The textile dyeing industry consumes large quantities of water and produces large volumes

of wastewater. The effluent of dye is the most toxic contaminant recognized as a

carcinogenic and mutagenic agent and needs complete removal from wastewater before
disposal. In the present study, a novel graphene-based adsorbent was synthesized from
sugar and river sand using a green chemistry approach, and the adsorption of methylene
blue as dye solution was studied by modification of Hummer's method. The graphene oxide
sand composites prepared through the solution method at 90℃. The characterized prepared
graphene sand composite (GSC) accomplished by Fourier transform infrared (FTIR)
spectroscopy and UV-Vis spectroscopy. The function of The Fourier transform infrared
(FTIR) spectroscopy was to confirm that the graphene oxide synthesized by this method can
convert graphite into graphene Sand Composites. Performance tests had been conducted to
purify contaminated water using dyes such as methylene blue. The initial concentration for
all dyes were for 20, 40, 60, 80, and 100 ppm. The highest concentrations of Methylene Blue
for 100 ppm have the highest removal. In addition, the relationship between amount or
dosage of adsorbent (GSC) is proportional to removal of Methylene Blue. The GSC was very
effective in removing methylene blue dyes at any concentration. This GSC composite
material has the potential to be apply for water purification.

Numerous treatment methods have been investigating for textile wastewater, and among
various advanced treatment methods, adsorption has proven to be a highly effective
technology for dye removal (Dutta et al., 2021; Gisi et al., 2016). Adsorption treatment
technology offers several advantages, including their flexibility, ease of construction, simple
operation, cost-effectiveness, high efficiency, recyclability, and environmental benefits.

In addition, including the presence aromatics, metals, chlorides, and other contaminants in
these effluents can render aquatic plants and animals toxic and unsuitable for human
consumption. Dye components, with their synthetic origins and complex aromatic molecular
structures, are often resistant to degradation, and even at concentrations as low as 1.0 mg/l,
they can contaminate water, rendering it unfit for drinking and other domestic uses.

7. Adsorption Process

Adsorption is a chemical process that involves two significant components: the

adsorbent and the adsorbate. The adsorbate refers to the molecule or ion present in a
gaseous or liquid bulk, while the adsorbent is a solid (sometimes liquid) material. In simple
terms, adsorption is the attraction of molecules onto the surface of a solid (Syed Shabudeen
P.S. et al., 2014). When a solution containing an absorbable solute comes into contact with
a solid that has a highly porous surface structure, the intermolecular forces of attraction
between the liquid and solid cause a concentration or deposition of the solute molecules on
the solid surface. In adsorption operations, the solute maintained on the solid surface is
called the adsorbate, while the solid on which it is kept is called the adsorbent (Mohamed
Nageeb Rashed et al., 2013). Adsorption refers to the buildup of adsorbate on the surface of
an adsorbent. Separation by adsorption technology is based on the formation of an
adsorbed phase with a composition different from that of the bulk fluid phase (Mohamed
Nageeb Rashed et al., 2013).

Physical adsorption, also known as physisorption, occurs when the adsorbate sticks to the
surface due to physical forces, while chemical adsorption, or chemisorption, occurs when the
adsorbate is chemically linked to the adsorbent's surface. Physisorption is driven by Van der
Waals interactions, which are attractive forces resulting from weak electrostatic interactions
between molecules (Pouran Pourhakkak, AliTaghizadeh, Mohsen Taghizadeh, Mehrorang
Ghaedi, and Sepahdar Haghdoust et al., 2021).

If the adsorbate molecules collide with the surface with low energy, the energy is dissipated
as heat by the solid's lattice, and they adhere to the surface. However, if the molecules strike
the surface with too much energy, the adsorbent cannot dissipate it, and the molecules
bounce away. Adsorption phenomena play a role in various natural physical, biological, and
chemical systems, and adsorption operations utilizing solids such as activated carbon and
synthetic resins are widely used in industrial applications and for water and wastewater
purification. The removal percentage of heavy metal ions is high at the initial stage of the
adsorption process, but it decreases until reaching equilibrium. Temperature significantly
affects the heavy metal adsorption process. Increasing the adsorbent dose generally
enhances catalytic activity due to the increase in total surface area and the number of active
sites on the adsorbent's surface. Understanding the factors that influence heavy metal
adsorption onto ISW (Industrial Solid Waste) will help optimize the conditions for heavy
metal adsorption (N.K. Solimana and A.F. Moustafab et al., 2020).

8. Adsorption Parameter

In this study, the performance of adsorption will be investigated under various

parameters. The reaction parameters play a critical role in determining the optimal conditions
for adsorption to effectively remove the maximum amount of MB (Methylene Blue) from
water. Commonly researched adsorption parameters include the concentration of adsorbate,
pH level, adsorbent dosage, mixing ratio, particle size, agitation speed, and temperature. In
this particular study, two adsorption parameters or factors that significantly impact the
adsorption efficiency will be examined.

2.8.1 Adsorbent Dosage

To achieve the highest percentage removal of MB from water, it is necessary to

adjust the amount of adsorbent used. Increasing the adsorbent dosage should theoretically
lead to a higher percentage removal of MB. In this study, the adsorbent dosage is measured
in terms of weight. The researchers employed adsorbent dosages ranging from 0.1 to 0.8 g.
In the study conducted by Md. Tamez Uddin, Md. Arifur Rahman, Md. Rukanuzzaman, and
Md. Akhtarul Islam et al. (2017), it was found that the highest adsorbent dosage resulted in
the highest adsorption capacity, ranging from 164 to 25 mg/g.

