Chapter 1

Introduction and Literature

Review

Carbon has this genius of making a chemically stable, two-dimensional, one-

atom-thick membrane in a three-dimensional world. And that, I believe, is going
to be very important in the future of chemistry and technology in general. -
Richard Smalley
Graphene is a one atom thick sheet of carbon atoms arranged in a hexago-
nal lattice. Since its experimental discovery in 2004, it has been the target for
extensive theoretical and experimental research. Graphene has been favourably
regarded as an indispensable component for synthesizing various functional and
innovative materials. It has attracted so much interest largely because of its un-
usual properties; graphene and graphene based materials have found applications
in a wide array of fields like nanotechnology, opto-electronics, high energy physics
etc. Graphene based materials can be prepared by various physical and chemical
methods. Among them, chemical methods have been found to be most effective
for producing chemically converted graphene based materials on large scale and
at comparatively low costs.

1.1 Carbon and its Allotropes

Allotropes are formed when atoms of an element are bonded together in different
manner. Carbon, which belongs to group IV of periodic table, is capable of form-
ing various allotropes because of its flexible bonding. The specific hybridization
between carbon atoms will determine which allotrope carbon will form. Carbon
1. Introduction and Literature Review

with sp3 hybridization forms a tetrahedral structure of diamond while carbon with
sp2 hybridization forms either hexagonal sheets of graphite, spherical fullerene or
carbon nanotubes. From the point of view of practical applications, graphene, a
single layer of graphite, has a set of remarkable electrical, thermal, and physical
properties.

1.2 Graphene
As mentioned previously, graphite exhibits a multi-layered structure. Each single
layer of graphite (two dimensional) is composed of hexagonal lattice wherein the
individual carbon atoms are chemically linked together by strong covalent bonds
(sp2 hybridised bonds). The individual carbon atoms are separated by a distance
as low as 0.142 nm in this mono-layered hexagonal lattice. Further, each single
layer of this hexagonal lattice is separated from adjacent layer by 0.335 nm to
give rise to multi-layered (thousands of individual layers of interlinked carbon
atoms) crystalline form of graphite.
Simply stated, graphene is nothing but hexagonal lattice structure of sp2
bonded carbon atoms (essentially representing the single layer of multi-layered
crystalline graphite). However, in spite of this structural similarity with graphite,
graphene surprisingly offers an entirely different yet magnificent set of properties.
As compared to graphite, which is brittle in nature and consequently cannot
be employed for structural reinforcement, graphene on the other hand is one
of the strongest material ever known to mankind. When measured objectively,
graphene is about forty times stronger than diamond. The electronic, thermal
and acoustic properties of graphite are highly anisotropic, largely attributed to
structural organisation of graphite (in-plane metallic bonding and weak van der
Waals forces between the layers). As a result, the passage of charge carriers
through graphite microstructure is relatively easy along the planes as compared
to through the planes. Since graphene is mono-layered and exhibits high electron
mobility, it facilitates electronic conduction due to presence of a free electron
for each individual carbon atom.
Thus graphene can safely be considered as one of the thinnest known mate-
rials with a remarkable set of properties that can have an enormous impact on
the development of future technology. As a conductor of electricity, graphene
significantly outperforms highly conductive metal like copper and as a conductor
of heat, it surpasses all other known materials (maximum thermal conductivity).

2
 1.2 Graphene

Though transparent in nature, it is still so dense that it is impermeable to even

gases (including helium with smallest gas atom).
Andre Geim and Konstantin Novoselov (University of Manchester) won the
Nobel Prize in Physics in 2010 for their innovatory experiments on 2-dimensional
graphene monolayer. Though graphene tops the list in the class of 2-dimensional
materials yet it can be foreseen as a building block of other allotropes of carbon.
It can be wrapped into 0-dimensional fullerenes, rolled into 1-dimensional CNTs
or stacked into 3-dimentional graphite (Geim & Novoselov (2007)). The reported
work on properties and applications of graphene and graphene based materials
has unlocked an era of promising new avenues and opportunities for systems and
devices of future.

Figure 1.1: Graphene-The mother of all graphites.Image adapted from Gao et al.
(2009)

3
 1.3 Properties of Graphene

1.3 Properties of Graphene

Though graphene can be prepared through various physical, chemical and elec-
trochemical strategies, chemical methods were found to be effective for producing
graphene. One of the most cost effective chemical ways of synthesizing graphene
is by reduction of graphite oxide to reduced graphene oxide. Such chemical syn-
thesis of graphene using graphite after oxygenation (graphite oxide (GO)) as
starting material not only helps in scalable synthesis of graphene but also ren-
ders graphene with new functions (Wang et al. (2015)). Thus it is important to
understand structural properties of both graphene and graphite oxide.

