PHOTOCATALYTIC ADSORPTION PROCESS USING

SYNTHESIZED CELLULOSE BASED QUANTUM-

DOTS ADSORBENT

By

WONG ZHI CHENG

A Report Submitted in Partially Fulfilment of the

Requirement for the Degree of BEng (Hons) Chemical
Engineering

Faculty of Engineering, Technology & Built Environment

UCSI University

May 2018

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 ACKNOWLEDGEMENT

First of all, I would like to take this opportunity to express my utmost gratitude
to my supervisor, Asst. Prof. Dr, Ng Ching Yin for her patience, valuable guidance and
advice throughout the whole project. Her encouragement, support, and inspiring
knowledge was much appreciated. I am grateful to be under her supervision and would
like to acknowledge her contribution during my final year project.

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

with a comfortable environment and instruments needed to carry out my final year
project. I also would like to take this opportunity to express uncountable thanks to the
lab officers for their help throughout the experimental work in indicating the equipment
and devices that I required and in making the setup for the process.

Last but not least, I would like to thank to my parents for their sincere supports,
invaluable assistance 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.

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 DECLARATION OF ORIGINALITY & EXCLUSIVENESS

I hereby declare that the dissertation entitled “REMOVAL OF DYE USING

QUANTUM-DOTS ADSORBENT SYNTHESIZED FROM CELLULOSE” is
based on my original work except for quotations and citations which have been
duly acknowledged. I also declare that it has not been previously or
concurrently submitted for any other degree at UCSI or other institutions.

___________________________
WONG ZHI CHENG
1001436835

Date:

Supervised by:

____________________________
ASST. PROF. DR. NG CHING YIN

Date:

ii
ABSTRACT

iii
 TABLE OF CONTENT

Page
ACKNOWLEDGEMENT i
ABSTRACT iii
TABLE OF CONTENT iv
LIST OF TABLES viii
LIST OF FIGURES ix
LIST OF EQUATIONS x
CHAPTER 1 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 2 8
2.1 OIL PALM 8

2.1.1 Oil Palm Empty Fruit Bunch (OPEFB) and its structure 9

2.2 CELLULOSE 10

2.2.1 Structure 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

2.3.3 Application of Carbon Quantum Dots 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

iv
 2.5.1 Dye 22

2.5.2 Current technologies for dye removal 23

2.6 DYE REMOVAL BY ADSORPTION 24

2.7 ADSORPTION ISOTHERM 27

2.7.1 Langmuir Isotherm 27

2.7.2 Freundlich Isotherm 29

2.8 ADSORPTION KINETICS 30

2.8.1 Pseudo-first-order kinetic model 30

2.8.2 Pseudo-second-order kinetic model 31

2.9 FACTOR AFFECTING THE PERFORMANCES OF ADSORPTION 31

2.9.1 Effect of pH 31

2.9.2 Effect of adsorbent dosage 32

2.9.3 Effect of contact time 32

2.10 RESEARCH SURFACE METHODOLOGY (RSM) 33

2.10.1 Central Composite Design (CCD) 33

2.10.2 Box-Behnken Design 34

2.11 CHARACTERIZATION TECHNIQUES 36

2.11.1 Scanning Electron Microscope (SEM) 36

2.11.2 UV-Vis 37

CHAPTER 3 38
3.1 MATERIALS AND CHEMICALS 38

3.2 EQUIPMENT 39

3.3 RESEARCH METHODOLOGY FLOW CHART 39

3.4 EXTRACTION OF α-CELLULOSE FROM AGROWASTE-OIL PALM

EMPTY FRUIT BUNCH (OPEFB) 41

3.4.1 Preparation of Palm Oil Empty Fruit Bunch (POEFB) 41

3.4.2 Pre-treatment of Palm Oil Empty Fruit Bunch (POEFB) 41

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 3.4.3 Bleaching Treatment 42

3.4.4 Extraction of alpha-cellulose 42

3.5 SYNTHESIS OF CARBON QUANTUM DOTS FROM EXTRACTED

ALPHA-CELLULOSE USING HYDROTHERMAL SYNTHESIS METHOD 44

3.5.1 Analysis of synthesised CQD 44

3.6 DYE REMOVAL 45

3.6.1 Calibration of Methylene Blue Solutions Standard Curve 45

3.6.2 Batch Adsorption Experiment 46

3.7 ADSORPTION PERFORMANCE USING RESEARCH SURFACE

METHODOLOGY (RSM) APPROACH 47

3.8 ISOTHERM ANALYSIS OF ADSORPTION 48

3.8.1 Langmuir isotherm model 49

3.8.2 Freundlich isotherm model 49

3.8.3 Temkin isotherm model 50

3.9 KINETICS STUDIES OF ADSORPTION 50

3.9.1 Pseudo-first-order kinetic model 50

3.9.2 Pseudo-second-order kinetic model 51

CHAPTER 4 53
4.1 EXTRACTION OF CELLULOSE 53

4.1.1 Percentage Yield of Cellulose 53

4.1.2 Analysis of Cellulose Content 53

4.2 ADSORPTION PROCESS ON REMOVAL OF DYE BY CELLULOSE 54

4.2.1 RSM Modelling 54

4.2.2 Isotherm Analysis 62

4.2.3 Kinetics Analysis 62

4.3 CQDs CHARACTERIZATION 62

4.4 USE OF CQDs ADSORBENT FOR DYE REMOVAL 62

4.4.1 RSM Modelling 62

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 4.4.2 Isotherm Analysis 66

4.4.3 Kinetics Analysis 66

4.5 COMPARISON OF CELLULOSE ADSORBENT AND CQDs ADSORBENT

IN DYE REMOVAL 67

vii
LIST OF TABLES

viii
LIST OF FIGURES

ix
LIST OF EQUATIONS

x
 CHAPTER 1

INTRODUCTION

1.1 INTRODUCTION

Nowadays, over thousands of various dyes are widely used in manufacturing,

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

Various methods such as coagulation/flocculation (Fosso-Kankeu et al., 2017),

membrane filtration (Melbiah et al., 2017), advanced oxidation (Miodrag, 2014),
electrolysis (Shen et al., 2001) and adsorption (Pang and Abdullah, 2013) have been
used in treating dye containing water. Adsorption has been broadly employed due to its
low costs, effectiveness and simple procedure to remove dyes from wastewater without
the generation of any by-products (Qiao 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, palm oil biomass is considered as the most

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abundant renewable resources, thus, palm oil empty fruit brunch (POEFB) agro-waste
will be used as a source for α-cellulose extraction in this study.

Cellulose is an important element of plant’s main cell wall. It is an organic

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

Quantum dots are referred as a high-quality colloidal semiconductor

nanocrystals, which have gained crucial attentiveness due to their size-tunable
properties and flexibility throughout the past several decades (Qian et al., 2006). The
number of atoms range from 1000 to 10000 in a quantum dot, causes it to be neither a
solid substance nor a single molecular entity. Recently, several methods have been
introduced to produce quantum dots and several factors can be controlled such as the
size of the QD particle, solubility and emission properties. (Njuguna et al., 2014)

The successful of producing quantum dots will definitely bring the cellulose
application to a higher level in cellulose study. To date, quantum dots are recognized as
a useful tool in monitoring the cancer cells, produces inexpensive white LEDs,
photovoltaic solar cells (Karmakar, 2015). In this study, dye is chosen as a first waste
element in determining the effectiveness of using quantum dots synthesized from
cellulose. This study can act as a first and primarily in nanotechnology research.

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1.2 PROBLEM STATEMENT

The contamination of water due to dye pollution has aroused the concern of the
global community. Hence, efficient dye removal application is a growing concern in
water resources management around the world. Adsorption on activated carbon can be
known as one of the best and widely used method for dye removal. However, it is very
costly. Therefore, there is a need to extract low-cost adsorbent from local biomass
resources that can be obtained readily. New inexpensive, easily obtainable and highly
effective adsorbents are still needed.

