 2012. Analysing quadratic effects
of formative constructs by means of variance-based structural equation modelling. European
Journal of Information Systems, 21(1), 99-112.
Ho, Y., and Mckay, G., 1999. Pseudo-second order model for sorption processes. Process
Biochemistry, 34(5), 451–465.
Ho, Y.S., Chiang, T.H., and Hsueh, Y.M., 2005. Removal of basic dye from aqueous
solutions using tree fern as a biosorbent. Process Biochemistry, 40, 119-124.
Hoffmann, M.R., Martin, S.T., Choi, W., and Bahnemann, D.W., 1995. Environmental
Applications of semiconductor photocatalysis. Chemical Reviews, 95(1), 69-96.
96
Houas, A., 2001. Photocatalytic degradation pathway of methylene blue in water. Applied
Catalysis B: Environmental, 31(2), 145–157.
Hu, S. et al., 2013. Chemical Regulation of Carbon Quantum Dots from Synthesis to
Photocatalytic Activity. Chemistry: An Asian Journal, 8, 1035-1041.
Huang, H., Lv, J.J., Zhou, D.L., Bao, N., Xu, Y., Wang, A.J., and Feng, J.J., 2013. One-pot
green synthesis of nitrogen-doped carbon nanoparticles as fluorescent probes for mercury
ions. RSC Advances, 3(44), 21691.
Hubbe, M.A., Rojas, O.J., Lucia, L.A., Sain, M., 2008. Cellulosic Nanocomposites: A
Review. BioResources, 3(3), 929-980.
Islam, M. T., Alam, M. M., Patrucco, A., Montarsolo, A., & Zoccola, M., 2014. Preparation
of Nanocellulose: A Review. AATCC Journal of Research, 1(5), 17–23.
Ji, X., Peng, F., Zhong, Y., Su, Y., and He, Y., 2014. Fluorescent quantum dots: Synthesis,
biomedical optical imaging, and biosafety assessment. Colloids and Surfaces B:
Biointerfaces, 124, 132-139.
Jin, L., Li, W., Xu, Q., & Sun, Q., 2015. Amino-functionalized nanocrystalline cellulose as
an adsorbent for anionic dyes. Cellulose, 22(4), 2443-2456.
Kandisa, R.V., & Kv, N.S., 2016. Dye Removal by Adsorption: A Review. Journal of
Bioremediation & Biodegradation, 07(06).
Kappe, C.O., 2004. Controlled Microwave Heating in Modern Organic

Synthesis. Angewandte Chemie International Edition, 43(46), 6250–6284.
Kargarzadeh, H., Ahmad, I., Abdullah, I., Dufresne, A., Zainudin, S. Y., and Sheltami, R.
M., 2012. Effects of hydrolysis conditions on the morphology, crystallinity, and thermal
stability of cellulose nanocrystals extracted from kenaf bast fibers. Cellulose, 19(3), 855–
866.
Kargarzadeh, H., Ioelovich, M., Ahmad, I., Thomas, S., and Dufresne, A., 2017. Methods
for Extraction of Nanocellulose from Various Sources. Handbook of Nanocellulose and
Cellulose Nanocomposites, 1-49.
Karmakar, R., 2015. Quantum Dots and its method of preparations – revisited. Prajnan O
Sadhona, 2, 116-142.
Kaufmann, B. A., & Christen, P., 2002. Recent extraction techniques for natural products:
Microwave-assisted extraction and pressurised solvent extraction. Phytochemical
Analysis, 13(2), 105–113.
Kester, J.J. and Fennema, O.R., 1986. Edible films and coatings. A review. Food Technology,
40 (12), 47-59.
97
Khalil, H. A., Davoudpour, Y., Islam, M. N., Mustapha, A., Sudesh, K., Dungani, R., and
Jawaid, M., 2014. Production and modification of nanofibrillated cellulose using various
mechanical processes: A review. Carbohydrate Polymers, 99, 649-665.
Khataee, A.R., Vafaei, F. and Jannatkhah, M., 2013. Biosorption of three textile dyes from
contaminated water by flamentous green agal Spirogyra sp.: Kinetics, isotherm and
thermodynamic studies. International Bioremediation & Biodegradation, 83, 33-40.
Khatod, I., 2013. Removal of methylene blue dye from aqueous solutions by neem leaf and
orange peels powder. International Journal Chemical Technology Resources, 5, 572-577.
Khattri, S.D. and Singh, M., 1999 Adsorption of basic dyes from aqueous solution by natural
adsorbent. Indian J. Chem. Technol. 6, pp. 112-116.
Kikuchi, M., Ogawa, K., Yamazaki, T., Kajiwara, S., and Shishido, K., 2002. Use of
molecular-genetically bred Coprinus cinereus strains for an efficient isolation of cellulose
from rice straw. Biosci. Biotechnol. Biochem., 66,199-201.
Klabunde, K.J., 2010. Visible and UV light Photocatalyst in environmental remediation.

