Science of the Total Environment 840 (2022) 156564

Contents lists available at ScienceDirect

Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Review

Removal of toxic metals from wastewater environment by graphene-based

composites: A review on isotherm and kinetic models, recent trends,
challenges and future directions
N. Nirmala a, V. Shriniti b, K. Aasresha b, J. Arun a, K.P. Gopinath b, S.S. Dawn a,c, A. Sheeladevi d, P. Priyadharsini c,
⁎
Kathirvel Birindhadevi e, Nguyen Thuy Lan Chi f, Arivalagan Pugazhendhi g,
a
Center for Waste Management ‘International Research Center’, Sathyabama Institute of Science and Technology, Jeppiaar Nagar (OMR), Chennai 603 119, Tamil Nadu, India
b
Department of Chemical Engineering, Sri Sivasubramaniya Nadar College of Engineering, Kalavakkam 603110, Tamil Nadu, India
c
Centre of Excellence for Energy Research, Sathyabama Institute of Science and Technology, Jeppiaar Nagar (OMR), Chennai 603 119, Tamil Nadu, India
d
Department of Biotechnology, Karpaga Vinayaga College of Engineering and Technology, Madurantakam 603308, Tamil Nadu, India
e
Center for Transdisciplinary Research (CFTR), Department of Pharmacology, Saveetha Dental College, Saveetha Institute of Medical and Technical Sciences, Saveetha University,
Chennai, India
f
School of Engineering and Technology, Van Lang University, Ho Chi Minh City, Vietnam
g
Emerging Materials for Energy and Environmental Applications Research Group, School of Engineering and Technology, Van Lang University, Ho Chi Minh City, Vietnam

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• This review articulates the application of

graphene oxides in heavy metal removal.
• Compares the advantages and disadvan-
tages of graphene oxides synthesis routes
• Heavy metals possess greater threat to en-
vironment and living beings.
• Pollutant interaction mechanism, iso-
therm and kinetics are discussed in detail.
• Regeneration studies exhibited economic
advantages for the process.

A R T I C L E I N F O A B S T R A C T

Editor: Huu Hao Ngo Access to clean water has reduced in recent years due to pollution and man-made activities. Wastewater treatment reg-
imens are many such as electrocoagulation, adsorption, ozonation, membrane and advanced oxidation processes.
Keywords: Owing to economical, resource availability and ease of operation adsorption has upper hand over all other methods
Heavy metals employed in wastewater treatment. Graphene based adsorbents attracted researchers due to their ability to play
Graphene oxides
dual role as adsorbent and photo-catalysts. When it comes to removal of heavy metals and dyes graphene-based
Wastewater
Adsorption
aerogels are successful. Graphene composites were predominantly synthesized by top-down and bottom-up approach
Isotherm methods. Graphene composites are mesoporous and have microporous structure on surface. Graphene has copper de-
Kinetics sorption efficiency of 90 % upon 10th consecutive cycle. Graphene based adsorbents have adsorption efficiency of 367,
246 and 106.3 mg−1 for lead, zinc and cadmium respectively. Though graphene possesses numerous applications, this
review was devoted towards heavy metals removal from aqueous environment. In detail, the synthesis routes and in-
teraction mechanism were explained and also the adsorption isotherms, kinetics were added. This review will serve as
support for future research directions on removal of wastewater contaminants (heavy metals).

⁎ Corresponding author at: Van Lang University, Ho Chi Minh City, Vietnam.
E-mail address: arivalagan.p@vlu.edu.vn (A. Pugazhendhi).

http://dx.doi.org/10.1016/j.scitotenv.2022.156564
Received 20 October 2021; Received in revised form 29 May 2022; Accepted 5 June 2022
Available online 9 June 2022
0048-9697/© 2022 Elsevier B.V. All rights reserved.
N. Nirmala et al. Science of the Total Environment 840 (2022) 156564

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Graphene: a modern adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Synthesis routes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. Morphology, types, properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3. Heavy metals: a threat to water and humans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1. Adverse effects of heavy metals on humans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4. Application of graphene on heavy metal removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.1. Interaction and removal methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.2. Adsorption isotherm models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.3. Adsorption kinetic models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5. Regeneration ability of graphene/desorption studies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
6. Challenges and future research perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
7. Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
CRediT authorship contribution statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Appendix A. Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