1.3.1 Structure of Graphene

Layers of graphene are stacked over each other to form graphite. The problem
over many years was how to peel off graphene monolayer from graphite. The basic
element of these two structures is carbon which is the sixth element of periodic
table. According to electronic configuration of carbon there are
2 electrons in 1s atomic orbital (full)
2 electrons in 2s atomic orbital (full)
1 electron in 2px atomic orbital (not full)
1 electron in 2py atomic orbital (not full)
0 electron in 2pz atomic orbital (empty)
1s orbital has very low energy but 2s and 2p are very similar in energy. The
2 electrons in 1s orbital are very stable and dont participate in conduction and
bonding. 2s, 2px , 2py and 2pz together can hold 8 electrons but they have 4
electrons. These four electrons in 2s, 2px , 2py and 2pz orbitals are responsible
for chemical bonding, conduction and physical properties. In one dimensional
graphene there is 1 electron in each of the three hybridized sp2 orbitals plus one
electron in 2pz orbital. The remaining pz orbital is perpendicular to x-y plane.
Strong and deep lying bonds among sp2 hybridised carbon atoms in the
plane provide honey-comb lattice framework. Single electrons in pz orbitals which
are perpendicular to the graphene plane are relatively free to move around above
and below the plane. Physics has much to do with these pz electrons. The
Bloch states of graphene are formed mainly by this valence pz orbital forming
bands (in shape of cones). This remaining pz orbital on each carbon overlaps
with its three neighbouring carbons to form a band of filled orbitals, known
as the valence band, and a band of empty orbitals, known as the conduction

5
1. Introduction and Literature Review

band. The out-of-plane interactions among pz orbitals are extremely weak. This
includes the propagation of free charge and thermal carriers, which leads to out-
of-plane electrical and thermal conductivities that are more than those of their
in-plane analogues (Allen et al. (2010)). This extraordinary structure gives rise to
the fascinating properties of graphene such as high carrier mobility, good optical
transparency, quantum hall effect at room temperature, large theoretical specific
surface area, high Youngs modulus and prominent thermal conductivity (Zhang
et al. (2012)).

1.3.2 Structure of Graphite Oxide

The most common chemical route for GO synthesis is the so-called modified-
Hummers method (Eda & Chhowalla (2010)), based on the original Hummers
process (Hummers & Offeman (1958)), in which graphite is first exfoliated to
few-layer graphene and oxidised by using strong oxidising agents. The detailed
structure of GO attracts continued interest of researchers (Dreyer et al. (2010)).
GO is amorphous with sp2 hybridised carbon (graphene) base littered with oxygen
groups. These oxygen containing groups disrupt the sp2 base forming sp3 sites
distorting GO (Fig. 1.2). A C/O ratio between 1.6 and 4 and a corrugated sheet
with thickness of 1 nm is formed (Dreyer et al. (2010)). The surface roughness is
approximately 0.6 nm (Dreyer et al. (2010)). The basal plane of graphene sheet
is mostly occupied by epoxide and hydroxyl functional groups while carboxyl
and carbonyl groups are located on the edges (Dreyer et al. (2010)) . The pres-
ence of these functional groups makes GO dispersible in water and other solvents.
The electronic structure of GO is predominated by the mixture of sp2 and sp3 hy-
bridisations generating an electrically heterogeneous structure (Eda & Chhowalla
(2010)). The reactive oxygen moieties of GO allow a variety of chemical func-
tionalities and modifications. Further upon reduction, most oxygen-containing
functional groups of graphene oxide are removed and the -electron conjugation
within the aromatic structure of graphite is partially restored. During this pro-
cedure of oxidation and reduction, the graphite sheets get more exfoliated and
lead to the synthesis of graphene.

1.3.3 Physical and Chemical Properties

Novoselov et al. (2004) first presented some of the surprising electrical prop-
erties of graphene layers isolated from graphite (Novoselov et al. (2004)). The

6
 1.3 Properties of Graphene

Figure 1.2: Structure of graphite oxide. Image adapted from Jeong et al. (2009)

rare kind of structure of graphene gives rise to fascinating properties of graphene