Nanoscale Materials in Chemistry: Environmental Applications, American Chemical
Society, 1045, 179-189.
Klemm, D., Kramer, F., Moritz, S., Lindström, T., Ankerfors, M., Gray, D., & Dorris, A.,
2011. Nanocelluloses: A New Family of Nature-Based Materials. Angewandte Chemie
International Edition, 50(24), 5438-5466.
Kontturi, E., Tammelin, T., and Österberg, M., 2006. Cellulose-model films and the
fundamental approach. Chem. Soc. Rev., 35(12), 1287-1304.
Krassig, H. and Schurz, J., 1986. Cellulose. Ullmann's Encyclopedia of Industrial Chemistry.
Weinheim, Germany: Wiley-VCH
Kudo, A. and Miseki, Y., 2009. Heterogeneous photocatalyst materials for water splitting.
Chemical Society Reviews, 38(1), 253-278.
Kumar, s., Ramalingam, S., Senthamarai, C., Niranjanaa, M.m Vijayalakshmi, P., and
Sivanesan, S., 2010. Adsorption of dye from aqueous solution by cashew nut shell: Studies
on equilibrium isotherm, kinetics and thermodynamics of interactions. Desalination, 261,
52-60.
Kushairi, A., Loh, S.K., Azman, I., Hishamuddin, E., Abdullah, M.O., Bidin, Z., Razmah,
G., Sundram, S., and
Kadir, G., 2018. Oil Palm Economic Performance in Malaysia and R&D Progress in 2017 –
Review Article. Journal of Oil Palm Research, 30(2), 163-195
Lakshmi, U.R., Srivastava, V.C., Mall, I. D., and Lataye, D. H., 2009. Rice husk ash as an
effective adsorbent: Evaluation of adsorptive characteristics for indigo Carmine dye. Journal
of Environmental Management, 90, 710-720.
98
Lata, H., Mor, S. Garg, V.K. and Gupta, R.K., 2008. Removal of a dye from simulated
wastewater by adsorption using treated parthenium biomass. Journal of Hazardous
Materials, 153, 213-220.
Leadbeater, N. E., 2005. Fast, easy, clean chemistry by using water as a solvent and
microwave heating: the Suzuki coupling as an illustration. Chemical Communications, 23,
2881.
Li, Y., Xiao, H., Chen, M., Song, Z., & Zhao, Y., 2014. Absorbents based on maleic
anhydride-modified cellulose fibers/diatomite for dye removal. Journal of Materials
Science, 49(19), 6696-6704.
Li, Y., Zhong, X., Rider, A. E., Furman, S. A., and Ostrikov, K., 2014. Fast, energy-efficient
synthesis of luminescent carbon quantum dots. Green Chem., 16(5), 2566-2570.
Lin, N., Huang, J., and Dufresne, A., 2012. Preparation, properties and applications of
polysaccharide nanocrystals in advanced functional nanomaterials: a
review. Nanoscale, 4(11), 3274.
Liu, D., Zhong, T., Chang, P. R., Li, K., and Wu, Q., 2010. Starch composites reinforced by
bamboo cellulosic crystals. Bioresource Technology, 101(7), 2529-2536.
Liu, H., Fu, S., Zhu, J., Li, H., & Zhan, H., 2009. Visualization of enzymatic hydrolysis of
cellulose using AFM phase imaging. Enzyme and Microbial Technology, 45(4), 274-281.
Liu, S., Tian, J., Wang, L., Zhang, Y., Qin, X., Luo, Y., and Sun, X., 2012. Hydrothermal
Treatment of Grass: A Low-Cost, Green Route to Nitrogen-Doped, Carbon-Rich,
Photoluminescent Polymer Nanodots as an Effective Fluorescent Sensing Platform for
Label-Free Detection of Cu(II) Ions. Advanced Materials, 24(15), 2037-2041.
Liu, T., Sun, S., Zhou, L., Li, P., Su, Z., and Wei, G., 2019. Polyurethane-Supported
Graphene Oxide Foam Functionalized with Carbon Dots and TiO2 Particles for
Photocatalytic Degradation of Dyes. Applied Sciences, 9(2), 293.
Lovingood, D.D., 2010. Synthesis and Analysis of the Quantum Dot Core and Surface
Structures Probed by Solid State Nuclear Magnetic Resonance. Thesis. The Florida State
University College of Arts and Science.
Lu, W., Qin, X., Liu, S., Chang, G., Zhang, Y., Luo, Y., and Sun, X., 2012. Economical,
Green Synthesis of Fluorescent Carbon Nanoparticles and Their Use as Probes for Sensitive
and Selective Detection of Mercury(II) Ions. Analytical Chemistry, 84(12), 5351-5357.
Mahfoudhi, N., & Boufi, S., 2017. Nanocellulose as a novel nanostructured adsorbent for
environmental remediation: a review. Cellulose, 24(3), 1171-1197.
Mallakpour, S., & Behranvand, V., 2018. Synthesis of mesoporous recycled poly(ethylene
terephthalate)/MWNT/carbon quantum dot nanocomposite from sustainable materials using
ultrasonic waves: Application for methylene blue removal. Journal of Cleaner
Production, 190, 525–537.
99
Malvern, 2013. Dynamic Light Scattering: An Introduction in 30 Minutes. [Online] Available
from:
<https://warwick.ac.uk/fac/cross_fac/sciencecity/programmes/internal/themes/am2/booking/pa
rticlesize/intro_to_dls.pdf> [Accessed 27 March 2019].
Mariano, M., Kissi, N.E., & Dufresne, A., 2014. Cellulose nanocrystals and related
nanocomposites: Review of some properties and challenges. Journal of Polymer Science
Part B: Polymer Physics, 52(12), 791–806.
Martindale, B.C.M., Hutton, G.A.M., Caputo, C.A., & Reisner, E., 2015. Solar Hydrogen
Production Using Carbon Quantum Dots and a Molecular Nickel Catalyst. Journal of the
American Chemical Society, 137(18), 6018-6025.
Melbiah, J. B., Nithya, D., & Mohan, D., 2017. Surface modification of polyacrylonitrile
ultrafiltration membranes using amphiphilic Pluronic F127/CaCO3 nanoparticles for
oil/water emulsion separation. Colloids and Surfaces A: Physicochemical and Engineering
Aspects, 516, 147–160.
Miao, R., Luo, Z., Zhong, W., Chen, S.-Y., Jiang, T., Dutta, B., and Suib, S. L., 2016.
Mesoporous TiO2 modified with carbon quantum dots as a high-performance visible light
photocatalyst. Applied Catalysis B: Environmental, 189, 26–38.
Mitra, S., Chandra, S., Kundu, T., Banerjee, R., Pramanik, P., & Goswami, A., 2012. Rapid
microwave synthesis of fluorescent hydrophobic carbon dots. RSC Advances, 2(32), 12129-
12131.
Mora-Seró, I., Giménez, S., Fabregat-Santiago, F., Gómez, R., Shen, Q., Toyoda, T. and
Bisquert, J., 2009. Recombination in Quantum Dot Sensitized Solar Cells. Accounts of
Chemical Research, 42(11), 1848-1857.
Morgan, ED., 1997. Experimental Design. Chemometrics, 15-117.
Nadimpalli, N. K. V., Bandyopadhyaya, R., and Runkana, V., 2018. Thermodynamic