When the adsorbent dosage is increased, the number of available sites for
adsorption also increases. This is because the adsorbents provide a surface for the dye
(MB) to attach to. Consequently, the percentage of dye removal should theoretically increase
as the adsorbent dosage is raised. However, studies conducted by Abuthahir et al. (2017),
Jawad et al. (2018), and Malik et al. (2016) have shown that maximum adsorption uptake
occurs at lower dosages within the respective ranges used. This is attributed to the
phenomenon of adsorbent particle agglomeration, where further increases in adsorbent
dosage do not lead to a corresponding increase in MB removal percentage (Jawad et al.,
2018). As a result, it can be concluded that the adsorption rate increases with higher
adsorbent dosages but eventually reaches a maximum dosage beyond which no further
adsorption takes place.

2. Concentration of Adsorbate

Adsorption is a process where chemicals accumulate at a surface, which can

occur between liquid-liquid, gas-liquid, gas-solid, or liquid-solid phases. The material being
adsorbed is called the adsorbate, while the adsorbing phase is referred to as the adsorbent.
The term sorption encompasses both adsorption and absorption, which describes the
transfer of components from one phase to another, with solid being the most commonly
involved phase. When a liquid is adsorbed on a solid surface (adsorbent), the extent of
adsorption is typically greater at higher concentrations of the adsorbate. The efficiency of the
adsorption process is generally higher when the initial concentration of the adsorbate is
lower, until it reaches a saturation value. Due to the surface forces imbalance, a solid
surface in contact with a solution tends to develop a surface layer of solute molecules,
leading to adsorption (Aderonke Ajibola Adeyemo, Idowu Olatunbosun Adeoye & Olugbenga
Solomon Bello et al., 2015). The adsorbate forms a molecular layer on the surface as a
result of adsorption, and an equilibrium concentration is often quickly established at the
surface, followed by a gradual diffusion onto the adsorbent particles.

9. Graphenic Material

Graphite is a crystalline form of carbon that consists of parallel planar layers stacked on top
of each other. The carbon atoms within each layer are arranged in orderly hexagons, with
each atom surrounded by three others. The distance between two adjacent graphite layers is
approximately 3.35 Å. The carbon-to-carbon distance within the hexagonal sequence is 1.42
Å. Intraplanar binding forces within each layer are stronger due to covalent and metallic
bonding, while interplanar van der Waals forces are weaker. Graphite can react with various
chemical reagents, leading to surface modification and intercalation compounds formation,
which enhances its adsorption capabilities (Ali et al., 2018). Graphite intercalation
compounds are particularly important in water treatment due to their excellent adsorption
properties for various pollutants. Graphene, a versatile carbon nanostructure, has gained
extensive applications in multiple technological fields, and innovations in industrial
production technology are crucial for its widespread use (Ali et al., 2018).

Graphene-based materials encompass graphene, graphene oxide, and reduced graphene

oxide, all belonging to the graphene family. These materials have similar structures, but they
differ in terms of the sp2 hybridization region and surface groups. Compared to traditional
materials like activated carbon, resins, and carbon nanotubes, graphene-based materials
exhibit superior adsorption capabilities. They have been widely explored for environmental
remediation applications, leveraging their high thermal and electrical conductivity, electronic
characteristics, quantum hall effect, and potential applications in drug delivery and DNA
sensing. Chemically produced graphene and graphene oxide can be attached to river sand
surfaces, forming efficient adsorbents for the removal of heavy metals, ions, contaminants,
and natural dyes (Radjenovic, 2004).

Figure 2.4 Chemical structural of graphene

Graphene, a two-dimensional carbon allotrope, is composed of carbon atoms

arranged in a hexagonal pattern, similar to chicken wire. A single layer of carbon atoms
arranged in a honeycomb pattern constitutes graphene. Multiple layers of graphene stacked
on top of each other form multi-layer graphene, which eventually transforms into graphite
after approximately 30 layers (although consistency in this regard is currently lacking)
(Graphene: Structure and Shape Graphene-Info, 2018). The chemical structure of graphene
is depicted in Figure 5.

10. Current Study of Graphenic Material in Wastewater Treatment

Activated carbon is commonly used as an adsorbent for removing colors from

industrial effluent. However, its high manufacturing and regeneration costs make it
impractical for large-scale industries or high dye concentration wastewater, limiting its
widespread use in dye wastewater treatment (Wang et al., 2011). Graphene, a novel
member of the carbon family, has gained attention as an alternative adsorbent. Lazar et al.
(2013) conducted an experimental and theoretical assessment of adsorption enthalpies on
graphenic adsorbents for various chemicals. Gupta et al. (2012) developed a novel
graphene-based adsorbent. Recent studies have demonstrated the potential of graphene-
based materials in environmental cleanup. Their large surface area, reduced cytotoxicity,
presence of large delocalized π electrons, and tunable chemical properties make them
promising candidates for chemical adsorption and water cleanup. Graphene-based materials
have also shown efficacy in arsenic removal (Maliyekkal et al., 2013).

Graphene's ability to photocatalyze and adsorb water pollutants is well-known. By creating

pores and microscopic openings in graphene, it can serve as a water filtration sieve. The
hydrated ions resemble graphene's atomically defined nanopores, allowing for fast and
selective water transport. Graphene's ultrathin thickness makes it suitable for membrane
design and fabrication in water treatment processes. It exhibits high flux efficiency, excellent
mechanical strength to withstand high pressures, and good chemical and thermal stability.
Graphene aerogels have been compressed to create graphene papers with consistent
thickness, and they have demonstrated potential in water desalination by membrane
distillation, exhibiting high salt rejection rates, contaminant removal capabilities, and
resistance to fouling (Abouimrane et al., 2010; Deepthi et al., 2013).

Furthermore, recent modeling research suggests that nanochannels between misaligned

graphene grains serve as ideal water reservoirs, facilitating water infiltration (Dwivedi et al.,
2019).