CHAPTER 1

INTRODUCTION

1.1 Research Background

Wastewaters generated from industrial activities contain a variety of potentially

toxic and environmentally harmful compounds. One of the common contaminant in

industrial wastewater is fluoride. Fluoride generally found in many untreated industrial

effluents that usually come from chemical plant manufacturing organofluorine

compounds, aluminum smelters, phosphate fertilizers, semiconductor manufacturing,

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

concentration of fluoride in industrial wastewater should be controlled in a reasonable

level. The recommended acceptable discharge condition of fluoride of industrial effluent

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].

1
 In view of this fact, it is essential to develop a fast, selective, economic and eco-

friendly method for fluoride removal in wastewater. Hence, numerous conventional

methods have been proposed to remove fluoride from wastewater including precipitation,

electrochemical treatment, ion exchange, membrane separation, adsorption, nano-

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

contained together in the wastewater [5].

In recent years, a number of carbon nanomaterial have been developed as an

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

effluents. Many adsorbents such as activated alumina, synthetic ion exchanger,

hydroxyapatite and bone charcoal have been widely implemented as defluoridation

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

fluoride removal in wastewater system.

Graphene oxide (GO) is an oxidized derivative of graphene contains a large

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

on synthesis and modification of GO with natural calcium-based adsorbent material.

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

produce a new selective adsorbent.

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,

eggshell is considered inexpensive and have little economic value to be developed.

Therefore, the synthesis and modification of GO with the eggshell adsorbent (GO/ES) to

remove fluoride in the wastewater is to be investigated.

3
1.2 Problem Statement

Today, fluoride contaminant in industrial wastewater effluent has become one of

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.

GO is widely used as an adsorbent for many applications owing to its hydroxyl,

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

adsorption capacity of synthesis materials need to be developed. Hence, natural calcium-

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

objectives for this study:

1. To study the effect of synthesis parameters of GO/ES ratio, synthesis temperature and

synthesis time on the GO on the fluoride removal.

2. To compare the adsorption capacity of modified GO/ES adsorbent with GO/CaCl2

towards fluoride removal.

1.4 Scope of Work

The natural calcium-based material in this study will be tested by introducing

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

adsorbent will be compared with the chemical calcium-based adsorbent, which is

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

adsorbent will be analyzed by using Fourier transform infrared spectrum (FTIR)

5
 CHAPTER 2

LITERATURE REVIEW

2.1 Fluoride in Industrial Wastewater

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

present in surface and groundwater as fluoride ion. In some instances, fluoride is a

common contaminant in a variety of industrial wastewater and often present in a variety

of untreated industrial effluent. Some of the industry are involving chemical plant

manufacturing organofluorine compounds, aluminum smelters, phosphate fertilizers,

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

concentration of fluoride in industrial wastewater should be controlled in a reasonable

level. The recommended acceptable discharge condition of fluoride of industrial effluent

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.

Table 2.1: Industrial effluent discharge limits [2]

Parameter Unit Standard

A B
Temperature - 40 oC 40 oC
pH Value - 6.0-9.0 5.5-9.0
BOD at 20oC mg/L 20 50
Suspended Solids mg/L 50 100
Fluoride mg/L 2.0 5.0
Colour ADMI* 100 200
*ADMI-American Dye Manufacturers Institute

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

fluoride in large scale.

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

with an alkalinitys portion to deliver insoluble aluminium hydroxide [Al(OH)3]. In the

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

from the process into the water.

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

membrane. It is a reverse of natural osmosis as a consequence of applied hydraulic

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

and disadvantages of different available technologies for fluoride removal.

Table 2.2: Advantages and disadvantages of available technologies

Technologies Advantages Disadvantages References

Coagulation and High efficiency and Expensive, efficiency

precipitation commercially depends of pH and
available chemical presence of co-ions in
water, formation of sludge [36]
with high amount of toxic
and high amount of
retained water (sludge
dewatering is required prior
disposal)

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

Electrochemical High efficiency and High cost during

treatments: high selectivity installation and
Electro-dialysis, maintenance [34,35]
electro-
coagulation

Ion-exchange High efficiency Expensive, replacement of

media after multiple [38,40]
regenerations, used media
present toxic solid waste,
re-generation creates toxic
liquid waste, efficiency
highly pH-dependent

Adsorption Greater accessibility, High efficiency often

materials: low cost, simple demand adjustment and re-
Activated operation and adjustment of pH, some [39]
alumina, activated availability of wide common water ions can
carbons and range of adsorbents interfere fluoride
synthetic adsorption
adsorbents

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

electrochemical treatment method that involve electro-dialysis or electro-coagulation and

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

advantages offered, adsorption is more favourable technology in industry nowadays.

