Synthesis and Characterization of reduced GO Composite

with Fe3O4 (Magnetite) Nanoparticles

BS Thesis
By
Mahpara Aslam
Anum Iqbal
Afsheen Abid

Supervised by
Dr. Shumaila Sajjad
Department of Physics,
FBAS
International Islamic University Islamabad
(2015)

Synthesis and Characterization of reduced GO composite

with Fe3O4 (Magnetite) Nanoparticles

Mahpara Aslam

Anum Iqbal

137-FBAS/BSPHY/S11

120-FBAS/BSPHY/S11

Afsheen Abid
127-FBAS/BSPHY/S11

Department of Physics
International Islamic University
Islamabad, Pakistan
(2015)

This thesis is submitted to the Faculty of Basic and Applied Sciences (FBAS),
International Islamic University Islamabad (IIUI) in partial fulfillment of the
requirement for the degree of BS Physics

Declaration of Originality

We hereby declare that the work contained in this thesis and the intellectual content of
this thesis are the product of our own work. This thesis has not been previously published in any
form nor does it contain any verbatim of the published resources which could be treated as
infringement of the international copyright law.
We also declare that we do understand the terms of copyright and plagiarism and that in
case of any copyright violation or plagiarism found in this work, we will be held fully
responsible of the consequences of any such violation.

Mahpara Aslam
Anum Iqbal
Afsheen Abid

Certificate
This is to certify that the work contained in this thesis entitled: Synthesis and
characterization of reduced GO composite with Fe3O4 magnetic Nanoparticles has been carried
out by Mahpara Aslam, Anum Iqbal and Afsheen Abid under my supervision. In my opinion, this
is fully adequate in scope and quality for the degree of BS Physics.

Supervisor

Department of Physics
International Islamic University

INTERNATIONAL ISLAMIC UNIVERSITY, ISLAMABAD

FACULTY OF BASIC AND APPLIED SCIENCES
DEPARTMENT OF PHYSICS
Dated: 02 -02-2015

FINAL APPROVAL
It is certified that the work presented in this thesis entitled Synthesis and Characterization of
reduced GO Composite with Fe3O4 (Magnetite) Nanoparticles by Miss Mahpara Aslam (137FBAS/BSPHY/S11) Anum Iqbal (120-FBAS/BSPHY/S11) and Afsheen Abid (127-FBAS/BSPHY/S11) (is of
sufficient standard in scope and quality for the award of degree of BS Physics from International
Islamic University, Islamabad.

COMMITTEE

External Examiner
Dr. Sadaf Jamil Rana
Assistant Professor
Department of physics

___________________________

Supervisor
Dr. Shumaila Sajjad
Assistant Professor,
Department of Physics, FBAS, IIUI

___________________________

Acknowledgment

Praise is to the One, the Almighty, the merciful and the beneficent Allah, who is the
source of all knowledge and wisdom, taught us what we knew not. We offer our humblest thank
to the holy Prophet (Peace be upon him) who is forever a model of guidance and knowledge for
humanity.
We are highly indebted to our affectionate supervisor Dr. Shumaila Sajjad for their inspiring
guidance, remarkable suggestions, constant encouragement, constructive criticism and cooperation during our project work. Without their support and guidance, this report could not have
been possible.
We are also grateful to all our friends and class fellows for giving us encouragement,
appreciation and helped in completing this project.

Mahpara Aslam
Anum Iqbal
Afsheen Abid

Dedication

This thesis is
Dedicated to
Our Beloved Parents

10

Table of contents
Chapter No.1: Introduction to Material01
1.1 An Overview of Graphite...01
1.2 An Overview of Graphite Oxide.....02
1.3 An Overview of Graphene Oxide ..03
1.3.1 Introduction....03
1.3.2 Structure of Graphene Oxide.03
1.3.3 Synthesis of Graphene Oxide.04
1.3.3.1 Broides Synthesis.....05
1.3.3.2 Staudenmaiers Synthesis..05
1.3.3.3 Hummers Synthesis......05
1.3.4

Properties of Graphene Oxide...06

1.3.4.1 Dispersibility..06
1.3.4.2 Toxicity..07
1.3.4.3 Reactivity.......07
1.3.4.4 Electrical Properties...09
1.3.4.5 Thermal Properties.09
1.3.4.6 Optical Properties...10
1.3.4.7 Mechanical Properties10
1.4 Introduction to Iron Oxides..11
1.4.1 Structure of Wstite...11
1.4.2 Structure of Hematite.12
1.4.3 Structure of Magnetite...12
1.4.4 Magnetite Nanoparticles....13
1.4.4.1 Natural Occurrence13
1.4.4.2 Crystal Structure of Magnetite Nanoparticles....14
1.4.4.3 Properties of Magnetite Nanoparticles...14
1.4.4.3.1 Optical Properties...14
1.4.4.3.2 Electrical Properties...15
1.4.4.3.3 Magnetic Properties...15
Chapter No.2: Literature Review...17
Chapter No.3: Experimental Work23
3.1 Synthesis of Graphene Oxide...23
3.2 Apparatus.....23
3.3 Preparation of Graphene Oxide...23
11

3.3.1 Materials ...23

3.3.2 Procedure..............................................................................................................24
3.4 Exfoliation of Graphene Oxide...25
3.4.1 Mechanism of Exfoliation....25
3.5 Preparation of r-GO.26
3.5.1 Reduction with NaOH......26
3.6 Formation of magnetite (Fe3O4) Nanoparticles...27
3.6.1 Materials....27
3.6.2 Procedure..............................................................................................................27
3.7 Composite Formation of r-GO with Magnetite Nanoparticles27
Chapter No.4: Results and Discussion..29
4.1 Morphological Investigation29
4.2 Structural Analysis..32
4.3 Compositional Analysis.....37
4.4 Photocaytalatic Activity of r-Go, Fe3o4 and Their Composite under UV Light..38
4.4.1 Photo Catalysis..40
4.4.2 Basic Mechanism of Photo Catalysis....41
4.4.3 Properties of Photo Catalysis....42
4.5 Photo Catalysis Mechanism of Composite (r-GO and Fe3O4).42
4.6 Observations....44
Conclusion....50
References.51

12

List of Figures
Fig: 1.1 Structure of Hexagonal Graphite..........................................01
Fig: 1.2 Structure of Graphene Oxide....................04
Fig:1.3 Digital pictures of GO dispersed in water and 4 organic solvents....06
13

Fig: 1.4 Time-dependent antibacterial activities of GO and r-GO ....07

Fig: 1.5 A proposed reaction pathway for ep-oxide reduction by hydrazine ....08
Fig: 1.6 Structure of unit cell of FeO ................11
Fig: 1.7 Structure of Hematite...12
Fig: 1.8 Structure of magnetite..........................................................13
Fig: 3.1 Dark yellow color of graphite during oxidation process..........24
Fig: 3.2 Graphene oxide flakes..........25
Fig: 3.3 Schematic diagram from Graphite to exfoliated Graphene oxide....26
Fig: 4.1 SEM images of reduced graphene oxide and graphite.....................................................30
Fig: 4.2 SEM images of r-GO/Fe3O4 composite at different resolutions .........32
Fig: 4.3 XRD graph of graphite and graphite oxide .33
Fig: 4.4 XRD graph of graphite and graphene oxide.....34
Fig: 4.5 XRD graphs of graphite oxide and graphene oxide.34
Fig: 4.6 XRD pattern of r-GO by using NaOH..35
Fig: 4.7 XRD pattern of r-GO/Fe3O4 composite and Fe3O4 NPs............................................36
Fig: 4.8 EDX graph of reduced graphene oxide....37
Fig: 4.9 EDX analysis of r-GO/Fe3O4 composite..38
Fig: 4.10 Basic mechanism of Photo Catalysis......41
Fig: 4.11 Nanocomposite of r-GO and Fe3O4 for photo catalysis ....43
Fig: 4.12 Pictorial representation of the photo catalytic mechanism of r-GO/ Fe 3O4
Composite..44
Fig: 4.13 Photo catalytic activity of r-GO to MB under UV light 45
Fig: 4.14 Photo catalytic activity of Fe3O4 to MB under UV light .......45

14

Fig: 4.15 Photo catalytic activity of r-GO and Fe3O4 composite (5%) to MB under UV
light46
Fig: 4.16 Photo catalytic activity of r-GO and Fe 3O4 composite (10%) to MB under UV
light47
Fig: 4.17 Photo catalytic activity of r-GO and Fe 3O4 composite (15%) to MB under UV
light47
Fig: 4.18 Graphical representation of photo catalytic activity of r-GO, Fe 3O4 and their
composite...48

List of Tables

Table 1.1: Reactivity of Functional Groups on GO with Different Chemical Reagents ..........08

15

Abstract
We have made the graphene oxide by using Hummers method. Which was further
reduced by using NaOH, which is as a reducing agent. Further magnetite nanoparticles were
prepared using co-precipitation method. Composite of r-GO/Fe3O4 in different ratios of magnetite
was formed. Different characterization techniques were done to understand the morphological
and structural properties of above mentioned materials. We also checked the photo catalytic
activity of GO, magnetite nanoparticles and their composite under UV light.

