CHAPTER 1

INTRODUCTION

This chapter includes a brief summary of nanotechnology, nanoscience,

nanomaterials, synthetic methods used to manufacture nanomaterials, graphene, graphene
oxide, reduced graphene oxide, applications for reduced graphene oxide-based composites,
and characterization techniques.

1.1. Nanotechnology

Nanotechnology refers to any technology that operates at the nanoscale and has a
wide range of practical uses. Nano means parts per billion, so nanotechnology deals with
materials measured in billionths of a meter. The word "nano" comes from the Latin word
nanus or the Greek word nanos which meaning "dwarf". A nanometer is 1/80,000 of the
diameter of a human hair, or about the width of ten hydrogen atoms (Kamel,
2007).Nanotechnology defined as the self-assembly or manipulation of individual atoms,
molecules, or molecular clusters into structures to produce materials and technologies with
novel or entirely distinct features. However, nanotechnology is not limited to small elements
but the science of nanotechnology is multidisciplinary. It contains information from several
academic fields, including physics, chemistry, and biology (Abiodun-Solanke et al., 2014).

Nanoscience is the term used to describe the growing field of study of objects with
dimensions between a few nanometers and less than 100 nanometers, which fall between the
largest molecules and the smallest structures (Ramsden, 2005). Nanoscience is not just about
size but it is the study of unique features that have arisen at the nanoscale by understanding
and modifying materials at the atomic, molecular, and macromolecular scales where their
features distinguish from those at a larger scale materials (Kumar and Kumbhat, 2016). The
research and development of highly efficient functioning devices, materials, and systems on
the length scale of 1–100 nm , it have become feasible because to technological
developments in nanoscience and nanotechnology. The primary difference between
nanoscience and nanotechnology is that the former provides information about atom
arrangements and fundamental properties at the nanoscale, while the latter uses technology to
control matter at the atomic level in order to create novel nanomaterials with unique
properties (GOKUL et al., 2023).

Information and communication, biotechnology, health care, energy, the environment,

and sensors are just a few of the industries that nanotechnology is helping to revolutionize. It
has been specifically demonstrated that the creation of nanoparticles with distinctive forms
and structures rather than just size reductions is a key idea in nanotechnology(Logothetidis,
2011). By bridging already-existing domains, nanotechnology has created a new one e.g.,
physics, materials, and electronics. Nanotechnology has infiltrated all sectors due to its
unique and evident impacts, which give the scientific community numerous breakthroughs in
the medical, agricultural, and other domains (Salem et al., 2022).

Nanomaterials" are the fundamental and vital elements of nanotechnology. Materials

that are smaller than 100 nm, at least in one dimension, are referred to as nanomaterials. This
indicates that they are much smaller than microscale . Typically, nanomaterials have a size of
10^9 m, or one billionth of a meter (Gajanan and Tijare, 2018). The physicochemical
properties of nanoparticles differ from those of the bulk material, and these differences are
intrinsically related to their size and shape. Remarkably, the nanomaterials alter size and
shape at the nanoscale level to create a distinct character with new properties and abilities
(Vollath, 2013) . Because of their improved performance compared to their bulk equivalents
and their controllable physical, chemical, and biological properties, nanomaterials have
gained significant attention in scientific advancements(Rao and Cheetham, 2001).

1.2. Nanomaterials

Nanomaterials are materials or chemical compounds that are produced and utilized on a very
small scale, meaning that they are smaller than 100 nm in at least one dimension (Chen et al.,
2013). Particles in bulk materials are larger than 100 nm in all dimensions. While physical
qualities of bulk materials are independent of size, the size and shape of nanometer-sized
particles can affect a variety of physical attributes (Gajanan and Tijare, 2018). Researchers
discovered that size affects a substance's physicochemical features, which include its
chemical, electrical, mechanical, and optical properties. This discovery led to the realization
of the significance of NMs. Because of these distinctive qualities, Nanomaterials have
attracted a lot of attention (Rao and Cheetham, 2001).
1.3. Unique Features of nanomaterials :

A wide variety of materials with at least one dimension between 1 and 100 nm make up the
remarkable class of materials known as nanomaterials. By thoughtfully creating
nanoparticles, exceptionally large surface areas can be attained (Zhang et al., 2014).
 Exceptional magnetic, electrical, optical, mechanical, and catalytic capabilities that
differ significantly from their bulk counterparts can be achieved by synthesizing
nanomaterials. By carefully regulating the size, shape, synthesis circumstances, and
suitable functionalization, the properties of the nanomaterial can be exactly tailored to
the desired results. Nanomaterials are currently used in electronics, cosmetics, sports
equipment, energy-storage devices, sensors, paints that don't scratch surfaces, and
environmental clean-up (Baig et al., 2021).
 When compared to their bulk counterparts, the characteristics of matter at the
nanoscale level differ significantly. At the nanoscale, size-dependent effects become
increasingly noticeable. For instance, au solution appears yellow in the bulk but turns
purple or red at the nanoscale (Arzt, 1998).
 At the nanoscale, the electrical properties are significantly altered in comparison to
bulk materials. The size of nanomaterials can be modified to modify its properties.
For instance, while a two-dimensional network of boron seems to be a good two-
dimensional metal, boron in bulk is not thought of as a metal.Because of gains in
crystal perfection or decreases in crystallographic defects, nanomaterials have
significantly better mechanical characteristics than their bulk counterparts(Mannix et
al., 2015).
 The mechanical features of nanoparticles are significantly better than those of their
bulk equivalents because of decreases in crystallographic defects or increases in
crystal perfection (Tomar et al., 2020)
 In general, the size, form, dimensionality, crystallinity, structure, composition, etc.,
are the most important physicochemical parameters. With the quick advancement of
nanoscience and nanotechnology, one or more of the previously mentioned
requirements can be adjusted to give nanomaterials the desired characteristics (Zou et
al., 2006).
 Nanoparticles' volume, surface, and quantum effects give nanomaterials their superior
mechanical properties. When ordinary material is mixed with nanoparticles, the grains
become somewhat more refined. This results in the formation of either an
 intragranular or an intergranular structure, which enhances the grain boundary and
improves the mechanical properties of the material(Zou et al., 2006; Wang et al.,
2011). For instance, concrete's bending, splitting, and compressive strengths can all be
increased by adding 3 weight percent nano-SiO2(Al Ghabban et al., 2018). Tensile
strength, elongation at break, and impact strength of kenaf epoxy composites can all
be significantly increased by adding 3% nano oil palm empty fruit string filler(Saba et
al., 2016).
 It appears significant to examine the upper and lower bounds of the NM grain sizes.
By NMs, materials are generally understood to be those in which the size of the
phases or grains that make up their structure does not exceed 100 nm at least in one
direction. This upper bound is highly arbitrary, and its value is determined more by
practical than by physical factors; however, straightforward estimations demonstrate
that, beginning at this size, the fraction of disordered interface regions becomes more
noticeable (this fraction is about 3s/D, where s is the width of the grain-boundary
region and D is the characteristic size); at reasonable values of s ≅ 0.5–1 nm, the
above fraction reaches several percent. On the other hand, as originally
indicated(Andrievski and Glezer, 2001).
 From basic principles to contemporary applications, size effects in nanostructured
(nanocrystalline, nanophase, or nanocomposite) materials (NMs) are extremely
significant. The latter has several connections, including the creation of novel NMs
and the choice of nanodevice component parts(Arzt, 1998).

1.4. Synthesis method for nanomaterial :

Nanomaterials are synthetized by different methods based on the types and nature of
the nanomaterials. In a broad sense “top-down” and “bottom-up” are the two foremost
methods to synthesize nanomaterials (Khan, 2020).

Top-down approach

Transformation of bulk material into small nano-sized particles is done using this approach.
Although top-down approaches are simple to use, they are ineffective for manufacturing
irregularly shaped and extremely small particles. The difficulty in obtaining proper particle
size and shape is the main downside of this approach(Vaseghi and Nematollahzadeh, 2020).

Bottom-up approach
The constructive technique is a term used to describe the bottom-up approach. The bottom-up
method is the polar opposite of top-down. NMs with well-defined shape, size, and chemical
composition are formed through the growth and self-assembly of atoms and molecules as
their building blocks(Kolahalam et al., 2019).

1.5. Classification of nanomaterial based on origin:

Based on their origin, nanomaterials can be classified into two groups: natural and
artificial nanoparticles (Khan and Hossain, 2022).

Natural nanomaterials :
Natural nanomaterials are found in nature in many different forms: viruses, protein
molecules, minerals (like clay)(Zhang et al., 2005), natural colloids (like milk and blood), fog
(aerosol type), gelatine (gel type), mineralized natural materials (like shells, corals, and
bones), insect wings and opals, spider silk, lotus leaves, gecko feet, volcanic ash, and ocean
spray(Khan and Hossain, 2022; Mekuye and Abera, 2023).

Artificial nanomaterial:
Artificial nanomaterials, such as carbon nanotubes and semiconductor nanoparticles
like quantum dots (QDs), are manufactured with selective care and attention in every aspect
using precise mechanical and manufacturing processes(Mekuye and Abera, 2023).

1.6. Classification of NM,s based on dimension :

Based on the general structure and dimensionality, nanomaterials (NMs) can be

divided into four classes: one-dimensional nanomaterials (1D), two-dimensional (2D), three-
dimensional (3D) nanomaterials (Pokropivny and Skorokhod, 2007)

Zero-dimensional nanomaterials

These nanomaterials are either non-dimensional outside the nanometric range (>10
nm) or have all three dimensions (x, y, and z) within the nanoscale range. 0D comprises
quantum dots (QDs), hollow sphere, metal, cube, nanorod, polygon, spherical NMs, and core-
shell NMs (Aversa et al., 2018). Examples of 0D nanomaterials are nanoparticles, fullerenes,
and QDs. They can take on different forms and shapes, be metallic or ceramic, amorphous or
crystalline, single crystalline or polycrystalline (Buzea et al., 2007; Fındık, 2021).

One-dimensional nanomaterials

This class of nanomaterials has one dimension (>10 nm) outside the non-metric range,
while two of the three dimensions (x, y) are in the nanoscale range. Needle-
shaped nanomaterials include 1D nanomaterials including thin films, nanowires, nanohorns,
nanotubes, and nanofibers. Nanowires, nanofibers, metallic, polymeric, ceramic, nanotube,
and nanorods filament or fiber are examples of 1D materials (Aversa et al., 2018). They can
be isolated materials or embedded in other media like metallic, ceramic, or polymeric ones.
They can also be amorphous or crystalline, single crystalline or polycrystalline, and pure or
impure chemically (Buzea et al., 2007).