In order to synthesis adsorbent that is more cost-effective, environmentally

friendly, and sustainable to be used in dye removal application, it is important to
produce adsorbent from inexpensive agriculture, agro-wastes, or wood. To date,
researchers have reported that palm oil empty fruit bunch (POEFB) can be used as an
effective adsorbent for removal of dyes. According to Hameed and El-Khaiary (2008),
POEFB has been successfully utilized as a low-cost adsorbent for the removal of
malachite green, and the adsorption results were investigated by adsorption isotherm.
Ofomaja and Ho (2007), also discovered the potential of POEFB as a good adsorbent
for the removal of anionic dyes. Besides, several modification techniques on POEFB
have been studied as an effective adsorbent for dyes removal from wastewater. For
example, Shanmugarajah et al. (2019) isolated nanocrystalline cellulose from POEFB to
study its methylene blue adsorption behaviour, and the modification was successful
where 144.93 mg/g of maximum monolayer adsorption capacity was determined.

Large specific surface area and high number of adsorption sites are absolutely
necessary for adsorption treatments in order to remove dyes impurities from
wastewater. Over the past decades, scientists have reported that nanosized adsorbents
are being used progressively in dye removal due to their greater active sites, higher
surface area and good adsorption efficiency (Savage and Diallo, 2005). Quantum dots
(QD) which was first discovered in glass crystals in 1980 by a Russian physicist,

3
Ekimov whose has brought the promotion in nanotechnology research (Ekimov and
Onoshchenko, 1982). According to Bajorowicz et al. (2018), QDs are the new category
of nano-dimension materials which have high functionalization possibility. QDs have
fascinated significant interest for their large surface to volume ratio and the quantum
confinement effects which resulting in extraordinary structural, optical and electronic
properties. Due to these properties, QD have been used commonly as an adsorbent to
remove organic dyes (Bajorowicz et al., 2018). Several researches have been reported
that carbon sources can be used to prepare carbon quantum dots (CQDs). Hence,
cellulose molecule that contains a large amount of hydroxyl and ether groups provide
the fundamental and structural basis for the formation of CQDs (Wu et al., 2017). The
existence of the great number of oxygen-containing functional groups such as -OH,
C=O, -NH2 and -COOH on the surface of CQD has caused high solubility in water and
functionalization ability with various substances (Zuo et al., 2015).

To date, various methods to synthesis QDs from natural resources have been
developed, For example, Pires et al. (2015) have reported that raw cashew gum is used
as precursor to obtain CQDs via microwave assisted method. Besides, Sahu et al.
(2012) synthesised CQDs using orange juice with ethanol via hydrothermal technique.
Grass was also used as precursor to synthesis quantum dots through hydrothermal
treatment (Liu, et al., 2012) However, no studies have been reported on the use of
POEFB for the synthesis of QDs and to be used in the application on dye removal.
Thus, this study is undertaken to investigate the adsorption efficiency using quantum
dots adsorbent for dye removal. The effects of pH, contact time and initial dye
concentration are evaluated by batch process with Research Surface Methodology
Approach. Investigation on adsorption isotherms and kinetics are also carried out.

4
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 palm oil empty fruit bunch
(POEFB).

ii. To synthesis quantum dots adsorbent from extracted cellulose.

iii. To investigate the performance of cellulose-based quantum dots in dye

removal application using RSM approach.

1.4 SCOPE OF STUDY

This study was firstly focus on the extraction of cellulose from agriculture wastes
which are palm oil empty fruit bunch (POEFB) that were discharged as biomass from
palm oil production. Pre-treatments of POEFB 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 POEFB.

The second part of this research was then proceeded to synthesis quantum dots
adsorbent from extracted cellulose. Hydrothermal method was conducted by adding

5
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 adsorption experiment was conducted to

investigate the performances of quantum dots adsorbents in dye removal application. In
this experiment, methylene blue dye was used as adsorbate. The adsorption capacities of
the methylene blue dye were determined and compared between cellulose adsorbent and
CQDs adsorbent. In adsorption studies, there were several factors taken into
consideration that will affect the adsorption efficiency in dye removal, for example, the
effect of pH, contact time, and initial concentration of dye. Best parameters for better
controlling of the adsorption process in dye removal were determined. Beside, best
fitting of adsorption isotherms were determined to identify the kind of interaction
between the adsorbate and adsorbent in dye removal application. The adsorption
kinetics which demonstrates the rate of transport of the dye particles from solution to
the surface of adsorbent were also investigated by pseudo-first order and pseudo-
second-order kinetic models.

1.5 ORGANIZATION OF THESIS

There are five chapters in this thesis and each of the chapter is focusing on
specific discussion on different aspects throughout the research project.

Chapter I describes the overview of this study “Use of Nanocellulose Quantum-

dots functionalized adsorbent for dye removal”. An introduction about the current water
pollution resulted from dye are presented. The problem statement further describes the
needs to functionalize nanocellulose into quantum dots which will be able to produce a
more efficient adsorbent for dye removal from wastewater. Besides, the objectives of

6
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 and classification of cellulose and nanocellulose.
The details and types of quantum dots, preparation and functionalization methods of
quantum dots, as well as further reviews on the application of quantum dots
functionalized materials are also illustrated. Other methods of dye removal are briefly
elaborated and the mechanism of adsorption method is explained. Lastly, the process
parameters that will affect the adsorption efficiency are described.

Chapter III provides the details of all the chemicals, equipment and methodology
in this research. Firstly, chemicals and equipment required in this study are listed down
and explained along with their respective purpose. A process flow chart is also
performed. The subsequent sections describe the procedures to conduct the experiment,
including extraction of nanocellulose from POEFB using acid hydrolysis,
functionalization of nanocellulose into quantum dots using microwave assisted method
and the analysis techniques to verify the quantum dots. Lastly, adsorption experiments
will be carried out to investigate the performances of adsorbent used in dye removal.

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 CHAPTER 2

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 palm oil
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 palm oil 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
MF 7.72
Palm Oil Mill Effluent (POME) 3.0

2.1.1 Oil Palm Empty Fruit Bunch (OPEFB) and its structure

8
 Oil palm empty fruit bunch (OPEFB) is one of the main solid wastes from palm
oil 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
palm oil refineries where some quantity of this is used as fuel, while the rest is left
unexploited (Abdul et al., 2012).

OPEFB is composed mainly of cellulose (41.3–46.5%), hemicellulose (25.3–

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

FIGURE 2.1 Schematic drawing of cell wall hierarchical structure of OPEFB [Adapted
from Kolakovic et al., 2012]

The existence of amorphous and crystalline regions is shown in lateral fiber

structure. This high in cellulose content properties of OPEFB represents quality as
potential natural fiber resource. Moreover, OPEFB consists of 42% C, 0.8% N, 0.06%

9
P, and 2.4% K and 0.2% Mg (Krause, 1994). Thus, exploring the beneficial and
practical oil palm biomass utilization as reinforcement in natural fiber based composites
will help to reduce the environmental problems issue as associated with the oil palm
wastes disposal in industry (Abdul Khalil et al., 2012a,b)

2.2 CELLULOSE

Cellulose is a natural occurring linear polymer of anhydroglucose that is found

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

2.2.1 Structure of cellulose

The native cellulose molecule consists of linear glucan chains with repeating
(1→4)- β-glucopyranose units. Cellobiose is the dimer of cellulose and it is the
repeating unit of the polymer, as shown in Figure 2.2. The degree of polymerisation is
determined by the number of single anhydroglucose units, and it varies depending on
the origin of cellulose. 30 anhydroglucose units give the polymer the characteristic
structure and properties of cellulose (Nehls et al. 1994) but the degree of polymerisation
can be up to more than 15 000 monomers.