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Chapter No. 1
Introduction to Material
1.1.

An overview of Graphite

Graphite is an allotropic form of carbon. It has low density and non-expensive material. For
many years microcrystalline graphite has been used as the active ingredient in lead pencils.[1]
Graphite is a major additive to many industrial systems where it provides functionality as a
refractory, lubricant, thermal conductor, electrical conductor, UV shield, electromagnetic pulse
shield, corrosion shield, pigment, etc. The word graphite is derived from the Greek
word graphei, which means, to write. It is an inorganic material and about 99% of graphite
synthesis from petroleum and other organic carbon sources .[2] Graphites electrical and thermal
conductivity is very high and dependent on its structure. Electrical resistivity of single crystal of
graphite is from (4 to 6x10-5) Ohm-cm, which has the same order of the conductivity as of poor
metal. Due to the crystal boundaries, the resistivity of polycrystalline graphite is much higher.
The structure of graphite is multi-layered and its each layer contains hexagonal lattice pattern.
As shown in Figure1.1,graphite is made of parallel layers of graphene.[3]

Figure 1.1: Structure of Hexagonal Graphite

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In figure, Yellow spheres show carbon atom and green lines show the covalent bonds between
carbon atoms. The weak Vander Waal forces are represented by dotted lines between the parallel
hexagonal rings that allow sliding movement. The angle of 120 is present between two covalent
bonds. The distance between each hexagonal lattice of the same plane is 1.42 and the space
between each lattice plane is 3.37.[4] Each layer of carbon atom of graphite is sp2 hybridized.[5]
Natural graphite is of three kinds: flake graphite, vein graphite and microcrystalline graphite. The
most

common

source

of

graphite

is

flake

graphite.[6]

Flake graphite is used in chemical reactions. It is a natural mineral. The purified flake graphite is
used to remove heteroatom contamination.[7] The electrical conductivity of pure graphite is high
because of its high crystalline structure. Microcrystalline graphite is also called amorphous.
Other than natural graphite, synthetic graphite is also present such as primary synthetic graphite
and graphite fiber. Due to unique properties of graphite, it can be used as carbon brushes,
refractory materials, lubricants, friction materials and cathode material in zinc-carbon and
lithium-ion batteries. [6]

1.2.

An Overview of Graphite Oxide

Graphite Oxide (named as graphitic acid before the discovery of graphene) is the combination of
carbon, oxygen and hydrogen. Graphite oxide has the structure of graphene oxide, which is very
hydrophilic in nature and is nearly amorphous.[8] there is a no much difference between graphite
oxide and graphene oxide .single layer of graphite oxide can be known as graphene oxide. when
graphite oxide dispersed in different solvents, it is exfoliated by the solvent molecules and
because of exfoliation the distance between the layers of graphite oxide increases and then it can
be referred as graphene oxide So thats why we generally abbreviate both graphite oxide and
graphene oxide as GO, since there is no much big difference between them, even in their of
electronic structures and properties (the case is different for graphite and graphene). So from
now we can refer both graphite oxide or graphene oxide or graphitic acid as GO.

CHAPTER 1
1.3.

TO MATERIAL

INTRODUCTION

An Overview Of Graphene Oxide

1.3.1. Introduction
Graphene oxide can also be named as graphitic acid or graphite oxide is a 1nm thick compound
of carbon, oxygen, and hydrogen in variable ratios. It contains hydroxyl, carboxyl, ketone, ester
& ep-oxide functional groups attached with carbon atoms.
It is (GO) is an oxygen-rich monolayer nanomaterial. It is provided by the controlled oxidation
of graphite. GO can be prepared by exfoliation or heat expansion of graphite oxide. [9] During
the oxidation of graphite using strong oxidizing agents, oxygenated functionalities are introduced
in the graphite structure which not only expand the layer separation, but also makes the material
hydrophilic. [10] This property enables the graphite oxide to be exfoliated in water using
sonication and ultimately produced single or few layer graphene oxide (GO). The main
difference between graphite oxide and graphene oxide is, thus, the number of layers. While
graphite oxide is a multilayer system in graphene oxide dispersion a few layers flakes and
monolayer flakes can be found.

1.3.2. Structure Of Graphene Oxide

It is a single-atom layer of carbon with functional groups containing oxygen. its composition is
not well defined, but is usually taken as approximately C4O(OH) for the most highly oxidized
form.[11] Structurally, Graphene Oxide can be visualized as a graphene sheet with its basal plane
decorated by oxygen-containing groups.[12]

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Figure 1.2: Structure of Graphene Oxide

Graphene oxide contains carboxylic acid group at edges and epoxy and hydroxyl groups on basal
planes.[13] Distribution of oxygen in GO is highly non-uniform, with approximately 2-3 nm
domain of very high oxidation. The average thickness of our single layer graphene oxide is 0.71.2nm.[14]. Graphene oxide is non-conducting due to the oxygen groups on the carbon layers
and the conductivity is restored through reduction by thermal or chemical means.[15] GO are
hydrophilic since the hydroxyl (OH) groups are bonded to the surface of the GO nanosheets,[16]
therefore GO is the precursor material for synthesis of hydrophobic graphene.[17]
Pure graphene is sp2-bonded, meaning that in the valence shell of each carbon atom, the 2s
orbital and two of the three 2p orbitals mix together to produce three hybridized sp 2orbitals.
Under local oxidation, however, the 2s orbital mixes with all three 2p orbitals, producing four
hybridized sp3orbitals, and thus the regions of GO where oxygen functional groups are attached
are sp3-bonded.[12, 15]

1.3.3. Synthesis Of Graphene Oxide

Natural graphite can be converted into Graphene Oxide by three different methods:

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1.3.3.1. Broides Synthesis

B.C. Brodie was a professor at the University of Oxford in 1859 who was First attempt to
oxidize the graphite.[12] This attempt of Brodie leaded to the formation of graphene oxide.
When Brodie used the mixture of potassium chlorate( KClO3) and fuming nitric(HNO3) acid
with graphite and after heating they observed that the dull grey graphite had gained weight and
taken on a light yellow color.[18] Upon weighing the substance, Brodie also noticed that the
substance had gained weight from the original graphite used: an indication of oxidization.

1.3.3.2. Staudenmaiers Synthesis

In 1898 by L.Staudenmaier takes Broides work to a next step, in which he introduced two major
changes in Broides method.
1) Added conc. sulfuric acid to increase the acidity of the mixture.
2) Added multiple aliquots of potassium chlorate solution into the reaction mixture over
the course of reaction. (This addition of potassium chlorate typically lasted over a week,
and during this reaction chlorine dioxide evolved, which needed to be removed by an
inert gas.
These changes lead to a highly oxidized product but the product composition was same as
that of Borides.
This reaction was a constant threat to explosion and very time consuming thats why this
process was not worth performing.

1.3.3.3. Hummers Synthesis

After almost 60 years of Staudenmaier experiment Hummers and Offeman made great
contribution for the synthesis of GO. He used sulfuric acid (H2SO4), sodium nitrate (NaNO3) and
potassium permanganate (KMnO4) for the oxidation of graphite and within 2-3 hours a highly
oxidized GO is produced.
Graphite oxide is also the middle product in the process of graphene synthesis since graphite
oxide can be fully exfoliated into graphene oxide sheet when it is in the form of aqueous
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colloidal suspensions. When graphite oxide sheets are dispersed in water ,they carry negative
charge.[19] Graphite oxide can form a stable aqueous suspension which is due to the electrostatic
repulsion.[9]

1.3.4. Properties Of Graphene Oxide

1.3.4.1. Dispersibility
GO and RGO can be dispersed in water by using sonication and mechanical stirring.
The sonication process is not much favourable because it creates defects and reduce size of GO
from microns to several hundred nanometers , mechanical stirring is more favourable but it is a
time consuming process than that of sonication.[20]
The dispersibility of GO depend upon the polarity of solvent .the more polar the solvent is, the
more dispersible the GO in it. GO dispersibility in water are usually on the order of 1-4 mg mL 1

.[21] GO can also be dispersed in organic solvents .such as ethylene glycol, DMF, NMP, THF

and etc.[20] Water dispersibility of GO is superior as compared to r-GO. [22]

Figure 1.3: Digital pictures of GO dispersed in water and 4 organic solvents through
ultrasonication (1 h). Top view: dispersions immediately after sonication. Bottom view:
dispersions 3 weeks after sonication obtained from reference [23]

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1.3.4.2. Toxicity
The evidence of GO and RGO antibacterial activity is reported by a Liu et al. [24] the sharp
edges of GO and RGO induced stress on the membrane of E.coli bacteria and cause physical
cell damage . GO shows good anti bacterial activity than RGO [24]

Figure 1.4: Time-dependent antibacterial activities of GO and r-GO has been shown in figure
obtained from reference [24]
Sometimes the toxicity of GO and RGO show dose dependent toxicity to bacteria. High
concentrations of GO or RGO can be harmful for human body, for example the effect of GO on
human fibroblast cells [25] is dose dependent.Hu et al. study shows that GO represent minimal
toxicity to bacteria (human alveolar epithelial A549 cells). GO does not enter the A549 cell but
high concentrations of GO can cause a oxidative stress in cell.[26]

1.3.4.3. Reactivity
In general chemistry, the term reduction is defined as the gain of electrons or loss of oxygen. In
fact, the qualitative definition of reduction in organic chemistry is conversion of a functional
group in a molecule from one category to a lower one. [27] there are many different mechanisms
7

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INTRODUCTION

for reduction while the exact mechanism of a reduction process is often difficult to deduce. The
GO reacts with different reducing agent but the most effective chemical used to reduce GO to
RGO is hydrazine. The first ever reduction was done by the Hofmann in 1934 using H2S.