Table 1.1 nanomaterial classification based on dimension

Dimensionality Type of Nanomaterial

Zero dimensional Nanoparticles, quantum dots
One Dimensional Nanorods, nanotubes, nanowires
Two dimensional Nanofilms, nanolayers.
Three dimensional or Bulk Core shells, a bundle of
nanomaterials nanowires, a bundle of nanotubes.

Two-dimensional nanomaterials

Nanomaterials that are two dimensional (2D) only have one nanoscale dimension; the
other two do not exist. The terms "2D" refer to crystalline or amorphous thin films,
nanoplates, nanocoating, single- and multi-layered materials (Aversa et al., 2018) .One
dimension, or 1D (x), is in the nanoscale (between 1 and 100 nm), whereas two dimensions
of 2D nanomaterials have plate-like structures outside the nanometer range.
Examples of two-dimensional nanomaterials are coatings and thin-film multilayers,
nano sheets or walls, free particles, tubes, fibers, ultrafine-grained over layers, wires, and
platelets. Two-dimensional nanomaterials can be crystalline or amorphous, composed of
different chemicals, coated on a substrate, or integrated into a polymeric, metallic, or
surrounding matrix material (Khan and Hossain, 2022).

Three-dimensional nanomaterials

Materials that are not limited to the nanoscale in any dimension or range of
dimensions are known as 3D nanomaterials or bulk materials. Since the bulk material is
composed of discrete blocks that fall inside the nanometer scale (1–100 nm), 3D
nanomaterials have three arbitrary dimensions above 100 nm. However, all of a 3D material's
dimensions are outside of the nanoscale range or larger than 100 nm. It consists of dispersed
nanoparticles, nanowire and nanotube bundles, and multi-nano layers with interfaces formed
by close interaction between 0D, 1D, and 2D structural elements. Three-dimensional
nanomaterials include free nanoparticles with different morphologies, colloids, and thin films
with atomic-scale porosity(Buzea et al., 2007).

1.7. Classification of nanomaterial based on carbon atom

Due to their rare array of chemical and physical properties (such as high mechanical
strength, high electrical and thermal conductivity, and optical qualities), carbon-based
nanomaterials (CBNs) have gained importance(Cha et al., 2013).Four fundamental elements
make up carbon-based nanomaterials: carbon nanotubes , fullerenes, carbon nanofiber and
graphene (Mekuye and Abera, 2023) .

Carbon nanotube

Carbon nanotubes are an essential member of the carbon nanomaterial family, and
they entered the carbon family in 1991 after being discovered by S. Iijima(Iijima, 1991).
Carbon nanotubes are rolled sheets of single-layered sp2-hybridized carbon atoms. The
surfaces of the nanotubes consist of sp2-hybridized carbon atoms that are arranged in
hexagons(Zaporotskova et al., 2016).

CNTs are essentially cylindrical graphene sheets with fullerene-like structures on top.
One way to create single-walled (SWCNTs) and multi-walled (MWCNTs) nanotubes is to
roll up single or several graphene lamella seamlessly. Their surface areas range from 150 to
1500 m2 g−1, which means they can function as effective sorbents(Hussain and Mitra, 2011)
To enable a more selective interaction with analytes, CNTs can also be readily
functionalized, either covalently or non-covalently, with a variety of organic compounds.
CNTs have been the most often utilized carbon-based nanomaterials for sample preparation
up to this point (Pérez-López and Merkoçi, 2012)

Fullerene :

Fullerenes are an amazing allotrope of carbon and are highly symmetrical cages of
sp2-hybridized carbon atoms. Fullerenes are distinct molecules, and they consist of a specific
number of carbon atoms, making them different from the other allotropes of carbon.
Fullerenes appear with different sizes according to the number of carbon atoms, such as C 60,
C70, C72, C76, C84, and C100(Mendes et al., 2013).Bucky balls are carbon nanoparticles with a
spherical or ellipsoidal configuration known as fullerenes. The spherical structure known as
fullerenes, which are made up of between 28 and 1500 carbon atoms, has diameters of up to
8.2 nm for single layers and 4 to 36 nm for multi-layered fullerenes.(Gu et al., 2022; Mekuye
and Abera, 2023).
Since fullerene is the only member of the nanocarbon family with a closed-cage
structure, the field of nanoscience has entered a new era. In 1985, Kroto et al. discovered
C60, the first fullerene (Kroto et al., 1985). Fullerene is the only soluble form of elemental
carbon among all known allotropes that is solely made up of sp2-hybridized carbon atoms
and has a distinct spherical molecular shape (Popov et al., 2013)

Carbon nanofiber:

Carbon nanofibers (CNFs) are solid carbon fibers that have diameters less than 100
nm and lengths of a few microns. The lack of a hollow chamber and the fact that CNFs often
have larger diameters than equivalent CNTs set them apart from CNTs.

Because of its consistent mesoporous magnitude and distribution and comparatively

high specific surface, CNFs continue to be extremely desirable. The maximum surface area
of carbon nanofibers has been reported to be 1877 m2 g−1, which is one of the highest values
ever recorded for nano-structured materials(Bui et al., 2009). Since CNFs have a large
specific surface area, good chemical stability, and distinctive mechanical features, they have
garnered significant interest in applications such as gas adsorbents and catalyst
supports(Boonjob et al., 2011)

Graphene :

Since its accidental discovery in 2004, graphene the thinnest substance in the
world ,has been the subject of extensive research. Graphene is a one-atom-thick single-layer
planar nanosheet with sp2 hybridized carbon atoms tightly packed in a hexagonal crystal
lattice(Novoselov et al., 2005) Graphene, a two-dimensional (2D) planar surface composed
of carbon atoms arranged in a hexagonal network of honeycomb lattices, has a sheet
thickness of around 1 nm (Gu et al., 2022). A wide range of exceptional characteristics are
exhibited by graphene nanosheets, such as high 3D aspect ratio, superior mechanical stiffness
and flexibility, exceptional electrical transport capabilities, good optical transmittance, big
specific surface area (SSA), and exceptional thermal responsiveness. As a result, a lot of
research has been done on creating materials based on graphene for a variety of uses.

Graphene can be generated using "top-down" processes such as sonication, liquid

phase exfoliation, and ionic-liquid assisted electrochemical exfoliation. Graphene was first
separated from graphite by simple scotch tape mechanical exfoliation. Together with these
"top-down" techniques, "bottom-up" synthesis methods include producing graphene
chemically from aromatic benzene derivatives, producing graphene through the CVD process
of hydrocarbons, and producing graphene through epitaxial growth on metal substrates (Kuila
et al., 2012).

1.8. Classification of nanomaterials based on the structural configuration/composition

Nanomaterials are categorized according to their structural composition or structure.

Four basic categories of nanoparticles can be distinguished depending on their structural
composition: organic/dendrimers, inorganic, carbon-based, and composite (Khan et al., 2022)

Organic nanomaterials

Organic molecules undergo conversion into organic nanomaterials at the

nanoscale(Zhang et al., 2016). Liposomes, dendrimers, micelles, and ferritin are a few
examples of organic nanoparticles or polymers. Because of their hollow interiors and
sensitivity to light, heat, and electromagnetic radiation, non-toxic biodegradable nanoparticles
called liposomes and nanocapsule micelles (Khan et al., 2022). Dendrimers are covered with
many chain ends that have the ability to carry out particular chemical reactions on their
surface. Dendrimers have use in light harvesting, nanosensing, molecular recognition, and
optoelectrochemical systems. Moreover, three-dimensional (3D) dendrimers may be helpful
for drug administration since they have interior holes that can hold extra molecules (Gu et al.,
2022).

Inorganic nano materials

The term "inorganic nanoparticles" refers to particles that are devoid of carbon atoms.
Generally speaking, metal-based or metal oxide-based nanomaterials make up inorganic
nanoparticles (Khan et al., 2022).

Metal-based nanoparticles

Metals such as aluminium (Al), cadmium (Cd), cobalt (Co), copper (Cu), gold (Au),
iron (Fe), lead (Pb), silver (Ag), and zinc (Zaporotskova et al.) are commonly utilized in the
creation of nanoparticles. Both constructive and destructive methods can be used to create
metal-based nanoparticles. Metal nanoparticles exhibit exceptional UV-visible sensitivity in
addition to electrical, catalytic, thermal, and antibacterial characteristics due to their quantum
effects and large surface-to-volume ratio. Because of their exceptional optical characteristics,
metal nanoparticles are employed in numerous fields of research(Khan et al., 2022).

Metal oxide nanoparticles

Positive metallic ions and negative oxygen ions make up metal oxide nanoparticles,
which are also referred to as metal oxide nanomaterials. Aluminium oxide (Al2O3), zinc
oxide (ZnO), silicon dioxide (SiO2), and titanium oxide (TiO2) are a few examples of metal
oxide nanoparticles that are commonly manufactured. When compared to their metal
analogues, these nanoparticles show some amazing features (Khan et al., 2022)

Ceramic nanomaterials

Ceramic nanoparticles are inorganic solids composed of oxides, carbides, carbonates,

and phosphates that are produced by heating prior to cooling.
Ceramic nanoparticles can be used in medication delivery systems, particularly for bacterial
infections, glaucoma, and malignancies. Furthermore because of its usage in processes like
photocatalysis, catalysis, photodegradation of dyes, and imaging applications, nanomaterials
additionally draw a lot of interest from researchers (Zhang et al., 2016; Ibrahim Khan and
Khan, 2017)

Carbon based nano materials

The carbon-based nanomaterial family consists of nanomaterials that have been

extensively explored for various applications due to their outstanding features. The
extraordinary properties of tunable carbon-based nanomaterials have attracted great interest
for use in new technologies and addressing modern challenges (Mauter and Elimelech,
2008).The exceptional physicochemical features of carbon-based nanomaterials, such as their
huge specific surface areas, superior acid stability, and thermal resistance, have garnered
significant attention in the field of pollution remediation (Liu et al., 2022)

1.9. Graphene as unique nanomaterial :

Since its first preparation by mechanical exfoliation in 2004, graphene , a single-

atom-thick sheet of sp2-hybridized carbon has drawn a lot of interest from the scientific and
engineering sectors(Novoselov et al., 2004). Graphene is the thinnest and strongest substance
in the universe due to its unique 2D honeycomb lattice structure, which also gives it many
superior chemical and physical capabilities(Geim, 2009).