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 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. Alkali treatment is
considered as most commonly used method for delignification of lignocellulosic
materials (Thomas et al., 2011). This treatment is applied to disrupt the lignin structure
and to allow the separation of the structural linkages between lignin and carbohydrates.
Chieng et al. (2017) has successfully extracted cellulose fibers from Oil Palm Mesocarp
Fiber (OPMF), where the OPMF was treated in reflux condition with 4 wt% NaOH
solution at 80℃. Then, the alkali-treated fibers were bleached three times to whitening
the products. According to Sun et al. (1998), cellulose was isolated from dewaxed
wheat straw after alkali extraction using sodium hydroxide solution.

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 Besides, Bhattacharya et al. (2008) isolated cellulose microfibers from
sugarcane bagasse (SCB) using a conventional pulping process to eliminate lignin and
hemicelluloses, mechanical homogenization, and acid hydrolysis. Hydrolysis of the
cellulose fibers with 60% (v/v) sulfuric acid for 2.5 hour at 60 ºC was optimum and
resulted in the removal of most of the amorphous domains without any significant
damage to the crystal structure. Furthermore, biological treatment was also used by
Kikuchi et al. (2002) with molecular-genetically bred Coprinus Cinereus monokaryotic
strains to isolate cellulose efficiently from rice straw.

2.3 QUANTUM-DOTS

Quantum dots (QDs) is first discovered by a Russian physicist named Ekimov in

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

FIGURE 2.3 Scheme of quantum dot structure

[Adapted from Bajorowicz et al., 2018]

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

FIGURE 2.4 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

13
detection (Gao et al., 2009), several types of QDs have been reported, for example,
silicon QDs, carbon quantum dots (CQDs), graphene QDs (GQDs), Ag2Se, Ag2S, InP,
CuInS2/ZnS (Zhu et al., 2013). Among these QDs, carbon quantum dots are the most
popular QDs due to their properties of non-toxic, excellent solubility in water, lower
cost and sustainable sources (Bajorowicz et al., 2018).

2.3.1 Carbon Quantum Dots

Carbon quantum dots (CQDs), which are also recognized as carbon dots (CDs),
are firstly introduced in 2004 during the purification of single walled carbon nanotubes
(Xu et al., 2004). The CQDs can be extracted from natural carbon sources (Pires et al.,
2015). Therefore, CQDs can be synthesised from natural resources which are cost-
effective and environmentally friendly. It has a spherical shape with the diameter less
than 10nm, and consisting numerous oxygen-containing functional groups such as -OH,
-COOH and -NH2 on the surfaces (Cao et al., 2007). The occurrence of functional
groups has provided the potential for further functionalization via surface passivation
agent compared to other carbon materials, which endowing different functional
properties (R. Wang et al., 2017).

FIGURE 2.5 Illustration of CDs (a)Elementary CDs; (b)After functionalization with

surface passivation reagents [Adapted from Zuo et al., 2015]

14
 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 synthesised “nitrogen doped carbon quantum dots for efficient removal of
methylene blue dye pollutant from contaminated water”, and Mallakpour and
Behranvand (2018) has proven the “synthesis of carbon quantum dots from sustainable
materials using ultrasonic waves in application for methylene blue removal”. This is due
to their high specific surface area, low toxicity, great water solubility, good
biocompatibility (Guo et al., 2017), low cost (Mallakpour and Behranvand, 2018) and
easy functionalization (Pires et al., 2015). Based on the extraordinary properties of
CQDs mentioned, they can be considered as a favourable material for removal of a
diversity of inorganic and organic pollutant.

2.3.2 Sources of Carbon Quantum Dots

Carbohydrate-based resources such as glucose, cellulose, starch and other raw

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

2.3.3 Application of Carbon Quantum Dots

Table 2.2 has shown the synthesis of CQDs by using different type precursors
that perform different application.

15
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 Methylene blue 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 Methylene blue removal (Tadesse et al., 2018)

2.4 SYNTHESIS OF CARBON QUANTUM DOTS

The CQDs which can be obtained from different carbon sources are synthesised
via ‘top-down’ and ‘bottom-up’ strategies. Top-down strategies state that where the
carbon sources were broken down using different methodologies such as
electrochemical oxidation, laser ablation, arch discharge and ultrasonic synthesis (D. da
Silva Souza et al., 2018). Whereas for bottom-up strategy, the CQDs can be obtained
from small precursor molecules such as biomass sources chitosan or lignocellulosic
materials by different heat treatments, for example, hydrothermal treatment or
microwave-assisted methods. (D. da Silva Souza et al., 2018). Most of the CQDs were
synthesised through the bottom-up strategies due to the availability of natural carbon
sources as the precursor molecules, easy operation of the techniques used and only few
reaction parameters such as temperature and pressure have to be controlled. Table 2.3
shows the methods for CQD synthesis with comparison of advantages and
disadvantages.

16
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 X. Yu et al (2013)

oxidation Large scale distribution.
production;
No elaborate
equipment.

Ultrasonic Easy operation Instrument wastage; Zhuo et al. (2012)

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

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.

17
2.4.1 Microwave Assisted Method

Microwave is a technique that utilizes electromagnetic waves with a broad

wavelength range of 1mm to 1m, corresponding to the frequency of 30GHz to 0.3 GHz,
which induces heat energy to breakdown the chemical bonds of a molecule (R. Wang et
al., 2017). Traditionally, a conventional hydrothermal synthesis which used water bath
or oil bath takes much longer time for transferring energy into the compound (Kappe,
2004). Thus, the synthesis of CQDs by microwave assisted methods is more preferable
due to higher reaction rate, lower energy usage as compared to conventional
hydrothermal synthesis. This has shown its advantages which allows quicker reactions
by heating the precursors on the molecular level through absorption of microwave
energy (Lovingood, 2010).

Zhu et al. (2009) have firstly reported an efficient and simplified microwave
assisted method to synthesis CQDs with outstanding water solubility using only few
minutes. Carbohydrate was used as the carbon source and PEG200 as the passivating
agent, both were mixed with the water which acts as solvent and gradually changed
from colourless to dark brown under 500 W of microwave power for 2 – 10 minutes.
Figure 2.5 has shown the synthesis of CQDs from carbohydrate and polyethylene glycol
via microwave assisted method.

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

18
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 as shown in figure 2.7. Both
produce heat by disturbance of weak hydrogen bonds enhanced by the dipole rotation of
the molecules without altering the molecular structure (Christen, 2002). The greater the
dielectric constant and polarity of the solution, the better the absorption of microwave
energy, hence the more optimal the heating (Christen, 2002). Therefore, water which is
polar, is an excellent 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.

19
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), orange juice was used as carbon
source for the green method of synthesis of CQDs as shown in Figure 2.9. The orange
juice was mixed with ethanol and then heated at 120°C for 150 min until a dark brown
solution formed in an autoclave.

FIGURE 2.9 Illustration of CQDs formation from orange juice via hydrothermal
treatment.

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

In comparison with other methods, the hydrothermal strategy has many

advantages. For example, it is environmentally benign because only water is used as the
reaction solvent. The reactions are generally carried out below 250 °C, which avoid
some problems encountered with high temperature processes such as high energy cost,
stress-induced defects caused by phase transformations that occur as the sample is
cooled to room temperature (Adschiri et al., 2013). Another main advantage of this
method is the easy combination with other techniques such as ultrasound, microwave,
and optical radiation, which can significantly improve the reaction kinetics and favour
the formation of new phase structures.

21
2.5 DYE REMOVAL

2.5.1 Dye

Dyes are basically organic compounds that contain colours and widely used in
industries to colour their products results in generating a large amount of coloured
wastewater (Kandisa et al., 2016). They can be obtained from animals, vegetables or
mineral origin, with no or very little processing. It consists of chromophore that
provides the colour and the functional groups which bonds dye onto the materials (M,
Stephenson and Judd, 1994). Dyes are difficult to be eliminated through conventional
methods of anaerobic digestion due to their chemical structure which are unaffected to
aerobic digestion and not biologically degradable (Robinson et al., 2001). If the dyes
are not removed from wastewater effluent and release to the environment, it will cause
pollution as they are highly toxic, mutagenic and carcinogenic. These toxic properties
has brought severe effects to humans, such as malfunction of the body system (Amran
et al., 2011; Kandisa et al., 2016). Dyes can be categorized into cationic, anionic, and
non-ionic dyes. Table 2.5 has shown the dyes classification.