Figure1.5: A proposed reaction pathway for ep-oxide reduction by hydrazine [9]

A group of different chemical reagents is given in the following table. In which it is shown that
how every reagent react with different functional groups to reduce GO .the properties of RGO
depend upon the reagent used to reduce GO.[8]

Table 1.1: Reactivity of Functional Groups on GO with Different Chemical

Reagents obtained from reference [23]

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INTRODUCTION

GO is a chemically reactive compound and can easily reduced to RGO (pristine graphene),
although no reagent gives a 100% reduction to form pure oxygen free graphene and left some
functional groups intact.

1.3.4.4.

Electrical Properties

Graphene oxide is electrically insulator in nature whereas graphene is electrical conductor due to
the presence of sp2 bonding in carbon atoms as in sp2 bonding delocalized pi electrons are
present which are responsible for graphene conducting behavior [28]but in graphene oxide this
sp2 bonding transforms in sp3 bonding due to the attachment of functionalized oxygen groups
with carbon atom at edges and basal planes of atomic layer.[29] This sp3 bonding of carbon
atoms reduces the presence of delocalized electrons in graphene oxide and thus reduces its
electrical conductivity.

1.3.4.5. Thermal Properties

Thermal properties of all materials are associated with vibrational energy of atoms. Atoms in
solid materials are constantly vibrating at high frequencies; these vibrations of adjacent atoms
are coupled by virtue of atomic bonding. Thus these vibrations are coordinated in lattice in such
a way that travelling lattice waves are produced. These waves are simply elastic waves having
short wavelength and higher frequencies which propagate through crystal at the velocity of
sound. These elastic waves are also called as phonons. These elastic waves or phonons
participate in transport of energy during thermal conductance. So the thermal conductivity in
case of graphene oxide can also be described in terms of these phonons.
The thermal conductivity of graphene oxide is only 5% to that of pristine graphene due to the
following reasons: Functional groups, [30] defects, [31] edge disorder and strain.[32]
Phonons in the graphene oxide sheet were scattered at the sp2-sp3 boundaries due to different
vibrational characteristics of these carbon atoms, lowering the thermal conductivity.[33] The
changes in vibrational characteristics of atoms are closely related to the type and length of the
bonds with which they are connected to each other. The bond length between those carbon atoms
9

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INTRODUCTION

showing the sp2-sp2 bonding is 1.41 in graphene and for carbon atoms showing sp2-sp3 bonding
is 1.51in graphene oxide, so it shows that carbon atoms exhibiting sp2-sp3 bonding is far apart
from each other and decreasing the vibrational energies of atoms thus decreasing the thermal
conductivity.
In addition, there exist an inverse relationship between the degree of oxygenation and the
thermal conductivity of GO. This relationship can be understood by the increase in phonon
scattering with increasing oxygenation.[34]

1.3.4.6.

Optical Properties

Optical properties of every material are dependent upon the nature of its band gap. In order to
understand the band gap of graphene oxide, first consider the band gap of graphene. As the
graphene has zero band gap due to sp2 bonding since sp2 bonding contains the delocalized
electrons which are responsible for good conduction properties [35] and this behavior supports
the low band gap energy values nearly about 0.5ev. Now when oxygenated functionalized groups
are attached at basal planes and at boundaries of one atom thick carbon sheets to form the
graphene oxide, then the bonding of carbon atoms bearing these functional group is changed into
sp3 bonding. As a result greater the concentration of sp3 bonds, the larger is the band gap.
Because sp3 bonding contains the localized electrons which are responsible for low conduction
properties and this behavior supports the greater band gap. Thats why graphene oxide has direct
band gap. [36]
Moreover, graphene oxide also shows the properties of Photoluminescence due to quantum
confinement.[37] This quantum confinement occurs because in graphene oxide pi electron wave
functions occupy a potential landscape with strongly repulsive hard wall barriers at oxidized
sites.[38]
1.3.4.7.

Mechanical Properties

Graphene oxide paper exhibit excellent mechanical properties (stiffness up to 40GPa, [39]in the
range of engineered materials such as concrete and tensile strength up to 125MPa similar to that
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of cast iron) [40] while remaining flexible and ductile. This desirable combination of properties
has been attributed to the numerous hydrogen bonding interactions between adjacent layers in
the paper structure. These interactions occur due to the presence of oxygenated functionalized
groups.[41]

1.4.

Introduction to Iron Oxides (FeO, Fe2O3, Fe3O4)

Iron oxides are those chemical compounds which are composed of iron and
oxygen. There are sixteen known forms of iron oxides which are found as
oxides and oxyhydroxides. Mainly, there are three forms of oxides:[42]
1. Iron (II) oxide, wstite (FeO)
2. Iron (II, III) oxide, magnetite (Fe3O4)
3. Iron (III) oxide, hematite (Fe2O3)
All these three forms of oxides are different on the basis of lattice structure and show different
properties which are related to the structure.

1.4.1. Structure Of Wstite

The wstite has the cubic unit cell in which large oxygen anions form a close packed FCC sub
lattice with the small Fe2+ cations located in the interstitial sites in such a way that all iron ions
are octahedraly coordinated to oxygen. The bond length between iron and oxygen atoms is 2.16
Armstrong.

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Figure 1.6: Structure of unit cell of FeO. Every Fe ion is surrounded by the six oxygen atoms in
a unit cell.

1.4.2. Structure of Hematite

The hematite consists of a hexagonal (Rhombohedral) crystal system (The Rhombohedral system
can also be thought of as a cubic system stretched along one body diagonal such that two interior
points equally spaced along a diagonal, the Rhombohedral consists of three basis vectors of
equal length and the angles , and are equal to each other, but are different from 90 degrees.),
constructed of iron atoms surrounded by six oxygen atoms. Rhombohedral crystal picture below
shows the stretch along one body diagonal.

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Figure1.7: Structure of hematite representing the stacking of sheets of octahedraly coordinated

Fe3+ions between two closed-packed layers of oxygen atoms.

1.4.3. Structure of Magnetite

Magnetite ( Fe3O4) is a ferrimagnetic mineral belonging to the family of inverse spinels
with chemical formula [Fe3+]A[Fe2+,Fe3+]BO4, A and B being the tetrahedral and
octahedral

sites, respectively.[43] Thus, Magnetite has cubic inverse spinel structure with

oxygen forming an FCC closed packing and Fe cations occupying interstitial tetrahedral sites and
octahedral sites. In this crystal structure Fe (II) ions and half of the Fe (III) ions occupy
octahedral

site

(where

Fe

ion

is

bounded

with

six

oxygen

atoms) and the other half of the Fe (III) occupies tetrahedral sites, means one Fe (II) ion and
one Fe (III) ion occupy octahedral sites but tetrahedral sites( the site where Fe ion is bounded
with four oxygen atoms) are occupied by only Fe (III) ion as small ions tend to have low
coordination number.

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Figure 1.8: Representation of crystalline structure of magnetite.