such as high carrier mobility (10,000 cm2 /V s) (Novoselov et al. (2004)), high
young modulus (1T P a) (Lee et al. (2008)), quantum hall effect at room tem-
perature (Novoselov et al. (2007)), good optical transparency ( 97.7)(Nair et al.
(2008)), large theoretical specific surface area (2630m2 /g) (Stoller et al. (2008)),
and excellent thermal conductivity (3000W/mK)(Stankovich et al. (2006)).
The localized -bonds between the planar orbitals of the nearest-neighbour
carbon atoms in the honeycomb lattice are responsible for most of the binding
energy and elastic properties of the graphene sheet (won Choi & Lee (2011)). The
remaining free pz orbitals exhibit symmetry orientation and can bind covalently
with neighbouring carbon atoms forming band. This band is half filled and
plays a major role in the electronic properties of graphene (won Choi & Lee
(2011)). The honeycomb lattice, formed by two sublattices A and B, contains
two atoms per unit cell. Each atom from sublattice A being surrounded by three
atoms from sublattice B, and vice versa. The basis of electron states contains two
pz states belonging to the atoms from sublattices A and B (Katsnelson (2007)).
Since there are two electrons per unit cell of graphene, the lower band is
completely filled. The valence and conduction bands of graphene are degenerate
at 6 points located on the corners of the first hexagonal Brillouin zone (won
Choi & Lee (2011)). Since the fermi level of graphene exists at the degeneracy
between valence band and conduction band, thus the density of states at the
fermi level is zero (Massimiliano Di Ventra & James R. Heflin (2004)). It was the
magneto-oscillation effects (Novoselov et al. (2005), Zhang et al. (2005)) which
demonstrated the massless Dirac fermion behaviour of charge carriers of graphene.
Thus graphene is usually considered as zero-gap semiconductor. Due to large
instrinsic mobility and small effective mass, its charge carriers can travel long

7
1. Introduction and Literature Review

distances without scattering. The properties of GO are highly dependent upon

the details of the synthesis process including graphite source, oxidation time and
oxidation chemicals (Dreyer et al. (2010)). In a recent study, Jeong et al. (?)
investigated the effect of oxidation time variation on the physical and chemical
properties of GO.

1.4 Types of Graphene Based Materials

1.4.1 Graphene Based Composites
Tremendous research in last few years has conclusively demonstrated that graphene
has a set of outstanding qualities; it is extremely strong, flexible, lightweight and
has an exceptional electronic and thermal conductivity. These peculiar properties
can be employed in practically feasible industrial applications by simply combin-
ing graphene with existing materials (composite materials); thereby opening new
possibilities. The scientists at The University of Manchester have successfully
synthesised rust-free paint by combining it with graphene; it can significantly
prolong the life of transport vehicles. It can further be used in food packaging
industry for enhancing shelf life of stored foods and even extended to construct
weather-proof houses. Other graphene based composite materials have rich po-
tential applications in aerospace, construction and transport industry. To cite
an example, graphene based composite material could lead the race in building
worlds lightest, safest and strongest aircraft by significantly reducing weight, en-
hancing fuel efficiency and limiting the damages caused by lightning strike. Most
of the graphene based composites usually have polymers, small organic com-
pounds, metals, metal oxides or carbon nanotubes as their second component.
Based on the architectures, graphene based composites can be simply classified
into three types.
In type I composites, chemically synthesized graphene sheets act as a sub-
strate for supporting the second components which adhere to graphene sheets as
nanoparticles. These composites have large specific surface areas inherited from
the exfoliated graphene sheets and have active sites due to the nanoparticles em-
bedded within the sheets. Due to this interactive behaviour they find application
in adsorption, sensing, catalysis etc. In type III composites, graphene sheets may
distribute in the continuous matrix of the second component (a polymer or an
inorganic compound) playing the role of a nanofiller. These conductive nanofiller
graphene sheets can improve the electrical, mechanical and thermal properties

8
 1.4 Types of Graphene Based Materials

of the composites. Type II composites have large interfacial areas as both the
components i.e. graphene and the second component are in continuous phases.
Composite films prepared by layer-by-layer assembly fall under this type. They
have potential applications in energy conversion or storage devices. Including the
above mentioned architectures and applications of composite materials based on
graphene, there are many more diverse types of classifications which cover the
main aspects of recent studies on the composite materials based on graphene.
The second component can be introduced into graphene by two methods: mix-
ing and in situ synthesis. For mixing either graphene is synthesized before the
second component is introduced (pre-graphenization) or a mixture of a graphene
precursor (usually graphene oxide) and the second component is prepared, fol-
lowed by subsequent reduction of the graphene precursor into chemically synthe-
sized graphene (post-graphenization). This method allows us to precisely control
the structure of the second component, because the second component can be
designed and synthesized without the disturbance of graphene or its precursor.
In situ synthesis involves simultaneous synthesis of second component together
with graphene in the system. Second component nanoparticles, deposited on the
reduced graphene oxide sheets act as spacers and thus prevent the restacking
of sheets. The above suggested types of graphene based material synthesis are
depicted in Fig. 1.3.

Figure 1.3: Synthesis of graphene based composites.