Strong ambipolar electric field effect, unconventional quantum Hall effect, high thermal
conductivity (5000 W m−1 K−1), high carrier mobility at room temperature (200 000 cm2 V−1
s−1), extremely high theoretical specific surface area (2630 m2 g−1), high transparency
(97.7%), excellent environmental compatibility, good electrical conductivity (2000 S m −1),
low production cost, high mechanical strength and high adsorption capacity for inorganic and
organic molecules are some of the exquisite graphene's prominent benefits(Nguyen et al.,
2012). Compared to other carbon allotropes (i.e., 0D fullerenes, 1D nanotubes, and 3D
graphite), 2D graphene has more promise applications in optical, electrical, biological, and
catalytic sectors because of these superior features(Allen et al., 2010).

Because of its crystal structure, graphene has an exceptional band structure. In two
dimensions, carbon atoms arrange themselves into a hexagonal lattice. Every carbon atom has
three neighbours, with whom it shares one 𝜎 bond, at a distance of approximately 𝑎 = 1.42
Å. A 𝜋-bond, which is orientated out of the plane in the 𝑧-direction, makes up the fourth
bond. The 𝜋 orbital can be visualized as two symmetric lobes that are cantered on the
nucleus and aligned along the 𝑧-axis. These 𝜋-bonds are present in every atom and combine
to produce the 𝜋-band and 𝜋∗-bands when they hybridize. The majority of graphene's
unusual electrical characteristics are caused by these bands. Graphene's hexagonal lattice can
be thought of as two interlocking triangle lattices (Wallace, 1947).

Figure 1.1 Graphene atomic structure

1.9.1. Structure of graphene :

Understanding graphene's structure is now essential before comprehending its special

properties (Hass et al., 2008). Thicker graphene sheets, which are of less scientific relevance,
are those made up of more than ten two-dimensional hexagonal sheets of carbon atoms or
layers. C atoms can stack in three different ways in bi- and few-layer graphene: hexagonally
(AA stacking), Bernally (AB stacking), and rhombohedrally (AB stacking) (Duplock et al.,

perpendicular 𝜋 orbitals are depicted. The out-of-plane σ bonds regulate the contact between
2004). There is a hybridized sp2 bonding in graphene. Three in-plane σ bonds/atom and

various graphene layers, while the strong σ bonds serve as the stiff framework of the
hexagonal structure(Liu et al., 2012; Li et al., 2013).

Figure 1.2 Graphene molecular structure

Graphene oxide as precursor :

Two prominent graphene derivatives are graphene oxide and reduced graphene oxide,
the latter of which is produced by the reduction reaction of GO(Feng et al., 2020). One of
graphene's derivatives, graphene oxide, has numerous oxygen-containing groups coupled to
its carbon atoms, including hydroxyl, carboxyl, epoxy, and ketone(Dreyer et al., 2010).

Graphite oxide and graphite have a similar layered structure, but graphite oxide's
carbon atom plane is highly wrapped with groups that include oxygen, which increases the
interlayer distance between layers and gives the atomic-thick layers a hydrophilic quality.
Thus, moderate ultrasonication in water can be used to exfoliate these oxidized layers.
Graphene oxide is the term for exfoliated sheets that have one or a few layers of carbon
atoms, similar to graphene(Marcano et al., 2010).

Graphene oxide is a single atomic layer, two-dimensional carbon material with

polydisperse sheet sizes. Graphene oxide has a more complex structure than graphene due to
the abundance of oxygen-containing functional groups on its sheet layer; consequently, the
properties of graphene oxide are dependent upon its structure. The L–K model is the
structural model of graphene oxide developed by Lerf and Klinowski (He et al., 1996). The
hydroxyl and epoxy groups are arranged in a random manner on the graphene oxide single
layer, whereas the carboxyl and carbonyl groups are introduced at the edge of the single layer
in it. The degree of oxidation and the random distribution on graphene oxide determine the
relative sizes of the two regions: the oxidized aliphatic six-membered ring region and the
unoxidized benzene ring region. The L–K structural model is dependent on specific
conditions, and it neglects the effects of raw graphene, oxidant, and oxidation techniques(Lerf
et al., 1998).

Many scientists have studied the synthesis and characteristics of graphene and
graphene oxide in great detail. They have discovered that the addition of oxygen atoms bound
to some carbons makes graphene and graphene oxide very different from one another.
Consequently, graphene is hydrophobic by nature, while graphene oxide is hydrophilic and
readily dissolved in water. Furthermore, the presence of both aliphatic (sp3) and aromatic
(sp2) domains in graphene oxide increases the variety of interactions that can take place on
its surface (Dimiev et al., 2012; Eigler and Hirsch, 2014).

Figure 1.3 structure of Graphene oxide

GO possesses two primary properties that are critical to the large-scale applications,
first, it can be made with cheap graphite as the raw material through high-yield, cost-effective
chemical processes; second, it is highly hydrophilic and can form stable aqueous colloids to
aid in the assembly of macroscopic structures through easy, low-cost solution
processes(Wintterlin and Bocquet, 2009) (Compton and Nguyen, 2010)

1.10. Reduced graphene oxide

Two significant graphene derivatives are graphene oxide (GO) and reduced graphene
oxide (rGO), the latter of which can be produced by the reduction reaction of GO (Feng et al.,
2020). The preparation of reduced graphene oxide (rGO) involves either chemical or thermal
reduction of graphene oxide (GO), resulting in an atomically planar structure made up of a
network of hexagonal carbon atoms connected by sp 2(Compton and Nguyen, 2010).
Remaining oxygen-containing functional groups, such as epoxy and hydroxyl (OH) groups,
make up the basal plane of rGO, whilst a small number of carbonyl (C––O) groups and
carboxylic (COOH) moieties make up the edge plane. These functional groups enable a
variety of applications that need chemically reactive locations and stable suspension
uniformity to fabricate materials(Razaq et al., 2022).
Because reduced graphene oxide has a heterogeneous structure made up of a basal plane that
resembles graphene and is additionally decorated with structural defects and populated with
areas containing oxidized chemical groups, it exhibits similar mechanical, optoelectronic,
and conductive properties as pristine graphene(Compton and Nguyen, 2010). Reduced
graphene oxide is a desirable material to be employed in a wide range of optoelectronic,
storage, biological, environmental, and sensory applications due to its graphene-like
characteristics. The surface area of RGO is increased upon reduction (2630 m2/g for single-
layer graphene, theoretically), demonstrating a high mechanical strength with an average
elastic modulus of approximately 32 GPa and a fracture strength of approximately 120 MPa.
The stability, dispersibility, aggregation, and chemical characteristics in aqueous solutions
are also affected by oxygen-containing groups(Azizighannad and Mitra, 2018).

Three partially reduced GO samples, for instance, reveal that the stability of rGO in
water declines with the degree of reduction on its functional groups. For example, rGO-1 h,
rGO-2 h, and rGO-5 h exhibit some suspension, but full precipitation for rGO-5
h(Chowdhury et al., 2015).

Figure 1.4 structure of reduced graphene oxide

Due to oxygen functionalization on the basal plane surface, graphene oxide (GO)
offers a wide range of applications in many industries, yet it has only been shown to have
limited uses in electrical and thermal transport(Dave et al., 2016). In order to get over GO's
drawback, reduced graphene oxide, or rGO, plays an important role in such a case. By
reducing GO, it is prepared. Its oxygen concentration can be lowered by using
microbial/bacterial, chemical, thermal, microwave, photochemical, and photothermal
processes in the synthesis of rGO. Even now, research must be conducted to fully understand
the rGO's numerous potential uses (Brownson et al., 2014). In comparison with GO, RGO
offers better features and potential uses, including improved optical qualities, high electron
mobility, high conductivity, chemical stability, strong adhesiveness, high surface area ,
greater thermal conductivity, and good flexibility (Mishra et al., 2019).
There are various pathways for graphene oxide reduction to RGO. Chemical, thermal, and
electrochemical are among them. The size, shape, and functional group based on the surface
of the materials determine the desired structure and attributes (Stankovich et al., 2007). Every
technique has certain advantages when it comes to creating rGO with varying morphologies,
electrical and optical characteristics, etc. depending on the demands of the particular
application. Adding chemical reducing agents to GO solutions is a conventional reduction
technique (Kavitha, 2022).
Dramatic changes in rGO's surface properties, including notable variances in the
material's mechanical strength, stability, dispersability, and reactivity, are a consequence of
the GO reduction process(Park et al., 2009). As a result, the removal of the majority of
oxygen-containing functional groups from GO partially restores the sp2 structure, improving
rGO conductivity by several orders of magnitude and giving it application in a variety of
fields, such as electronics energy storage and conversion devices like supercapacitors or
chemical sensors and biosensors. rGO also has excellent electrical conductivity of 6300 S
cm−1 and a high mobility of 320 cm2 V−1 s−1(Lu et al., 2011; Chen et al., 2012).

Recently, a variety of techniques have been brought to create rGO, including

chemical reagents, bio- reductants, thermal reduction, irradiation reduction, and others. The
final goal is to alter the function of the rGO by introducing various residue groups and
structural defects. The synthesis of rGO has mostly focused on two factors: low energy
consumption and non-toxicity, particularly for large-scale industrial manufacturing (Peng et
al., 2016).
Reduced graphene oxide based composite

Because of the distinct electrical, chemical, and biological properties of rGO-based

composite materials, which include Fe3O4, TiO2, SnO2, and ZnO, these materials have
gained a lot of interest(Geim, 2009).
RGO and TiO2 can work well together as co-catalysts to improve photocatalytic
redox capabilities in both visible and UV light. It can also efficiently separate photogenerated
electrons to exceed the electron–hole recombination rate because of its greater electronic
mobility. GO or RGO, however, accelerates the photocatalytic degradation process due to
their π-π interaction with organic dyes and the creation of hydrogen bonds amongst organic
contaminants(Dai et al., 2018).
RGO hybrid M/MO Nano composites are widely used in a number of industries,
including optoelectronics, sensors, water purification, gas treatment, energy storage, and
corrosion resistance(Kavitha, 2022).

Application in industrial waste water

Demand for clean water has increased due to the severe pollution and extreme strain
that fast industrialization, urbanization, and population growth have placed on water
resources. One reason for water contamination has been identified: water has the highest
solubility of any liqid on the planet. Water resources like rivers, reservoirs, lakes, and our
ocean are drowning in chemicals, garbage, plastics, and other hazardous pollutants because of
this feature, which makes water contamination easy.(Xu et al., 2018).

A wide variety of organic pollutants are discharged into natural water resources from
a variety of industries, including the textile, paper, and pulp, dye and dye intermediates,
pharmaceutical, tannery, paint, and craft bleaching industries. From the above, the textile
industry (54%) generates half of the dye effluents currently observed in the global
environment, followed by the dyeing (21%) and paper and pulp (10%) industries, tannery and
paint industries (8%), and the dye manufacturing industries (7%)(De Gisi et al., 2016).