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, Reactive
Direct dyes 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 Current technologies for dye removal

22
 There are various treatment technologies ranging from physical, chemical, and
biological methods that can be applied to remove dye before wastewater are allowed to
be discharged into the environment without causing any harms. However, not all
processes work for all coloured wastewaters. Some studies have shown the successful
decolorization using different treatment method despite the fact that the treated
wastewater still has low colour intensity. Only a few cases have been reported when
they succeed in decolorization. As a whole, each of the technique has its own
advantages and disadvantages that need to be considered as shown in Table 2.6.

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
flocculation be removed effectively
Chemical oxidation Simplicity of application
Ozonation Less wastewater and sludge
produced
Photochemical Sludge free;
odours can be reduced
Photocatalytic Different kinds of dyes can
be eliminated effectively
Radiolysis High efficiency;
Sludge free
Electrochemical No consumption of
destruction chemical
Expensive chemicals reagent;
pH modification is needed
Sludge is produced;
Difficult in handling and
disposal
Agents need to be activated
Shorter half-life of 20 mins
Formation of by-products
By-products are produced;
Difficult to penetrate UV light
in the water
Not suitable for dispersed
dyes;
Shorter half-life
High flow rates

TABLE 2.5 - Continued

Technology Advantages Disadvantages

23
 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 DYE REMOVAL BY 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. The one that deposited at the surface is called adsorbate and the one on which
adsorption happens is adsorbent (A. Da˛browski, 2001). The size of the pores
determines the availability of adsorbate molecules into the internal adsorption surface of
adsorbent, therefore the pore sizes distribution is an important property for
characterizing adsorptivity of the adsorbents. Hence, a good adsorbent should have the
properties of high porous structure with liquid-solid intermolecular forces of attraction

24
(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 2.7 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
Dyes Sorbent Capacity References
(mg/g)
2,4-dinitrophenylhydrazine Bamboo waste; activated 884.96 Nwabanne and Mordi,
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; activated 221.23 Demirbas et al., 2008
carbon
Basic Blue 3 Hevea brasiliensis; seed 227.27 Maneed and Daud,
coat 2008
Basic Red 13 Tree fern 408.00 Ho et al., 2005
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

TABLE 2.6 - Continued

Sorption
Dyes Sorbent Capacity References
(mg/g)
Methyl violet Sunflower (Helianthus 92.59 Hameed, 2008
annuus L.) seed hull

Mansonia wood sawdust 23.80 Ofomaja and Ho, 2008

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

25
 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 guajava) 295.00 Ponnusami et al., 2008
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
Rhodamine B Rhizopus oryzae 11.25 Das et al., 2008
Parthenium biomass 59.17 Lata et al., 2008

Adsorption can be categorized into two types of mechanism which are

chemisorption and physisorption. 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.
Meanwhile, 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 removal
capacity of dyes through the adsorption is depends on the surface chemistry of the
adsorbent and properties of the dye adsorbate (Noroozi et al., 2007). For example,
higher adsorption efficiency will be obtained by the adsorption between negatively
charged adsorbent and the positively charged dye adsorbate due to the interaction of
electrostatic forces (G. Wang et al., 2017). Moreover, surface area and polarity are the
surface properties to characterize adsorbents. High adsorption efficiency can be
obtained by using adsorbent of high specific surface area, but the formation of a large
internal surface area in a limited volume unavoidably gives rise to large numbers of
small sized pores between adsorption surfaces (Suzukl, 1990).

2.7 FACTOR AFFECTING THE PERFORMANCES OF ADSORPTION

26
2.7.1 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 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.

2.7.2 Effect of adsorbent dosage

Usually, the dye removal efficiency increases when the dosage of adsorbent
used increases. This is due to the number of adsorption sites on the surface of the
adsorbent which will be enhanced by increasing the dose of the adsorbent. Moreover,
the effect of adsorbent dosage gives an indication of the maximum percentage of dye
adsorption with the least amount of adsorbent”(Yagub et al., 2014).

2.7.3 Effect of contact time

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

27
indicates the maximum adsorption capacity of the adsorbents”(Hameed, Ahmad and
Aziz, 2007).

28
2.8 ADSORPTION ISOTHERM

The isotherms of adsorption process are important to identify the adsorption

capacity between adsorbent and adsorbate interaction. Mechanism of adsorption can
also be explained using adsorption isotherm. The surface phase can be characterized
into monolayer or multilayer (Yagub et al., 2014). The uptake behaviour of adsorbate is
described by isotherm model such as Langmuir or Freundlich isotherm analysis in batch
adsorption process. Linear regression analysis can be applied to determine the
parameters of each isotherm and the square of the correlation coefficients (R 2) can be
generated. The value of R2 gives an indication of best fitting isotherm model. The
acceptable range of R2 is 0.95 < R2 < 1.00 and the highest R2 value gives the best-fitting.

2.8.1 Langmuir Isotherm

Langmuir isotherm model was the first isotherm model derived. Langmuir
isotherm model assumes that only homogenous adsorbent surface exists or in other
words, monolayer type of adsorption occurs which is probably reasonable for the
assumption in gas adsorption process (Droste, 1997; Seader and Henley, 2003). At
equilibrium, saturation point was been achieved with no further adsorption process to be
taken place, therefore, it is assumed that only one molecule will be occupied one single
site. Linearized form of Langmuir equation is stated in Equation 2.1.

Equation (2.1):
1 1 1
= +
Qe Q0 Q0 K L C e

Where Qe is the amount of dye adsorbed at equilibrium ove unit mass of sorbent (mg/g),
C eis the equilibrium concentrations of dye, Q0 is the maximum adsorption capacity
(mg/g) and KL is the Langmuir constant (L/mg).

29
 Linear plot of 1/Qe vs 1/Ce will be plotted in order to determine the best fit
isotherm data for the adsorption system. Crucial characteristic of Langmuir adsorption
model was expressed as dimensionless separation factor, RL which can be derived from
Equation 2.2.

Equation (2.2):
1
R L=
1+ K L Co

Where,
C o(mg/L) = Highest concentration of solution
RL = favourable condition of adsorption
KL (L/mg) = Langmuir constant

Overall, RL values indicate the adsorption process to be unfavourable if R L > 1,

linear if RL = 1, favourable if 0 < R L < 1, and irreversible if RL = 0 (Mahida and Patel,
2016).

2.8.2 Freundlich Isotherm

Another popular isotherm model applied to the adsorption process was

Freundlich adsorption isotherm. Freundlich model suggested that sorption process
involved heterogeneous sorption with different classes of adsorption sites ( Hameed et al.,
2007). Freundlich assumes that heterogeneous type of adsorption occurs with non-uniform
distribution of heat over the surface of the adsorbent (Brunauer, 1943). Freundlich isotherm is
expressed as in Equation 2.3 and linearized equation is shown in Equation 2.4.\

Equation (2.3):

Q e =K F C e1 /n

Equation (2.4):

30
 1
ln Q e =ln K F + ln Ce
n

Where,
C e(mg/L) = Equilibrium concentrations of dye
Qe (mg/g) = Adsorption capacity at equilibrium
KF (L/mg) = Freundlich constant
n = 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.

2.9 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.

31
2.9.1 Pseudo-first-order kinetic model

Pseudo-first-order was theorised by Lageegran as shown in Equation 2.5 which

is further integrated as linearized form shown in Equation 2.6 (Azizian, 2004).

Equation (2.5):

d Qt
=k 1 (Q e −Q t )
dt
Equation (2.6):

K1
log(Q e −¿ Q t )=log Q e − t¿
2.303
Where,
K1 (min-1) = Pseudo-first-order rate constant
Qe (mg/g) = Adsorption capacity at equilibrium
Qt (mg/g) = Adsorption capacity at time, t
t (min) = Contact time

Linear plot of log (Qe – Qt) versus t was used in determination of K1 constant
(min-1) and R2 values which indicates the best fitted kinetic model.