1. Introduction
In developing countries, modernization of industrial metal smelting,
mining operations, electroplating of natural and anthropogenic sources
have led to the contaminations of heavy metals in the wastewater streams
(Ali et al., 2019). Discharge of heavy metals into the water environment
leads to the accumulation of heavy metals into the aquatic living organisms
which in turn causes adverse effect to the environment as well as to the
organism (Kumar et al., 2019b). World Health Organization (WHO) have
set guidelines to limit the presence of heavy metals at a permissible concen-
tration for the quality of drinking water are chromium (50 μg/L), cadmium
(3 μg/L), mercury (3 μg/L), lead (10 μg/L), arsenic (10 μg/L) and nickel
(700 μg/L) (Baby et al., 2019). Exposure to these heavy metals cause gastro-
intestinal and kidney dysfunction, nervous system disorders, skin lesions,
vascular damage, immune system dysfunction, birth defects, and cancer.
Chemical precipitation, membrane filtration, electrochemical coagula-
tion, adsorption, ion exchange and flotation are the common technologies
that are suggested for the removal of heavy metal from the contaminated
wastewater streams (Yang et al., 2019). Among these suggested technolo-
gies, Adsorption process was considered as flexible technologies due to its
low cost and effective heavy metal removal. Activated carbon was the
conventional adsorbent used for the heavy metal removal process initially
but now, chitosan-based adsorbents, Nano cellulose and carbon nanotubes
are attaining attention (Abu-Nada et al., 2020). However, in case of these
Nano-adsorbents, the disadvantages are irregular pore structures, extreme
pH and low specific surface areas have resulted in lower adsorption ability
of heavy metal removal from the wastewater stream.
Graphene based composite materials are getting attention and in fact
they have proved to be a competent candidate for the removal of heavy
metals from water system. Graphene oxide (GO) are produced through
the oxidation of graphite by top-down methods, which can be further
reduced by chemical or thermal reaction to produce reduced graphene
oxide (rGO). The developments of graphene-based nanocomposite are
achieved with metal oxides and organic molecules in the form of 3D
structures, membranes, sheets, nanotubes to improve their absorption
characteristics. GO is recommended as a suitable adsorption material
because of the presence of layered structure of graphite and expanded inter-
layer separation with polar oxygen groups with C/O ratio between 1:1 to
4:1 (Baby et al., 2019). The rGO was produced by performing chemical
reduction or thermal and hydrothermal reduction of graphite material
with C/O ratio of 10.
In order to improvise the adsorption characteristics of GO and rGO, the
formation of hybrid structures using transition metals like zinc, copper,
nickel and cobalt; organic metals like cellulose and chitosan; inorganic
materials line zeolites, silica nanostructure, polymers and metal organic
framework (MOF) synthesis were also attempted (Zhang et al., 2020).
The adsorption affinity of the ions onto GO and rGO is purely depends on
the electro negativity, stability constant and reduction potential (Peng
et al., 2017). Freundlich, Langmuir, Redlich-Peterson, Sips and Temkin
models are the isotherm models that are most commonly fitted for the
adsorption capacities of heavy metals over graphene material. In general,
contact time, pH, temperature, adsorbent dosage and metal ion initial
concentration are the major factors tend to affect the adsorption process.
Therefore, the GO is an efficient and economically feasible adsorbent for
the effective removal of heavy metals from wastewater.
This review provides a literature review on recent published articles on
removal of heavy metals from wastewater. Keywords like “graphene
oxides”, “heavy metals”, “synthesis of graphene oxides”, “regeneration
and reuse” are utilized for selection of appropriate articles from “science
direct”. This review provides the dimensions of graphene oxides as adsor-
bent to remove heavy metals from wastewater. The synthesis routes of
graphene oxides and its adsorption characteristics of heavy metals with
interaction mechanisms are consolidated from the recently published arti-
cles. The regeneration capability of graphene oxides provides a better econ-
omy for industries by minimizing the challenges in using graphene oxides.
2. Graphene: a modern adsorbent
2.1. Synthesis routes
Graphene is predominantly synthesized by two methods namely the
top-down approach and bottom-up approach. The top-down approach is
inclusive of mechanical exfoliation, chemical exfoliation and chemical
fabrication. Whereas the bottom-up approach is inclusive of pyrolysis,
epitaxial growth and plasma synthesis (Lim et al., 2018). Fig. 1 describes
the two different pathways adopted for graphene synthesis. In the top
down approach, the graphite material is subjected to chemical or mechan-
ical destruction, which is used to produce thin graphene sheets from the
graphite. During mechanical exfoliation method, longitudinal or transverse
stress is applied to the graphite material to peel off or to exfoliate to obtain
sheets of graphene (Lim et al., 2018). Exfoliation can be brought out by
techniques such as the scotch tape method, or by applying electric field or
by the ultra-sonication method (Ci et al., 2009). Due to the application of
stress, the Van der Waals forces by which different layers are held within
graphite are broken. Exfoliation can also be done by chemical means.
Chemical exfoliation follows two steps, the first to reduce the strength of