Toxic chemical compounds are now the primary source of water contamination in the
last few decades. For example, organic dyes are frequently released into the surrounding
environment together with wastewater that has not been properly treated(Li et al., 2014). The
efficient and quick extraction of organic dyes from wastewater has proven to be a difficult
problem for scientists .Such pollutants have been eliminated from water by the use of
technologies such as ion-exchange, precipitation, membrane separation, adsorption, and
amalgamation. Adsorption has been shown to be more cost-effective and efficient than
alternative technologies, particularly when it comes to eliminating contaminants from diluted
solutions. The target pollutants' affinity for the adsorbents plays a major role in the
effectiveness and usefulness of adsorbents(Zabihi et al., 2009)
Heavy metals and other contaminants are frequently removed from aqueous solutions
using carbon, a flexible adsorbent. The adsorption effectiveness of several types of carbon
and their composites has been studied. For environmental remediation, bulk carbon is most
commonly utilized and significant application. Carbon is a versatile adsorbent that is heavily
used in the removal of various pollutants including heavy metals from aqueous
solutions(Demirbas, 2009). The availability of surface functional groups and substantial
surface area in carbon single sheets and their composites make them an appealing adsorbent
choice for water filtration. The adsorption effectiveness of several types of carbon and their
composites has been studied (Demirbas, 2009).

As the newest member of the carbon family, graphene is thought to be among the
most intriguing materials of this century. Because of its unique two-dimensional nature and
related band structure, graphene and its composites are useful in a variety of applications. For
catalytic or electrical applications, the majority of these composites have been
recommended(Yang et al., 2010).

Graphenic materials are, nevertheless, rarely used for practical, large-scale uses like
water filtration. This is primarily due to the challenge of large-scale synthesis. The prospect
of mass producing graphene in solution phase was made possible by the chemical synthesis
of graphene oxide (GO) and its subsequent reduction to graphene oxide(Hummers Jr and
Offeman, 1958). When used to remove arsenic from water, RGO-magnetite and GO-ferric
hydroxide composites have been shown in publications to have better binding capacities than
free nanoparticles(Chandra et al., 2010). A study also showed that RGO is antibacterial and
this property may help in preventing the development of biofilm on the filter surface due to
bacterial growth, which can cause unwanted tastes and odors or prematurely clogging of
filters(Trogolo, 2006).
Particularly from the textile industry, these industries' effluents have a detrimental
effect on the environment. Because almost 10,000 distinct textile dyes are manufactured
based on a color index, resulting in the creation of approximately 700,000 tons of dye
worldwide, it has a significant influence on our environment(Moussavi and Mahmoudi,
2009). Wastewater containing color is an inevitable by-product of multiple industries,
including dyestuffs, textile, paper, and plastics. These industries employ dyes to color their
goods(Ozmen et al., 2008). About 10-15% of dyes are thought to be wasted into the
environment after being used in the dyeing unit. The textile industry, which produces
wastewater with bright colors and usually has a concentration in the range of 10–200 mg/L, is
one of the most significant industries using dyes(Arslan-Alaton et al., 2008)

The present work focuses on the synthesis of a composite material based on reduced
graphene oxide, with molybdenum trioxide serving as a metal oxide precursor. It also
examines the effectiveness of this material as an adsorbent for the removal of rhodamine B
dye, a common organic dye found in industrial wastewaters. This dye is a basic organic dye
that is highly water soluble and belongs to the xanthene class; it is chemically stable, non-
biodegradable, and is widely used as a textile colorant, a food additive that is prohibited, and
as a chemical stain in biochemical research.

Aims and Objectives

 To synthesize graphene oxide (as precursor) by modified Hummer method and

reduction by solvothermal method to reduced graphene oxide.
 To synthesize reduced graphene oxide-based composite by hydrothermal approach.
 To investigate the effect of rGO-based composite on wastewater.
Chapter 2
Review of literature
2.1. Nanotechnology
The word nano has come from the Greek word “nanos” meaning dwarf.
Nanotechnology has been defined by the size at which it operated, one billionth of a meter or
one tenth of a human hair. In simple terms, it is engineering at the atomic or molecular level.
Nanotechnology might control and restructure matter at the atomic and molecular level in the
range 1-100nm and utilized the properties and phenomena at that scale compared to single
atoms or molecules or bulk. The goal is to create materials, devices, and systems with
completely new properties and functions by engineering at small scale. This is the ultimate
way to change material properties economically and the shortest length scale for
manufacturing and molecular medicine (McNeil, 2005). The same principles and tools may
be applied to all areas of interest and can help to create a common platform for science,
engineering, and technology at the nanoscale. We are just crossing the threshold where single
atoms or molecules has behaved like single entities and nanotechnology used that natural
threshold(Roco, 2011).

Two major approaches have been adopted in the field of nanotechnology: (i) the "top-
down" method, which involves breaking down larger structures into their smaller, composite
parts or shrinking them to the nanoscale without atomic-level control (such as in the case of
electronics miniaturization); and (ii) the "bottom-up" method, also known as "molecular
nanotechnology" or "molecular manufacturing. “by which materials are created via self-
assembly or assembly from atoms or molecular components(Drexler et al., 1991). Molecular
nanotechnology has enormous potential for advancements in materials and manufacturing,
electronics, energy, medicine and healthcare, biotechnology, information technology, and
national security, despite the fact that most modern technologies use a "top-down"
methodology(Sobolev and Gutiérrez, 2005).
 Figure 2.1 nanotechnology approaches

Applications of nanotechnology in functionalized and modified biomedical fields include

drug transport, genetic material sequencing, bioimaging, diagnosis and therapy, biosensors,
active packaging, agriculture, and environmental protection. There are many uses for
nanoparticles, nanoencapsules, nanotubes, nanospheres, and nanochips in the realms of
medicine, agriculture, health, and environmental safety. By employing nanoparticles as a
photocatalyst, hazardous organic compounds and industrial pollutants can be broken down
and transformed into safe forms. Emerging as a breakthrough technology, nanotechnology
offers benefits over traditional approaches in solving a wide range of challenges(Sharma et
al., 2021).
2.2. Nanosciences

The study of structures and molecules at nanoscales, or between 1 and 100 nm, has
been referred to as nanoscience. Nanotechnology, on the other hand, is the technology that
applies this knowledge to real-world applications, such electronics (Gnach et al., 2015). In
contrast, one must be aware that the radius of the DNA double helix is one nm, while a single
human hair is 60,000 nm thick. When it comes to manipulating materials at the atomic and
molecular levels, physics, materials science, and biology come together in nanoscience. On
the other hand, nanotechnology deals with the observation, measurement, manipulation,
assembly, control, and creation of matter at the nanoscale scale(Mansoori and Soelaiman,

2005).

The field of "nanoscience" refers to the study of objects with dimensions ranging
from a few nanometers to less than 100 nanometers, which are in between the largest
molecules and the smallest structures that can be created using current photolithography. This
range of sizes has historically been linked in chemistry to very big molecules or aggregates of
numerous molecules, colloids, micelles, polymer molecules, phase-separated areas in block
copolymers, and similar structures (Lieber, 2003; Grimshaw, 2004). Structures like
compound semiconductor quantum dots, silicon nanorods, and buckytubes have become
particularly intriguing kinds of nanostructures in more recent times. Nanoscience is most
commonly connected with quantum behavior and the behavior of electrons and photons at
nanoscale structures in physics and electrical engineering. Many of the most fascinating
structures in biology, such as DNA, viruses, subcellular organelles, and gap junctions, might
be considered as nanostructures(Bamford, 2000; Service, 2002).

Modern day living has become less difficult owing to nanoscience advancements in
nearly every scientific discipline and nanotechnologies. Because of the way atoms are
arranged on the 1-100 nm scale, structures, devices, and systems with unique features and
functionalities are being studied in the rapidly growing fields of nanoscience and
nanotechnology(Bayda et al., 2019).
As the discipline of nanotechnology develops quickly, nanoscience is at the forefront
of advances. Numerous goods and services that could improve public health and the practice
of medicine are being transformed by nanosciences and nanotechnology. At the nanoscale,
molecular diagnostics' capabilities are expanded by nanotechnology(Roco,
2006).Nanotechnology is already having a positive impact on a number of medical fields and
finds applications in electronics, physics, material science, biotechnology, medicine, and
pharmaceuticals(Menezes et al., 2011).
2.3. Nanomaterials

Nanomaterials has been a class of materials having at least one dimension between 1
and 100 nm. They are based on the fundamental ideas of nanoscience and nanotechnology,
the applications of which extend a broad range of interdisciplinary research and development
activities that are rapidly expanding globally. Nanomaterials can change into functionalized
substitutes that can be used again and again. Common forms of nanomaterials include
fullerenes, quantum dots (QDs), dendrimers, and nanotubes. Due to its distinct optical
properties, which have a substantial impact on a wide range of fields, including electronics,
mechatronics, pharmaceuticals, polymers, ionic liquids, and medicine, nanomaterials are
becoming more and more well-known(Bianco et al., 2013). With so many useful
applications, nanomaterials have become an innovative new class of materials that are highly
desirable. Five silicon atoms or ten hydrogen atoms lined up, each measuring one nanometer,
can be used to illustrate the length of a nanometer. Materials that fall between 1 and 100 nm
in size or one of their dimensions are classified as nanomaterials(Heiligtag and Niederberger,
2013)
They have been unique in their comparatively large surface area which activates the
innovative theory of quantum effects. The material qualities and traits that result in novel
optical, electrical, and magnetic behaviors may be more important when taking into account
the reaction at the nanoscale level because of the quantum effects(Bogani and Wernsdorfer,
2009) Because of their specialization, nanomaterials can exhibit higher chemical reactivity
due to their significantly higher surface area to volume ratio when compared to macro-
materials (Awade, 2010).

Nanomaterials have found commercial use in products like self-cleaning windows,

sunscreen, cosmetics, and sports equipment; in windows, bicycles, cars, and sports
equipment; as filler in dental fillings and cosmetics; and in textiles, electronics, paints, and
varnishes that are wrinkle- and stain-resistant.(Eustis and El-Sayed, 2006). Nanomaterials
have a broad range of applications due to their unique mechanical, thermal, electrical, optical,
electrochemical, and catalytic capabilities that set them apart from macro-materials. Among
these are fuel-efficient vehicles, strong magnets, sensitive sensors, high-energy density
batteries, and the elimination of contaminants, car with more powerful, superior weaponry
platforms, satellites with more durable, superior insulation materials, next-generation CPUs,
food additives, farming, food processing, animal feed, biomedical, high-frequency,
machinable ceramics, large electrochromic displays(Gajanan and Tijare, 2018)

2.4. Properties of nanomaterial

2.4.1. Thermal properties

One significant nanomaterial characteristic that has a direct impact on its use is
thermal conductivity. The thermal stability of nanomaterials depends on a number of
parameters that are often negligible in bulk materials. Examples of thermal properties that
only depend on particle size of materials include specific heat, melting point, glass transition
temperature, and thermal conductivity (the main difference between macro and nanomaterial)
(Zubar et al., 2018). Nanomaterials, which comprise materials doped to produce point defect
scattering and nano-grain sized materials, have low thermal conductivity due to their intrinsic
atomic structure and interatomic bonding(Qi, 2005).