9
 1.4 Types of Graphene Based Materials

1.4.2 Graphene Based Thin Films

With constant ongoing research and a recent upsurge in discovery of novel practi-
cal applications, graphene has emerged as a promising tool in large scale synthesis
and manufacture of nanoelectronic devices, transparent conducting electrodes,
supercapacitors etc. Graphene sheets can be pulled off graphite using mechan-
ical exfoliation scotch-tape method, however, only small amount of graphene
can be isolated for effective practical use. Similarly, chemical vapour deposition
(CVD) can also be used to grow graphene on metal surface, however, it is capital
intensive and requires significant expertise. Alternatively, cost-effective and less
arduous methods of graphene synthesis have also been devised. Graphite oxide
(GO), which is hydrophilic and an insulator, can be easily synthesised using Hum-
mers method. Several solution techniques such as dip-coating, spin coating etc.
and deposition on substrates like silicon dioxide, glass or PET enable fabrication
of GO films. Reduced GO (rGO), which is conductive, can also be prepared by
chemical treatment of GO films. Prominent contemporary and potential appli-
cations of reduced graphene oxide films have been listed below:

1. The property of electrical conductivity of rGO can be exploited in gener-

ation of thin film transistors, gas sensors, supercapacitors and electronic/
optoelectronic devices.

2. Techniques have been devised to maintain high flexibility and tensile strength
of GO after its reduction.

3. Indium tin-oxide (ITO) which is expensive, rigid and easily breakable is

presently used in transparent conductors. rGO polymer films are much
stronger and flexible and can effectively replace ITO in touch screens and
solar cells as material of choice.

4. rGO film based sensors can detect agents used in chemical warfare at ex-
tremely minute concentrations, opening new avenues in molecular sensing.

5. rGO based newer generation supercapacitors with large specific capacitance

can potentially replace batteries in cell phones, laptops and tablets in near
future.

6. In addition to large capacitance, flexibility and high tensile strength of rGO

films allows emergence of flexible supercapacitors for portable technology.

11
1. Introduction and Literature Review

7. Since GO/rGO films are fluorescent, they can be employed in medical ap-
plications like fluorescence based bio-sensors used for DNA detection.

GO and rGO films have many superior properties which will make them valu-
able for future technologies at a time when hi-tech companies are looking to
replace expensive materials with cheaper ones. For instance, they have potential
to be used in many peripherals to make a flexible cell phone. rGO films are read-
ily available for further research, so that they may soon be used in demanding
applications.

1.4.3 Other Graphene Based Materials

Nanoribbons, narrow strips of graphene and various othe forms of graphene also
exhibit extraordinary properties that have prospects in future nanoelectronic
technologies. Graphene oxide based paper has high tensile strength and polymer
based graphene oxide exhibits photoconducting properties. Flexible solid-state
supercapacitors based on graphene fibers have been demonstrated. Reinforcing
graphene with carbon nanotubes improves electronic and mechanical properties
of both the materials.

1.5 Applications of Graphene Based Materials

Graphene, used in isolation or in graphene-based composites, offers an enormous
range of defining applications - be it medicine, molecular sensing technology,
transport, wearable electronic devices or electronic storage devices. Medical pro-
cedures are set to be transformed with use of nanotechnology. Contemplated drug
delivery systems are no more a distant future, thereby offering a sea change in
treatment strategies for conditions like malignancies and Parkinsonism. Graphene
can redefine water purification systems by providing highly efficient desalination
plants. Advanced paints combined with graphene limit corrosion and enhance
energy efficiency. Graphene based sensing devices can detect minute traces of
dangerous chemicals (chemical warfare) and gases. Extremely lightweight, strong
and flexible, graphene based cell phones, cameras and wearable electronic devices
with tremendous battery life are no longer a distant reality. The same set of prop-
erties also hold the potential for building of highly fuel efficient and safer modes
of transport. Graphene based lithium ion batteries are expected to be light, flex-
ible and with significantly improved lifespan. These batteries can be recharged

12
 1.6 Literature Survey

by solar energy and can further be stitched to clothing, thereby enabling pro-
longed stays in the field for combat soldiers. Graphene based supercapacitors can
hold extensive amount of energy and are lightweight, their application can reduce
weight of cars and aircrafts.

1.6 Literature Survey

Graphene was first theoretically discussed in 1946 by Philip Russel Wallace (Wal-
lace (1947)). But he was able to develop only a two dimensional clone, graphene,
from which he could explain the properties of graphite. In 1986, Hanns-Peter
Boehm (Boehm et al. (1986)) coined the term graphene as a combination
of graphite and the suffix -ene (aromatic hydrocarbon) to describe single-layer
carbon foils. Then there were several attempts to isolate graphene. Synthesis
of monolayer graphite was tried as early as in 1975, when Lang (Lang (1975))
showed formation of mono- and multi-layered graphite by thermal disintegration
of carbon on single crystal Pt substrates. However, Novoselov et al. has been
credited for the discovery of graphene in 2004 (Novoselov et al. (2004)). They
have first shown repeatable synthesis of graphene through exfoliation. The tech-
nique has been and is being followed by many research groups known as scotch
tape method for synthesizing graphene. Since then efforts to develop new pro-
cessing routes for efficient synthesis of large-scale graphene are being made. Based
on the theoretical studies, Semenoff, in 1982, remarked various types of interca-
lated or exfoliated graphite must exist from which it may be possible to produce
a graphite monolayer (Semenoff (1984)). Several attempts have been made to
isolate graphene from such graphitic derivatives such as graphite oxide. The
first attempts to synthesize graphite oxide can be traced back to 1859, when
Brodie followed chemical processes to oxidize graphite (Brodie (1859)). Cur-
rently, graphene which can be prepared via different strategies and a related
material called reduced graphene oxide which is synthesized using graphite oxide
as a precursor, have been studied extensively for more than 170 years [Schafhaeutl
(1840a), Schafhaeutl (1840b), Dreyer et al. (2010), Gao et al. (2009)].

