Professional Documents
Culture Documents
INTRODUCTION
glass and brick making industries and coal power plants [1]. Generally, fluorides are
considered as serious contaminants even when they are present at low levels since it
persists for a long time in air, soil, and water and exerts negative effects at all levels of an
ecosystem. High concentration of fluoride can cause poor development of infants brain,
osteosclerosis, dental fluorosis, cancer and impairment in human being [3]. Therefore, the
as stated in Malaysia Environmental Quality Act 1974 in Fifth Schedule are 2.0 mg/L for
1
In view of this fact, it is essential to develop a fast, selective, economic and eco-
methods have been proposed to remove fluoride from wastewater including precipitation,
filtration, electro coagulation flotation and phytoremediation [4]. Among these methods,
adsorption is favourable due to its low operating cost, simple operation and design
requirements, low residual product generation and lack of interaction with toxic that
adsorbent have gained a growing interest since they are especially useful in the removal
of heavy metal ions such as mercury, lead, chromium and arsenic from the wastewater
adsorbent [6]. However, these type of adsorbent have low adsorption capacity, high cost
and bad selectivity that limit their large range application. Hence, searching for adsorbents
with excellent performance and cost-effective is necessary in recent years. The initiation
of graphene-based material has paid more attention as a favourable adsorbent due to its
lower cost, high adsorption capacity and very promising adsorbent for different genre of
pollutants [7]. From this viewpoints, graphene is served as a suitable adsorbent for the
amount of reactive oxygen atoms on the surface. The presence of epoxide, hydroxyl and
2
carboxyl groups, which lead to the formation of reactive oxygen atom, cause the GO easily
react in aqueous solution [7]. As an extension of the application of GO, the study focuses
Besides, the composition of metal oxide with some biological and organic material which
also a good adsorbent can enhance the adsorption capacity than the individual materials
[8]. Hence, it indicates that GO that modified with another adsorbent material able to
Calcium adsorbent have been widely proposed in current years to remove fluoride
contaminant such as calcium hydroxide [Ca(OH)2], calcium chloride (CaCl2) and calcium
sulphate (CaSO4) [9]. Although there have been several attempts with different adsorbent,
the cheap and effective in long term has yet to be definitely proven. Thus, the natural
calcium-based that produce from waste material is suggested to overcome those problems.
In fact, there are different natural calcium-based adsorbents that locally available such as
calcined clay, pine apple peel powder, chalk powder, orange peel powder, bone charcoal,
bivalve shell and eggshell [10]. Generally, these materials are locally available in large
quantities since the waste such as eggshell is produce in high rate every day. Thus,
Therefore, the synthesis and modification of GO with the eggshell adsorbent (GO/ES) to
3
1.2 Problem Statement
the most crucial environmental problems. The removal of fluoride is essential since it
could cause significant pollutant to the environment, damage to ecosystem and to human
health. Concerning to this issue, various methods for fluoride removal from wastewater
have been extensively studied. In fact of various available method to remove fluoride
from wastewater, the favourable adsorption method has a few advantages such as low
operating cost, simple operation and design requirements and high adsorption capacity.
epoxy and carboxylic acid groups which give high dispersion in water. In view of this
fact, GO can acts as a highly ecient adsorbent to remove organic or inorganic matter
from water [31]. Currently, the synthesis of GO with composite materials such bentonite,
aluminum polycation, iron oxide and iron acetate have been studied as the adsorbent to
remove heavy metals such as ammonia, nitrogen oxide, arsenic and mercury from
wastewater [11]. However, for economic reason, a simple, less expensive and high
based adsorbent such as eggshell, which abundantly available from waste production and
could offer less cost and high adsorption capacity is favourable. In addition, the study
involving eggshell and GO modification has yet to be conducted. The recycling or reuse
of the eggshell has the potential to reduce environmental pollution while acting as a cost
effective material for the immobilization of heavy metals in wastewater and soil.
4
1.3 Research Objectives
The main objective of this study is to develop an efficient graphene oxide / eggshell
(GO/ES) modified adsorbent for fluoride removal in wastewater. Below are the specific
1. To study the effect of synthesis parameters of GO/ES ratio, synthesis temperature and
eggshell (ES) as material to be modified with graphene oxide (GO). Next, the synthesis
will be done by using impregnation method and the effect of important parameters such
as GO/ES ratio (5:1, 1:1 and 1:5), synthesis temperature (30 oC, 45 oC and 60 oC) and
synthesis time (30, 60 and 90 minutes) will be investigated. The effect of each parameter
towards fluoride removal analysis will be studied by a set of constant parameters. The
adsorption capacity of fluoride and fluoride percentage removal of the modified GO/ES
GO/CaCl2. Lastly, in order to investigate the properties of the adsorbent materials towards
fluoride removal, the characterization study on functional group of the new modified
5
CHAPTER 2
LITERATURE REVIEW
Fluorine (F) is a halogen, which has atomic weight of 18.998, atomic number of 9
and valence of 1. Fluorine (F2), which is its elemental state, is the most electronegative
element known and is a very powerful oxidizer in the gaseous form of F2 gas. Because of
the strong oxidizing power of F2, fluorine exists naturally as fluoride ion (F-) [32]. This
ionic form is the most common and environmentally reactive form. In addition, fluoride
(F) is characterized by small radius, great tendency to behave as ligand and easy to form
a great number of different organic and inorganic compounds in soil, rocks, air, plants and
animals [12]. Some of those compounds are quite soluble in water and thus, fluoride is
of untreated industrial effluent. Some of the industry are involving chemical plant
semiconductor manufacturing, glass and brick making industry and also coal power plants
[1].