2.9.2 Pseudo-second-order kinetic model

Pseudo-second-order kinetics was expressed in Equation 2.7 (Azizian, 2004).

Equation (2.7):

t 1 1
= + t
Qt K 2 Qe Qe
2

32
Where,
K2 (g/mg.min) = Pseudo-second-order rate constant
Qe (mg/g) = Adsorption capaity at equilibrium
Qt (mg/g) = Adsorption capacity at time, t
t (min) = Contact time

K2 can be derived from linear plot of t/Qt versus t.

2.10 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.

2.10.1 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 center point (α, center point created by nominal

33
design). CCD is very important in providing information on the experimental variable
effects and the overall experimental error in a minimum number of runs. However, the
adjustments of level are sometimes difficult to achieve due to the present of star points,
α outside design (Morgan, 1997). The design for CCD with three factors and α star
point were illustrated in Figure 2.8.

FIGURE 2.8 Geometric view of Central Composite Design for three factors (Ferdosian
et al., 2007)

2.10.2 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

34
variables. Table 2 shows the number of experiments for different factors with three
replications.

TABLE
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).

35
2.11 CHARACTERIZATION TECHNIQUES

2.11.1 Scanning Electron Microscope (SEM)

FIGURE 2.10 Typical SEM instrument [Adapted from Swapp, 2010]

One of the most common techniques for surface morphology studies is scanning
electron microscope (SEM), which can give information about the chemical
composition, morphology and different structures in the sample. Instead of a light–beam
which is used as an ordinary light–microscope, SEM produces an electron beam which
is focused by going through both lenses and magnetic fields before it strikes the sample.
Some electrons, but also X-rays, are ejected from the sample. These X-rays and
electrons are collected by a detector which produces an 2D image (Schweitzer, 2010). It
allows for magnification at higher levels, since it has much higher resolution, and it is
easier to have a wider focus for that this type of microscope has a large depth of field
(Schweitzer, 2010). SEM works under vacuum conditions to prevent dust to interfere.
An electron gun generates an electron beam which is focused by condenser lenses and
passed through deflection coils. When the sample is hit by the high intensity electron
beam, information is available from the secondary electrons, X-rays, light and back–
scattered electrons (Swapp, 2010). Depending on which detector is used, different data
is collected and used for gaining information about the sample. Such information is
usually surface topography, morphology, chemical composition, conductivity etc. The

36
resolution can be as good as down to 1 nm. One important factor to consider is the
voltage of the beam. Higher voltage increases the resolution but decreases the surface
sensitivity since the beam penetrates deeper into the sample. 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.

2.11.2 UV-Vis

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 colored metal complexes. In fact, the usage of UV-VIS
can also be interrupted by colored substances that was present in the specific sample
(Zeiner et al. 2016).

37
 CHAPTER 3

RESEARCH METHODOLOGY

This chapter describes the methodologies of the study “Use of Nanocellulose

Quantum-dots functionalized adsorbent for dye removal”. It involves the
functionalization of nanocellulose into quantum dots with microwave assisted methods,
experimental design software used to optimize the experimental parameters and several
analyses. Comparison of adsorption efficiency between nanocellulose and
functionalized nanocellulose 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 3.7 List of materials and chemicals used

Materials/Chemicals Sources
Palm oil empty fruit bunch (POEFB) Ulu Langat Palm Oil Mill Sdn. Bhd.
Distilled water KG02
Filter paper R&M Chemical
Sodium Hydroxide (NaOH) Pellets R&M Chemical
Methylene Blue R&M Chemical
Ethanol R&M Chemical
Hexane R&M Chemical
Glacial Acetic Acid R&M Chemical
Sodium Hypochlorite R&M Chemical
Hydrochloric Acid R&M Chemical

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.

38
 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 CQDs
Surface ζ –Potential Analyser Analysis o CQDs

3.3 RESEARCH METHODOLOGY FLOW CHART

The overall research methodology for this research presented in Figure 3.1.

39
 Start

Pre-treatment of POEFB:
 Size Reduction
 Removal of dirt and waxes using 1:2 v/v ethanol/hexane
 Bleaching treatment
OBJECTIVE I

Alkaline treatment
Extraction of α-cellulose from POEFB
 Type of chemical used: 17.5 wt% NaOH
 Temperature: 80 °C
 Contact time: 30 minutes

Hydrothermal treatment
Synthesis of Carbon Quantum Dots (CQDs) from α-cellulose using
OBJECTIVE II

Teflon stainless steel autoclave

Analysis of produced CQDs¶characterization

 Scanning Electron Microscope (SEM)
 Surface ζ –Potential Analyser

Adsorption experiments
Adsorbate: Methylene blue dyes
Adsorbent: Comparison between cellulose and CQDs

Optimization using RSM Box-Behnken method

- pH: 2, 7, 11
OBJECTIVE III

- Contact time (mins): 10, 25, 40

- Initial concentration of dyes (mg/L): 2, 6, 10

Adsorption Isotherm modelling

 Langmuir isotherm
 Freundlich isotherm

Adsorption Kinetics Studies

 Pseudo-first-order kinetic
 Pseudo-second-order kinetic

End

FIGURE 3.11 Research Methodology Flow Chart

40
3.4 EXTRACTION OF α-CELLULOSE FROM AGROWASTE-OIL PALM
EMPTY FRUIT BUNCH (OPEFB)

3.4.1 Preparation of Palm Oil Empty Fruit Bunch (POEFB)

POEFB were collected from a palm oil mill company which located at Ulu
Langat, Selangor, in Malaysia. POEFB samples were blended into smaller pieces to
enhance the extraction and application of chemical treatments.

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

The blended POEFB samples were washed and soaked in distilled water for 20
hours to remove dust and dirt. Then, the samples were added into ethanol/hexane
solvent at 1:2 v/v ratio for 20 hours to remove impurities such as wax, resins, fats and
oils. The POEFB samples were then rinsed five times with distilled water to remove
solvent traces and dried under the sun until constant weight.

FIGURE 3.12 Washed POEFB in Ethanol/Hexane Mixed Solvent

41
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 POEFB 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 3.13 POEFB 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

42
prepared by dissolving 17.5 g of NaOH pellet in 100 mL of distilled water. Bleached
POEFB fibers were treated with 17.5 wt% NaOH solution at 1:10 g/mL ratio of
bleached fibers to NaOH solution to prevent degradation of cellulose due to severe
condition. The alkaline treatment was carried out at 80℃ for 30 minutes. The treated
fibers were then filtered and washed using distilled water until pH 7 was obtained. The
extracted cellulose were dried under the sun until constant weight.

FIGURE 3.14 Alkaline treatment of bleached fibers

FIGURE 3.15 Extracted Cellulose

43
The percentage of cellulose yield can be obtained by applying the Equation (3.1):

Equation (3.1):
Cellulose weight ( g )
Yield ( % )= x 100 %
Sample weight(g)

3.5 SYNTHESIS OF CARBON QUANTUM DOTS FROM EXTRACTED

ALPHA-CELLULOSE USING HYDROTHERMAL SYNTHESIS
METHOD

The carbon quantum dots (CQDs) were synthesized by hydrothermal method.

Cellulose fibers were dissolved in distilled water and sealed in a Teflon-lined stainless
steel autoclave shown in Figure 3.2 and treated at 180℃ for reactions to occurred. After
the reaction, the autoclave was placed overnight to cool down to room temperature. A
yellow coloured solution was obtained which was filtered to remove the remaining
cellulose fibers. Yellow luminescence emissions colour was observed under the
irradiation of UV light, indicates the formation of CQDs.

FIGURE 3.16 Teflon-lined stainless steel autoclave

3.5.1 Analysis of synthesised CQD

44
 The synthesised CQD adsorbents were characterized to determine the specific
physical and chemical properties using respective techniques listed in table 3.3.