A fundamental thermodynamic property of every material is its melting point. The

dependence of nanoparticle melting temperature (Tm) on particle size has been empirically
and conceptually well-established. Surface atoms have an excessive amount of impact over
the physical and chemical characteristics of nanoparticles due to their high surface to volume
ratio. When it comes to the phenomena of Tm reduction of particles in small dimensions,
nanoparticles of different sizes exhibit varying Tm. This effect is interesting at nanoscale
particles; for example, metals with nanometer-sized particles can have Tm reductions of tens
to hundreds of Kelvin degrees(Shibuta and Suzuki, 2010).
A number of thermal analysis (TA) methods have been employed to examine the
unique characteristics of the nanomaterials. A branch of materials science known as "TA
techniques" investigates into how a material's characteristics vary with temperature.
Differential scanning calorimetry (DSC), evolved gas analysis (EGA), differential thermal
analysis (DTA), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA),
thermomechanical analysis (TMA), and evolved gas analysis (EGA) are some of the
commonly used techniques that have been differentiated by the measuring attributes. Thermal
analysis methods that are often used to examine the characteristics of nanomaterials across a
wide temperature range include DSC, TGA, TMA, DTA, EGA, and DMA(Jain and Sharma,
2011).

2.4.2. Mechanical properties

The mechanical qualities of materials under varying external stresses and conditions
are referred to as their mechanical properties. The mechanical characteristics of various
materials differ from one another. For conventional materials, brittleness, strength, plasticity,
hardness, toughness, fatigue strength, elasticity, ductility, rigidity, and yield stress are the ten
main components of a metal's mechanical characteristics. The majority of non-metallic
inorganic materials are brittle, lacking attributes like toughness, ductility, elasticity, and
plasticity. Additionally, certain organic materials lack stiffness and brittleness and are instead
flexible(Zou et al., 2006; Wang et al., 2011).

Because of the volume, surface, and quantum effects of nanoparticles, nanomaterials

has exceptional mechanical characteristics. When added to a common material, nanoparticles
will considerably optimize the grain, providing an intergranular or intergranular structure that
will strengthen the grain boundary and improve the mechanical characteristics of the
material(Wang and Meng, 2014). For instance, the compressive, bending, and breaking
tensile strengths of concrete can potentially be increased by adding 3 wt/% nano-SiO2. Kenaf
epoxy composites' tensile strength, elongation at break, and impact strength has potentially
increased by adding 3% nano oil palm empty fruit string filler. Nanomaterials have many
potential uses in the future because of their superior mechanical qualities and special qualities
not present in macroscopic materials(Saba et al., 2016).

2.4.3. Optical properties

Since the electronic structure of the nanomaterials depends considerably on surface

atoms, the optical properties of the materials such as reflection, transmission, absorption, and
light emission , are entirely dependent on their electronic structure, which varies significantly
for different morphologies. Nanomaterials' size-dependent optical characteristics have been
influenced by two factors: surface plasmon resonance and increased energy level spacing
(quantum effect)(Mittal and Banerjee, 2016). Particle sizes as small as 10 nm have size
effects on optical characteristics. Since nanoparticles are so tiny, their electrons are not as
free to travel as they would be in bulk material. In accordance with this electron quantum
confinement, nanoparticles respond to light differently than bulk material. Reduction in
dimensionality in electronic structure of the nanomaterials has primarily affected the
energies of the lowest empty molecule orbital, which is basically the conduction band, and
the highest occupied molecular orbital, which is a valence band(Karak, 2019).

When an electron moves from these two bands, optical characteristics including
emission and absorption take place. When particle size decreases, this optical bandgap rises,
particularly for semiconductor nanomaterials. A photon of wavelength λ¼hc/ΔE is released
when an electron transits from a higher energy state to a lower energy state. The Plank's
constant, light speed, and energy differential between allowed electron energy levels are
represented by h, c, and ΔE, respectively. The wavelength (blue shifted) decreases with
increasing ΔE. Because of these quantum confinement phenomena, semiconductor
nanomaterials absorb and emit light at specific wavelengths that are highly dependent on both
particle size and form.(Bhagyaraj and Oluwafemi, 2018). It is possible to adjust the emission
wavelengths of the nanomaterials from the ultraviolet through visible to the near-infrared
spectrum by varying their size and composition. For instance, the emission wavelength of
colloidal CdSe-CdS core-shell nanoparticles may be altered by size reduction from 2 to 6 nm
in diameter, with the bigger particles generating red light and the smaller particles emitting
blue light(Roduner, 2006).

2.4.4. Electrical properties

Electrical properties has characteristics like resistivity and conductivity. At the

nanoscale level, these characteristics have the capacity to fluctuate, just as optical or
magnetic properties. The mobility of the charge carriers is the primary aspect of
nanomaterials' electrical characteristics. It is inevitable for the quantum-size effect and the
quantum confinement effect to manifest when a material's dimensions reduce into the
nanoscale range(Singh et al., 2012). Under specific voltages, certain conductive metal
nanoparticles can become nonconductive due to the quantization of electron energy. For
instance, if the size of a metal is decreased to a few nanometers, it can lose its conductivity.
On the other hand, if the size of an insulating substance is reduced, it can lose its insulating
qualities and become conductive, such as silicon dioxide(Ramasamy and Purniah, 2001).
Grain size, doping impurities, increased interfacial atoms or ions and sinking a significant
amount of defects near the grain boundaries have been the main factors that control the
dielectric properties, resistivity, and electrical transports of nanomaterials(Singh et al., 2018).

Since the band gap energy of nanomaterials increases with decreasing particle size,
especially in the case of semiconductor nanoparticles, their electrical conductivity is often
lower than that of macroscopic materials. For instance, gold nanoparticles, although metallic,
become insulators once the energy bands stop overlapping at the 2-3 nanometer region. An
energy range in a material where no electron state is permitted is called a band gap. In
momentum space, a uniform bandgap indicates that the minimum (lowest energy state) of the
conduction band is located exactly above the maximum (highest energy level) of the valence
band.(Liu and Corma, 2018).

The difference between the lowest unoccupied molecular orbital (LUMO) and the
highest occupied molecular orbital (HOMO) at the bottom of the conduction band is known
as the electrical band gap. This distance between the neighboring energy levels mostly
controls the electrical conductivity. The nanoparticles' electrical structure is significantly
influenced by their particle size. The number of energy states reduces with decreasing size in
discrete nanoclusters which are made up of relatively few atoms, and as a result, the gap
between adjacent energy levels increases, causing the nanocluster's conductive characteristics
to change from metallic to semiconducting and insulating. To summarize, a decrease in the
size of the material will lead to an increase in crystal perfection or a decrease in defects.
which in turn, will decrease defect dispersion and, ultimately, reduce resistivity and boost
conductivity(Karak, 2019).

2.4.5. Quantum confinement

In addition to their large surface area, nanomaterials may differ from bulk materials in
various ways due to potential quantum phenomena that manifest at the nanoscale. Electrons
are described as potential wells, valence bands, conduction bands, electron energy band gaps,
and energy levels according to the quantum confinement effects. The "dimensionality" of a
system in the nanometer range is associated with quantum size effects, since the quantum
confinement effect is only seen when the particle's size is too tiny to be compared to the
electron's wavelength (Schoenhalz, 2010 #211).

The fundamental cause of the quantum confinement effect is modifications to the

atomic structure induced by the energy band structure being directly impacted by ultra-small
length scale. However, in the case of nanomaterials, surface atom contribution rises with
decreasing particle size; as a result, surface atoms have a major impact on nanomaterial
characteristics. Surface atoms often have unique localized electronic states and have a crucial
role when determining the material's characteristics. Restricting the mobility of randomly
moving electrons to distinct energy levels is known as confinement. When particles are
reduced to nanoscale size, the material's bandgap increases and energy levels become distinct
due to the restricting dimensions (Neikov, 2009).

When compared to bulk materials, the bandgap has (at nanoscale) increased because
to the quantum size effect, which results in a range of luminescent colors that represent
minute variations in particle size. The larger the gap between the energy levels, the smaller
the nanostructure's dimensions, resulting in a spectrum of distinct energies. Properties
including melting point, fluorescence, electrical conductivity, magnetic permeability, and
chemical reactivity vary as a function of particle size when it gets closer to the nanoscale.
However, the materials' size is not the only factor that affects these qualities. It is becoming
increasingly evident that the structure of the materials also plays a crucial role in regulating
the characteristics of nanoparticles as nanotechnology advances toward applications in
electronics and health (Geoffrion, 2020 #210).
2.4.6. Surface charge and stability

Surface charge has been important factor in describing the characteristics and uses of
nanomaterials. The stability, aggregation, and affinity of nanomaterials towards the
environment and functional groups are largely determined by the type and magnitude of the
surface charge. Another important factor influencing colloidal behavior is surface charge,
which modifies the size and structure of aggregates or agglomerates which directly affect an
organism's reaction to nanomaterial exposure. A particle's surface undergoes protonation and
deprotonation when it is submerged in an aqueous medium, which charges the particle and
causes the formation of an electric double layer(EDL) to balance the surface charge. Within
the EDL, counterions are depleted while more are accumulated(Barisik et al., 2014).