analysis of hydrothermal synthesis of nanoparticles. Fluid Phase Equilibria, 456, 33-45.
Nakata, K. and Fujishima, A., 2012. TiO2 photocatalysis: Design and applications. J.
Photochem. Photobiol. C, 13, 169-189.
Nandi, B.K., Goswami, A., and Purkait, M. K., 2009. Removal of cationic dyes from aqueous
solutions by kaolin: kinetic and equilibrium studies. Applied Clay Science, 42, 583-590.
Narayanasamy, L., & Murugesan, T., 2013. Degradation of Alizarin Yellow R using
UV/H2O2 advanced oxidation process. Environmental Progress & Sustainable
Energy, 33(2), 482–489.
Nehls, I., Wagenknecht, W., Philipp, B., and Stscherbina, D., 1994. Characterization of
cellulose and cellulose derivatives in solution by high resolution carbon-13 NMR
spectrometry. Progress in Polymer Science, 19(1), 29-78.
100
Nemr, A. E., Abdelwahab, O., El-Sikaily, A., and Khaled, A., 2009. Removal of direct blue-
86 from aqueous solution by new activated carbon developed from orange peel. Journal of
Hazardous Materials, 161, 102-110.
Nemr, A.E., Abdelwahab, O., E1-Sikaily, A., and Khaled, A., 2009. Evaluation of metal
hydroxide sludge for reactive dye adsorption in a fixed bed column system. Water Research,
38, 71-78.
Nguyen, T., Roddick, F., & Fan, L., 2012. Biofouling of Water Treatment Membranes: A
Review of the Underlying Causes, Monitoring Techniques and Control
Measures. Membranes, 2(4), 804–840.
Njoku, V. O., Foo, K. Y., Asrif, M. and Hameed, B. H., 2014. Preparation of activated
carbons from rambutan (Nephelium Iappaceum) peel by microwave-induced KOH
activation for acid yellow 17 dye adsorption. Chemical Engineering Journal, 250, 198–204.
Njuguna, J., Ansari, F., Sachse, S., Zhu, H., & Rodriguez, V., 2014. Nanomaterials,
nanofillers, and nanocomposites: types and properties. Health and Environmental Safety of
Nanomaterials, 3–27.
Nonviho G., 2015. Valorisation chimique de la biomasse oléagineuse d’origine béninoise:

Lophira Lanceolata et Carapa procera. Thèse de doctorat en chimie. Université d’Abomey-
Calavi, 196 (2015).
Noroozi, B., Sorial, G., Bahrami, H., & Arami, M., 2007. Equilibrium and kinetic adsorption
study of a cationic dye by a natural adsorbent—Silkworm pupa. Journal of Hazardous
Materials, 139(1), 167–174.
Nsami, J. N., and Mbadcam, J. K., 2013. The Adsorption Efficiency of Chemically Prepared
Activated Carbon from Cola Nut Shells by on Methylene Blue. Journal of Chemistry, 2013,
1–7.
Nwabanne, J.T., and Mordi, M.I., 2009. Equilibrium uptake and sorption dynamics for the
removal of a basic dye using bamboo. African Journal of Biotechnology, 8(8), 1555-1559.
Ofomaja, A. E., and Ho, Y.S., 2008. Effect of temperature and pH on the methyl violet
biosorption by Mansonia wood sawdust. Bioresource Technology, 99, 5411-5417.
Olgun, A., and Atar, N., 2008. Equilibrium and kinetic adsorption study of Basic Yellow 28
and Basic Red 46 by a boron industry waste. Journal of Hazardous Materials, 161 (1), 148-
156.
Ong, S.T., Lee, W.N., Keng, P.S., Lee, S.L., Hung, Y.T., Ha, S.T., 2010. Equilibrium studies
and kinetics mechanism for the removal of basic and reactive dyes in both single and binary
systems using EDTA modified rice husk. International Journal of Physical Sciences, 5(5),
582-595.
Otto, M., 2007. Chemometrics: statistics and computer application in analytical chemistry,
Microchemical Journal, 68(1), 87–88.
101
Ouasif, H., Yousfi, S., Bouamrani, M.L., El Kouali, M., Benmokhtar, S., Talbi, M., 2013.
Removal of a cationic dye from wastewater by adsorption onto natural adsorbents, J. Mater.
Environ. Sci,4(1), 1-10.
Pandit, V.K., Arbuj, S.S., Pandit, Y.B., Naik, S.D., Rane, S.B., Mulik, U.P., Gosavic, S.W.
and Kale, B.B., 2015. Solar Light driven Dye Degradation using novel Organo–Inorganic
(6,13- Pentacenequinone/TiO2) Nanocomposite. RSC Adv., 5, 10326-10331.
Pang, Y. L. and Abdullah, A. Z., 2013. Current status of textile industry wastewater
management and research progress in Malaysia: A review. Clean Soil Air Water, 1-14.
Park, S.H., Kim, H.J., & Cho, J.I., 2008. Optimal Central Composite Designs for Fitting
Second Order Response Surface Linear Regression Models. Recent Advances in Linear
Models and Related Areas, 323-339.
Pathak, S., Cao, E., Davidson, M.C., Jin, S., and Silva, G.A., 2006. Quantum Dot
Applications to Neuroscience: New Tools for Probing Neurons and Glia. Journal of
Neuroscience, 26(7), 1893–1895.
Paulo, S., Palomares, E., and Martinez-Ferrero, E., 2016. Graphene and Carbon Quantum
Dot-Based Materials in Photovoltaic Devices: From Synthesis to
Applications. Nanomaterials, 6(9), 157.
Payen, A., 1842. Troisieme memoire sur le development vegetaux. Extrait des memoires de
l’Academie Royale des Sciences: Tomes III des Savants Etrangers. Paris: Imprimerie Royale.
Peng, B.L., Dhar, N., Liu, H.L., and Tam, K.C., 2011. Chemistry and applications of
nanocrystalline cellulose and its derivatives: A nanotechnology perspective. The Canadian
Journal of Chemical Engineering, 89(5), 1191-1206.
Pires, N. R., Santos, C.M.W., Sousa, R.R., Paula, R.C.M.D., Cunha, P.L.R., and Feitosa,
J.P.A., 2015. Novel and Fast Microwave-Assisted Synthesis of Carbon Quantum Dots from
Raw Cashew Gum. Journal of the Brazilian Chemical Society, 26(6), 1274-1282.
Ponnusami, V., Vikram, S., and Srivastava, S. N., 2008. Guava (Psidium guajava) leaf
powder: Novel adsorbent for removal of methylene blue from aqueous solutions. Journal of
Hazardous Materials, 152, 276-286.
Qian, H., Qiu, X., Li, L., Ren, J., 2006. Microwave-assisted aqueous synthesis: A rapid
approach to prepare highly luminescent ZnSe(S) alloyed quantum dots. Journal of Physical
Chemistry B, 110(18), 9034-9040.
Qiao, H., Zhou, Y., Yu, F., Wang, E., Min, Y., Huang, Q., Pang, L., and Ma, T., 2015.
Effective removal of cationic dyes using carboxylate-functionalized cellulose nanocrystals.
Chemosphere. 141, 297-303.
Ragonese, R., Macka, M., Hughes, J. and Petocz, P., 2002. The use of the Box–Behnken
experimental design in the optimisation and robustness testing of a capillary electrophoresis
102
method for the analysis of ethambutol hydrochloride in a pharmaceutical formulation.
Journal of Pharmaceutical and Biomedical Analysis, 27(6), 995-1007.
Rathod, S.D., Dandge, R.K., and Ubale, M.B., 2016. Removal of Methylene Blue using
Thick Rind of Water Melon as an adsorbent. International Journal of Green and Herbal
Chemistry, 5(3), 272-282.
Robinson, T., Mcmullan, G., Marchant, R., and Nigam, P., 2001. Remediation of dyes in
textile effluent: a critical review on current treatment technologies with a proposed
alternative. Bioresource Technology, 77(3), 247–255.
Rusli, R., and Eichhorn, S. J., 2008. Determination of the stiffness of cellulose nanowhiskers
and the fiber-matrix interface in a nanocomposite using Raman spectroscopy. Applied
Physics Letters, 93(3), 033111.
Sachdev, A., Matai, I., Kumar, S. U., Bhushan, B., Dubey, P., and Gopinath, P., 2013. A
novel one-step synthesis of PEG passivated multicolour fluorescent carbon dots for potential
biolabeling application. RSC Advances, 3(38), 16958.
Sahu, S., Behera, B., Maiti, T. K., and Mohapatra, S., 2012. Simple one-step synthesis of
highly luminescent carbon dots from orange juice: application as excellent bio-imaging
agents. Chemical Communications, 48(70), 8835.
Sahu, S., Behera, B., Maiti, T. K., and Mohapatra, S., 2012. Simple one-step synthesis of
highly luminescent carbon dots from orange juice: application as excellent bio-imaging
agents. Chemical Communications, 48(70), 8835.
Salleh, M. A. M., Mahmoud, D. K., Karim, W. A. W. A., and Idris, A., 2011. Cationic and
anionic dye adsorption by agricultural solid wastes: A comprehensive
review. Desalination, 280(1-3), 1–13.
Samaj, D. and City, F., 2017 ‘Microwave Assisted Synthesis: Review of Recent
Development. International Journal of Advance Research in Science and Engineering, 6(3),
220-226.
Santhi, T., and Manonmani, S., 2009. Removal of Methylene blue from aqueous solution by
bioadsorption onto Ricinus communis epicarp activated carbon, Chemical Engineering
Research Bulletin, 13(1), 1-5.
Sarabia, L.A. and Ortiz, M.C., 2009. Response surface methodology. Comprehensive
Chemometrics: Chemical and Bio-chemical Data Analysis, 1, 345-390.
Savage, N., and Diallo, M.S., 2005. Nanomaterials and Water Purification: Opportunities
and Challenges. Journal of Nanoparticle Research, 7(4-5), 331–342.
Schweitzer J., 2010. Scanning electron microscope. Radiological and environmental