3.6 DYE REMOVAL

3.6.1 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. Calibration graphs of methylene blue was plotted as shown in Figure 3.7 and
Equation 3.2 used to determine the concentrations of dye solutions during adsorption
process.

Dye Calibration Curve

3.00

f(x) = 0.27 x + 0.07

2.50 R² = 1

f(x) = 0.81 ln(x) + 0.4

2.00 R² = 0.88

1.50
ABS

1.00

0.50

0.00
0.00 2.00 4.00 6.00 8.00 10.00 12.00
Conc. of dye (mg/L)

FIGURE 3.17 Calibration Curve of Methylene Blue Dye

Equation (3.2):

45
 mg |−0.0741|
Concentration of unadsorbed MB∈solution ( )=
L 0.2705

3.6.2 Batch Adsorption Experiment

The batch adsorption experiments were carried out with the various
combinations of different factors. 50 mL of methylene blue (MB) solution at different
concentration and 50 mg of adsorbents were added in a beaker and agitated using
magnetic stirrer. The residual concentration of the dye in the filtrate was determined
using a UV-Vis spectrophotometer at λmax of 668 nm.

The percentage removal of dye was calculated using the Equation 3.1:

Equation (3.3):
C o −Ce
Removal ( % )= ×100 %
Co

and the adsorption capacity (Qe) was calculated using Equation 3.2:

Equation (3.4):
Qe = (Co – Ce) x V/m

Where,
Qe (mg/g) = Amount of dye adsorbed onto unit mass of adsorbent at equilibrium
Co (mg/L) = Initial concentrations of dye
Ce (mg/L) = Equilibrium concentrations of dye
V (L) = Volume of dye solution
m (g) = Mass of adsorbent

46
3.7 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 3.8 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 3.9 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
(Khajeh 2009) has proven that whenever a system of study that involves 3
significant factors to be as the variables X 1, X2 and X3, the mathematical relationship of

47
response relating the 3 variables will be represented by the following second -order
polynomial model expressed as in Equation (3.3):

Equation (3.5):

Y = β0 + β 1 X 1 + β 2 X 2 + β 3 X 3 + β 12 X 1 X 2 + β 13 X 1 X 3 + β 23 X 2 X 3 + β 11 X 21 + β 22 X 22+ β33 X 23

Where,
Y = Predicted response
β0 = Constant
β1, β2 , β3 = Linear coefficient
β 11 , β22 , β 33 = Quadratic coefficient
β 12 , β 13 , β 23 = Interaction coefficient
X1 , X2 , X3 = Independent variables

3.8 ISOTHERM ANALYSIS OF ADSORPTION

The adsorption data will be analysed by fitting to isotherm models which are
Langmuir, Freundlich, and Temkin models. This is to reveal the interactive behaviour
between the adsorbent and adsorbate molecules. The isotherm experiments will be
carried out at optimum parameters determined.

3.8.1 Langmuir isotherm model

Langmuir stated that adsorption took place on the homogeneous surface of

adsorbent with identical binding sites and there is no transmigration between the
adsorbed species occurs. The Langmuir mathematical equation is stated in equation 3.6.

48
Equation (3.6):
Ce Ce 1
= +
Qe Q0 Q0 K L
Where,
C e(mg/L) = Equilibrium concentrations of dye
Qe (mg/g) = Amount of dye adsorbed onto unit mass of adsorbent at equilibrium
Q0 (mg/g) = Maximum adsorption capacity
KL (L/g) = Langmuir constant

3.8.2 Freundlich isotherm model

Freundlich model assumes that the uptake of adsorbate occurs on a

heterogeneous adsorbent surface. The mathematical equation of Freundlich isotherm is
expressed as in equation 3.7.
Equation (3.7):
Q e =K F C e1 /n
Where,
C e(mg/L) = Equilibrium concentrations of dye
Qe (mg/g) = Amount of dye adsorbed onto unit mass of adsorbent at equilibrium
KF (L/g) = Freundlich constant
n = Freundlich exponent which calculated from the slopes of plot

3.8.3 Temkin isotherm model

49
 Temkin isotherm stated that the heat of adsorption of all molecules in layer
decreases linearly with coverage of adsorbent surface due to adsorbate–adsorbent
interactions. The equation of Temkin isotherm is expressed in equation 3.8.
Equation (3.8):
RT
Qe = ¿
bT
Where,
R (J/mol K) = Gas constant
T (K) = Absolute temperature
AT (L/g) = Equilibrium binding constant
bT (kJ/mol) = Temkin constant related to the heat of adsorption

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.

3.9.1 Pseudo-first-order kinetic model

The linearized mathematical form of pseudo-first-order model is expressed in

equation 3.9.

Equation (3.9):
k1
log ( Q e −Q t )=logQ e − (t)
2.303
Where,
K1 (min-1) = Pseudo-first-order rate constant
Qe (mg/g) = Amount of dye adsorbed onto unit mass of adsorbent at equilibrium
Qt (mg/g) = Amount of adsorbate on the adsorbent surface at time, t

50
t (min) = Contact time

3.9.2 Pseudo-second-order kinetic model

The linearized mathematical form of pseudo-second-order model is expressed in

equation 3.10.
Equation (3.10):
t 1 t
= +
Qt K 2 Qe Qe
2

Where,
K2 (gmg-1min-1) = Pseudo-second-order rate constant
Qt (mg/g) = Amount of adsorbate on the adsorbent surface at time, t
Qe (mg/g) = Amount of dye adsorbed onto unit mass of adsorbent at equilibrium
t (min) = Time

51
 CHAPTER 4

RESULTS AND DISCUSSION

4.1 EXTRACTION OF CELLULOSE

4.1.1 Percentage Yield of Cellulose

The yield of cellulose extracted from the bleached OPEFB was measured after
the alkaline treatment. The average percentage yield of cellulose was ranged from 48%
to 62%, which the average yield percentage of 53%. However, this value is only
indicative since the actual yield strongly depends on the preparation conditions and pre-
treatment such as filtration, which inevitably induces loss of material inherent to this
process.

4.1.2 Analysis of Cellulose Content

52
4.2 ADSORPTION PROCESS ON MB REMOVAL BY CELLULOSE

4.2.1 RSM Modelling

The Box-Behnken model of RSM was employed in these experiments to obtain

a polynomial model from 13 experiment design runs with one centre point. The ranges
and levels of the three independent variables such as contact time (min), pH and initial
concentration of methylene blue (mg/L) were investigated as shown in TABLE 3 .9.
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 .10.

TABLE 4.10 Box-Behnken design matrix of three factors along with experimental
and predicted responses for methylene blue dye removal

Experimental Factors Response (MB Removal Percentage)

Run
X1 X2 X3 Experimental (%) Predicted (%)
1 10 3 6 83.04 81.64
2 25 7 6 92.25 92.10
3 10 7 10 94.45 93.92
4 40 3 6 79.61 79.95
5 40 7 2 73.94 74.38
6 25 7 6 92.08 92.10
7 25 7 6 92.08 92.10
8 10 11 6 92.46 92.03
9 25 3 10 79.00 80.88
10 25 3 2 65.00 64.04
11 10 7 2 73.25 75.58
12 25 11 10 92.31 93.20
13 40 11 6 89.94 91.25
14 40 7 10 95.08 92.65
15 25 11 2 75.38 73.42
Note. X1: Contact Time (min), X2: pH, and X3: Initial concentration of MB (mg/L)

53
 The regression equation obtained after analysis of variance gives the level of
adsorption of dye as a function of different contact time (min), pH, and initial
concentration of methylene blue (mg/L). All terms regardless of their significance are
included in the following equation:

Equation (4.1):

MB Removal % (coded) = 36.037 – 0.1059X1 + 6.2947 X2 + 8.0863 X3 + 0.0008 X12 –

0.3792 X22 – 0.5093 X32 + 0.0038 X1X2 – 0.0003 X2X3 + 0.0459 X2X3

where X1, X2 and X3 are the coded values for the three variables, i.e. contact time (min),
pH, and initial concentration of MB (mg/L), respectively.