13
1. Introduction and Literature Review

1.6.1 Synthesis of Graphene :Top Down and Bottom Up

Approach
The top-down and bottom-up approaches for grahene synthesis originating from
different carbon sources are considerable. Top-down approaches involve breaking
apart the stacked layers of graphite to produce single graphene sheets (microme-
chanical cleavage [Kusmartsev et al. (2015), Geim & MacDonald (2007), Jayasena
& Subbiah (2011), Jayasena et al. (2013)], electrochemical exfoliation [Su et al.
(2011), Parvez et al. (2013), Liu et al. (2008)], solvent-based exfoliation [Oyer
et al. (2012), Sun et al. (2014)], exfoliation of graphite intercalation compounds
[Avdeev et al. (1996), Berger & Maire (1977), Yoshida et al. (1991), Kovtyukhova
et al. (2014)], unzipping carbon nanotubes [Jiao et al. (2009), Kosynkin et al.
(2009))]. Bottom-up methods involve synthesis of graphene from alternative car-
bon containing sources (epitaxial growth on silicon carbide [Emtsev et al. (2009),
?], chemical vapour deposition on metals [Yu et al. (2008), De Arco et al. (2009),
Reina et al. (2009)], substrate-free methods [Dato et al. (2008), Liu & Zhang
(2010)], graphene synthesis via the flash pyrolysis of the solvothermal product
of sodium and ethanol, etc. (Choucair et al. (2009)). In order for graphenes
potential to be fully accomplished and to satisfy requirements for applications,
convenient methods for its synthesis should be developed. It is possible to pro-
duce graphene sheets from a stacked layered graphite sheet, if the interplanar
week van-der-Waals are broken. The most popular top-down method is via the
oxidative exfoliation of graphite. The above mentioned methods can produce
graphene with a relatively perfect structure and excellent properties, while in
comparison, graphite oxide has two important characteristics:

1. It can be produced using inexpensive graphite as raw material by cost-

effective chemical methods with a high yield.

2. It is highly hydrophilic and can form stable aqueous colloids to facilitate

the assemblage of macroscopic structures by simple and cheap solution
processes. Both of these features are important to the large-scale uses of
graphene.

A key topic in the research and applications of GO is its reduction, which partly
restores the structure and properties of graphene. Various reduction processes
available result in different properties of reduced GO (rGO), which in turn affect
the final performance of device materials composed of rGO.

14
 1.6 Literature Survey

1.6.2 Synthesis of Graphite Oxide

Graphite oxide is usually synthesized by either the typical method proposed by
Hummer (Hummers & Offeman (1958)), Brodie (Brodie (1859)), Staudenmaier
(Staudenmaier (1898)) or some modification of these methods. Graphite oxide
thus synthesized was exfoliated into graphene oxide sheets by few hours of ul-
trasonication in water to form a stable aqueous dispersion of graphene oxide.
Recently, an improved method was reported by Marcano et al. (Marcano et al.
(2010)). They used KM nO4 as the only oxidant and an acid mixture of concen-
trated H2 SO4 and H3 P O4 (9:1) as the acidic medium. This technique greatly in-
creased the efficiency of oxidizing graphite to GO. Shen et al. (Shen et al. (2009))
oxidized graphite using benzoyl peroxide at 110o C for 10 min in an opened system
(as benzoyl peroxide can be explosive in closed container) to GO. This technique
provides a fast and efficient route to synthesis of graphene oxide.