management. Purdue University, West Lafayette.
103
Shahryari, Z., Goharrizi, A.S., and Azadi, M., 2010. Experimental study of methylene blue
adsorption from aqueous solutions onto carbon nanotubes. Int. J. Water Resour. Environ.
Eng, 2, 16-28.
Shanmugarajah, B., Chew, I.M., Mubarak, N.M., Choong, T.S.Y., Yoo, C.K. and Tan, K.W.,
2019. Valorisation of palm oil agro-waste into cellulose biosorbents for highly effective
textile effluent remediation. Journal of Cleaner Production, 210, 697-709.
Sharma, Y.C, 2009. Optimization of parameters for adsorption of methylene blue on a low-
cost activated carbon. Journal of Chemical & Engineering Data, 55, 435-439.
Shen, Z., Wang, W., Jia, J., Ye, J., Feng, X., and Peng, A., 2001. Degradation of dye solution
by an activated carbon fiber electrode electrolysis system. Journal of Hazardous
Materials, 84(1), 107–116.
Singh, V., Sharma, A.K., Tripathi, D.N. and Sanghi, R., 2009. Poly(methylmethacrylate)
grafter chitosan: An efficient adsorbent for anionic dyes. Journal of Hazardous Materials,
161, 955-966.
Siqueira, G., Tapin-Lingua, S., Bras, J., Perez, D.D.S., and Dufresne, A., 2010.
Morphological investigation of nanoparticles obtained from combined mechanical shearing,
and enzymatic and acid hydrolysis of sisal fibers. Cellulose, 17(6), 1147-1158.
Song, Y.K., Chew, I.M.L., Choong, T.S.Y., Tan, J., & Tan, K.W., 2016. Isolation of
Nanocrystalline Cellulose from oil palm empty fruit bunch – A response surface
methodology study. MATEC Web of Conferences, 60, 04009.
Souza, D. R. D. S., Caminhas, L. D., Mesquita, J. P. D., and Pereira, F. V., 2018.
Luminescent carbon dots obtained from cellulose. Materials Chemistry and Physics, 203,
148–155.
Souza, D.R.D.S., Mesquita, J.P.D., Lago, R.M., Caminhas, L.D., & Pereira, F.V., 2016.
Cellulose nanocrystals: A versatile precursor for the preparation of different carbon
structures and luminescent carbon dots. Industrial Crops and Products, 93, 121–128.
Sun, R.C., Lawther, J.M., and Banks, W.B., 1998. Isolation and characterization of
hemicellulose B and cellulose from pressure refined wheat straw. Ind. Crops Prod., 7, 121-
128.
Sun, Y.-P., Zhou, B., Lin, Y., Wang, W., Fernando, K. A. S., Pathak, P., and Xie, S.Y., 2006.
Quantum-Sized Carbon Dots for Bright and Colorful Photoluminescence. Journal of the
American Chemical Society, 128(24), 7756–7757.
Sun, Y.P., Zhou, B., Lin, Y., Wang, W., Fernando, K.A.S., Pathak, P., Meziani, M.J.,
Harruff, B.A., Wang, X., Wang, H.F., Luo, P.G., Yang, H., Kose, M.E., Chen, B.L., Veca,
L.M. and Xie, S.Y., 2006. Quantum-Sized Carbon Dots for Bright and Colourful
Photoluminescence. Journal of American Chemical Society, 128, pp. 7756-7757.
Suzuki, M., 1990. Adsorption engineering. Tokyo: Kodansha.
104
Swapp, S., 2012. Scanning Electron Microscopy (SEM) [Online]. Available from:
<https://serc.carleton.edu/research_education/geochemsheets/techniques/SEM.html>
[Accessed 8 March 2019].
Tadesse, A., Ramadevi, D., Hagos, M., Battu, G., & Basavaiah, K., 2018. Synthesis of
nitrogen doped carbon quantum dots/magnetite nanocomposites for efficient removal of
methyl blue dye pollutant from contaminated water. RSC Advances, 8(16), 8528–8536.
Tan, I.A.W., Ahmad, A.L., and Hameed, B.H., 2008b. Adsorption of basic dye on high-
surface-area activated carbon prepared from coconut husk: Equilibrium, kinetic and
thermodynamic studies. Journal of Hazardous Materials, 153, 337-346.
Tang, J., Sisler, J., Grishkewich, N., & Tam, K.C., 2017. Functionalization of cellulose