6
The treatment of fluoride-containing wastewaters is of high concern and strictly
regulated since fluoride discharge into surface water can lead to ground water
contamination, with various possible adverse effects especially on human health and
environment. The most common effect resulting from long-term excessive exposure is the
accumulation of fluoride in human bones and the potential for skeletal fluorosis and bone
fractures at the possibly total intakes of 14 mg fluoride per day. The high concentration of
fluoride can cause poor development of infants brain, osteosclerosis, dental fluorosis,
cancer and impairment in human being [3]. Furthermore, natural fluoride concentrations
in freshwater which usually lower to affect aquatic organisms, which may, however, be
adversely affected by nearby discharges from human activities [33]. Therefore, the
as stated in Malaysia Environmental Quality Act 1974 in Fifth Schedule are 2.0 mg/L for
Standard A and 5.0 mg/L for Standard B [2]. Table 2.1 shows the parameters and their
standard disposal limit from the Environmental Quality (Sewage and Industrial Effluents)
Regulations 2009.
7
2.2 Technologies Available for Fluoride Removal
In recent years, various methods are accessible for the removal of fluoride from
industrial wastewater. Some of the common methods are coagulation and precipitation,
reverse osmosis (RO), ion-exchange and adsorption [4]. Each approaches have their
advantages and limitations and worked productively under ideal condition to remove
Coagulation and precipitation usually use lime and alum as a coagulant throughout
the process. As a first step, precipitation occur by insert the lime which is trailed by second
step in which alum is added to promote coagulation process. At the point when alum is
added to water, basically there are two reactions happen. In the first reaction, alum reacts
second reaction, alum reacts with fluoride ions in the water. It is stated that test fluoride
removal is at pH range of 5.5 7.5 [13]. However, this process require high dosage of
coagulant and the treated water turn to hazardous effluent due to the aluminum released
Reverse Osmosis (RO) is stated as a physical process in which the anions are
removed by applying pressure on the feed water to direct it through the semi permeable
pressure to the high concentration side of the solution. The applied pressure forces the
solvent filter through the membrane, against a pressure gradient into the lower-
concentration of solution. Sanghratna S.W. and Tanvir A. observed that the adsorption of
fluoride ion was regularly higher than 98%, considering that the RO membrane was
8
completely recovered after every arrangement of analysis [13]. However, RO has some
limitation since it is an expensive technique and the treated effluent turn to acidic solution.
Fluoride can be removed from water with the fundamental of anion-exchange resin
that containing ammonium functional group. Ion-exchange process require fluoride ions
substitute the chloride ion of the resin. This process proceeds until every one of the sites
on the resin are exchanged. The resin is then backwashed with water that is supersaturated
with dissolved sodium chloride salt. New chloride ions then substitute the fluoride ions
and beginning the process once more. In some instances, the limitation of this process is
occur from the high concentration of chloride on the treated water. Even though it
produces high productivity which is 90% to 99% of fluoride removal, however, this
process is not favourable due to its high cost [13]. Table 2.2 summarizes the disadvantages
9
Membrane High efficiency by High capital, high running
filtration: removing other and maintenance costs,
Reverse osmosis, contaminates toxic waste water produced [37]
nano-filtration
From Table 2.2, it found that coagulation and precipitation process that usually
using calcium hydroxide and aluminum hydroxide as reagent can promote advantages
such as high efficiency and the reagent chemicals are commercially available. However,
this method is expensive since sludge dewatering is needed resulting from the high amount
of retained water. In fact, this method will produce sludge with high amount of toxic. The
formation of toxic technically require additional steps to eliminate the toxic before
proceed with further process. Next, membrane filtration method that involve reverse
osmosis or nano-filtration offer high efficiency. In spite of that, high cost is needed in
10
capital, running and maintenance cost which is less favourable in industry. Same goes to
ion-exchange method, they can generate high removal efficiency but require high cost. On
top of that, adsorption method that usually use adsorptive material such as activated
alumina, activated carbons and synthetic carbons have greater accessibility, simple
operation, wide availability of adsorbents and require low cost. However, the efficiency
is often depend on adjustment and re-adjustment of solution pH. Hence, with those
concentration of molecular species on another substance surface through the bulk film.
When a solid surface is exposed to a gas or a liquid, molecules from the gas or the solution
a well-established and most favourable technique for treating domestic and industrial
adsorbents. Adsorption onto solid surface is flexible and suitable procedure for treating
water systems. In addition, adsorption technique is efficient and can remove ions over an
various methods used for defluoridation of water, this process is widely used based on the
satisfactory results and offers attractive factor such as lower cost and simplicity of design
11
In fact of this technology has been widely implemented, there are many type of
adsorbent that practically used in wastewater treatment. Some of the adsorbent are carbon
nanomaterial, activated alumina, iron-based adsorbent and clay mineral [15]. The removal
of fluoride is less effective in acidic solution due to the electrostatic repulsion. However,
when the pH is greater than 7.0, the adsorption capacity decreased resulting from
electrostatic repulsion of fluoride ions to the negatively charged surface of alumina [12].
Furthermore, for clay mineral adsorbent, they are generally modified with physico-
chemical modification such as metal oxide amendment, acid treatment and thermal
activation to increase their adsorption capacity [15]. The modification has increase the
stability on the optimal operating pH, accessibility of active site and surface area.