Among these main three oxides magnetite has the distinctive magnetic property because of its
structural features. But further oxidation of magnetite in oxygen rich environments results in the
transformation of magnetite into hematite that loses its magnetic property.[44]

1.4.4. Magnetite Nanoparticles

Magnetite nanoparticles are the magnetic engineered nanomaterial of less than 100nm that can
be manipulated under the influence of an external magnetic field.[45]

1.4.4.1. Natural Occurrence

Magnetite nanoparticles are naturally found as reduction products of ferric oxy-hydroxides in
anoxic (contain no measurable dissolved oxygen) sediments and soils. Their formation typically
involves bio-mineralization (Bio mineralization is the process by which living organisms
produce minerals) by iron-reducing bacteria which gain energy through oxidization of organic
matter using nitrate and Fe (III). [46] As organic matter is coupled with oxidized forms of metal
ions Fe (III) in sediments so oxidization of organic matter results in the reduction of metal ions,
because electrons that are released during oxidation of organic matter are absorbed by the metal
ions that were already in oxidized state before absorbing these electrons. So this reduction of
Fe(III) oxy-hydroxides results in the formation of soluble Fe(II) ions and these ions completely
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INTRODUCTION

recrystallize themselves into a new phase which is at Nano scale So, in this way the reduction of
ferric Fe (III) oxy-hydroxides results in the formation of magnetite nanoparticles in the presence
of metal reducing bacteria.[47]

1.4.4.2. Crystal Structure of Magnetite Nanoparticles

Magnetite nanoparticles still exhibit a face-centered cubic unit cell. Crystal structure of nanoscale magnetite remains constant but according to electron probe analyses imply that oxygen
concentrations within magnetite particles decline as particle size is reduced. As a result of it, a
relative decrease in iron valence is observed, generating greater ferrous ion presence.[48]

1.4.4.3. Properties Of Magnetite Nanoparticles

1.4.4.3.1. Optical properties
Band gap and optical properties of magnetite are related to quantum confinement phenomena.
Variation in the sizes of nanoparticles brings variations in their physical and chemical properties.
Through UVVisible diffuse reflectance spectroscopy analysis it was observed that the band gap
of magnetite nanoparticles (2025 nm) is 2.12ev whereas magnetite nanoparticles of size range
(3035 nm) have band gap value 2.05ev. This variation in band gap is due to quantum size
confinement.
The photoluminescence spectra of the Fe3O4 nanoparticles were recorded at room
temperature which showed display weak excitonic-emission in the UV region due to the
recombination of free excitons, but strong emission bands were observed

in the visible

range caused by electronic transitions involving defect-related energy levels in the band
gap of Fe3O4 nanoparticles. Structural defects like oxygen vacancies can be generated during
the synthesis of magnetite nanoparticles because of the occurrence of few processes such as rapid
evaporation, incomplete oxidation, and fast crystallization. These defects may induce the
formation of new energy levels in the band gap of Fe3O4 nanoparticles.
The high efficiency of luminescence in the UV to visible regions of the spectrum makes
Fe3O4 an attractive material for optoelectronics applications and in photo catalysis.[43]

1.4.4.3.2. Electrical Properties

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In the magnetite structure, there is the presence of ferrous and ferric species at octahedral sites.
The electrons coordinated with these iron species are thermally delocalized and migrate within
the magnetite structure which cause high conductivity. Due to this electron delocalization effects
Magnetite can be slightly metal deficient on octahedral sites, such deficiency allows for n- and ptype magnetite semiconductors. Conductivities range found in magnetite is from (102103 1

cm-1) which support its semiconducting behavior. Semi-metallic behavior is further supported by

magnetites relatively low band gap (0.1 eV).

But in magnetite nanoparticles due to size reduction its band gap is about 2.12 eV which strongly
support its semiconducting behavior. Metals, semiconductors, and insulators historically exhibit
band gaps ranging from 0.0, 0.23.0, >3.0 eV. Furthermore, Magnetite incorporation into
polymeric substances causes resistivity modification from insulator realm to semi-conductor
regime.[48]

1.4.4.3.3. Magnetic Properties

At bulk state magnetite is ferromagnetic in nature, because the magnetic moments on tetrahedral
sites, occupied by ferric species, are Ferro-magnetically aligned while magnetic moments on
octahedral sites, occupied by ferrous and ferric species, are anti Ferro-magnetic and cancel each
other; such combined behavior is termed as ferrimagnetic.[48]
But magnetite nanoparticles are super paramagnetic in nature. Its magnetic nature changes from
ferrimagnetic to super paramagnetic due to size reduction. As when ferromagnetic material are
brought at Nano scale, then at this scale these materials consist of a single magnetic domain and
maintain one large magnetic moment which makes them super paramagnetic in nature.[49]
Super paramagnetic nanoparticles have some resemblance to that of paramagnetic materials, in
that they have zero magnetization in the absence of an applied magnetic field at sufficiently high
temperatures because their magnetic dipole- dipole interaction energy is much weaker than the
thermal energy but they have large magnetic susceptibilities (means that how much material is
magnetized in the presence of magnetic fields or tendency of a material to become magnetize in
the presence of external magnetic fields) similar to that of ferromagnetic materials because of
the presence of single magnetic domain.[50]
16

CHAPTER 1

TO MATERIAL

INTRODUCTION

Super paramagnetic magnetite nanoparticles exhibit zero coercivity and remanence in hysteresis
loops which means that when external magnetic field is switched off, the internal magnetic
dipoles become randomize again and hence no energy is required to demagnetize the material
again as thermal energy will be higher than the magnetic dipole- dipole interaction energy.[51]
So super paramagnetic materials are very useful in biomedicine due to their zero coercivity at
zero magnetic field.

17

CHAPTER 2

LITERATURE REVIEW
Chapter No. 2
Literature review
Graphene oxide has attracted the attention of researchers because of its extensive use in
electronic, optoelectronic devices and also in biomedical fields.[52] It also act as the starting
substance for graphene which is used in polymer composites sensors, paper-like materials,
field-effect transistors (FET) and in biomedical applications. Chemical modification of graphene
oxide is a promising route to achieve mass production of CMG (chemically modified graphene)
platelets.[23] Optical, electrical and magnetic properties of graphene oxide are highly tunable
because its chemical and physical properties can be tuned by bringing change in its structure and
bonding. There are various methods to synthesize graphene oxide some of them are bottom up
and some includes top down approaches.
Top down approaches include Boride, Staudenmaier, Hummers method, modified hummers
method, improved hummers method (Tours method). All these methods require graphite
sources and strong oxidizers, followed by exfoliation to obtain graphene oxide.[53]
Dreyer, D.R.et al. explained that Brodie and Staudenmaier both used KClO 3and nitric acid to
synthesize graphene oxide. Nitric acid is a strong oxidizing agent and reacts strongly with carbon
surfaces. Oxidations by HNO3 resulted in the liberation of gaseous NO2 and/or N2O4. Similarly,
potassium chlorate KClO3 is a strong oxidizing agent commonly used in blasting caps or other
explosive materials. Thus their methods were highly unsafe and also produced many side
products. Instead of it, Hummers method used a combination of potassium permanganate and
sulfuric acid.[23]
Sun, L. and B. Fugetsu used modified Hummers method which was much safe way to
synthesize graphene oxide than conventional Hummers method. Sun determined that
spontaneous expansion approach was introduced with expanded graphite as the precursors. He
noticed that intercalating agent (H2SO4) was able to penetrate into the expanded graphite which
further expanded the graphite and as a result, a foam-like intermediate was produced. This foamlike graphite was more easily oxidized in reaction with the oxidant (KMnO 4) to form graphene
18

CHAPTER 2

LITERATURE REVIEW
oxide (GO). Sun focused upon a spontaneous-expansion-step modification which resulted in a
preparation that strongly contributes to safety, efficiency, and productivity and the use of
expanded graphite which was taken as starting material. He noticed that if graphite is preexpanded with a larger inter-layer space, then the intercalation would process faster and
expanded graphite has some hydrophilicity because of the preliminary oxidization during the
production. So because of these reasons expanded graphite is the best precursor for the synthesis
of GO. Sun also stated some important features of modified hummers method that full mixing of
graphite and potassium permanganate in advance to the addition of H 2SO4 that ensured
homogeneity and because of the foam-like intermediate, water addition was free from security
and oxidization failure and thus followed by the high-temperature hydrolysis, the foam-like
intermediate was finally changed into a suspension with both color and volume distinctly
changed. [54]
Song, J., X. Wang, and C.T.Chang also synthesized GO from modified Hummers method and
determined microscopic morphologies of GO sheets by transmission electron microscopy
(TEM). UV spectrometer (UV-VIS) was used by them to measure the optical absorption
properties of the GO sheet and measurement showed that graphene oxide possessed a good
absorption in the visible range (380~800nm), but absorption in the ultraviolet range was also
slightly decreased. Thus photo response of GO sheet not only in ultraviolet range but also in
visible range was found, which implied the enormous potential for application of light. .He also
analyzed average crystalline properties of the GO sheets through XRD and results of XRD
proved the successful synthesis of GO sheet.[55]
Marcano, D.C. et al. demonstrated improved Hummers method (Tours method) that excluding
the NaNO3 and increasing the amount of KMnO 4 and performing the reaction in a 9:1 mixture of
H2SO4 /H3PO4 improves the efficiency of the oxidation process. Hummer's method yielded 80 85% whereas Tours yielded 90 - 95% moreover Hummers method took 2 - 3h and Tours
accomplished in 12 - 13h.[56]
From the above observations it can be concluded that, the mixed highly explosive oxidants can
decompose in an exothermic process or as a large explosion; therefore, off-the-rack methods
starting with graphite are still flawed. [54]
19