Table 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. The F-value of a factor is used to measure the
assessment of the variance which is related to that factor and the residual variance. This
value is calculated by dividing the mean square of the factor by the residual mean
square. In most cases, in order to realise the configuration of interactions among the
variables as the criteria, the P-value and F-value can be applied. The corresponding
variables 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, the model F-value was 28.5, and the low
probability value (0.001), which was less than P-value at the 95% confidence limit,
verified that the model terms were significant, and all the coefficients were highly
important for removal of MB. It shows that the linear effects and quadratic effects of
pH (X2, X22) and initial concentration of MB (X3, X32) were significant except the
interaction terms of contact time. Hence, the contact time did not give an effect to
remove the methylene blue by cellulose adsorbent. It might due to the leaching effect.

54
 TABLE 4.11 ANOVA for the response surface quadratic model

Mean P-Value
Model Terms Sum of Square F-value
Square Prob>F
Regression 1272.34 141.371 28.5 0.001
       
X1 0.56 0.565 0.11 0.749
X2 134.9 134.898 27.19 0.003
X3 260.09 260.085 52.43 0.001
2
X1 0.13 0.132 0.03 0.877
X22 135.89 135.89 27.39 0.003
2
X3 245.17 245.17 49.42 0.001
X1X2 0.21 0.21 0.04 0.845
X1X3 0 0.001 0 0.989
X2X3 2.16 2.157 0.43 0.539
       
Residual Error 24.8 4.961    
Lack of fit 24.78 8.262 892.48 0.001
Pure Error 0.02 0.009    
Cor Total 1297.14      
2
R 0.9809      
2
R (adjusted) 0.9465      
Note. X1: Contact Time (min), X2: pH, and X3: Initial concentration of MB (mg/L)

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 methylene blue by using the cellulose adsorbent. The parity plot shows

55
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.

Predicted vs Experimental Values for MB Removal Percentage

95.00

90.00
Predicted (%)

85.00

80.00

75.00
75.00 80.00 85.00 90.00 95.00 100.00

Experimental (%)

FIGURE 4.18 Plot of Correlation between Predicted and Experimental values for
MB Removal Percentage by Cellulose Adsorbent

4.2.2 Effect of Experimental Parameters on MB Removal

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. When a circular 3D response of the surfaces
was found, the interaction between the related variables was negligible. 2D contour and
3D surface plots for the predicted response were analysed.

56
 (a) Surface Plot of MB Removal % vs pH, Contact Time

Hold Values
Initial C onc. of MB 6

95

90
MB Removal %
85
10
80 8
6 pH
10 4
20
30
40
Contact Time

(b) Contour Plot of MB Removal % vs pH, Contact Time

11
MB
Removal
10 %
< 82
9 82 – 84
84 – 86
86 – 88
8 88 – 90
90 – 92
92 – 94
pH

7
> 94

6 Hold Values
Initial C onc. of MB 6

3
10 15 20 25 30 35 40
Contact Time

FIGURE 4.19 (a) Response surface plots and (b) Contour for MB removal
percentage by cellulose as a function of pH and Contact time [Condition: initial
concentration of MB = 6 mg/L]

57
 (a)
Surface Plot of MB Removal % vs Initial Conc. of MB, Contact Time
Hold Values
pH 7

96

88
MB Removal %

80
9

6
Initial C onc. of MB
10 3
20
30
40
Contact T ime

(b) Contour Plot of MB Removal % vs Initial Conc. of MB, Contact Time

10
MB
Remov al
9 %
< 75
8 75 – 80
80 – 85
Initial Conc. of MB

85 – 90
7 90 – 95
> 95
6 Hold Values
pH 7
5

2
10 15 20 25 30 35 40
Contact Time

FIGURE 4.20 (a) Response surface plots and (b) Contour for MB removal
percentage by cellulose as a function of initial concentration of MB and Contact
time [Condition: pH = 7]

58
(a) Surface Plot of MB Removal % vs Initial Conc. of MB, pH
Hold Values
Contact Time 25

100

90
M B Removal %
80

70 9

6
Initial C onc. of MB
4 3
6
8
pH 10

(b)
Contour Plot of MB Removal % vs Initial Conc. of MB, pH
10
MB
Remov al
9 %
< 65
8 65 – 70
70 – 75
Initial Conc. of MB

75 – 80
7 80 – 85
85 – 90
90 – 95
6
> 95

5 Hold Values
Contact Time 25

2
3 4 5 6 7 8 9 10 11
pH

FIGURE 4.21 (a) Response surface plots and (b) Contour for MB removal
percentage by cellulose as a function of initial concentration of MB and pH
[Condition: Contact time = 25 mins]

59
 (a) Effect of pH

The effect of pH was analysed using RSM and the results of contour and
response surface plots and are presented in Figure 4.2 with initial concentration of
methylene blue at 6 mg/L and Figure 4.4 with constant contact time at 25 minutes. From
Figure 4.2 and 4.4, it can be inferred from the plots that the percentage removal of
methylene blue dye from solution onto cellulose adsorbent increased with increasing pH
up to pH 10.5, thereafter, it decreases.

As observed in Table 4.2, the effect of pH on percentage removal of methylene

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

According to Nonviho (2015), cellulose and hemicellulose which contains

hydroxide groups or oxides, charge negatively in aqueous media. Thus, the increase in
pH favours the development of the negative electrical charge of the surface, resulted in
an increase of available binding sites. This negative charge exhibits an electrostatic
attraction with respect to the methylene blue which is a cationic dye. With dominated
negatively charged species responsible for acquiring negative charge on the surface of
the adsorbanet, the increasing electrostatic attraction between positively charged
adsorbate species and negatively charged adsorbent particles would lead to an increased
in dye adsorption (Khatrri et al. 2009). On the other hand, the hydrogen ions that were
positively charged were attached to the surface area of adsorbent. This caused the
surface charge became positive charge and electrostatic repulsion happened because of
the positively charged methylene blue (Nurul et al. 2016). Similar results were also
reported by Abkenar et al. (2015), where pH 10.5 is chosen as the optimum pH value of
methylene blue solution for the adsorption experiment.

60
 (b) Effect of Contact Time

The results of contour and response surface plots shown in Figure 4.2 and 4.3
presented the effect of contact time at constant initial concentration of methylene blue at
6 mg/L and constant pH at 7 respectively. It can be observed from Figure 4.2 and 4.3
that, the percentage removal of methylene blue decreased with increasing contact time.
The reduction can be supported from the model Equation (4.1) where negative (-) sign
was presented for contact time (X 1). However, the P-value > F for effect of contact time
is more than 0.05, indicated that this effect is not significant.

According to Enenebeaku (2017), this is due to the adsorbed methylene blue

molecules were weakly held on adsorbent during saturation. This is feasible for the
formation a secondary adsorption layer (held with weak bond) on a primarily adsorbed
methylene blue layer (having stronger attachment with the adsorbent substrate).
Assuming the methylene blue molecules absorb on heterogeneous sites on the adsorbent
surface, such could also provide an uneven spread of energy between the primary and
secondary adsorption layers and, hence, facilitate the dislodging of methylene blue dye
with increasing of contact time.

(c) Effect of Initial Concentration of Methylene Blue

From the contour and response surface plots shown in Figure 4.3 and 4.4, effect
of the initial concentration of methylene blue at constant pH at pH 7 and contact time at
25 mins were shown respectively. From the findings, the percentage removal of
methylene blue by cellulose increased with increasing initial concentration of methylene
blue. This can be explained by the model Equation (4.1) in which positive (+) sign was
observed for effect of initial concentration of methylene blue (X3). Moreover, this effect
is significant with the P-value > F lower than 0.05.

61
 This phenomenon can be attributed to the fact that the initial concentration of
dye plays an important role which provided the necessary driving force to overcome the
resistances to the mass transfer of methylene blue between the aqueous and the solid
phases (Ouasif et al, 2013). Thus, the adsorption of methylene blue and subsequent
permeation into the pores of the adsorbent, are both facilitated with increasing dye
concentration. Hence, a higher initial concentration of methylene blue increased the
percentage removal of methylene blue.