nanocrystals for advanced applications. Journal of Colloid and Interface Science, 494, 397–
409.
Tanpichai, S., Quero, F., Nogi, M., Yano, H., Young, R.J., Lindström, T., and Eichhorn, S.J.,
2012. Effective Young’s Modulus of Bacterial and Microfibrillated Cellulose Fibrils in
Fibrous Networks. Biomacromolecules, 13(5), 1340–1349.
Tchuifon T.D.R., Ndifor-Angwafor, N.G., Ngakou, S.C., Kamgaing, T., Ngomo H.M.,
Anagho, S.G., Ketcha, J.M., 2016. Optimization of cadmium (II) adsorption onto modified
and unmodified lignocellulosics (rice husk and eguissi peeling). International Journal of
Basic and Applied Sciences, 5(1), 45-51.
Thinakaran, N., Panneerselvam, P., Baskaralingam, Elango, D., and Sivanesan, S., 2008.
Equilibrium and kinetic studies on the removal of Acid Red 114 from aquoues solutions
using activated carbons prepared from seed shells. Journal of Hazardous Materials, 158,
142-150.
Thomas, S., Paul, S. A., Pothan, L. A., and Deepa, B., 2011. Natural Fibres: Structure,
Properties and Applications. Cellulose Fibers: Bio- and Nano-Polymer Composites, 3-42.
Tolstoguzov, V., 2004. Why are polysaccharides necessary? Food Hydrocolloids, 18(5),
873–877.
Tsai, W.T., Hsu, H.C., Su, T.Y., Lin, K.Y., and Lin, C. M., 2008. Removal of basic dye
(methylene blue) from wastewater utilizing beer brewery waste. Journal of Hazardous
Materials, 154, 73-78.
Tunc, O., Tanaci, H., and Aksu, Z., 2009. Potential use of cotton plant wastes for the removal
of Remazol Balck B reactive dye. Journal of Hazardous Materials, 163, 187-198.
Turabik, M., 2008. Adsorption of basic dyes from single and binary component systems onto
bentonite: Simultaneous analysis of Basic Red 46 and Basic Yellow 28 by first order
derivative spectrophotometric analysis method. Journal of Hazardous Materials, 158, 52-
64.
105
Ucun, H., Bayhana, Y.K., Kaya, Y., Cakici, A., and Algur, O.F., 2003. Biosorption of lead
(II) from aqueous solution by cone biomass of Pinus sylvestris. Desalination, 154, 232-238.
Uddin, Md. T., Islam, Md. A., Mahmud, S. and Rukanuzzaman, Md., 2009. Adsorptive
removal of methylene blue by tea waste. Journal of Hazardous Materials, 164, 53-60.
Wang, B.E., and Hu, Y.Y., 2008. Bioaccumulation versus adsorption of reactive dye by
immobilized growing Aspergillus fumigates beads. Journal of Hazardous Materials, 157, 1-
7.
Wang, G., Wang, S., Sun, Z., Zheng, S., and Xi, Y., 2017a. Structures of non-ionic surfactant
modified montmorillonites and their enhanced adsorption capacities towards a cationic
organic dye. Applied Clay Science, 148, 1–10.
Wang, Q., Liu, X., Zhang, L., & Lv, Y., 2012. Microwave-assisted synthesis of carbon
nanodots through an eggshell membrane and their fluorescent application. The
Analyst, 137(22), 5392.
Wang, R., Lu, K.Q., Tang, Z.R. and Xu, Y.J., 2017b. Recent progress on carbon quantum
dots: synthesis, properties and applications in photocatalysis. Journal of Materials Chemistry
A.
Wang, Y., Hu, R., Lin, G., Roy, I., and Yong, K.T., 2013. Functionalized Quantum Dots for
Biosensing and Bioimaging and Concerns on Toxicity. ACS Applied Materials &
Interfaces, 5(8), 2786–2799.
Wissing, S., Kayser, O., and Müller, R, 2004. Solid lipid nanoparticles for parenteral drug
delivery. Advanced drug delivery reviews, 56(9), 1257-1272.
Wu, H., Mi, C., Huang, H., Han, B., Li, J., and Xu, S., 2012. Solvothermal synthesis of
green-fluorescent carbon nanoparticles and their application. Journal of