However, industry nowadays have turn their attention to adsorbent that provide
inexpensive cost, high adsorption capacity and very promising efficiency for different
genre of pollutants. Table 2.3 shows various type of adsorbent material that commercially
Table 2.3: Various types of adsorbent used for fluoride removal applications
12
Commercial activated 9.0 32.0 [47]
carbon (CAC)
Bentonite clay 6.0 49.6 [44]
Bentonite/Fe2O3 clay 6.0 80.4 [44]
Graphene 7.0 72.0 [48]
red mud that generally consist of aluminum and iron oxide as the major component has
been widely used as an adsorbent due to its availability and low cost [44]. It has the ability
to remove 75% of fluoride at the optimum pH of 5.5. Next, researchers state that
(MAAA) offer more effective fluoride removal compared to activated alumina with the
percent fluoride removal as high as 95% at neutral condition [44]. In addition, adsorption
of fluoride onto MAAA is pH-dependent and the increase of pH could decrease the
percentage fluoride removal. Bone char is a type of carbon-based adsorbent that has
widely implemented as a low-cost adsorbent in fluoride removal and has the 70.64%
Chitosan is a type of adsorbent that could be modified with rare earth material such
as lanthanum (La). Researchers conclude that La/chitosan adsorbent has 97% of fluoride
removal at optimum pH of 5.0 which is higher than chitin and chitosan alone [46]. It is
due to the presence of anions, particularly carbonate and bicarbonate that diminished
fluoride ion (F-) adsorption. Nevertheless, low-cost clay mineral type of bentonite
adsorbent has the fluoride removal of 49.6% and yet, the modified bentonite clay with
iron oxide has increase the percent removal to 80.4% at the optimum pH of 6.
13
Lastly, graphene is a carbon-based nanomaterials with high specific surface area
and good chemical stability. It is available in various forms such as pristine graphene,
graphene oxide and reduced graphene oxide [42]. Previous study stated that graphene has
Graphene oxide (GO), which has irregular edges, rough surface, and lots of crush
resulted from the scrolling of GO sheets, is easy to distribute in water and other organic
solvents due to the presence of the oxygen functionalities [16]. This is attributed to its
oxidized derivative of graphene, has resulting the extended graphene sheet decorated with
epoxy (C-O-C) and hydroxyl (-OH) functional groups in the basal plane and carboxylic
acid (-C=O) group at the edges [17]. Moreover, the hydrophilic characteristic of GO
provides high negative charge density that arise from the formation of oxygen-containing
functional group. High negative charge density can provide reactive sites for the
In solution phase, GO exists as a single layer and possesses the ability to intercalate
water molecules. GO acts as a weak acid cation exchange resin which allow ion exchange
with metal cations or organic material anions resulting from the ionizable carboxyl groups
[18]. Furthermore, because of its aromatic structure similar to the graphene, the GO can
easily adsorb organic compounds on its surface due to interactions of the stacking
14
[16]. The nature of GO and characteristics of its functional group is effectively utilized
and thus, recommended GO as highly suitable for adsorption. Table 2.4 presents studies
that have been done for graphene-based adsorbent material in fluoride removal
application.
Liquid CoF = 25
Graphene phase - 35.59 mg/L [48]
exfoliation T = 298 K
pH = 7.0
In-situ CoF = 80
GO /FeOOH hydrolysis FeO 17.65 mg/L [49]
of FeCl3 T = 298 K
pH = 6.3
Supercritical CoF = 50
rGO/AlOOH of scCO2 Al2O3 118.7 mg/L [50]
T = 298 K
pH = 6.5
As stated in Table 2.4, graphene as an adsorbent has been prepared by liquid phase
exfoliation has the adsorption capacity of 35.59 mg/g at the temperature of 298 K, pH 7.0
and the initial concentration of fluoride at 25 mg/L. The synthesis of GO with hydroxide
of goethite (FeOOH) has lower adsorption capacity at 17.65 mg/L at the temperature of
298 K, pH 6.3 and initial concentration of fluoride at 80 mg/L. Lastly, the synthesis of
reduced GO (rGO) with boehmite (AlOOH) has highest adsorption capacity of 118.7 mg/g
15
at the temperature of 298 K, pH 6.5 and initial concentration of fluoride at 50 mg/L.
Hence, it proves that modified GO with other adsorbent material gives higher adsorption
adsorbent material. This is due to the efficiency of GO as an adsorbent affected by its large
surface area and good chemical stability which enhance the adsorption capacity.