Similar trend was noticed by Amel et al. (2012), an increase in the initial ions
concentrations of methylene blue will enhance the number of collisions resulted
between the dye ions and the adsorbent, thus, improves the adsorption process. Based
on Enenebeaku (2017), assuming the formation of weak bonds between primary and
secondary adsorption layers or between methylene blue and heterogeneous sites on
cellulose, such effects could conveniently be overcome by increasing initial dye
concentration. This is the reason that the percentage removal of methylene blue
continued to increase as initial concentration of methylene blue increased.

4.2.3 Isotherm Analysis

The distribution of methylene blue molecule between the liquid phase and the
adsorbent id a measure of the position of equilibrium in the adsorption process and can
generally be expressed by one or more series of isotherm models. Adsorption isotherms
are critical in optimizing the use of adsorbents, and the analysis of the isotherm data by
fitting them to different isotherm models is an important step to find the suitable model
that can be used for design purposes (Dawood and Sen, 2012). The Langmuir isotherm
and Freundlich isotherm studies were conducted using various initial concentration of
methylene blue from 2 mg/L to 10 mg/L in the presence of 0.5 g cellulose fibers. The
applicability of the isotherm equation was compared by the linear correlation
coefficients, R2.

62
 Langmuir Isotherm Plot
7.00

6.00 f(x) = 6.42 x − 7.66

R² = 0.98
5.00

4.00
1/Qe

3.00

2.00

1.00

0.00
1.20 1.40 1.60 1.80 2.00 2.20 2.40
1/Ce

FIGURE 4.22 Langmuir Isotherm Plot for Methylene Blue dye onto Cellulose

Freundlich Isotherm Plot

0.00
-0.20 f(x) = 3.53 x + 0.85
R² = 0.98
-0.40
-0.60
-0.80
-1.00
ln Qe

-1.20
-1.40
-1.60
-1.80
-2.00
-0.90 -0.80 -0.70 -0.60 -0.50 -0.40 -0.30 -0.20
ln Ce

FIGURE 4.23 Freundlich Isotherm Plot for Methylene Blue dye onto Cellulose

63
TABLE 4.12 Comparison of Langmuir and Freundlich isotherm constants for
removal of methylene blue by cellulose

Langmuir Isotherm Freundlich Isotherm

Qo (mg/g) KL (L/mg) R2 n Kf (mg/g) R2
0.130 1.194 0.9820 0.284 2.339 0.9778

Figure 4.5 and 4.6 showed the linear plot of linearized Langmuir and Freundlich
isotherm analysis for batch adsorption of methylene blue using cellulose, respectively.
The calculated constants and regression values of these isotherm models are listed in
TABLE 4 .12. 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 methylene blue onto cellulose
adsorbents and also the homogeneous distribution of active sites on the adsorbent, since
the Langmuir equation assumed that the surface is homogeneous (Dakhil, 2013). This
model also assumed uniform energies of adsorption onto the surface and no
transmigration of adsorbate in the plane of the surface (Dada et al. 2012).

In addition, the separation factor, RL which is a dimensionless constant related to

the propitiousness of the adsorption has been calculated from Langmuir isotherm plot as
shown in Figure 4.7. It can be found that the calculated RL values lie between 0 and 1 at
different initial concentration of methylene blue suggesting the isotherm to be
favourable at the concentrations studied. Besides, lower RL values at higher initial
methylene blue concentrations showed that adsorption was more favourable at higher
concentrations.

64
 0.35

0.3

0.25

0.2

RL
0.15

0.1

0.05

0
1 2 3 4 5 6 7 8 9 10 11
Co (mg/L)

FIGURE 4.24 Plot of Separation Factor vs Initial concentration of methylene blue

4.2.4 Kinetics Analysis

Kinetics models have been used to investigate the mechanism of adsorption and
potential rate controlling steps, which is helpful for selecting optimum operating
conditions for the full-scale batch process (Santhi and Smitha, 2010). The kinetic of the
methylene blue adsorption on cellulose were examined using pseudo-first and pseudo-
second order equation, as presented in Figure 4.8 and 4.9.

Pseudo-first-order kinetic model

12

10

8
log(qe-qt)

0
0 f(x)10= 0 20 30 40 50 60 70
R² = 0
t

FIGURE 4.25 Pseudo-first-order kinetic for adsorption of methylene blue onto cellulose

65
 Pseudo-second-order kinetic model
70
60 f(x) = 1.09 x + 0.2
R² = 1
50
40
t/qt

30
20
10
0
0 10 20 30 40 50 60 70
t

FIGURE 4.26 Pseudo-second-order kinetic for adsorption of methylene blue onto

cellulose

TABLE 4.13 Comparison of pseudo-first and pseudo-second order for removal of

methylene blue by cellulose

pseudo-first-order kinetic model pseudo-second-order kinetic model

K2
K1 qe qe
-1
R2 (g/mg.min R2
(min ) (mg/g) (mg/g)
)
0.041 0.059 0.827 5.946 0.917 0.9999

Kinetic parameters obtained from fitting model plots during contact time of 5
mins to 60 mins were listed in TABLE 4 .13. Based on the correlation coefficients with
both models, removal of methylene blue by cellulose 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 methylene blue on cellulose was more
appropriately described by pseudo-second-order model which is based on the
assumption that the rate limiting step may be chemical sorption or chemisorption
involving valency forces through sharing or exchange of electron between sorbent and
sorbate (Ho and Mc Kay, 2000).

66
4.3 CQDs CHARACTERIZATION

(a) (b)
FIGURE 4.27 CQDs solution under (a) white light; (b) UV light

4.4 USE OF CQDs ADSORBENT FOR DYE REMOVAL

4.4.1 RSM Modelling

67
(a) Effect of pH and Contact Time at Constant Initial Concentration of MB

Surface Plot of MB Removal % vs pH, Contact Time

Hold Values
Initial C onc. of MB 6

95

90
MB Removal %
85
10
80
8
6 pH
10 4
20
30
40
C ontact T ime

Contour Plot of MB Removal % vs pH, Contact Time

11
MB Removal
%
10 < 80.0
80.0 – 82.5
9 82.5 – 85.0
85.0 – 87.5
87.5 – 90.0
8 90.0 – 92.5
92.5 – 95.0
> 95.0
pH

7
Hold Values
6 Initial C onc. of MB 6

3
10 15 20 25 30 35 40
Contact Time

68
(d) Effect of Initial Concentration of MB and Contact Time at Constant pH

Surface Plot of MB Removal % vs Initial Conc. of MB, Contact Time

Hold Values
pH 7

100

M B Removal % 90

80 9

6
Initial C onc. of M B
10 3
20
30
40
Contact T ime

Contour Plot of MB Removal % vs Initial Conc. of MB, Contact Time

10
MB
Remov al
9 %
< 80
8 80 – 85
85 – 90
Initial Conc. of MB

90 – 95
7 > 95

Hold Values
6 pH 7

2
10 15 20 25 30 35 40
Contact Time

69
(e) Effect of Initial Concentration of MB and pH at Constant Contact Time

Surface Plot of MB Removal % vs Initial Conc. of MB, pH

Hold Values
Contact Time 25

90

MB Removal % 80

70 9

60 6
Initial Conc. of MB
4 3
6
8
pH 10

Contour Plot of MB Removal % vs Initial Conc. of MB, pH

10
MB
Remov al
9 %
< 65
8 65 – 70
70 – 75
Initial Conc. of MB

75 – 80
7 80 – 85
85 – 90
90 – 95
6
> 95

5 Hold Values
Contact Time 25

2
3 4 5 6 7 8 9 10 11
pH

70
4.4.2 Isotherm Analysis

4.4.3 Kinetics Analysis

71
4.5 COMPARISON OF CELLULOSE ADSORBENT AND CQDs
ADSORBENT IN DYE REMOVAL

72
73
74
75