1.6.3 Reduction Strategies of Graphite Oxide Towards

Reduced Graphene Oxide
The graphene oxides are then reduced into graphene by means of thermal anneal-
ing [Schniepp et al. (2006), Sheng et al. (2011), Zhu et al. (2010b)], solvothermal
reduction [Dubin et al. (2010), Nethravathi & Rajamathi (2008)], electrochem-
ical reduction [Wang et al. (2009b), An et al. (2010)], hydrogen plasma treat-
ment (Gmez-Navarro et al. (2007)) or radiation-induced reduction [Zhu et al.
(2010a), Hassan et al. (2009)] etc. Among other methods, the most customarily
used method is chemical reduction using reductants such as hydrazine[Zhu et al.
(2009), Robinson et al. (2008b), Stankovich et al. (2007)], sodium borohydride
(Shin et al. (2009)), metal Zinc (Sarkar & Basak (2013)), Vitamin C (Zhang
et al. (2010a)), dimethylhydrazine,(Stankovich et al. (2006)), alcohols(Liu et al.
(2012a)) and hydroquinone (Wang et al. (2008)). Usually, the reduction can
be realized at room temperature or by moderate heating. As a result, the re-
quirement for equipment and environment is not as critical as that of thermal
annealing treatment, which makes chemical reduction a cheaper and easily avail-
able way for the mass production of graphene compared with thermal reduction.
The reduction of graphite oxide by hydrazine was used before the discovery of
graphene, while the use of hydrazine to prepare chemically derived graphene was
first reported by Stankovich et al. (Stankovich et al. (2007)). The schematic
illustration of synthesis of graphene using this method is shown in Fig. 1.4.

15
1. Introduction and Literature Review

Figure 1.4: Synthesis of graphene using oxidative reaction of graphite.

1.6.4 Reduced Graphene Oxide (RGO) Based Materials

Graphene, a one-atom layer of graphite, possesses a fascinating two-dimensional
structure and excellent thermal, mechanical and electrical properties. Thus, it
has been regarded as an essential component for making various functional ma-
terials. Despite the fact that the conductivity of RGO is orders lower compared
to the pristine graphene due to the presence of residual oxygenated groups and
defects, the reactive surfaces of GO and RGO provide the tunability in electronic
and optoelectronic properties via chemical reactions [Mattevi et al. (2009), Eda
et al. (2010), Yan et al. (2011)], and the feasibility for composite incorporation
(Stankovich et al. (2006)).

1.6.5 Reduced Graphene Oxide Thin Films

Incredible applications of graphene require the synthesis of mono- or few- layer
graphene or graphene based composite films. Good quality graphene films can be
directly synthesized by chemical vapor deposition [Dong et al. (2011b), Li et al.
(2010b)]. An alternative approach for scalable production of graphene films is
using chemically reduced graphene oxide (Dreyer et al. (2010)). This method
requires formation of GO films using GO dispersions, and then reducing these
films using various chemical environments towards reduced GO (rGO) films[Bai
et al. (2011), Park & Ruoff (2009), Loh et al. (2010)]. Various methods for
GO thin-film preparation include drop-casting, spincoating, [Watcharotone et al.
(2007), Becerril et al. (2008)], dip-coating (?), spraying [Blake et al. (2008), Li
et al. (2008)], vacuum filtration [Eda et al. (2008), De et al. (2010)] spin as-
sisted assembly, Langmuir Blodgett (LB) assembly [Cote et al. (2009), Kim et al.
(2010a)] and other self assembly processes at liquid air [Zhu et al. (2009), Chen

16
 1.6 Literature Survey

et al. (2009), Zhao et al. (2010), Kim et al. (2010c)] or liquid liquid interfaces
[Kim et al. (2010a), Biswas & Drzal (2009), Xu & Shi (2011)]. The most exciting
vantages of these rGO based thin films are their low cost production and massive
scalability (Allen et al. (2010)).

1.6.6 Role of Graphene in Graphene/Metal Oxide Com-

posites
Graphene synthesis through the top-down approach has been followed to obtain
graphene based composites which have diverse applications due to the intriguing
interaction between the components and graphene. There have been many reports
on synthesis methods followed for transition-metal oxides/ graphene composites,
such as M nO2 graphene (Chen et al. (2010a)), F e3 O4 graphene (Zhou et al.
(2010)), T iO2 graphene (tengl et al. (2011)), SnO2 graphene (Lu et al. (2010)),
Co3 O4 graphene (Wu et al. (2010e)). The poor electrical conductivity and low
mechanical and chemical stability of transition metal oxides usually demand the
addition of conductive supportive matrix (like graphene) to enhance its charge
transfer rate. RGO can also be used with a variety of metal compounds for syn-
thesizing graphene/metal oxide composites materials. The metal oxides include
F e2 O3 [Morishige & Hamada (2005), Bashkova & Bandosz (2009)], F e3 O4 [Yang
et al. (2009), Wang et al. (2014a)], Al2 O3 [?, Fan et al. (2010)], SnO2 [Li et al.
(2014), Paek et al. (2009)], N iO (Mai et al. (2012)), M nO2 (Yan et al. (2010a)),
T iO2 [Williams et al. (2008), Lambert et al. (2009)], ZnO [Lee et al. (2009),
Zhang et al. (2009)], Cu2 O (Xu et al. (2009)) and Co3 O4 [Yan et al. (2010b),
Liang et al. (2011)], hydroxides (e. g. Co(OH)2 (He et al. (2010)) and N i(OH)2
(Wang et al. (2010a)). The synthesis methods used are mostly in-situ growth and
pre-or post-graphenization mixing. In post-graphenization, a metal salt is mixed
with graphene oxide initially. Then step by step first metal salt is reduced to cor-
responding oxide or hydroxide, followed by reduction of graphene oxide to reduced
graphene oxide [Chen et al. (2012a), Zhang et al. (2010c)] . Pre-graphenization
is also an important route to RGO/metal oxide composites as RGO synthesized
in different ways can be used without incorporporation of reducants into the final
composites [Wang et al. (2009a), Lin et al. (2010), Mai et al. (2012)]. However,
graphene sheets have a natural tendency to stack into multilayers and therefore
lose their benefits of high surface area and peculiar chemical and physical prop-
erties. A facile in situ route has been used for integrating graphene sheets with
metal oxide nanoparticles during a simultaneous synthesis strategy to attenuate