An oppositely charged ion layer in the solution at a certain distance from the surface
balances the surface charges and generates an electrostatic potential between the surface and
any point in the mass of the suspending liquid. The term "zeta potential" describes this
electrostatic potential at the EDL surrounding a nanoparticle in solution. Zeta potential is a
typical unit of measurement for surface charge. The electrostatic repulsion between
neighboring and similarly charged particles in dispersion is indicated by the magnitude of the
zeta potential. Colloidal stability increases with magnitude, while aggregation decreases with
it(Clogston and Patri, 2011)

2.4.7. Magnetic properties

Nanomaterials have shown a wide range of anomalous magnetic behavior as

compared to bulk materials due to surface or interface phenomena, such as charge transfer,
symmetry breaking, electronic environments, and magnetic interaction. Furthermore, in
contrast to bulk materials, individual atoms of nanostructures have a distinct magnetic
interaction with surrounding atoms due to their significantly high surface-area to-volume
ratio(Mohan Bhagyaraj and Oluwafemi, 2018). Ferromagnetic materials' magnetic domain
structure serves as the foundation for fine particle magnetism. Larger ferromagnetic particles
with several domains exhibit non-uniform magnetism, whereas single-domain particles,
smaller than critical size, exhibit uniform magnetism. A number of variables, including the
magnetic saturation value, the intensity of the crystal anisotropy and exchange forces, the
surface or domain-wall energy, and the particle shape, influence the critical size of the single
domain. Remanence and coercivity are the two primary characteristics that define how
ferromagnetic materials react to an applied field(Akbarzadeh et al., 2012).

The coercivity of magnetic materials has a notable influence on particle size, on comparison
with resistivity. The coercivity increases with decreasing particle size, reaching a maximum
at the single domain size. Due to thermal factors, it subsequently declines for very small
particles, reaching zero at the superparamagnetic particle size. As a result, even if the bulk
materials (that correspond to the nanoparticle) are not magnetic, the nanomaterials may
become superparamagnetic. For instance, despite the ferromagnetic nature of bulk iron oxide
(Fe3O4), Fe3O4 nanoparticles exhibited superparamagnetic-like behavior. This effect is caused
by the Fe3O4 nanoparticles' exceptional surface energy and their spin electrons' flipped
orientation(Karak, 2019).
In the absence of any external magnetic field, superparamagnetic nanoparticles have
no magnetic properties; but, upon application of an external magnetic field, they rapidly
acquire magnetic properties. Once an external magnet is removed, the nanoparticles may
rapidly return to a nonmagnetized condition when they are below the superparamagnetic
diameter. A wide range of crystalline materials, including Fe, Co, and Ni, are ferromagnetic.
Among them, superparamagnetic nanoparticles of ferrite oxide-magnetite (Fe3O4) are the
most often utilized for a variety of biological purposes(Xu et al., 2014).

2.5. Synthesis methods of nanomaterials:

For the synthesis of nanomaterials, top-down and bottom-up methods have been the
two main strategies.

2.5.1. Top-down approaches

In top-down methods, nanostructured materials have been generated by dividing bulk

materials. Top-down techniques include sputtering, electro-explosion, etching, laser ablation, and
mechanical milling(Baig et al., 2021).

2.5.1.1. Mechanical milling

A cheap way to produce materials at the nanoscale level from bulk materials is by
mechanical milling. In order to form blends of various phases and to produce
nanocomposites, mechanical milling is a useful technique(Zhuang et al., 2016). Copper,
nickel, magnesium, and oxide- and carbide-based nanoalloys, wear-resistant spray coatings,
and a variety of other nanocomposite materials are all made via mechanical milling. As a
unique kind of nanomaterial, ball-milled carbon nanomaterials provide the potential to meet
the needs of energy conversion, energy storage, and environmental remediation (Lyu et al.,
2017).
2.5.1.2. Lithography

Using a concentrated beam of light or electrons, lithography is a helpful technique for

creating nanostructures. Masked and maskless lithography are the two primary categories of
lithography.(Matsumoto et al., 2020).With masked nanolithography, a particular mask or
template is used to transfer nanopatterns across a large surface area. Photolithography,
nanoimprint lithography, and soft lithography are examples of masked lithography. Electron
beam, focussed ion beam, and scanning probe lithography are examples of maskless
lithography. Maskless lithography does not require the use of a mask in the arbitrarily
nanopattern writing process. Through the employment of a focused ion beam along with wet
chemical etching, 3D freeform micro-nano-fabrication may be obtained(Garg et al., 2020).
2.5.1.3. The arc discharge method

Arc discharge is an effective technique for producing diverse nanostructured

materials. It is well recognized for creating materials based on carbon, such amorphous
spherical carbon nanoparticles, few-layer graphene (FLG), carbon nanotubes, fullerenes, and
carbon nanohorns (CNHs). When producing fullerene nanomaterials, the arc discharge
process is very important. During the formation process, two graphite rods are adjusted
within a chamber that maintains a certain pressure of helium. It is crucial to fill the chamber
completely with helium as fullerene synthesis is inhibited by moisture or oxygen. Arc
discharge occurs between the ends of the graphite rods, which drives the vaporization of
carbon rods. The synthesis of novel nanomaterials is greatly influenced by the circumstances
surrounding arc discharge(Zhang et al., 2019)
Since various carbon-based nanomaterials have distinct development methods, so they
are gathered from different places during the arc discharge procedure. Deposits at either the
anode or cathode, or at both electrodes, can yield MWCNTs, high-purity polyhedral graphite
particles, pyrolytic graphite, and nano-graphite particles(Jones et al., 1996; Liang et al.,
2012).Carbon-based nanomaterials can be extracted from the inner chamber in addition to the
electrodes. Various atmospheres can yield distinct morphologies of single-wall carbon
nanohorns (SWCNHs). For instance, "bud-like" SWCNHs are formed in CO and CO2
atmospheres, whereas "dahlia-like" SWCNHs are produced in ambient air(Li et al., 2010).

2.5.1.4. Laser ablation

In laser ablation synthesis, a strong laser beam is used to target material and create
nanoparticles. Because of the high intensity of the laser irradiation during the laser ablation
process, the source material or precursor vaporizes, forming nanoparticles. The production of
noble metal nanoparticles by laser ablation can be regarded as a green method as no
additional chemicals or stabilizing agents are required(Amendola and Meneghetti, 2009).
Using pulsed laser ablation in liquids instead of ligands or surfactants is an innovative way to
create monodisperse colloidal nanoparticle solutions. Laser salt addition, wavelength, and
fluence adjustments may all be used to modify the characteristics of nanoparticles, including
average size and distribution. It appears that the pulsed laser's wavelength and fluence have a
significant impact on the sizes of the Pd nanoparticles as they are being formed(Park et al.,
2017).
2.5.2. Bottom-up approaches
The bottom-up method is referred to as the constructive methodology. The complete
opposite of the top-down approach is the bottom-up approach. As their building blocks,
atoms and molecules expand and self-assemble to produce NMs with distinct size, shape, and
chemical makeup(Kolahalam et al., 2019).

2.5.2.1. Chemical vapor deposition (CVD)

For the production of carbon-based nanomaterials, chemical vapor deposition technique is

very important. In CVD, vapor-phase precursors react chemically to generate a thin coating
on the substrate surface(Shah and Tali, 2016). If a precursor is inexpensive in cost, non-
hazardous, has a long shelf life, high chemical purity, good stability during evaporation, and
sufficient volatility, it is deemed appropriate for CVD. Moreover, no leftover contaminants
should emerge from its breakdown. For example, high temperatures are applied to a substrate
in an oven during the CVD process to produce carbon nanotubes. Then, as a precursor, a gas
containing carbon (such hydrocarbons) is gradually added to the system. Carbon atoms are
released during the breakdown of the gas at high temperatures, and these atoms then
recombine to form carbon nanotubes on the substrate. Yet, the type and form of the resulting
nanomaterial are greatly influenced by the catalyst of choice. Ni and Co catalysts produce
multilayer graphene in the CVD-based method of graphene synthesis, while a Cu catalyst
produces monolayer graphene(Machac et al., 2020). In general, CVD is a very effective
technique for generating superior nanomaterials, and it is widely recognized for its ability to
produce two-dimensional nanomaterials (Wu et al., 2016).

2.5.2.2. Solvothermal and hydrothermal methods

The hydrothermal process is one of the most popular and widely applied techniques
for producing materials with nanostructures(Cao et al., 2016). Using a sealed vessel and high
pressure and temperature near the critical point, a heterogeneous reaction is carried out in the
hydrothermal process to produce nanostructured materials(Chen and Holt-Hindle, 2010).
Similar to the hydrothermal process is the solvothermal method. It is conducted in a non-
aqueous medium, which is the sole distinction. In most cases, closed systems are used for
hydrothermal and solvothermal procedures. Combining the best features of hydrothermal and
microwave techniques, the microwave-assisted hydrothermal approach has attracted a lot of
interest lately for the engineering of nanomaterials(Meng et al., 2016). Exciting and efficient
methods for creating different nano-geometries of materials, such as nanowires, nanorods,
nanosheets, and nanospheres, are hydrothermal and solvothermal processes(Chai et al., 2018;
Dong et al., 2020).
2.5.2.3. The sol–gel method

The sol–gel method is a widely utilized wet chemical process in the production of
nanomaterials. High-quality metal-oxide-based nanomaterials of diverse types are produced
using this methodology. The reason this process is named a sol–gel technique is that the
liquid precursor is changed into a sol during the production of the metal-oxide nanoparticles,
and the sol is then turned into a network structure known as a gel. (Danks et al., 2016). Metal
alkoxides are the standard starting point for the sol-gel process of creating nanomaterials. The
kind of precursor, rate of hydrolysis, length of time aged, pH, and molar ratio of the precursor
to H2O are the variables that influence the final product formed by the sol–gel process(de
Coelho Escobar and dos Santos, 2014). In addition to being a cost-effective technique, the
sol-gel process offers several additional benefits, including homogenous material production,
low processing temperatures, and ease of use in the production of complex nanostructures
and composites(Parashar et al., 2020).

2.1. Graphene as emerging nanomaterial

 Ever since it was initially created in 2004 by mechanical exfoliation, graphene—a
single-atom-thick sheet of sp2-hybridized carbon—has drawn a lot of interest from the
scientific and engineering industries. Graphene is the thinnest and strongest substance in the
universe due to its unique 2D honeycomb lattice structure, which also gives it numerous
superior chemical and physical capabilities(Geim, 2009).
2.1.1. Structure of graphene

The crystal structure of graphene allows for an extraordinary band structure. In two
dimensions, carbon atoms arrange themselves into a hexagonal lattice. Every carbon atom has
three neighbors, with whom it shares one 𝜎 bond, at a distance of about 𝑎 = 1.42 Å. A 𝜋-
bond, orientated in the 𝑧-direction (out of the plane), is the fourth type of bond. The 𝜋
orbital can be seen as two symmetric lobes that are centered on the nucleus and directed
along the 𝑧-axis. These "𝜋-bonds" are present in every atom and combine to produce the
"𝜋-band" and "𝜋∗-bands" when they hybridize. The majority of graphene's unusual
electrical characteristics are caused by these bands. It is possible to think of graphene's
hexagonal lattice as two interlocking triangle lattices(Wallace, 1947). Graphene is one of the
graphitic compounds that can be wrapped around carbon atoms to form thin graphene sheets,
fullerene, and carbon nanotubes(Geim and Novoselov, 2007).