potassium chlorate (ClO3-) to the slurry of graphite in fuming nitric acid [11]. This method
is then improved by replacing about two thirds of fuming nitric acid (HNO3) with
Despite the above progress, new synthesis method have been developed and lead
to the common implementation in recent years. The most common method involved
by varying the oxidizing agents used to exfoliate graphite flakes. The stepwise of graphite
oxidation by Hummers method involve the presence of graphite powder and sodium
nitrate (NaNO3) and mix into sulphuric acid (H2SO4). The procedure require the solution
yellow colour. After filtration and drying under vacuum at room temperature, the GO is
16
present as a powder [19]. Next, the introduction of Modified Hummers method has offer
a huge improvement in GO synthesis method. This method involves both oxidation and
exfoliation of graphite sheets due to thermal treatment of solution. The additional steps
involved in this modified method is the mixture is keep in reflux system with temperature
in range of 25 oC to 30 oC for normally 2 hours before the solution is being treated with
hydrogen peroxide (H2O2). The remaining steps is remain the same as previous method
Graphene oxide (GO) can be readily modified for particular applications due to
material which are biocompatible and hydrophilic, have wide potential applications in
oxygen functionality such as carboxylic acid groups at their edge, and epoxy and hydroxyl
groups on the basal planes [17]. In some instances, GO has reach an ideal approach on the
Recent years, adsorption technique is commonly used and adsorbent using low-
cost compound and more sophisticated ones such as aluminum based material, clay and
soils, calcium based mineral, synthetic compounds, seaweed species and carbon based
materials are widely practiced [22]. Researchers state that, instead of using commercial
activated carbon, calcium-based materials such as cockle shell, sawdust, mango leaves,
17
chitosan, egg shell and other adsorbents are potentially good adsorbent since they offer
high adsorption capacity and locally available [21]. On the other hands, these materials
are easily available from agricultural and food waste. In addition, the high contain of
cellulose level, hemicellulose, lignin and proteins can lead to a renewable natural
resources and inexpensive ecofriendly and sustainable materials [23]. Since agricultural
and food wastes are generated in large scales, these materials are considered potential
source for the preparation of low-cost sorbents in a variety of applications. Table 2.5
Eggshell 80 [9]
Seashell 84 [10]
Table 2.5 shows the fluoride removal efficiency for different natural calcium-
based material which can be collected from waste material. Chalk powder which generally
contain of 98% to 99% of calcium carbonate offer 86% of fluoride removal. This is due
to the high porosity and void ratio of chalk powder. Because of high porosity and its
18
chemical composition which contains high percent of calcium carbonate, it can be used as
an adsorbent [24]. Next, eggshell has the 80% of fluoride removal capacity but however,
its non-toxic and versatile have witnessed a systematic growth in the use of eggshell for
calcium carbonate (94%), magnesium carbonate (1%), calcium phosphate (1%) and
organic matter (4%). It is particularly attractive for synthesizing metal nanoparticles due
to its strong metal-protein bonding can be readily utilized [25]. In addition, eggshell has a
cellulosic structure and contains amino acids and thus, it is expected to be a good
biosorbent [26]. Besides, eggshell is locally available and the waste is highly produced in
daily routines. In view of this fact, egg shell is a calcium-rich substance that can be
magnesium carbonate (1%) and organic substances (4%). In fact, eggshell is a rich source
of mineral salts which mainly calcium carbonate. Therefore, eggshell can be served as a
good biosorbent to be modified with GO. In addition, this study involving eggshell and
GO modification has yet to be conducted. The recycling or reuse of the eggshell has the
potential to reduce environmental pollution while acting as a cost effective material for
19
CHAPTER 3
RESEARCH METHODOLOGY
There are various type of chemicals that will be used in this research. Table 3.1
lists the chemicals and materials according to their function and also the purity of each
chemical material.
Table 3.1: List of chemicals and materials used and their function
(KMnO4)
20
3.2 Equipment
For this experiment, the main equipment used were analytical balance, magnetic
3.3 Flowchart
Eggshell (ES) have been chosen as raw material for this study. The feasibility study of
GO and its potential to become as an effective adsorbent was discussed in Chapter 2. The
research parameters were separated into three major parts, namely the effect of GO/ES
ratio, effect of synthesis time and the effect of synthesis temperature. Modified GO/ES
adsorbent was characterized using FTIR or the determination of functional group. Figure
21
Synthesis of GO
Modification of GO
with ES material
Fluoride
Analysis
No
Yes
Characterization
analysis
22
3.4 Synthesis of Graphene Oxide (GO)
The GO was prepared according to the Modified Hummers method. Firstly, 2.5 g
of graphite powder and 1.25 g sodium nitrate (NaNO3) were mixed into 60 ml sulphuric
acid (H2SO4) (98wt%) in a 250 mL flask in an ice bath at least 5 C. After one hour, with
vigorous stirring, 7.5 g of potassium permanganate (KMnO4) were slowly added into the
flask. The solution was maintained below 10 oC to control the exothermic reaction and
keep stirring at a controlled cold temperature for 2 hours. Then, the ice bath was removed.
The mixture then kept in the room temperature condition and keep stirring for overnight
until it produced brownish pasty. Next, 135 mL of DI water were added while vigorously
stirring. The solution was heated up to 50 oC in water bath and maintain the temperature
for 1 hour. The solution have been treated with 25 ml hydrogen peroxide (H2O2) by which
color changed to bright yellow. The resulting mixture repeatedly washed by centrifugation
with 400 mL hydrochloric acid (HCl) for twice and then with deionized (DI) water several
times until it obtained the pH near 3. After centrifugation the gel like substance were
Eggshells were washed with DI water several times and dried in hot air oven at
45oC for overnight. Consequently, eggshells were grinded into a powder form in a grinder,
23
Three different ratios of GO/ES (5:1, 1:1, and 1:5) were firstly synthesized by
impregnation method. Briefly, 1 g of GO in slurry form were added in a beaker with 300
the GO solution were sonicated for at least 1 hour to enhance its exfoliation. After an hour,
different amounts of ES (0.2 g, 1 g, and 5 g) were added to the dispersion beaker. The
procedures were continued for different synthesis time (30 min, 60 min and 90 min) with
constant parameter (GO/ES 5:1, T = 45 oC) and different temperature (30 oC, 45 oC and
60 oC) with constant parameter (GO/ES 5:1, t = 60 min). Lastly, suspension were collected
The stock solution of fluoride (1000 mg/L) was prepared by dissolving 2.210 g of
sodium fluoride (NaF) in 1.0 L of distilled water. The solution then was diluted to required
The analysis were carried out by batch adsorption method, with 0.04 g of the
GO/ES adsorbent was added into 200 mL of NaF solution with initial concentration
prepared was 30 mg/L. The mixed solution was shaked at 200 rpm by using rotating shaker
for 2 hours. Next, the final concentration of fluoride solution was analyzed by SPADNS
was prepared by inserting 3 to 5 mL of NaF solution into sample cuvette. Then, 2.0 mL
24
3.7 Adsorption Analysis
While conducting the first parameter, which was GO/ES ratio, the other
parameters during sonication were set constant such as temperature at 45 oC and time at
60 minutes. Meanwhile, the GO/ES ratio was set 5:1 and time at 60 minutes during
performing the next synthesis temperature parameter. Lastly, while conducting synthesis
time parameter, the constant values were GO/ES 5:1 ratio and temperature at 45 oC.