Luminescence, 132(6), 1603–1607.
Wu, P., Li, W., Wu, Q., Liu, Y., and Liu, S., 2017. Hydrothermal synthesis of nitrogen-doped
carbon quantum dots from microcrystalline cellulose for the detection of Fe3 ions in an acidic
environment. RSC Advances, 7(70), 44144-44153.
Xiao, D., Yuan, D., He, H., and Gao, M., 2013. Microwave assisted one-step green synthesis
of fluorescent carbon nanoparticles from ionic liquids and their application as novel
fluorescence probe for quercetin determination. Journal of Luminescence, 140, 120–125.
Xu, X., Ray, R., Gu, Y., Ploehn, H. J., Gearheart, L., Raker, K., & Scrivens, W.A., 2004.
Electrophoretic Analysis and Purification of Fluorescent Single-Walled Carbon Nanotube
Fragments. Journal of the American Chemical Society, 126(40), 12736–12737.
Xue, Y., Hou, H., and Zhu, S., 2009. Adsorption removal of reactive dyes from aqueous
solution by modified basic oxygen furnace slag: Isotherm and kinetic study. Chemical
Engineering Journal, 147, 272-279.
106
Yagub, M.T., Sen, T.K., Afroze, S., & Ang, H., 2014. Dye and its removal from aqueous
solution by adsorption: A review. Advances in Colloid and Interface Science, 209, 172–184.
Yan, C.F., Yu, H.Y. and Yao, J.M., 2015. One-step extraction and functionalization of
cellulose nanospheres from lyocell fibers with cellulose II crystal structure. Cellulose, 22(6),
3773-3788.
Yang, S.T., Wang, X., Wang, H., Lu, F., Luo, P.G., Cao, L., and Sun, Y.P., 2009. Carbon
Dots as Nontoxic and High-Performance Fluorescence Imaging Agents. The Journal of
Physical Chemistry C, 113(42), 18110-18114.
Yu, H., Qin, Z., Liang, B., Liu, N., Zhou, Z., and Chen, L., 2013. Facile extraction of
thermally stable cellulose nanocrystals with a high yield of 93% through hydrochloric acid
hydrolysis under hydrothermal conditions. Journal of Materials Chemistry A, 1(12), 3938.
Yu, X., Liu, R., Zhang, G., and Cao, H., 2013. Carbon quantum dots as novel sensitizers for
photoelectrochemical solar hydrogen generation and their size-dependent
effect. Nanotechnology, 24(33), 335401.
Zhang, M., Yao, Q., Lu, C., Li, Z., & Wang, W., 2014. Layered Double Hydroxide–Carbon
Dot Composite: High-Performance Adsorbent for Removal of Anionic Organic Dye. ACS
Applied Materials & Interfaces, 6(22), 20225-20233.
Zhao, Y., Zuo, S., and Miao, M., 2017. The effect of oxygen on the microwave-assisted
synthesis of carbon quantum dots from polyethylene glycol. RSC Advances, 7(27), 16637–
16643.
Zhu, H., Wang, X., Li, Y., Wang, Z., Yang, F., and Yang, X., 2009. Microwave synthesis of
fluorescent carbon nanoparticles with electrochemiluminescence properties. Chemical
Communications, (34), 5118.
Zhu, J.J., Li, J.J., Huang, H.P., and Cheng, F.F., 2013. Quantum Dots for DNA
Biosensing. SpringerBriefs in Molecular Science, 2, 9-25.
Zhuo, S., Shao, M., & Lee, S.T., 2012. Upconversion and Downconversion Fluorescent
Graphene Quantum Dots: Ultrasonic Preparation and Photocatalysis. ACS Nano, 6(2), 1059–
1064.
Zuo, J., Jiang, T., Zhao, X., Xiong, X., Xiao, S., & Zhu, Z., 2015. Preparation and
Application of Fluorescent Carbon Dots. Journal of Nanomaterials, 2015, 1–13.
107
APPENDICES
APPENDIX 1
PICTORIAL FLOW DIAGRAM
i. Extraction of Cellulose
ii. Extraction of cellulose-based CQDs
108
iii. 10 mg/L Methylene blue solution
iv. Adsorption Experiment using cellulose fibers adsorbent
v. Photocatalytic Adsorption Experiment using cellulose-based CQDs adsorbent
109
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 MB