CHAPTER 2

LITERATURE REVIEW
Tang, L. et al. told that main drawbacks of this top-down approach are the use of strong
oxidizing agents and proposed a self-assembly method to synthesize GONs with tunable
thickness. He prepared GONs by a hydrothermal method using glucose as a sole reagent. The
method was environmentally friendly, facile, low-cost as well as capable of scaling up for mass
production. [52]
Sun, L.W.et al. also showed that graphene oxide nanoribbons can be synthesized by
hydrothermal method.[57]
There are various method to transform GO into r-GO by thermal and chemical reduction of GO.
Recently many researchers have focused upon the environmentally friendly reduction of GO by
using nontoxic/non explosive reducing agents.
Bo, Z.et al. highlighted some reducing agents such as metals (e.g., iron, zinc, and aluminum),
alkaline solutions (e.g. sodium hydroxide and potassium hydroxide), phenols (e.g., Gallic acid,
Tannin acid, dopamine, and tea poly-phenol), alcohols (e.g., methyl alcohol, ethyl alcohol, and
isopropyl alcohol), sugars (e.g., glucose, fructose, sucrose, and natural cellulose), microbes (e.g.,
Escherichia coli and bakers yeast) and other substances (e.g., glycine, vitamin C, sodium citrate,
and protein bovine serum albumin). Generally, with eco-friendly reducing agents, the reduction
of GO was successfully demonstrated to eliminate the environmental issues. Bo. Z et al reduced
GO by using caffiec acid as a reducing agent and then used CA- r-GO for sensors and energy
storage purposes. After CA reduction, they observed the intrinsic features of r-GO such as large
(few-micron size), transparent, and thin nanosheets with typical wrinkled and scrolled structure.
To reveal the thickness change in the GO sheet, they used atomic force microscopy (AFM)
imaging. The thickness of GO measured from AFM data was larger than the thickness of CA-r
GO, suggesting the effective reduction of GO with CA. Bo and his co workers determined
atomic structures and interlayer spacings of the GO and rGO samples by using X-ray diffraction
(XRD).[58]
Ma, J.et al. reduced Graphene Oxide by using L-lysine as a reducing agent. They used UV
visible absorption spectroscopy to monitor the deoxygenating process. Then the reduction of the
GO was verified by Fourier transform infrared spectroscopy, X-ray diffraction, Raman
20

CHAPTER 2

LITERATURE REVIEW
spectroscopy and X-ray photoelectron spectroscopy. They prepared ordered porous RGO/CMS
foams and used as absorbents for copper ions. Since L-Lys and CMS are natural and edible
chemicals, this approach provided them a green method to produce stable RGO from GO on a
large scale. Thus, the nontoxic biodegradable RGO/CMS foams show potential applications for
metal ions removal from wastewater.[59]
Gurunathan, S.et al. developed a green, simple and cost effective approach to produce r-GO by
using an Escherichia fergusoni as a reducing agent. The resulting reduced graphene oxide (rGO)
was characterized by a wide range of analytical techniques such as UV-Vis spectra of the
samples to confirm the transition of graphene oxide (GO) into r-GO. X-ray diffraction (XRD)
was used to investigate the crystalline of reduced GO.[60]
Petcharoen, K. and A. Sirivat prepared magnetic nanoparticles by chemical co-precipitation
method using ammonium hydroxide as the precipitating agent and the size of the magnetite
nanoparticles was carefully controlled by controlling the reaction temperature. They determined
structure and morphology by the Fourier transform infrared spectroscopy (FTIR), the X-ray
diffraction (XRD) and the field-emission scanning electron microscopy (FE-SEM). The
magnetite nanoparticles were successfully synthesized in range of 1040 nm yielding different
electrical and magnetic properties. This synthesis produced the spherical-shaped morphology of
magnetite. They also observed that the electrical conductivity decreases with increasing particle
size and the presence of the coating agent. For the magnetic properties, particles prepared
through this method exhibit the super-paramagnetic behavior at room temperature. [61]
Zhu, Y. and Q. Wu explained the formation of magnetite nanoparticles through a novel approach
called forced mixing in aqueous solution without any surfactants. Instead, of surfactant they used
forced mixing method. This method provided an easy way to obtain a high product saturation
degree with constant pH value of the reaction system. Magnetite nanoparticles obtained through
this approach can be used as a source for direct incorporation of the nanoparticles into ultra-thin
films without adding purification steps to remove the surfactant. [62]
Mamani, J., A. Costa-Filho, et al. also synthesized magnetic nanoparticles through coprecipitation chemical process by using ferrous oxide and then coated the resultant nanoparticles
21

CHAPTER 2

LITERATURE REVIEW
with lauric acid and dispersed in aqueous medium containing surfactant that yielded a stable
colloidal suspension. The structural properties were characterized through X-ray diffraction
(XRD) analyses. Mamani and coworkers performed the magnetic characterization using SQUID
and FMR, which showed the super paramagnetic properties of the nanoparticles. Mamani and
her co workers also explained some advantages of co-precipitation method over other routes to
synthesize magnetic nanoparticles. One of the advantages of this technology is the capacity of
mass production of MNPs which are properly functionalized. This synthesis method was chosen
because of its potential for large-scale manufacturing, cost-effectiveness, easiness of production,
and hydrophilicity of nanomaterials (important property for bio-medical applications). In this
method as iron oxide MNPs are synthesized through the co-precipitation of aqueous solutions
containing Fe2+and Fe3+ salts after the addition of a base so the control of size, shape and
composition depends on the salts used (chlorides, sulfates, nitrates, and so on), Fe2+and Fe3+
ratio, pH, and ionic strength of the medium. [63]
Peik-See, T., A. Pandikumar, et al. formed reduced graphene oxide nanocomposite with
magnetite nanoparticles at room temperature through a facile, eco-friendly and cost-effective
approach. See and his coworkers used different characterization techniques to determine the
morphology of resultant nanoparticles. They used TEM which revealed the average size of
nanocomposite and also showed that magnetite nanoparticles were uniformly distributed or
embedded on the surface of r-GO sheets. They found this composite was super-paramagnetic in
nature at room temperature and this team also checked the photo catalytic activity of
nanocomposite in the presence of natural sunlight by using methylene blue (MB) as an organic
pollutant. Their observations revealed that bare magnetite was not act as a good photo catalyst
but under consideration nanocomposite showed excellent photo catalytic performance because of
efficient photo generated charge transfer from Fe3O4 to reduced graphene a oxide sheet which
facilitates increased electron-hole pair separation and as a consequence better photo catalytic
performance was achieved. They also suggested magnetic separation technique which gave an
easy and convenient way to remove or recycle the photo catalyst. Therefore, the rGO/Fe3O4 can
be easily repeated and recycled after photo catalytic process. Moreover, TEM images also clearly
indicated that no significant change in the morphology of rGO/Fe3O4 nanocomposite is
observed before and after the photo catalytic studies. [64]
22

CHAPTER 2

LITERATURE REVIEW
Zhang, X., B. Jiang, et al. prepared rGO/Fe3O4 nanocomposite through simple one pot
hydrothermal approach and used it in lithium ion storage batteries. They used various
characterization tools to characterize their nanocomposite such as crystal structure was
investigated by using XRD. Good crystallization was achieved which was confirmed by the
sharp and strong reflection peaks obtained in XRD pattern. Morphology of the nanocomposite
was studied by using SEM and TEM techniques. The SEM image of the rGO/Fe3O4
nanocomposite showed that r-GO sheets were uniformly decorated with Fe3O4 nanoparticles and
these nanoparticles also formed some void spaces on the r-GO sheets. These voids spaces are
favourable sides to store lithium charges. Furthermore in TEM images they also noticed the
strong interaction between magnetite nanoparticles and r-GO sheets, which can provide fast
electron transport from Fe3O4 nanoparticles to r-GO sheets inducing the enhanced
electrochemical performance. Team also tested good magnetic properties of rGO/Fe3O4
nanocomposite by using vibrating sample magnetometer. Because of these properties Zhang and
his co workers suggested that this nanocomposite can be used for lithium ion storage batteries
and in drug delivery applications. [65]
Liu, S., T. H. Zeng, et al. explained antibacterial activity of four types of graphene-based
materials (graphite (Gt), graphite oxide (GtO), graphene oxide (GO) and reduced graphene oxide
(r-GO)) toward a bacterial model; Escherichia coli. They used Scanning electron microscopy
(SEM) to show different behaviors of GO and r-GO dispersions toward bacterial cells. They also
used

Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) to characterize GO

sheets. They also explained the mechanism of the destruction of E.coli cells like they revealed
that E. coli cells were individually wrapped by thin layers of GO nanosheets whereas E. coli cells
were usually embedded in large rGO aggregates therefore r-GO has a lower antibacterial activity
compared with GO. Thus, they concluded that irreversible damages can be induced on bacterial
cells through direct interaction with graphene based materials. They used Colony counting
method to determine this activity which showed that their antibacterial activities are time and
concentration dependent.[24]

23

CHAPTER 3

EXPERIMENTAL WORK
Chapter No. 3
Experimental Work
3.1.

Synthesis of Graphene Oxide

We have synthesized graphene oxide by Microwave assisted Hummers method.

3.2.