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Fig. 1. Top down and bottom up synthesis routes of graphene oxides (Lim et al., 2018).

the van der Waals forces and the second is to extract layers of graphene. The
second process can be facilitated by the application of heat or by sonication
(Lim et al., 2018). There are different methods by which chemical exfolia-
tion can be carried out, a few of them are, the Hummers, modified hummers
and improved hummers method (Chen et al., 2013), Staudenmaier method
(Staudenmaier, 1898) and Brodie method. Another method of synthesizing
graphene by top-down approach is by chemically reducing graphite oxide.
Usually, reduction is done by using a suitable reducing agent or by electro-
chemical reduction. The most common reducing agents used are pyrrole,
phenylhydrazine, hydroquinone, hydroxylamine. This process comes
under the category chemical fabrication.
In the bottom-up approach, a carbonaceous gas was used to produce
graphene. In the epitaxial growth method, Silicon carbide was first
heated and then allowed to cool down. It was seen that there was

Fig. 2. Removal of pollutants by graphene oxides in wastewater treatment process.

3
N. Nirmala et al.
some deposition of graphene on the silicon side and growth of graphene
on the carbon side (Chaste et al., 2017). In the chemical vaporization
method, a deposition or coating of a gaseous reactant is allowed on a
substrate at suitable temperature and pressure conditions (Tetlow
et al., 2014). For example, a precursor, camphor was evaporated and
pyrolyzed using a carrier gas such as argon. Evaporation was carried
out at 180 °C and pyrolysis was carried out at 700–850 °C (Somani
et al., 2006). The chemical vapor deposition is enhanced by integrating
it with plasma synthesis or by doping of plasma to produce graphene
(Wang et al., 2013b).
2.2. Morphology, types, properties
Graphene and graphene-based materials are widely being used as adsor-
bents due to their ability to provide a large surface area for adsorption.
Fig. 2 explains the mode of graphene oxide usage for treatment of wastewa-
ter. Mainly two- and three-dimensional graphene are used, out of which
three-dimensional graphene (3D) are more commonly used because of
their physiochemical properties and their ability to retain the inherent char-
acteristics of the monomers (Liu and Qiu, 2020). Graphene and graphene-
based materials are commonly used in wastewater treatment as adsorbents
due to their ability to easily transport the pollutants present in the aqueous
media into their three-dimensional structures which have ample active sites
for capturing the pollutants (Lai et al., 2019).
In order to improve the efficiency of the adsorption process, pure
graphene are coupled with other heteroatom's like Boron (B), Phosphorus
(P), Sulfur (S) and Nitrogen (N) in order to increase the number of active
sites present on the surface and to improve the electrochemical activity.
Graphene is also coupled with nanoparticles like Iron (Fe) which shows
magnetism in order to achieve an effective separation using a magnetic
field. Graphene is also coupled with those nanoparticles which exhibit
Fig. 3. Major sources of heavy metal entry into the environment.
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Science of the Total Environment 840 (2022) 156564
photocatalytic degradation properties to degrade toxic pollutants (Liu and
Qiu, 2020). Apart from conventionally used graphene adsorbents, deriva-
tives of graphene such as graphene oxides used either independently or
modified to suit the needs chemically or those which are integrated with
other nanomaterials (Liu et al., 2019).
Pure oxidized graphene or graphene oxides are known to have func-
tional groups like carboxyl's and hydroxyls which improve the adsorption
of heavy metal pollutants from water (Liu et al., 2019). But it was observed
that the efficiency of the adsorption process decreased due to the aggrega-
tion of the graphene oxide in wastewater (Zhao et al., 2011c). Due to this
reason graphene oxides are modified chemically by introducing a covalent
group such as amines which are substituted (Kumar et al., 2013). Graphene
oxides are also coupled with metallic oxides like ferric oxide which inde-
pendently is used as an adsorbent owing to its high surface area available
for adsorption and its magnetism properties (Chen et al., 2018;
Nizamuddin et al., 2018). Together graphene oxides and ferric oxide help
to achieve a high degree of separation (Zong et al., 2013). Nowadays,