2.3 Adsorption of Fluoride

Adsorption is defined as a process of accumulation of any substance from higher

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

phase (adsorbate) accumulate or concentrate at the surface (adsorbent) [3]. Adsorption is

a well-established and most favourable technique for treating domestic and industrial

effluents. This method is important because of its accessibility in extensive variety of

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

extensive variety of pH to a lower concentration compared to precipitation [13]. Among

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

and operation [14].

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

efficiency of fluoride by using activated alumina is influenced by solution pH and the

optimum operating pH is found at range of 5 to 7 [14]. Researcher explains that adsorption

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

available in fluoride removal application.

Table 2.3: Various types of adsorbent used for fluoride removal applications

Adsorbent Optimum pH Percent removal (%) References

Red mud 5.5 75.0 [44]

Alumina/MgO 7.0 95.0 [44]

Bone char 7.0 70.64 [45]
La/Chitosan beads 5.0 97.0 [44,46]

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]

According to studies done by various researchers as represent in Table 2.3, firstly,

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

Alumina/MgO adsorbent or also known as magnesia-amended activated alumina

(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%

removal of fluoride at neutral condition [45].

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

72% of fluoride removal at the optimum pH of 7 [18].

2.4 Graphene Oxide (GO) as Fluoride Adsorbent

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

excellent physicochemical and mechanical properties. The preparation of GO from the

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

adsorption of a variety of adsorbate. In addition, the formation of stable aqueous colloid

can be obtained from the functional group.

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.

Table 2.4: Graphene-based adsorbent in fluoride removal application

Adsorbent Preparation Chemical Adsorption Condition Reference

Method Additive Capacity
(mg/g)

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

capacity compare to graphene by itself.

2.5 Synthesis Method of Graphene Oxide (GO)

Many researchers are attracted to the properties of graphene oxide (GO) as an

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.

However, the synthesis of GO in an economical and efficient way remains a great

challenge. Generally, GO is synthesized via chemical oxidation of natural graphite as an

alternative of electrochemical oxidation. Graphite oxide is synthesized by adding

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

concentrated sulphuric acid (H2SO4) and feeding the chlorate in batches.

Despite the above progress, new synthesis method have been developed and lead

to the common implementation in recent years. The most common method involved

chemical modification of synthesis by Hummers method. This method can be performed

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

to be treated with hydrogen peroxide (H2O2) to terminate the reaction by appearance of

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

until it produces GO powder [19].

Graphene oxide (GO) can be readily modified for particular applications due to

the existence of abundant oxygen-containing functional groups. Graphene oxide-based

material which are biocompatible and hydrophilic, have wide potential applications in

biomedical engineering and biotechnology. The GO mainly consist of chemically reactive

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

chemical modication which it would utilize orthogonal reactions of these groups to

selectively functionalize one site over another [20].

2.6 Modification of Graphene via Calcium-based Material

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

shows the percentage of fluoride removal for various adsorbent materials.

Table 2.5: Percentage of fluoride removal for different adsorbent materials

Calcium-based Material Fluoride Removal (%) References

Pine Apple Peel Powder 82 [25]

Orange Peel Powder 79 [25]

Chalk Powder 86 [25]

Eggshell 80 [9]

Seashell 84 [10]

Horse Gram Powder 75 [25]

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

the removal of variety of organic as well as inorganic hazardous chemical from

wastewater. Generally, the chemical composition of (by weight) of eggshell consist of

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

considered as a natural calcium-based in this research.

Mainly, eggshell contains of calcium carbonate (94%), calcium phosphate (1%),

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

the immobilization of heavy metals in wastewater and soil.