APPARATUS

Magnetic stirrer
Mechanical stirrer
Heating plate
Beaker
Ultrasonic bath
Microwave oven
Funnel
Watt man filter paper
Spatula
Centrifuge machine
Centrifuge tube
Permanent magnet

3.3. Preparation Of Graphene Oxide

3.3.1. Materials
KMnO4 (Potassium permanganate)
Expanded graphite
H2SO4 (Concentrated sulphuric acid)
Deionized water
HCl
NaOH (Ammonium hydroxide)

3.3.2. Procedure
Firstly, 7.5g of potassium permanganate and 2.5g of expanded graphite was stirred until it
becomes homogeneous. Expanded graphite is an intercalated structure which is not fully
oxidized and its structure lies between graphite and true graphite oxide, expanded graphite can
24

CHAPTER 3

EXPERIMENTAL WORK
be produced if powder graphite is treated with some oxidizing agent and subjected to heat
treatment which will cause the expansion in intercalated graphite compound. Later, concentrated
sulphuric acid (50ml) was added to the mixture .Above reaction was carried out in Ice bath. At
this stage uniform liquid paste was formed. Ice water bath was used to keep the temperature low.
After the formation of this paste water bath was removed. After stirring, intermediate foam like
suspension was formed. During the above process graphite oxide experienced exfoliation which
increased in the thickness of the graphene solution. To form dilute solution, deionized water
(200ml) was added and rapid stirring was carried out. Then a homogeneous suspension was
obtained by placing the flask at 90 degree centigrade that resulted in dark brown yellow solution.

Figure 3.1: Dark yellow color of graphite during oxidation process

In the next step centrifugation (6000 rpm for 15 minutes) was carried out to separate the
particles from solution. After that 1M HCl solution was added and the resulting solution was kept
in slow stirring for 3 to 4 hours. In the last step, washings of the solution were carried out. HCl
solution was used to remove sulfates that could have been precipitated on the product. Purified
water was used to set its PH of 4 to 5.
After washings, the sonication of the above final solution was done by adding 3/4 th water in the
solution. Sonication prevented the aggregation of GO particles.
25

CHAPTER 3

EXPERIMENTAL WORK

Figure 3.2: Graphene oxide flakes

3.4.

Exfoliation of Graphene Oxide

To exfoliate the graphene oxide, left the suspension of graphene oxide in water for three days at
60 70 degree centigrade with continuous magnetic stirring.

3.4.1. Mechanism of Exfoliation

Basically in exfoliation of graphene oxide, functional groups present on the planes and edges of
graphene oxide layers vary their Vander Waal interactions among graphene oxide layers due to
which it becomes strongly hydrophilic and readily swell in water.
In fact, the absorbed water increased the interlayer distance among the graphene oxide layers and
further treatment of magnetic stirring and heating caused ionization of hydroxyl and carboxyl
groups on the graphene oxide layers as a result of which growing negatively charges on the
graphene oxide layers caused the electrostatic repulsion between the layers. Therefore, Vander
Waal interaction among graphene oxide layers was further decreased.
Exfoliation may also occur due to the decomposition of the epoxy and hydroxyl sites into CO 2
.which exert pressure to decrease the Vander Waal interaction among the graphene layers.
26

CHAPTER 3

EXPERIMENTAL WORK

Figure 3.3: Schematic diagram from graphite to exfoliated graphene oxide

3.5.

Preparation of r-GO

In order to reduce graphene oxide, NaOH was added to graphene oxide and left the mixture to
stir at room temperature for a long time.

3.5.1. Reduction with NaOH:

Due to the weak connection of oxygen atoms with carbon atoms, these oxygen atoms can be
washed away with base and caused the reduction of graphene oxide.
Similarly GO can be reduced to R-GO by using NaOH solution. Reduction mechanism contains
OH- (hydroxyl ion), Na+ (sodium ion) and H2O molecules. Firstly the OH- ions react with the GO
in solution and results in negatively charged GO by transferring its electron to GO sheet. Then
Na+ cations are attracted towards the negatively charged GO sheet. As graphene oxide contain a
lot of polar C-O bonds. So by the addition of Na + ions an external electric field is created which
weakens the bond strength of the C-O bond and this could lower the barrier of the reduction of
Graphene Oxide. In this reduction process NaOH works as a catalyst. Other metal oxides can
also be used as an oxidizing agent for the reduction of Graphene Oxide.[66]

3.6. Formation of Magnetite (Fe3O4) Nanoparticles

3.6.1. Materials
FeCl3 (Iron chloride)
FeSO4 (Iron sulphate)
HCl (Hydrochloric acid)
27

CHAPTER 3

EXPERIMENTAL WORK
NH4OH (Ammonium hydroxide)

3.6.2. Procedure
For the formation of magnetite nanoparticles 6.1g of ferric chloride (FeCl 3) and 4.2g of ferrous
sulfate (FeSO4) was dissolved in 50ml of purified water and then stirred. Then few drops of HCl
were added to the above mixture at 85 degree centigrade, after 45 minutes stirring mixture was
allowed to be cooled at low temperature. Then 7ml of ammonium hydroxide (NH 4OH) solution
was added. The resulting solution will be precipitate out in approximately one hour. After all the
steps the color of the solution will be changed from light orange to black. The resulting solution
was then heated to obtain a desire product.
The chemical reaction of Fe3O4 formation may be written as follows:
2Fe+3 + Fe+2

+ 8OH Fe3O4 + 4H2O

3.7. Composite

Formation

Of

r-GO

With

Magnetite

Nanoparticles
Three different composites were prepared; these composites are different from each other in a
sense that they contain different proportion of magnetite nanoparticles, whereas quantity of r-GO
is kept constant for all these composites.

First composite was formed by taking 0.75g of R-GO and magnetite (5% of the total
value of R-GO). 1ST solution was prepared by mixing 0.75g of R-GO in 10ml ethanol and
the 2ND solution was prepared in similar fashion by mixing 0.037g of magnetite in 10ml
ethanol. After that, mixed above two solutions with constant stirring for about 45 minutes

and then heated at appropriate temp to get the desired sample.

Second composite was formed by taking 0.75g R-GO and magnetite (10% of the total
value of R-GO). 1St solution was prepared by mixing 0.75g of r-GO in 10ml ethanol and
the second solution was prepared in similar fashion by mixing 0.075g of magnetite in
10ml ethanol. After that, mixed these two solutions with constant stirring for about 45
minutes and then heated at appropriate temp to get the desired sample.
28

CHAPTER 3

EXPERIMENTAL WORK

Third composite was formed in the similar manner as prepared before by using 0.75g of
R-GO and 0.11g of magnetite (10% of the total value of R-GO).

29

CHAPTER No.4

RESULTS AND
DISCUSSION

Chapter No.4
Results and Discussions
Characterization is a process by which a materials structure and properties and can be analyzed.
Without characterization an understanding about a material is not possible
We characterizes over data using different characterization techniques.

4.1.

Morphological Investigations

30

CHAPTER No.4

RESULTS AND
DISCUSSION

Figure 4.1: SEM images of reduced graphene oxide 1(a), 1(b), 1(c), 1(d), 1(e) at different
resolutions and graphite oxide 1(f)
Surface morphology of graphene oxide and reduced graphene oxide were analyzed from the
SEM images in fig 1(a) to 1(f). From fig1 (a), 1(b) and 1(c) it was revealed that graphene oxide
and reduced graphene oxide materials have layered folded films containing lots of wrinkled and
kinked areas. In these films edges of individual sheets can be easily distinguished.

31

CHAPTER No.4

RESULTS AND
DISCUSSION

Fig 1(d) to 1(e) confirmed the partial reduction of graphene oxide, as black spots on few sheets
represents the uniform and dense surface coverage of graphene oxide layers with oxygenated
functional groups. Whereas reduced graphene oxide layers are free from these spots representing
the removal of functional groups.
Moreover morphological studies of graphene oxide and reduced graphene oxide layers look like
waves due to ripples and wrinkled areas but folding of these layers showed their resemblance
like typically folded papers.
These images also showed the low degree of agglomeration of layers in reduced graphene oxide
and graphene oxide materials means that these flakes are overlapped rather than aggregated.
Presence of these ripples wrinkles and folded structure cause the roughness of surface. Sources
of these ripples and wrinkles are exfoliation and reduction processes. Both of these phenomena
cause sub surface gas production (because of the presence of functional groups) which cause the
surface cracking, blister explosion and deformation of the surface, this release of gases also
cause the folding of layers at the edges.
Wrinkled sites are much rough as compared to wrinkle free sites in these layers, therefore
wrinkled areas can scatter light more strongly which causes higher optical loss, thus decreasing
the transparency of layers.
SEM images of graphite oxide in fig 1(f) showed the compact arrangement of layers or stacking
of layers in graphite oxide material. In such structure edges of these layers cannot be
differentiated from each other. But the surface of these layers is also rough due to the oxidation
processes which were carried out in graphite.