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 y = 0.2667x
R² = 0.9874
2.00
ABS
1.50
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)
110
APPENDIX 4
ADSORPTION OF MB ON CELLULOSE FIBERS
Contact Time Initial Conc. of MB ABS Final Conc. Adsorption

Run pH st Avg ABS
(min) (mg/L) 1 2nd 3rd
(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
111
APPENDIX 5
PHOTOCATALYTIC ADSORPTION OF MB ON CELLULOSE-BASED CQDs
Contact Time Initial Conc. of dye ABS Adsorption

Run pH st Avg ABS Conc.
(min) (mg/L) 1 2nd 3rd 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
112
APPENDIX 6
SIZE DISTRIBUTION OF CQDS
i. 1st analysis
ii. 2nd analysis
iii. 3rd analysis
113
APPENDIX 7
ZETA POTENTIAL OF CELLULOSE
i. 1st analysis
ii. 2nd analysis
iii. 3rd analysis
114
APPENDIX 8
ZETA POTENTIAL OF CQDS
i. 1st analysis
ii. 2nd analysis
iii. 3rd analysis
115
APPENDIX 9
ISOTHERM STUDIES DATA
Co ABS Ce Qe 1/Qe 1/Ce lnQe lnCe RL
2 0.122 0.457443 0.153 6.522 2.186 -1.875 -0.782 0.295219
4 0.158 0.592426 0.333 3.005 1.688 -1.100 -0.524 0.173171
6 0.178 0.667417 0.526 1.902 1.498 -0.643 -0.404 0.12252
8 0.182 0.682415 0.716 1.397 1.465 -0.334 -0.382 0.094793
10 0.205 0.768654 0.901 1.109 1.301 -0.104 -0.263 0.0773

i. Adsorption of MB 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 MB on cellulose-based CQDs
[condition: pH=11, time = 25mins, adsorbent = 0.5g, MB = 0.05L]
116
APPENDIX 10
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]
117
APPENDIX 11
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
118

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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 who have aided me professionally

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

Carbon Quantum Dots (CQDs) were synthesized by hydrothermal treatment using

DECLARATION OF ORIGINALITY & EXCLUSIVENESS ii

LIST OF TABLES viii

LIST OF EQUATIONS xiii

LIST OF ABBREVIATIONS AND SYMBOLS xv

CHAPTER II LITERATURE REVIEW 8

2.1 Oil Palm 8

3.1 Materials and Chemicals 43

CHAPTER IV RESULTS AND DISCUSSION 58

4.1 Percentage Yield of Cellulose 58

4.7 Kinetics Analysis 86

CHAPTER V CONCLUSION AND RECOMMENDATIONS 89

Table No. Page

2.1 Annual Generation of Oil Palm Biomass 8

2.2 Synthesis CQD from various carbon sources relevant to different

2.3 The advantages and disadvantages of different synthesis methods

2.4 Classification of dyes 23

2.5 Dye removal technology with respect to their advantages and

2.6 Previous research on the removal of different dyes by agricultural

2.7 Number of experiments for different factors 40

3.1 List of materials and chemicals used 43

3.2 List of equipment used 44

3.3 Experimental range and factor level of process variables applied 50

3.4 Design matrix for experimental factors at different factor level 50

4.1 Box-Behnken design matrix of three factors along with

4.2 ANOVA for the response surface quadratic model for MB

4.3 RSM Optimization for adsorption of methylene blue on cellulose 68

4.4 Box-Behnken design matrix of three factors along with

4.6 RSM Optimization for adsorption of MB on cellulose 80

4.7 Comparison of cellulose adsorbent and CQDs adsorbent in removal

4.8 Comparison of Langmuir and Freundlich isotherm constants for

4.9 Comparison of pseudo-first and pseudo-second order for removal

Figure No. Page

2.1 Schematic drawing of cell wall hierarchical structure of OPEFB 9

2.2 Structure of cellulose 11

2.3 Scheme of quantum dot structure 12

2.4 Colour emission of carbon dots solution under UV radiation 13

2.5 Illustration of CDs (a)Elementary CDs; (b)After 14

2.6 Scheme representation of microwave assisted method 19

2.7 Schematic representation of the microwave assisted method to 19

2.8 A typical hydrothermal autoclave 21

2.9 Illustration of CQDs formation from orange juice via 21

2.11 Basic process of adsorption 26

2.12 Schematic Diagram and Steps involved in Heterogeneous 30

2.13 Geometric view of Central Composite Design for three factors 39

3.1 Research Methodology Flow Chart 45

3.2 Washed OPEFB in ethanol/hexane mixed solvent 46

3.3 OPEFB fibers after bleaching treatment 47

3.4 Alkaline treatment of bleached fibers 48

3.5 Extracted cellulose 48

3.6 Teflon-lined stainless steel autoclave 49

3.7 Calibration curve of MB dye 52

3.8 Adsorption experiment for MB removal (a) Before (b) After. 53

3.9 Photocatalytic adsorption of MB on cellulose-based CQDs 54

4.1 Plot of correlation between predicted and experimental values 61

4.2 (a) Response surface and (b) Contour for MB percentage 62