Figure 2.2 Schematic of the structure of a graphene sheet.

Monolayer graphene has amazing optical features, an anomalous half integer quantum
Hall effect, ultra-high intrinsic strength, excellent thermal conductivity, and extraordinarily
high charge carrier mobility because of its massless Dirac fermions and exceedingly high
internal crystal quality(Lee et al., 2008). Because of its distinct Dirac cone band structure
close to the Fermi level, it is known as a zero-gap semiconductor, exhibiting an
extraordinarily high concentration of charge carriers and ballistic transport. Furthermore,
even at normal temperature, it is possible to study the quantum effects in graphene due to the
massless electrons' ability to propagate across the honeycomb lattice at a sub-micrometer
distance without scattering(Novoselov et al., 2004; Kim et al., 2009).
Carbon nanotubes, fullerene buckyballs, 3D graphite, and many other carbonic
compounds are constructed from graphene. Because of its special structure, it has both
exceptional electrical and mechanical qualities brought about by strong planar σ and 𝜋
bonds. With its great electron mobility and strong heat conductivity, graphene is regarded as
the thinnest stretchable crystal. In many fields, including optoelectronics, sensors,
biomaterials and bionics, batteries and energy storage, electrochemical performance, thermal
management, armor material, and cigarettes, it swiftly became indispensable(Geim and
Novoselov, 2007). Graphene's long-range π-conjugation produces remarkable mechanical,
electrical, and thermal characteristics, which have long piqued the curiosity of theoretical
researches and have more recently emerged as an intriguing field for experimenters(Yu et al.,
2020).

2.2. Graphene oxide

Graphene oxide (GO) research is one particular area of graphene study. For the
creation of graphene using chemical or thermal reduction procedures, this might be thought
of as a precursor. The process of producing graphite oxide (GO), which is a single layer of
graphite oxide, typically involves oxidizing graphite and then dispersing and exfoliating it in
water or other appropriate organic solvent(Ramanathan et al., 2008). Throughout the years,
several structural models have been put out in relation to its construction. According to them,
GO has a variety of functional groups that include oxygen. On the basal plane, the oxygen
functional groups have been shown to be mostly hydroxyl and epoxy groups, with lesser
quantities of carboxy, carbonyl, phenol, lactone, and quinone toward the sheet
borders(Dreyer et al., 2011).
 Figure 2.3 graphene oxide structure

In actuality, the structure of GO incorporates a variety of nanoscale inhomogeneities,

and the stoichiometry variation according to the reaction's intensity and the synthesis
procedure. The perfect stoichiometry has never been reached, in actual(Gómez-Navarro et
al., 2010). Oxygenated groups in graphene oxide (GO) can significantly impact its
mechanical, electrical, and electrochemical characteristics. Thus, they explain the variations
between pure graphene and GO. On the one hand, the covalently oxygenated functional
groups in graphene oxide (GO) can lead to notable structural defects as compared to pure
graphene.This results in a little decrease in electrical conductivity, which may restrict the
direct use of GO in electrically active materials and gadgets(Bissessur and Scully, 2007).

In contrast, the existence of these functional groupings may also offer benefits for
utilizing GO in a variety of different contexts. The first reason is that GO is very hydrophilic
due to its polar oxygen functional groups. As a result, GO has strong dispersibility in a wide
range of solvents, especially water. The resultant GO-stable dispersion may then be coated
using standard techniques like drop-casting, spraying, or spin-coating on a variety of
substrates to create thin conductive films.These are excellent electrodes material(Compton
and Nguyen, 2010).
Furthermore, these functional groups can be used as sites for chemical modification or
functionalization of GO using designed chemistry techniques. This can then be used to
immobilize different electroactive species through covalent or noncovalent bonds for the
creation of electrochemical systems that are sensitive. Thus, the physicochemical features of
GO may be tuned due to its chemical composition, which can be altered chemically,
thermally, or electrochemically (Mohanty and Berry, 2008). For instance, GO may be
converted into an insulating, semiconducting, or semimetallic material by carefully adjusting
the oxidation or reduction parameters in order to regulate the structural disorder.
Accessibility, simplicity in synthesis, solution processability, and its adaptable characteristics
make graphene oxide (GO) appealing for both fundamental research and applications, despite
the absence of the special relativistic nature of charge carriers and other condensed-matter
effects seen in "nearly ideal" graphene(Eda and Chhowalla, 2010).
Carbon atoms in GO that are covalently bound to oxygen functional groups (epoxy,
carboxy, and hydroxyl) have sp3 hybridization. These have become oxidized spots that break
the original honeycomb-lattice structured graphene sheet's extended sp2 conjugated network.
the latter might be consider as the unoxidized areas. These sp3 hybridized carbon clusters are
positioned slightly above or below the graphene plane in a consistent yet random
manner(Kim et al., 2010).
GO has a number of exceptional qualities because of its unique 2D structure and the presence
of many oxygenated functional groups. These include chemical reactivity as well as
mechanical, electrical, optical, thermal, and electrochemical characteristics. The chemical and
atomic structures of GO sheets have a significant impact on their electronic characteristics,
such as conductivity. More precisely, they are dependent on the level of structural disorder
that results from a significant sp3 carbon percentage(Eda et al., 2008).
The highly particular features of GO-based materials, which are important to GO but
not typical of graphene, are what make them significant in electrochemistry. These include
the material's ease of production, great dispersibility across a variety of solvents, capacity to
couple electroactive species to surfaces, and distinct visual characteristics(Mohanty and
Berry, 2008). Control of the local microenvironment is another benefit of using GO-based
products. This is such that, through solution processing, GO-based materials may often be
deposited with incredibly well-defined surfaces. This may be very helpful when adding
electroactive or sensitive species to an electrochemical system (Wang et al., 2011). When
GO-based devices are manufactured, the cost of production can be lower than that of
traditional electrodes. This is due to the fact that solution processed thin film deposition
requires a very little quantity of GO-based components. Furthermore, a higher surface area-
to-volume ratio may be achieved by depositing GO-based thin conductive films onto an
affordable base material, which further reduces the electrode's cost(Xu et al., 2010). In the
meantime, a greater number of active sites and frequently a higher signal-to-noise ratio may
be obtained because to the huge effective surface area. GO-based materials have been utilized
to develop and produce GO-based electrodes for a variety of applications in electrochemical
sensors and electroanalysis because of these desirable particular features(Liang et al., 2009).
2.3. Reduced graphene oxide

Two significant graphene derivatives are graphene oxide (GO) and reduced graphene
oxide (rGO), the latter of which is produced by the reduction process of GO.(Feng et al.,
2020). The preparation of reduced graphene oxide (rGO) involves either chemical or thermal
reduction of graphene oxide (GO), resulting in an atomically planar structure made up of a
network of hexagonal carbon atoms connected by sp2(Compton and Nguyen, 2010).
Remaining oxygen-containing functional groups, such as epoxy and hydroxyl (OH) groups,
make up the basal plane of rGO, whilst a small number of carbonyl (C––O) groups and
carboxylic (COOH) moieties make up the edge plane. These functional groups enable a
variety of applications that need chemically reactive locations and stable suspension
uniformity to fabricate materials(Razaq et al., 2022)

Reduced graphene oxide has same mechanical, optoelectronic, and conductive

characteristics as of pristine graphene due to its heterogeneous structure, which is made up of
a basal plane that resembles graphene but is also filled with oxidized chemical group areas
and structural defects. Due to its graphene-like characteristics, reduced graphene oxide is a
widely desirable material for usage in a wide range of optoelectronic, storage, biological,
environmental, and sensory applications(Tarcan et al., 2020)
Reduced graphene oxide has become very attractive material to be employed in a
wide range of optoelectronic, storage, biological, environmental, and sensory applications
due to its graphene-like characteristics. The surface area of RGO is increased upon reduction
(2630 m2/g for single-layer graphene, theoretically), demonstrating a high mechanical
strength with an average elastic modulus of around 32 GPa and a fracture strength of
approximately 120 MPa. Additionally, the stability, dispersibility, and aggregation in aqueous
solutions, as well as the chemical characteristics, are affected by the oxygen-containing
groups.(Azizighannad and Mitra, 2018). Three partly reduced GO samples, for instance,
reveal that the stability of rGO in water declines with the degree of reduction on its functional
groups. For example, rGO-1 h, rGO-2 h, and rGO-5 h exhibit modest suspension, but full
precipitation for rGO-5 h(Chowdhury et al., 2015).
2.4. Synthesis of reduced graphene oxide: reduction strategies
2.4.1. Chemical reduction

Two distinct oxidizing agents, ascorbic acid and hydrazine, had been employed in the
chemical reduction of graphene oxide. By combining 800 mg of hydrazine monohydrate and
800 mg of graphene oxide solution, the chemical reduction with hydrazine was accomplished.
For three hours, the mixture was kept at 90 °C with continuous stirring. Following reduction,
the mixture was centrifuged, and the resultant product, called Hydrazine Reduced Graphene
Oxide (H-RGO), was filtered and cleaned with deionized water till pH = 7 in order to get rid
of any leftover hydrazine. The resulting solid was then dried for a whole night at 80 °C (Park
et al., 2011).

As previously mentioned, hydrazine was chosen due to its strong potential for reduction;
nonetheless, it is an extremely hazardous substance that poses a threat to the environment.
This led to the proposal of ascorbic acid as a substitute reducing agent. This substance is safe
and kind to the environment. Ascorbic acid (800 mg) and graphene oxide solution (800 mg)
were combined to perform the chemical reduction. For 48 hours at room temperature, the
reduction was kept up with continuous stirring. Following the reduction, the mixture was
centrifuged to extract the ascorbic acid reduced graphene oxide (A-RGO), which was then
filtered and repeatedly rinsed with deionized water (pH = 7) to get rid of any leftover acid.
The final step was to dry the solid at 80 °C for a whole night(Zhang et al., 2010).