order to get fluoride concentration value. The adsorption capacity can be calculated by
= [ ] (3.1)
weight of adsorbent (g/L). The percentage of fluoride removal can be calculated by using
% = [ ] 100 (3.2)
25
3.8 Characterization Analysis
Scientific Fourier Transform Infrared Spectrum (FTIR) with the wave number in range
between 5000 cm-1 to 400 cm-1. The function of FTIR is generally to identify the presence
interferometer, sample, detector and computer. The source provides infrared energy beam
that will pass through and enter the interferometer to create spectral coding. The beam
then enters the sample compartment where it is transmitted through the surface of the
sample, and send the signal to the detector. The measured signal is digitized and sent to
the computer.
26
CHAPTER 4
4.1 Introduction
Hummers method. GO in slurry form was then modified with eggshell (ES) powder, as a
project are to study the effect of GO/ES ratio, effect of synthesis temperature and effect
of synthesis time on the GO/ES modification. The effect for each parameter were
modified GO/ES adsorbent was compared with modified GO/CaCl2 adsorbent, which
each parameter were characterized by using Fourier transform infrared spectrum (FTIR).
The GO/ES ratio were introduced at 5:1, 1:1 and 1:5, as 1 g amount of GO was
proposed. The effect of these ratio amount were analyzed on the concentration of fluoride
by performing fluoride removal analysis. Table 4.1 shows the adsorption capacity after
27
2 hours of adsorption period with 0.2 g/L of the modified adsorbent weight. The other
variables were kept constant during this modification process such as temperature at 45
o
C and time at 60 minutes.
60
50
40
30
20
10
0
(5:1) (1:1) (1:5)
Ratio (GO/ES)
The result of this effect clearly indicates adsorption capacity of 46.45 mg/g, 50.45
mg/g and 53.40 mg/g at GO/ES ratio of 5:1, 1:1 and 1:5. At higher ratio of eggshell (1:5),
sorption sites, meanwhile at lower eggshell ratio, the number of fluoride ions is relatively
the behavior of the eggshell that consist 94% of chemical composition of calcium
28
The effect of GO/ES ratio on percentage removal of fluoride were observed to
analyze the trend that arised across the fluoride adsorption. As shown in the plotted trend
above, the ratio is constructed from high GO composition of 5:1, equal composition of 1:1
and high eggshell composition of 1:5. It interprets that the fluoride removal percentage is
constantly rise from 31.30% to 34.0% and has the highest removal at 35.99%. Hence, the
the GO surface. In view of this fact, this is influenced by the characteristic of the eggshell
FTIR spectra was then conducted to determine the presence of functional groups
in GO after modification with the eggshell, within the range 4000 to 500 cm-1. The
functional group trend was compared for each parameter as shown in Figure 4.2.
GO
GO/ES (5:1)
GO/ES (1:1)
GO/ES (1:5)
29
Initially, the functionalization of GO was analyzed. The broad peak at 3175.94
cm-1 is assigned to the O-H group stretching vibration. The peak at 1714.52 cm-1 and
1621.16 cm-1 are associated with the stretching band of C=O in carbonyl moiety, including
carboxylic acid functional group. Meanwhile, the peak observed at 1041.10 cm-1
confirmed as stated that oxidized graphene by using modified Hummers method would
extended graphene sheet with decorated of epoxy (C-O-C) and hydroxyl (-OH) functional
groups in the basal plane and carboxylic acid (-C=O) group at the edges [17].
ratio. The spectrum of GO/ES at first ratio (5:1) differs from that of GO as evidence by
the weakening of the hydroxyl peak at 3251.11 cm-1. This result indicates that the O-H
bond was reduced after depositing of eggshell powder onto the GO surface. This
deposition can be proved by the shift of the C=O peak (1714.52 cm-1 and 1621.16 cm-1)
on GO to a new peak at 1392.17 cm-1 and 870.51 cm-1 which refer to the formation of C-
H alkane bend before the possibility of stretching and bending of metal component (refer
The next ratio shows that the composition of GO is reduced (1:1) and the
peak can be observed at the region between 3500 cm-1 to 3000 cm-1 due to the domination
of Ca component bound onto the GO surface. However, during the third ratio (1:5), there
is a new peak developed at 2358.59 cm-1 which does not lies on any functional group but
indicates the intensity is dropped possibly due to large amount of Ca component to bound
30
Generally, this functional group affects the fluoride adsorption due to the bonding
of fluoride ion (F-) to that particular functional group. The intensity or the percentage
transmittance is refine where the adsorption reaction was occurred at the peak. Based on
the FTIR spectrum analysis, the functional groups that caused the fluoride adsorption are
O-H and C-O group. It can be observed by the slight change of intensity between those
ratio occurred at range between 2500 to 3500 cm-1 and between 1000 to 1500 cm-1 as well.