32

CHAPTER No.4

RESULTS AND
DISCUSSION

Figure 4.2: SEM images of r-GO/Fe3O4 composite at different resolutions

Morphological characterization of rGO/Fe3O4 Nano composite was also carried out by SEM
which is showed in fig 2(a) to 2(c). These images showed the heavy coverage of magnetite
nanoparticles over the reduced graphene oxide layers. This distribution of magnetite
nanoparticles showed the strong coordination or surface interaction of magnetite nanoparticles
with the surface of reduced graphene oxide layers which is highly favorable for its application in
photo catalysis.

4.2.

Structural Analysis

Structural properties of graphite, graphite oxide, graphene oxide, reduced graphene oxide and
composite of reduced graphene oxide with magnetite nanoparticles were characterized by XRD
analyses.

33

CHAPTER No.4

RESULTS AND
DISCUSSION

Figure 4.3: XRD graph of graphite and graphite oxide

In XRD results of graphite and graphite oxide, sharp and highly intense peak of graphite was
obtained at 2 =26.3 degree which refers the inter layer spacing d002 = 0.348 nm and indicates the
highly organized layer structure. Sharp and high peak of graphite shows its high crystalline
structure and high degree of order. Whereas in graphite oxide broad peaks shows the Increased
interlayer spacing in graphite oxide as compared to that found in graphite at 2= 9.6 degree the d
spacing is about 0.9671nm .This is due to the presence of polar functional groups produced
during oxidation. It can also be seen easily that the large peak of graphite is gone. It shows the
full oxidation of graphite

34

CHAPTER No.4

RESULTS AND
DISCUSSION

Figure 4.4: XRD graph of graphite and graphene oxide

Figure 4.5: XRD graph of graphite oxide and graphene oxide

35

CHAPTER No.4

RESULTS AND
DISCUSSION

From the XRD data of graphene oxide it was noticed that peak of graphite oxide was shifted at
an angle of 2 =10.2 degree and 2 =23.8 degree during the exfoliation process to produce
graphene oxides.
Peak of graphene oxide at 2 =10.2 degree refers the interlayer spacing 0.857nm. The presence
of polar functional groups possesses strong hydroscopic properties as a result water molecules
entered within the space between the graphite oxide layers form bonding with the functional
groups present over there and cause a further increase between the layers of graphite oxide to
form graphene oxide.
Moreover another broad peak of graphene oxide at 2 =23.8 degree is due to the exfoliation and
thermal process of graphite oxide. As in exfoliation of graphite oxide due to the thermal
treatment some oxygenated functional groups were also removed. Which cause a bit decrease in
it interlayer distance than that of graphite oxide.

Figure 4.6: XRD pattern of r-GO by using NaOH

36

CHAPTER No.4

RESULTS AND
DISCUSSION

XRD of reduced graphene oxide showed different structural changes in graphene oxide structure.
After the reaction of GO with NaOH many sharp peaks arise in XRD pattern. These tiny sharp
peaks represent partially amorphous nature of r-GO. Destruction of epoxy groups due the
presence of NaOH leads to a slightly amorphous structure. These tiny peaks also explained the
change in bond lengths. This change in bond lengths is due to the change in hybridizations from
SP3 to SP2. But partially reduction contain both structures.

Figure 4.7: XRD pattern of r-GO/Fe3O4 composite and Fe3O4 NPs

In XRD analyses of reduced graphene oxide/Fe3O4 composite, Peaks at

2 =30, 35.4, 43.1, 57

and 62 degrees showing the reference peaks of Fe3O4 and representing the inverse spinal
structure for magnetite nanoparticles but if we give a look to the reduced graphene oxide/Fe 3O4
composite XRD results it is observed that sharp peaks of r-GO at about 25.7 degree. The
positions and relative intensities of the all diffraction peaks match well with the standard XRD
data of cubic Fe3O4 (JCPDS card No. 86-1359). These XRD results confirm the successful
deposition of Fe3O4 NPs on the surfaces of rGO sheets.

37

CHAPTER No.4

RESULTS AND
DISCUSSION

4.3.

Compositional Analysis

Figure 4.8: EDX graph of reduced graphene oxide

This graph showing a composition analysis of reduced graphene oxide where in the sample of
reduced graphene oxide the % of oxygen decreased than that of oxygen present in graphene
oxide due to the removal of oxygenated functional groups. As NaOH is used as a reducing agent,
a well defined peak of Na is also shown in a graph.

38

CHAPTER No.4

RESULTS AND
DISCUSSION

Figure 4.9: EDX analysis of r-GO/Fe3O4 composite

Above graph confirmed the presence of Iron oxide (Fe 3O4) in a composite. A high percentage of
C and O confirmed the r-GO presence.

4.4. Photocaytalatic Activity of R-Go, Fe3O4 and Their

Composite under UV Light
Currently there are various existing energy sources like fossil fuels which are being used by the
human population. Fossil fuels are hydrocarbon deposit, such as petroleum, coal, or natural gas
that are derived from the accumulated remains of ancient plants and animals and used as fuel.
Because of these hydrocarbons, the serious disadvantage associated with these energy sources is
environmental pollution. The pollution of the atmosphere is primarily due to the combustion of
fossil fuels in energy conversion devices which is referred as air pollution. Some water and land
pollution also arise during the use of these fossil fuels.
The main air pollutants resulting from fossil fuel combustion are the following:

Carbon monoxide:

39

CHAPTER No.4

RESULTS AND
DISCUSSION

Carbon monoxide (CO) produced due to the incomplete combustion of any fuel. It is highly
poisonous gas. The main cause of CO pollution is the urban automobiles and transportation
vehicles.

Oxides of sulfur, SO2 and SO3 (represented as SOx)

Sulfur oxides produce during combustion of sulfur in sulfur containing fuels which can be some
coals and some petroleum-based products.
S (in fuel) + O2 SO2
Sulfur dioxide has an irritating odor and it irritates the eyes and respiratory tract. Furthermore,
when it is released to the atmosphere, it can react with oxygen in the air to form sulfur trioxide:
2SO2 + O2 2SO3
Sulfur trioxide forms sulfuric acid on dissolving in water, which is a strong acid capable of
corroding many materials. Sulfur trioxide also absorbs moisture from the atmosphere to form
very fine droplets of sulfuric acid. These droplets are harmful for the respiratory system. Sulfur
trioxide can interact readily with rain drops, and fall to the earth as acid rain.

Oxides of nitrogen, NO and NO2 (NOx)

There are two major causes of the formation of nitric oxide:

When nitrogen atoms present in the fuel are oxidized during the combustion process to form
nitric oxide:
2N (in fuel) + O2 2NO
Secondly some combustion processes operate at such high temperatures that cause nitrogen
molecules to oxidize into nitric oxide.
N2 (in air) + O2 2NO
Further oxidation of nitric oxide causes the formation of nitric dioxide.

40

CHAPTER No.4

RESULTS AND
DISCUSSION

2NO + O2 2NO2
Nitrogen dioxide is a poisonous gas that can cause inflammation of the lungs and, at high
concentrations, even death. The main role of nitrogen oxides is in the formation of nitric acid:
4NO2 + 2H2O + O2 4HNO3
Nitric acid is also a major component of acid rain.

Soot is formed due to the incomplete combustion of carbon into carbon oxides.
Fly ash is also the inorganic, non-combustible residue of coal combustion.

These solid particles are very small and light weighted, thus they can escape out from the boiler
into the atmosphere.
Besides the fossil fuels there are various other activities which cause harm effects on our natural
water reservoirs and generates the water pollution. Fresh water is requirement of all living
organisms including human beings and such availability is a foremost problem throughout the
world at present. Particularly, the rapid increase of textile and dying industries has imposed
critical environmental problems. Industrial wastes of these industries can pollute the ground
water resources and the further utilization of these contaminated water sources creates many
toxic and harmful effects on human beings.[64]
These energy and environmental challenges can be overcome by the use of solar energy and
biomass. Solar energy is clean and abundant, but its utilization is still very low. Now scientists
have been developed a sustainable and cost-effective manner by exploiting the properties
nanomaterial for harvesting solar energy to satisfy the growing energy demand of the world with
a minimal environmental impact. [67]
Photo catalysis is the most investigated phenomena for this purpose as it plays an important role
for the conversion of solar energy into chemical fuel, electricity and in the decomposition of
organic pollutants.

4.4.1. Photo Catalysis

41

CHAPTER No.4

RESULTS AND
DISCUSSION

In photo catalysis, light is used to activate the catalyst to initiate the redox reaction between the
photo generated (electrons and holes) and the adsorbed species on the surface of the catalyst.

4.4.2. Basic Mechanism of The Photo Catalysis

Following are the basic steps of photo catalysis;

Firstly, the incident light interacts with the semiconductor material, known as photo
catalyst. If the incident light energy is larger than the band gap of the photo catalyst, then
this light energy will be absorbed by the photo catalyst and further excite the electrons

from the valence band (VB) to the conduction band (CB), leaving free holes in the VB.
Secondly after the formation of photo generated electron hole pair, two possibilities can
arise. One of the possibilities is the recombination of these species which creates heat
and second possibility is the migration of these species towards the surface to initiate the

redox reaction.
At surface, photo generated electrons initiate the reduction reaction with adsorbed
species whereas holes generate strong oxidizing agents like hydroxyl radical by directly

42

CHAPTER No.4

RESULTS AND
DISCUSSION

reacting

with

surface

hydroxyl

groups

or

oxidizing

adsorbed

specie

Figure 4.10: Basic mechanism of photo catalysis

Besides these reduction and oxidation reactions in photo catalysis, there are some secondary
reactions also occur, which becomes the driving force of a number of important photo catalytic
applications.