2.4.2. Thermal reduction

An additional method for obtaining rGO is thermal reduction.It involves inserting the
GO into a hot, inert environment. These conditions lead to the instability of carbon dioxide,
water vapor, and carbon monoxide, which deoxygenates the substance. (Bagri et al., 2010).
In order to perform the thermal reduction procedure, 5 g of graphite oxide were added to a
laboratory drying oven and heated to 250 °C. After a set amount of time (usually between 20
and 40 minutes), the carbon material expanded, separating the graphene layers and removing
some oxygen functional groups from the structure. Thermally Reduced Graphite Oxide (T-
RGO) is the name given to the final product.
Following the process of thermal reduction, 800 mg of T-RGrO underwent a 2-hour
sonication at 30% amplitude in 800 mL of deionized water to finalize its exfoliation referred
as Thermally-Reduced Graphene Oxide (T-RGO)(Oliveira et al., 2018).
2.4.3. Photocatalyst reduction

With the aid of a photocatalyst such as TiO2, GO may also be reduced by photo-chemical
processes in contrast to the photothermal reduction previously discussed. According to
reports, under ultraviolet (UV) irradiation, GO can be reduced in a colloid form with the help
of TiO2 particles. As the reduction of GO continues, a color shift from light brown to dark
brown to black is seen. It has previously been proposed that this color shift represents a
partial repair of the conjugated network in the carbon plane, similar to what occurs during
chemical reduction processes(Williams et al., 2008).
2.4.3. Electrochemical reduction
Electrochemical elimination of oxygen functional groups is another promising
approach to reduce GO. Use of an aqueous buffer solution at ambient temperature facilitates
the electrochemical reduction of graphene oxide (GO) sheets or films in a standard
electrochemical cell. The primary source of the reduction is typically the electron exchange
between the graphene oxide (GO) and electrodes, and no particular chemical agent is
required. This has the advantage of avoiding the use of hazardous reductants (hydrazine, for
example) and removing byproducts(An et al., 2010).
2.4.4. Solvothermal reduction
Solvothermal reduction is another newly developed chemical reduction technique. In
a solvothermal process, the solvent is heated to a temperature much over its boiling point by a
rise in pressure brought on by this process, all within a sealed container(Zhou et al., 2009).
Overheated supercritical (SC) water may act as a reducing agent in a hydrothermal process
and provides an eco-friendly chemical substitute for organic solvents. Furthermore, a wide
range of heterolytic (ionic) bond cleavage processes in water can be catalyzed due to its
physiochemical characteristics being very sensitive to variations in temperature and pressure.
The extraordinary transformation of carbohydrate molecules into homogenous carbon
nanospheres and nanotubes has been achieved through the application of hydrothermal
methods(Luo et al., 2005).

2.5. Reduced graphene oxide based composite

Graphene oxide (GO) and noble metal precursors were simultaneously reduced inside
the GO gel matrix to effectively construct reduced graphene oxide-based composite
hydrogels containing silver nanoparticles in situ. An arrangement of cross-linked nanosheets
makes up the hydrogels as they have been produced. In situ co-reduction of GO and silver
acetate happened inside the hydrogel matrix to generate RGO-based composite
gel. Meanwhile, the gel composite system managed to stabilize silver nanoparticles as well. It
was discovered that on the surface of the RGO nanosheets within the composite gel, the as-
formed silver nanoparticles were consistently and homogeneously distributed. More
significantly, this composite hydrogel matrix with RGO and silver nanoparticles functions as
a possible catalyst for the removal of organic dye contaminants from an aqueous
environment. Unexpectedly, after the reaction, the as-prepared catalytic composite matrix
structure is easily isolated from an aqueous environment, indicating the potential large-scale
uses of the composite hydrogels containing nanoparticles based on reduced graphene oxide
for the removal of organic dyes and the treatment of wastewater(Jiao et al., 2015)

In order to generate reduced graphene oxide (GO)/mono and bimetallic composites

utilizing scrap extract from Arachis hypogaea, a simple green process was created for the
simultaneous reduction of metallic ions and GO. The face-centered-cubic and highly
crystalline structures of the monometallic Ag and bimetallic Ag–Pd nanoparticles, with an
average particle size of 7 nm, were successfully attached across the rGO sheets. The
monometallic Ag and bimetallic Ag–Pd nanoparticles attached over the rGO sheets
maintained their spherical shape, average particle size, and structure without any impact from
surfactants or passivating agents. The functional groups of Arachis hypogaea scrap that are
responsible for the reduction of GO and metallic precursors were revealed by the Fourier
Transform Infrared spectra of the produced nanostructures. Under neutral circumstances, the
benefits of produced nanostructures with regard to enzyme-free hydrogen peroxide (H2O2)
sensor performances were evaluated. The as-fabricated rGO/Ag–Pd/GCE showed a low level
detection limit of 1.1 μM toward H2O2 electrooxidation, a sensitivity of 342 μA mM−1
cm−2, and a linear response to the concentration of H2O2 throughout a broad range of 0.005
to 14.65 mM. Consequently, the suggested methodology has not only yielded noteworthy
insights into the creation of ecologically sustainable rGO-based composites, but it has also
customized the processes for novel uses of green catalysts in enzyme-free H2O2
sensors(Amala et al., 2017)

A simple thermochemical reaction between graphite oxide and FeSO4·7H2O

produced iron oxides and reduced graphene oxide composites. It is convenient to obtain α-
Fe2O3/reduced graphene oxide and Fe3O4/reduced graphene oxide composites by varying
the reaction temperature. For the first time, it was shown that graphene oxide and reduced
graphene oxide sheets control the phase transition from α-Fe2O3 to Fe3O4 via γ-Fe2O3. It is
thought that these phase transitions are significantly influenced by the hydroxyl groups that
are bonded to the graphene oxide sheets and the H2 gas that is produced during the annealing
process. These samples' electromagnetic complementary effect allowed them to exhibit good
electromagnetic wave absorption capability. The electromagnetic wave absorption qualities
of these samples are significantly superior to those of the separately generated Fe3O4 mixture
with rGO, indicating the critical significance that synthesis methods play in defining the final
product's features. These samples also work far better than store-bought absorbers. Above all,
these composites' exceptional stability is a huge benefit for uses as high-temperature
electromagnetic wave absorption materials(Zhang et al., 2015).

Two distinct ionic liquids, 1-(2-methoxyethyl)-3-methylimidazolium

methanesulfonate (IL1) and 1-(2-methoxyethyl)-3-methylimidazolium tetrafluoroborate
(IL2), were used to create TiO2 nanoparticles and TiO2-RGO (reduced graphene oxide)
composite through an ionothermal method for 24 hours at 100 and 120 °C (An et al.). The
composites' BET surface area analysis revealed that the TiO2 and TiO2-RGO composites had
surface areas of 170 and 161 m2 g−1, respectively. TiO2 NPs were evidently present on the
graphene sheet's surface in the composite, as demonstrated by TEM pictures, which indicate
that the particles have diameters of about 4 nm. Without the necessity for heat treatment
(TT), the usage of IL2 results in high crystalline TiO2 NPs with pure anatase phase.
When TiO2 NPs or TiO2-RGO composites are formed in ILs without thermal treatment (TT),
the rate of hydrogen generation by UV light is lower than that of TiO2 P25. A greater rate of
H2 generation (up to 0.76 mmol h−1 g−1) was observed following TT at 400 °C because of
the rise in crystallinity. For the TiO2-RGO composite, the photocatalytic activity was
considerably increased. It is true that the composite's graphene's electron-accepting and
electron-transporting capabilities may reduce charge recombination and enhance
photocatalytic activity(Nagaraju et al., 2013).

2.6. Application of reduced graphene based composite

Due to the widespread and serious harm that modern industrialization has caused to
the environment and public health, one of the main environmental issues that has arisen is
water pollution. Treatment of wastewater is a crucial step in many industrial processes. As a
result, a number of cutting-edge techniques (such as adsorption, burning, membrane
separation, and photocatalytic degradation) have been effectively used to purify
wastewater(Lei et al., 2013).

Malachite green (MG) dye has been successfully eliminated from simulated
wastewater by employing high surface area reduced graphene oxide (rGO). Based on
spectroscopic investigations (FTIR and Raman) and nanostructural characteristics (HRTEM)
of rGO, the likely interaction paths between MG dye and rGO are inferred. The adsorption of
MG dye on rGO has been helped by a number of factors, including the high surface area (931
m2⋅gm−1), the π-π interaction between the aromatic rings of MG dye and the graphitic
skeleton, the electrostatic interaction of the cationic center of MG dye with π-electron clouds,
and the negatively charged residual oxygen functionalities of rGO. For MG dye, the rGO has
an adsorption capability of up to 476.2 mg⋅g−1. The temperature-dependent isotherms'
thermodynamic characteristics indicated that the adsorption was an endothermic, spontaneous
process. These findings demonstrated that high surface area rGO may be useful for treating
wastewater by effectively removing cationic dyes(Thakur and Kandasubramanian, 2019).

Chemical spills, agricultural runoff, and industrial effluents all emit organic dyes into
the water system. Societies and regulatory bodies around the world have been greatly
concerned about the acute toxicity, stability, and long-term persistence in the environment. A
large amount of water is needed for the dyeing process, and this water is continuously
released into the environment(Dowd et al., 1998). The dyeing industries produce dangerous
and carcinogenic effluent that is toxic to fish, aquatic microbes, and mammals. It also poses
major risks to aquatic plants' ability to photosynthesise, which ultimately leads to the
devastation of the aquatic ecosystem. The environmental impact of dye effluents from the
textile and photography industries is increasing due to their toxicity, unsatisfactory color,
high chemical oxygen demand content, and resistance to degradation by chemicals,
photochemical reactions, and biological processes. The majority of colors are hazardous to
life, mutagenic, and cause cancer(Fu et al., 2011).

Dyes have been linked to a number of allergic reactions, including contact dermatitis,
respiratory conditions, eye and respiratory tract irritation, and even kidney, bladder, and
lesion cancer. Extremely poisonous dyes can impact aquatic plants' ability to
photosynthesize, which can result in an oxygen shortage in the aquatic ecosystem. They can
also reduce the amount of light that can pass through water, lowering its quality and
transparency. Several studies have always focused on the handling of such organic dyes in
micro-polluted water(Yanagisawa and Ovenstone, 1999).
Utilizing photocatalysts to break down synthetic and organic contaminants, like
chemicals and dyes, has become a popular and efficient waste water treatment technique. Our
attention has been directed towards photocatalytic materials that rely on two-dimensional
carbonous nanostructures, such as reduced graphene oxide (RGO) or graphene oxide (GO),
which have significant surface area, high oxygen functionality, and efficient adsorption sites.
In order to fully investigate the impact of photocatalytic activities on loading of GO/RGO
with metal oxides and polymer-based composites, the composites of GO/RGO surpass
electron-hole pairs recombination rate and reduce energy gap by modifying valence band
level (VBL) and conduction band level (CBL). This results in better adsorption of light
radiation that enhances photodegradation performance of metal oxides and polymer-based
composites. Additionally, for efficient degradation of the composite surface, the effects of
pH, starting dye concentration, photocatalyst dose, and surface charge have all been
studied(Khan et al., 2020).

CHAPTER 3