diffusing to the surface of the adsorbent, where they bond with the solid surface or are
The synthesis temperature were introduced at 30oC, 45 oC and 60 oC, with other
variables were keep constant such as ratio of GO/ES of 5:1 and synthesis time at 60
minutes. The effect on adsorption capacity and fluoride removal percentage, after 2 hours
of adsorption period with 0.2 g/L of the modified adsorbent weight was analyzed.
31
60
50
40
30
20
10
0
30 45 60
Temperature (oC)
The result shows that adsorption capacity is increase from 44.00 mg/g to 46.45
mg/g as the temperature increase from 30oC to 45oC. Meanwhile, the highest adsorption
capacity 53.90 mg/g is recorded at 60oC temperature. This is due to the efficient size
reduction of particles during sonication as the temperature increase [53]. Greater size
reduction can provide large surface area or small diameter of the adsorbent. In fact, small
greater removal percentage and adsorption capacity of heavy metal removal can be
achieved.
The plotted trend exhibits that the removal percentage of fluoride increase as the
32
temperature increased to 45 oC, the fluoride removal percentage is increase to 31.30%.
within the range 4000 to 500 cm-1. The functional group trend was analysed as shown in
GO
GO/ES (T=30oC)
GO/ES (T=45oC)
GO/ES (T=60oC)
The FTIR spectra of GO/ES at different temperature shows similar active surface
functional groups in the region of 3500 cm-1 to 3200 cm-1 that represents the O-H
stretching vibrations including hydrogen bonding in water molecules. Other peaks are
found at sharp bends between 1370 cm-1 to 1350 cm-1 which indicates the formation of
C-H alkane group. Another prominent peak at 1000 cm-1 to 650 cm-1 can be observed for
33
all modified samples, which assigned Ca component bound onto =C-H surface,
respectively.
A close analysis of the FTIR spectrum indicates that the intensity of the peaks for
temperature 30oC and 45oC are increased at the region 3000 cm-1 to 1500 cm-1 and there
is a new peak appeared at the region between 2500 cm-1 to 2200 cm-1 for temperature
60oC.
diffusing to the surface of the adsorbent, where they bond with the solid surface or are
held there by frail intermolecular forces. The functional group of O-H and C-O have affect
the fluoride adsorption due to the bonding of fluoride ion (F-) to that particular group. The
intensity or the percentage transmittance is refine where the adsorption reaction was
occurred at the peak. It can be observed by the major switched of intensity that occurred
at range between 2500 to 3500 cm-1 and small change at 1000 to 1500 cm-1 as well.
The synthesis time were introduced at 30 minute, 60 minute and 90 minute, with
other variables were keep constant such as ratio of GO/ES of 5:1 and synthesis
temperature at 45 oC. The effect on adsorption capacity and fluoride removal percentage,
after 2 hours of adsorption period with 0.2 g/L of the modified adsorbent weight was
observed.
34
60
50
40
30
20
10
0
30 60 90
Time (minutes)
The tabulated data reveals that the increasing synthesis time had increase the
is 45.50 mg/g and the adsorption capacity is slightly increase to 46.45 mg/g when 60
minutes of synthesis time was introduced. Meanwhile, the adsorption capacity is intensely
increase to 51.90 mg/g at the synthesis time of 90 minutes. This behavior is attributed by
the fact the time increasing lead to the stable and constant adherence of the ionic liquid
onto the solid surface. In fact, the adsorbent obtained in stable constant condition will
develop the highest efficiency in heavy metal removal [41]. However, in order to obtain a
the synthesis time, but the percent of amplitude during the modification is more important.
35
Hereby, the shifted of fluoride removal percentage with increasing synthesis time
was investigated. Adsorption of fluoride by using GO/ES adsorbent was strongly affected
by the synthesis time. The inclination of the percent removal is slightly increase from
30.67 % to 31.30 % as the synthesis time rise from 30 minutes to 60 minutes. In spite of
that, the percent removal is drastically increase to 34.97% as the 90 minutes of synthesis
time was introduced. It is suggested that the adsorbent requires more time to enhance a
stable and constant adherence on the impregnated adsorbent so that the fluoride removal
can be enhanced.
FTIR spectrum analysis was then conducted to discover the existence of functional
groups in GO after impregnated with the eggshell at different synthesis time, within the
range 4000 to 500 cm-1. The functional behavior was characterized as shown in Figure 4.6
below.
GO
GO/ES (t=30 min)
GO/ES (t=60 min)
GO/ES (t=90 min)
36
All modified adsorbent at different synthesis time effectuated the same trend of
functionalization. The active surface functional group lies in range between 3500 cm -1 to
3200 cm-1 which exhibits O-H stretching vibration with bonded hydrogen. The next
functional group is observed at sharp bends between 1370 cm-1 to 1350 cm-1 which shows
the formation of C-H alkane group. Another functional peak at between 1000 cm-1 to 650
cm-1 can be observed, which assigned that Ca component attached onto =C-H surface,
respectively.