17
1. Introduction and Literature Review

the aggregation of graphene sheets [Singh et al. (2009b), Yao et al. (2009)]. These
RGO based composites synthesized by various methods have been used in variety
of applications due to the outstanding properties of graphene.

1. Due to the rapid recombination of photogenerated electrons and holes within

metal oxide based photocatalysts, their practical applications in hydrogen
generation and dye degradation is limited. Considering the high specific
surface area, conjugated two dimensional structure and prominent electron
mobility, graphene can be used as a fast electron scavenger to accelerate
the photo-induced charge transfer and to curb the backward reaction [Tran
et al. (2012), Agegnehu et al. (2012), Xiang et al. (2011), Zhang et al.
(2010e), Liu et al. (2012b)].

2. Graphene and graphene based materials are able to store lithium through
the surface absorption by functional groups and possess high conductivity.
Therefore, many metal oxide nanomaterials have been synthesized with
graphene for lithium ion batteries [Zhang et al. (2010c), Wu et al. (2010e),
Wang et al. (2010b), Zhou et al. (2010)]. Using graphene based materials
as platform for in situ synthesis and loading of the metal oxide nanostruc-
tures was found to improve electrical conductivity in M n3 O4 (Wang et al.
(2010b)), SnO2 (Kim et al. (2010b)), T iO2 (Wang et al. (2009a)), F e3 O4
(Zhou et al. (2010)) and even distribution of nanoparticles on graphene
sheets without agglomeration like Co3 O4 graphene (Wu et al. (2010e))
and Cu2 O graphene (Xu et al. (2009)) composites.

3. A number of metal oxides, such as ZnO (Zhang et al. (2009)), SnO2 (Lim
et al. (2013)), Co3 O4 (Xiang et al. (2013)), M nO2 (Yu et al. (2011)) and
RuO2 (Amir et al. (2013)) have been incorporated with graphene to pre-
pare electrodes for supercapacitors. Intervening RGO sheets were found to
enhance the specific capacitance of the composite material.

4. Graphene sheets exhibit very good adsorption properties because they have
a high specific surface area with a conjugated structure that provides a
large number of sites where gases can react. Thus graphene based materials
like SnO2 graphene (Zhang et al. (2011b)), W O3 RGO (Esfandiar et al.
(2014)), T iO2 RGO (Esfandiar et al. (2012)), M nO2 RGO (?), Al2 O3
RGO (Jiang et al. (2011)) etc. are ideal choice for sensing applications.

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 1.6 Literature Survey

1.6.7 Other Composites of Graphene

To date, graphene-based composites have been successfully made with inorganic
nanostructures [Bai & Shen (2012), Nethravathi & Rajamathi (2008), Tian et al.
(2014)], organic crystals [Wang et al. (2010c), Han et al. (2010)], polymers [Qi
et al. (2010a), Qi et al. (2010b), Yang et al. (2010)], metal-organic frameworks
(MOFs) [Jahan et al. (2010), Petit & Bandosz (2010), Petit et al. (2011)], bio-
materials (Lu et al. (2009a)) and carbon nanotubes (CNTs) [Dong et al. (2011a),
Tung et al. (2009)] and are intensively explored in applications such as batteries
[Wang et al. (2014b), Guo et al. (2011)], supercapacitors [Pham et al. (2015),
Zhang et al. (2010b)], fuel cells [Liu et al. (2014), kumar et al. (2014)], photo-
voltaic devices [Yu et al. (2010), Xu et al. (2010)], sensing platforms [Zheng et al.
(2013), Al-Mashat et al. (2010)], photocatalysis [Ameen et al. (2012), Yang et al.
(2013a)], Raman enhancement (Yu et al. (2014)) and so on.