4.4.3. Properties Of Photo Catalyst

In order to show excellent photo catalytic performance photo catalysts must have characteristic
properties, like small particle size, specific surface area or large space between the electronic
levels to avoid the recombination of photo generated electron hole pair. All these properties can
be achieved by using Nano photo catalyst. [68]

43

CHAPTER No.4

RESULTS AND
DISCUSSION

One major problem that is encountered with photo catalyst is its separation from the reaction
medium. To overcome this problem, magnetic separation of photo catalyst has been proposed as
a promising solution.
The magnetically separable photo catalytic systems are easy to handle as their separation from
reaction medium do not require filtration or centrifugation process. Hence, the physical
separation of a photo catalyst can easily be accomplished by using the magnetically separable
photo catalysts.

4.5.

Photo Catalysis Mechanism Of Composite (r-GO with Fe3O4)

As we have checked the photo catalytic performance of magnetite nanoparticles, reduced

graphene oxide and three different composites of magnetite and reduced graphene oxide having
different percentage of magnetite nanoparticles. The mechanism of photo catalysis for composite
nanoparticles has been discussed below.
Upon UV light irradiation, the Fe 3O4 nanoparticles present on the rGO sheet surface undergoes
charge separation due to the absorption of photons that leads to transfer of valence band (VB)
electrons into the conduction band (CB), leaving a hole in the VB (Eqn. (1)), whereas the MB
molecules excited to cationic MB radicals (MB*)because of the absorption of photons. (Eqn. (2))
These photo generated electrons in the conduction band then migrated to rGO sheets (Eqn. (3))
where they captured by dissolved O 2to generate reactive oxidation species, such as .OH and O
i.e. hydroxide radical and super oxide anion (Eqn. (4)).
On the other hand, the photo induced holes are important for oxidation process and it effectively
oxidizes the adsorbents, usually it reacts with adsorbed H 2O/OH- to form strong hydroxyl
radicals (.OH) (Eqn. (5)).
Finally, these (.OH) radicals then interact with the adsorbed MB molecules and convert the
cationic MB radicals (MB*) into CO2 and H2O (Eqn. (6)) because of the -
stacking/electrostatic interactions on the active sites of rGO/Fe3O4 nanocomposite.

44

CHAPTER No.4

RESULTS AND
DISCUSSION

Figure 4.11: Nanocomposite of r-GO and Fe3O4 for photo catalysis

Equations
Fe3O4+ h

Fe3O4 (e- + h+)

MB + h

MB*

(2)

Fe3O4 (e-) + Graphene

Fe3O4+ Graphene (e-)

(3)

Graphene (e-) +O2

Graphene +O2

(4)

Fe3O4 (h+) + OH-

Fe3O4+ .OH

(5)

MB* + .OH

CO2+ H2O

(6)

(1)

Thus reduced Graphene oxide possesses high surface area and excellent thermal, mechanical and
electrical properties that make it as a good supporting material for inorganic nanoparticles
towards various energy and environmental applications. Introduction of magnetic Nano photo
catalyst materials into the reduced graphene oxide sheets can provide a convenient magnetic
separation technique in order to remove and recycle the magnetic Nano composite photo
catalysts under an external magnetic field.

45

CHAPTER No.4

RESULTS AND
DISCUSSION

Figure 4.12: Pictorial representation of the photo catalytic mechanism of r-GO and Fe3O4
composite obtained from reference [64]

4.6.

Observations

On checking the photo catalytic performance of magnetite nanoparticles, reduced graphene oxide
and three different composites of magnetite and reduced graphene oxide having different
percentage of magnetite nanoparticles following results are obtained.
Reduced graphene oxide(r-GO) showed 100% degradation of methylene blue in first 60 mints of
irradiation with UV light because of the enhanced specific surface area of reduced graphene
oxide sheets, increased interaction with dye molecules, improved light absorbance properties
which increased the charge separation.

46

CHAPTER No.4

RESULTS AND
DISCUSSION

Figure 4.13: Photo catalytic activity of r-GO to MB under UV light (a) Before exposure to UV
light (b) after 40 mints (c) after 60 mints.
Whereas, bare Fe3O4 nanoparticles showed very little photo degradation of methylene blue
within 150 mints irradiation of UV light. The poor photo catalytic performance of the bare Fe 3O4
nanoparticles is because of the aggregation caused by the high surface area of Fe 3O4
nanoparticles and magnetic interactions between these particles which lead to the formation of
larger size particles and decreases the light absorption properties.

Figure 4.14: Photo catalytic activity of Fe3O4 to MB under UV light (a) Before exposure to UV
light (b) after 70 mints (c) after 150 mints.

47

CHAPTER No.4

RESULTS AND
DISCUSSION

But on the other hand, maximum photo degradation of MB was observed in 20 mints of light
irradiation when Fe3O4 nanoparticles were incorporated in reduced graphene oxide sheets to use
as a photo catalyst.
Among the photo catalysts, the 5% composite, exhibited excellent photo catalytic activity and
100 % of MB was decolorized upon 20 mints of light irradiation. It was observed that lower the
content of Fe3O4 nanoparticles in the Nano composites, offer smaller particle size with high
surface area without heavy aggregation of Fe3O4 nanoparticles and therefore they offer excellent
decolourization activity.

Figure 4.15: Photo catalytic activity of r-GO and Fe3O4 composite (5%) to MB under UV light
(a) Before exposure to UV light (b) after 20 mints.
The 10% composite and 15% composite, showed 100 % degradation of MB after 25 and 30
mints of UV irradiation respectively.

48

CHAPTER No.4

RESULTS AND
DISCUSSION

Figure 4.16: Photo catalytic activity of r-GO and Fe3O4 composite (10%) to MB under UV light
(a) Before exposure to UV light (b) after 25 mints.

Figure 4.17: Photo catalytic activity of r-GO and Fe3O4 composite (15%) to MB under UV light
(a) Before exposure to UV light (b) after 30 mints.
The maximum photo catalytic activity exhibited by the r-GO/Fe 3O4 nanocomposite photo
catalysts is due to the following reasons:

49

CHAPTER No.4

RESULTS AND
DISCUSSION

Efficient photo generated charge transfer from Fe3O4 to Reduced graphene oxide sheets
which facilitates the increased electron-hole pair separation and as a consequence better

photo catalytic performance was observed.

Secondly the enhanced MB dye absorption on rGO/Fe3O4 photo catalysts is due to the
presence of large phenyl ring structure of reduced graphene oxide sheets in the Nano

composites.
Moreover, reduced graphene oxide is a 2D crystalline structure and has a large surface
area, superior electrical conductivity and unique transport property; all these factors make
it a great electron-transport material in the process of photo catalysis.

The photo catalytic activity is highly affected by the concentration of photo generated charge
carriers during the reaction. Therefore, the strong attachment of Fe 3O4nanoparticles on
electrons of rGO sheets gives rise to an increased migration of photo excited electrons from
the conduction band of Fe3O4 to rGO sheets.

50

CHAPTER No.4

RESULTS AND
DISCUSSION

Figure 4.18: Graphical representation of photo catalytic activity of r-GO, Fe3O4 and their
composite.
Here in the above graphical data we can clearly seen that as the concentration of Fe 3O4 is
increased in the composite the photo catalytic activity is decreased. While Fe 3O4 itself does
not show good catalytic activity but when added in a composite it enhanced the photo
catalytic activity of r-GO.

51

CONCLUSION
Conclusions
We reported the preparation of graphene oxide by Hummers Method and also discussed the
eco-friendly reduction of graphene oxide by using sodium hydroxide as a reducing agent for the
production of reduced graphene oxide. Magnetite nanoparticles were formed by copercipitation
method. Finally reduced graphene oxide/ Fe3O4 Nano composites having fixed amount of
reduced graphene oxide but Varying in percentage of magnetite nanoparticles were synthesized
by eco-friendly and cost effective approach at room temperature. Structural characterization of
all these materials was carried out by using XRD. SEM was used to study the morphological
features of graphene oxide, reduced graphene oxide, magnetite nanoparticles and Nano
composite. Chemical composition of each sample was determined by using EDX. In last, photo
catalytic activity of all synthesized samples was investigated by using methylene blue as an
organic pollutant model. Among these samples reduced graphene oxide/Fe 3O4 Nano composite
having low percentage of magnetite nanoparticles showed excellent photo catalytic property.
Thus reduced graphene oxide/Fe3O4 a magnetic separable photo catalyst is most effective for the
photo degradation of organic pollutant as its separation from reaction media is easy.

52

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