A close analysis of the FTIR spectrum indicates that the intensity of the peaks are
constantly increase as the time increase. In addition, the trend for every peak are almost
similar for each time. Hereby, it interprets that synthesis time is not much affecting the
the functional groups that contributed to the fluoride adsorption are O-H and C-O group.
It can be observed by the change of intensity that occurred at range between 2500 to 3500
cm-1 and at 1000 to 1500 cm-1 as well. The intensity or the percentage transmittance is
refine where the adsorption reaction was occurred at the peak. Hence, it exhibits that the
calcium carbonate (CaCl2) which had been modified with GO to be compared with
modified GO/ES as a natural-based calcium. The variables were set constant such as ratio
of 5:1, synthesis temperature at 45oC and synthesis time at 60 minute. Next, the
37
application was developed on fluoride removal with 2 hours of adsorption period and 0.2
Table 4.1 shows the adsorption capacity and fluoride removal percentage obtained
As shown in the Table above, GO/CaCl2 adsorbent has offer greater adsorption
capacity at 48.95 mg/g with 32.99% of fluoride have been removed. Meanwhile, GO/ES
adsorbent has 46.45 mg/g of adsorption capacity with 31.30% fluoride removal
percentage. This is due to the behavior of CaCl2 that increase the acid strength of the GO
increasing acid strength on the adsorbent surface promote protonation of oxide surface
sites on the permanent charge sites in which the reactive surface of the oxides and
chlorides are dissolved [43]. The increasing acid strength however, will increase
concentration of the adsorbent that will increase the effectiveness of the heavy metal
removal. Hereby, the combination of CaCl2 with GO can enhance the fluoride removal
38
compared to GO/ES adsorbent which may dependent on the behavior of the eggshell by
itself.
GO/ES
GO/CaCl2
Both modified adsorbent displayed the same trend of functionalization. The active
surface functional group lies in range between 3500 cm-1 to 3200 cm-1 which exhibits O-
Nevertheless, the new functional group for modified GO/CaCl2 is arise at region between
1250 cm-1 to 1200 cm-1 which indicate the formation of C-N stretching. Another functional
peak at between 850 cm-1 to 550 cm-1 can be observed, which assigned the formation of
C-Cl stretching. It explains that Cl component is attached onto GO surface at that region.
39
CHAPTER 5
5.1 Conclusion
In summary, the graphene oxide (GO) with eggshell (ES) were modified and its
application for the removal of fluoride in wastewater were demonstrated. The main
objectives of this study are to investigate the effect of GO/ES ratio, synthesis temperature
and synthesis time on fluoride removal application. This study also aimed the comparison
wastewater.
Firstly, by varying the modified GO/ES ratio, it explained that as the composition
of eggshell increase during the modification, the adsorption capacity and fluoride removal
percentage were increase due to the domination and behavior of the eggshell as a good
adsorbent. Next, by varying synthesis temperature, the trend of fluoride removal were
increase as the synthesis temperature increase. Also, the synthesized adsorbent showed an
improvement in fluoride removal analysis when synthesis time were increasing. The FTIR
characterization of the modified adsorbent proved that GO were successfully formed and
ES had been coated over GO surface. FTIR results confirmed the synthesis of natural
calcium by the formation of chemical bonding between ES and GO. Different parameters
40
indicated small significance changes on the intensity which might happened due to
synthesis reaction. The functional region were almost similar at different parameters.
GO/ES adsorbent.
5.2 Recommendations
A few recommendations are needed to be done for the improvement of this study
i) The interval time during fluoride removal analysis should be taken at least
5 points to get more accurate result. The removal trend can be observed at
procedures.
41
REFERENCES
[2] Environmental Quality Act 1974: Clean Air Regulation, Ministry of Health
Malaysia, 2016
[6] J. Zhu, X. Lin, P. Wu, Q. Zhou, and X. Luo, "Fluoride removal from aqueous
solution by Al(III)Zr(IV) binary oxide adsorbent," Applied Surface Science, vol.
357, pp. 91100, 2015.
[9] S. K. Nath and R. K. Dutta, "Fluoride removal from water using crushed
limestone," Indian Journal of Chemical Technology, vol. 17, no. 1, pp. 120125,
2010.
42
[10] K. M. Rao., and M. Metre, "Effective Low Cost Adsorbents for Removal of
Fluoride from Water: A Review," International Journal of Science and Research
(IJSR), vol. 3, no. 6, pp. 120 124, 2012.
[11] X. Zhang and X. Wang, "Removal of cu(II) from water environment using
Lignocellulose/ Montmorillonite Nanocomposite-An industrial waste
Adsorbent," Asian Journal of Chemistry, vol. 26, no. 23, pp. 81738180, 2014.
[13] N. R. Neelo Razbe, "Various options for removal of fluoride from drinking
water," IOSR Journal of Applied Physics, vol. 3, no. 2, pp. 4047, 2013.
[15] A. Vinati, B. Mahanty, and S. K. Behera, "Clay and clay minerals for fluoride
removal from water: A state-of-the-art review," Applied Clay Science, vol. 114,
pp. 340348, 2015.
43
[18] P. Banerjee, S. Sau, P. Das, and A. Mukhopadhayay, "Optimization and modelling
of synthetic azo dye wastewater treatment using Graphene oxide nanoplatelets:
Characterization toxicity evaluation and optimization using artificial neural
network," Ecotoxicology and Environmental Safety, vol. 119, pp. 4757, 2015.