19
 CHAPTER 3

RESEARCH METHODOLOGY

3.1 Chemicals and Materials

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

Chemicals / Materials Purity Function

Commercial graphite powder 99.99% Synthesis of Graphene Oxide(GO)

Sulphuric acid (H2SO4) 96% Synthesis of Graphene Oxide(GO)

Sodium nitrate (NaNO3) 99.00 100.5% Synthesis of Graphene Oxide(GO)

Hydrogen peroxide - Synthesis of Graphene Oxide(GO)

Potassium permanganate 99.00 100.5% Synthesis of Graphene Oxide(GO)

(KMnO4)

Hydrochloric acid (HCl) - Modification of GO with NCa

20
3.2 Equipment

For this experiment, the main equipment used were analytical balance, magnetic

stirrer, micropipette, oven, orbital shaker (AAH31105K; Model: SK-300), centrifuge

(Kubota 4200), portable spectrophotometer (HACH DR 2700) and Fourier Transform

Infrared Spectroscopy (FTIR) (Model: Nicolet 6700 FT-R).

3.3 Flowchart

The main aim of this experiment is to synthesis GO with natural calcium-based.

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

3.1 illustrated the flowchart throughout this project.

21
 Synthesis of GO

Modification of GO
with ES material

Parameter of Parameter of Parameter of Comparison GO/ES

GO/ES ratio synthesis time synthesis temperature with GO/CaCl2

Fluoride
Analysis
No

Yes

Characterization
analysis

Figure 3.1: Experimental flowchart

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

collected [19, 30, 51].

3.5 Synthesis of GO/ES

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,

and sieved to obtain 250 m size particles [28, 29].

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

ml DI water and sonicated with constant parameter (T = 45 oC, t = 60 minutes). Initially,

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

and centrifuged at 3000 rpm and dried at 60 C overnight [5].

3.6 Fluoride Removal

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

initial concentration which is 30 mg/L by exact dilution procedure.

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

method by using Hach DR 2800 Spectrophotometer. Generally, blank solution was

prepared by inserting 3 to 5 mL of deionized water into blank cuvette. Sample solution

was prepared by inserting 3 to 5 mL of NaF solution into sample cuvette. Then, 2.0 mL

of SPADNS Reagent Solution was added into each sample cell.

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.

The fluoride concentration (mg/L) was analyzed by using spectrophotometer in

order to get fluoride concentration value. The adsorption capacity can be calculated by

using the following equation [3].

= [ ] (3.1)

where, Qe is the amount (mg/g) of fluoride adsorbed at equilibrium, Co is initial

concentration (mg/L), Ct is the equilibrium concentration (mg/L) at time t and m is the

weight of adsorbent (g/L). The percentage of fluoride removal can be calculated by using

following equation [3].

% = [ ] 100 (3.2)

where, Co and Ct have the same meaning.

25
3.8 Characterization Analysis

GO/ES and GO/CaCl2 adsorbent were characterized by using Nicolet, Thermo

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

of certain functional groups in a molecule. Basically, analysis of FTIR consists of source,

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

RESULTS AND DISCUSSIONS

4.1 Introduction

In this project, GO was synthesized from graphite powder by using Modified

Hummers method. GO in slurry form was then modified with eggshell (ES) powder, as a

natural calcium-based adsorbent by using impregnation method. The objectives of this

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

investigated by performing fluoride adsorption analysis. Next, the adsorption capacity of

modified GO/ES adsorbent was compared with modified GO/CaCl2 adsorbent, which

refer to chemical calcium-based. Lastly, the functionalization of GO/ES modification for

each parameter were characterized by using Fourier transform infrared spectrum (FTIR).

4.2 The effect of GO/ES ratio

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)

Adsorption capacity, mg/g Percentage removal, %

Figure 4.1: Fluoride adsorption analysis for ratio parameter

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),

there is a high possibility of sorbent-sorbate interaction due to the increase in number of

sorption sites, meanwhile at lower eggshell ratio, the number of fluoride ions is relatively

higher compared to the availability of adsorption sites [52]. In addition, it is supported by

the behavior of the eggshell that consist 94% of chemical composition of calcium

carbonate and serve as a good biosorbent [26].

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

trend is increasing as the modified adsorbent dominated by the eggshell composition on

the GO surface. In view of this fact, this is influenced by the characteristic of the eggshell

as an efficient adsorption material in fluoride removal.