1.6.8 RGO/Zinc Oxide (ZnO) composite

As discussed in earlier sections, graphene decorated with metal oxide nanopar-
ticles has attracted a great deal of attention in many technological fields due to
potential applications. Out of these semiconductor oxides, ZnO is an impor-
tant II-VI semiconductor that has a wide direct band gap of 3.37 eV at room
temperature and a high exciton binding energy of approximately 60 meV (Lyu
et al. (2002)) and high mechanical, thermal and chemical stability (Huang & Lin
(2013)). ZnO also has several useful characteristics, such as a large piezoelectric
constant (Emanetoglu et al. (1999)) and an electrical conductivity that can be
easily modified (Kashani (1998)). ZnO has received considerable attention over
the past few years because of these unique properties, and has been used in a
variety of applications, such as photocatalysis, field effect transistors, chemical
sensors, field emitters, transparent conductors and ultraviolet light emitting de-
vices (Cho et al. (2010)). It is expected that incorporation of graphene sheets
into RGO/ZnO composite materials is an effective and efficient way to harness
the intriguing properties of graphene based materials. RGO/ZnO nanocompos-
ite has been found to provide admirable performance aiming to enhance and
expand the applications of ZnO. From the photoluminescence results of Zou
et al. it was inferred that anchoring of ZnO nanoparticles on graphene sheets
improves the photoinduced charge separation which implies that graphene/ZnO
composite can be used in photoelectrochemical cells (Zou et al. (2011)). Thus
as compared to bare ZnO nanoparticles, graphene/ZnO nanocomposites showed

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1. Introduction and Literature Review

advanced photocatalytic activity [He et al. (2014), Saravanakumar et al. (2013),

Roy et al. (2013)]. Kim et al. reported that the ZnO nanostructures grown on
graphene were of high optical quality (Kim et al. (2011)). Due to the outstanding
electrical and mechanical properties of graphene, its heterostructures with ZnO
were found to possess excellent field emission properties, improved gas sensing
and higher photocatalytic activity than pure ZnO (Zou et al. (2013)). Similar
works have been reported by Ding et al. [Ding et al. (2012)), Chen et al. (?)Yi
et al. (Yi et al. (2011a)].

1.7 Outline of Current Thesis

Though a large volume of literature is available on graphene based materials, their
synthesis and applications, yet there is enough scope for study on low cost pro-
cessing of graphene based materials and exploring further applications. Inspired
by novel properties and vast applications in various areas, reduced graphene oxide
or graphene based composites can be used as precursors to produce functional ma-
terials. In this thesis work my prime aim is to synthesize various graphene based
materials like reduced graphene oxide thin films and graphene based composites.
These materials were further characterized to explore improvement in application
avenues. More specifically in this work I have tried to use cost effective and facile
methods for graphene based material synthesis which were characterized for ap-
plications such as photocatalysis, solar cells, diodes and gas sensors. The detail
of layout of my thesis work is listed in the following text.
1. The focus of 2nd Chapter is on the characterization techniques followed in
different experiments. After the synthesis of material it is necessary to
analyze its physical and chemical properties. I have discussed briefly about
a few characterization techniques used by me such as XRD, FESEM, UV-vis
spectroscopy and a gas sensing unit which has been designed and developed
in the lab.

2. 3rd Chapter deals with the chemical synthesis of graphite oxide and produc-
tion of graphene oxide thin films on glass substrate by spin coating. These
graphene oxide films were exposed to three environments to fabricate re-
duced graphene oxide thin films. Amount of reduction of graphene oxide
was studied by investigating optical properties. This chapter focusses on
easy synthesis technique for reduced graphene oxide based thin film which
can be brought to use in various applications.

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 1.7 Outline of Current Thesis

3. After synthesizing reduced graphene oxide thin film as a graphene based

material, attention was diverted towards graphene based composites. 4th
Chapter deals with the synthesis and characterization of graphene/zinc ox-
ide nanocomposite material. In this experimental study I have investigated
the effect of second component precursor on structural, optical and thermal
properties of the obtained graphene based materials. The results clearly
pointed towards appropriate zinc precursor which can be used in graphene
based composites.

4. In 5th Chapter I have investigated the gas sensing characteristics of graphene/zinc

oxide composite. With this study it has been found that the peculiar prop-
erties of graphene can influence sensing mechanism and provide fascinating
gas sensing properties to graphene based materials. Key synthesis parame-
ters such as the graphene content and operating temperature were optimized
in experiments.

5. In 6th Chapter I investigated the role of graphene in photocatalytic inves-

tigations of graphene/Zinc oxide composite. Considering its superior elec-
tron mobility and macroporous structure, it is found that that graphene
has played a crucial role in improving the photocatalytic performance of
pure zinc oxide. The effect of synthesis technique on interfacial interaction
between graphene and second component in graphene based composite is
also investigated.

6. In 7th Chapter an attempt was made to modify the above mentioned syn-
thesis strategy by involving a surfactant. The surfactant helps in preventing
the particle aggregation on graphene sheets. This sample is characterised for
electrical properties and it is found that synthesized material demonstrates
non-linear diode characteristics. The random potential barrier networks
between graphene and zinc oxide are expected to be responsible for these
results.

All these issues are elaborately discussed in the following chapters.

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