[19] P. B. Arthi G and L. BD, "A simple approach to stepwise synthesis of Graphene
oxide Nanomaterial," Journal of Nanomedicine & Nanotechnology, vol. 06, no.
01, 2015.
[21] G. K. S. Geetha K.S, "Removal of heavy metals and dyes using low cost
Adsorbents from aqueous medium-, A review," IOSR Journal of Environmental
Science, Toxicology and Food Technology, vol. 4, no. 3, pp. 5668, 2013.
[22] J. Li, X. Zeng, T. Ren, and E. van der Heide, "The preparation of Graphene oxide
and its derivatives and their application in Bio-Tribological systems," Lubricants,
vol. 2, no. 3, pp. 137161, 2014.
[25] T. K. Sen, "Review on dye removal from its aqueous solution into alternative cost
effective and non-conventional Adsorbents," Journal of Chemical and Process
Engineering, 2013.
[26] R. Bhaumik et al., "Eggshell powder as an Adsorbent for removal of fluoride from
aqueous solution: Equilibrium, kinetic and thermodynamic studies," Journal of
Chemistry, vol. 9, no. 3, pp. 14571480, 2012.
44
[27] A. Mittal, M. Teotia, R. K. Soni, and J. Mittal, "Applications of egg shell and egg
shell membrane as adsorbents: A review," Journal of Molecular Liquids, vol. 223,
pp. 376387, 2016.
[28] W.-T. Tsai, K.-J. Hsien, H.-C. Hsu, C.-M. Lin, K.-Y. Lin, and C.-H. Chiu,
"Utilization of ground eggshell waste as an adsorbent for the removal of dyes from
aqueous solution," Bioresource Technology, vol. 99, no. 6, pp. 16231629, 2008.
[29] M. Masukume, M. S. Onyango, and J. P. Maree, "Sea shell derived adsorbent and
its potential for treating acid mine drainage," International Journal of Mineral
Processing, vol. 133, pp. 5259, 2014.
[30] M. Lee, B.-H. Kim, Y. Lee, and J. B. Park, "Synthesis and Characterization of
Graphene and Graphene Oxide Based Palladium Nanocomposites and Their
Catalytic Applications in Carbon-Carbon Cross-Coupling Reactions," Bulletin of
the Korean Chemical Society, vol. 35, no. 7, pp. 19791984, 2014
[32] J.L. Lepo and A.S. Richard., Impact of Fluoridation of the Municipal Drinking
Water Supply: Review of the Literature, The Center for Environmental
Diagnostics and Bioremediation University of West Florida, 2000.
[33] Green Facts: Facts on Health and the Environment, IPCS Environmental Health
Criteria for Fluorides (EHC 227), 2010.
[34] Meenakshi. R.C.; Maheshwari. J., Fluoride in drinking water and its removal. J.
Hazard. Mater. vol.137, pp. 456463, 2016
[35] Bhatnagar. A., Kumar. E., Sillanp. M. Fluoride removal from water by
adsorptionA review. Chem. Eng. J. vol. 171, 811840. 2011.
45
[36] El-Gohary, F., Tawfik, A., Mahmoud, U. Comparative study between chemical
coagulation/precipitation (C/P) versus coagulation/dissolved air flotation
(D/DAF) for pre-treatment of personal care products (PCPs) wastewater.
Desalination, vol. 252, pp. 106112. 2010.
[37] Chakrabortty. S., Roy. M., Pal. P., Removal of fluoride from contaminated
groundwater by cross flow nanofiltration: Transport modeling and economic
evaluation. Desalination, vol. 313, pp. 115124. 2013.
[38] Piddennavar. R., Review on defloridation techniques of water. Int. J. Eng. Sci.,
vol. 2, pp. 8694. 2013.
[40] Tomar. V., Kumar. D., A critical study on efficiency of different materials for
fluoride removal from aqueous media. Chem. Cent. J. vol. 7, pp. 115. 2013.
[43] A., Ahmad., Study on Effect of HCl and CaCl2 on Extraction of Heavy Metals
From Contaminated Soils, Asian Journal of Chemistry. vol. 21, no. 3, pp. 1690-
1698. 2009.
46
[45] A. Bhatnagar, E. Kumar, and M. Sillanp, "Fluoride removal from water by
adsorptionA review," Chemical Engineering Journal, vol. 171, no. 3, pp. 811
840, 2011.
[49] Liyuan K., et al., FeOOH-graphene oxide nanocomposite for fluoride removal
from water: Acetate mediated nano FeOOH growth and adsorption mechanism,
Journal of Colloid and Interface Science, vol 490, pp. 259 269, 2015.
[50] R. Sun, H.-B. Zhang, J. Qu, H. Yao, J. Yao, and Z.-Z. Yu, "Supercritical carbon
dioxide fluid assisted synthesis of hierarchical AlOOH@reduced graphene oxide
hybrids for efficient removal of fluoride ions," Chemical Engineering Journal, vol.
292, pp. 174182, 2016.
[52] M. Poudyal, and S. Babel., Removal of Fluoride using Granular Activated Carbon
and Domestic Sewage Sludge, 2015 4th International Conference on Informatics,
Environment, Energy and Applications. vol. 82, pp. 139 143, 2015.
47
[53] L. A. Perez-Maqueda., F. Franco., and J. L. Perez-Rodriguez., Comparative study
of the sonication effect on the thermal behavior of 1:1 and 2:1 aluminium
phyllosilicate clays, Journal of the European Study. vol. 25, pp. 1463 1470.
2005.
48