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)

Figure 4.2: FTIR spectrum at different ratio

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

correspond to alkoxy C-O stretching vibration. Therefore, the formation of GO is

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].

Next, the functionalization of modified GO/ES was analyzed at each different

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

to Ca) onto =C-H surface, respectively.

The next ratio shows that the composition of GO is reduced (1:1) and the

composition of eggshell is increased (1:5), respectively. The enhanced intensity of O-H

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

onto the GO surface.

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.

Adsorption capacity or percentage removal relies on upon adsorbate (F-) in liquid

diffusing to the surface of the adsorbent, where they bond with the solid surface or are

held there by frail intermolecular forces.

4.3 The effect of synthesis temperature

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)

Adsorption capacity,mg/g Percentage removal, %

Figure 4.3: Fluoride adsorption analysis for temperature parameter

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

diameter of adsorbent can contribute on effective adsorption process [42]. Therefore,

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

synthesis temperature increase. Nevertheless, 29.65% of fluoride had been removed by

the modified GO/ES adsorbent at synthesis temperature of 30 oC. As the synthesis

32
temperature increased to 45 oC, the fluoride removal percentage is increase to 31.30%.

The greatest removal is observed at 60 oC as 36.32% of fluoride is removed.

Functional analysis was then conducted to determine the presence of functional

groups in GO after modification with the eggshell at different synthesis temperature,

within the range 4000 to 500 cm-1. The functional group trend was analysed as shown in

Figure 4.4 below.

GO
GO/ES (T=30oC)
GO/ES (T=45oC)
GO/ES (T=60oC)

Figure 4.4: FTIR spectrum at different synthesis temperature

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.

Adsorption capacity or percentage removal relies on upon adsorbate (F-) in liquid

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.

4.4 The effect of synthesis time

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)

Adsorption capacity, mg/g Percentage removal, %

Figure 4.5: Fluoride adsorption analysis for time parameter

The tabulated data reveals that the increasing synthesis time had increase the

adsorption capacity, respectively. The adsorption capacity at synthesis time of 30 minutes

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

stable and homogenous impregnation of modified adsorbent, it is not necessary to increase

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)

Figure 4.6: FTIR spectrum at different synthesis time

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

functionalization of modified GO/ES adsorbent. Based on the FTIR spectrum analysis,

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

adsorption process is active at those range of functional group.

4.5 Comparison analysis between GO/ES with GO/CaCl2

The comparison was made by introducing chemical-based calcium which is

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

g/L of GO/ES adsorbent.

Table 4.1 shows the adsorption capacity and fluoride removal percentage obtained

from the adsorption analysis.

Table 4.1: Fluoride comparison analysis

Adsorbent Initial Final Adsorption Percentage

concentration, concentration, capacity, Qe removal (%)

Co (mg/L) Ct (mg/L) (mg/g)

GO/ES 29.68 20.39 46.45 31.30

GO/CaCl2 29.68 19.89 48.95 32.99

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

during modification which attribute to effective fluoride removal in wastewater. In fact,

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

Figure 4.7: FTIR spectrum for GO/ES and 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-

H stretching vibration with bonded hydrogen to prove the existence of GO particles.

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

CONCLUSION AND RECOMMENDATIONS

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

between GO/ES adsorbent with GO/CaCl2 adsorbent on removing fluoride from

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.

Lastly, the modified GO/CaCl2 contributed to a greater fluoride removal compared to

GO/ES adsorbent.

5.2 Recommendations

A few recommendations are needed to be done for the improvement of this study

in future. The recommendations are detailed as follows:

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

various contact time to enhance the trend observation.

ii) Adsorbent characterization must require more analysis parameter to be

analyzed. The Brunauer Emmet Teller (BET) analysis, titration for

checking surface acidity, thermogravimetric analysis (TGA), scanning

electron microscopy (SEM), transmission electron microscopy (TEM) and

X-ray diffraction (XRD) should be taken into consideration in order to get

a more detail properties of the adsorbent.

iii) The preparation of GO by using modified Hummers method must be

performed carefully and efficiently since the process is exothermic reaction

and really sensitive to controlled temperature throughout the synthesis

procedures.
41
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