graphene oxides are combined with metallic oxides like zinc oxide and
titanium di-oxide to achieve photocatalytic removal of heavy metals
(Liu et al., 2019).
3. Heavy metals: a threat to water and humans
A heavy metal is a metallic element that was greatly released by
manmade and natural activity into the environment and in return this led
to health problems or environmental damage (Ahmad et al., 2020). Fig. 3
explains the various entry or source point of heavy metals. Heavy metals
are major pollutants in wastewater. Processes, such as machinery
manufacturing, mineral smelting, electroplating, electronic manufacturing,
oil refining and chemical processing are the main sources of heavy metals
(Li et al., 2018). Accumulation of heavy metals was caused due to the
N. Nirmala et al.
improper disposal or proper prior treatment of wastewater (Mahmoud
et al., 2010). Heavy metals, like chromium (Cr), lead (Pb), cadmium (Cd),
mercury (Hg), copper (Cu) and nickel (Ni) enter into the water environ-
ment through sewage discharge, atmospheric deposition and rain erosion
(Shukla et al., 2006). Due to high toxicity, refractory biodegradation and
easy bioaccumulation, heavy metals have toxic effects on aquatic organisms
even at low concentrations. They can also enter into human bodies through
the food chains; interrupt the usual physiological deeds, and cause disease
and even death, resulting in serious threats to aquatic organisms and
human health (Shukla et al., 2006).
Heavy metals usually persist in aqueous systems for a longer time
because of their non-biodegradability and toxic nature (Ma et al., 2020).
Eco-friendly and economically viable treatment methods have to be devel-
oped for the removal of heavy metals from the aquatic system and to protect
the environment (Joseph et al., 2019; Ajiboye et al., 2020). Common treat-
ment techniques are chemical precipitation, ion exchange, chemical oxida-
tion, reduction, reverse osmosis, ultra-filtration, photo electro-catalysis,
electro dialysis and adsorption used in removing heavy metals in aqueous
systems (Ye et al., 2020). People in the normal world have less awareness
and knowledge about exposure to heavy metals and its consequences
for human health, especially in the developing countries (Kumar et al.,
2019a). They might be exposed to heavy metals in the work place and in
the environment. Human exposure to toxic chemicals in the work place is
known as occupational while exposure to such chemicals in the general
environment is called non occupational or environmental exposure
(Wang et al., 2020).
3.1. Adverse effects of heavy metals on humans
Workers are exposed to heavy metals in mining and industrial opera-
tions where they may inhale dust and particulate matter containing metal
particles. Fig. 4 elaborates the adverse effects of exposure to heavy metals.
People extracting gold through the amalgamation process are exposed to
Hg vapors (Aghaei et al., 2019). It has been reported that welders with
occupational prolonged exposure to welding fumes had significantly higher
levels of the heavy metals Cr, Ni, Cd, and Pb in blood than the control and
showed increased oxidative stress. Cigarette smoking is also a principal
source of human exposure to cadmium (Cd) and other toxic heavy metals
present in the tobacco leaves (Kostelli et al., 2020). The effects caused by
individual depends on its own characteristics and the signs associated
Fig. 4. Adverse effects of commonly encountered heavy metals on different human organs.
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Science of the Total Environment 840 (2022) 156564
with cadmium, lead, arsenic, mercury, zinc, copper and aluminum poison-
ing are gastrointestinal disorders, diarrhea, stomatitis, tremor, hemoglobin-
uria causing a rust-red color to stool, ataxia, paralysis, vomiting and
convulsion, depression and pneumonia, when volatile vapors are inhaled
(Levin et al., 2020). Also, toxicity due to lead accumulation may lead to a
decrease in hemoglobin production, kidney, joint, reproductive and cardio-
vascular systems disorders and long-term injury to the central and periph-
eral nervous systems (Gao et al., 2018a).
To provide safer environment to the next generation these heavy metals
must be removed from the aqueous environment. Table 1 provides the
detailed note on the various heavy metals removed from graphene-based
adsorbents. Graphene as such and in oxide form (graphene oxide) are
preferred for the removal of heavy metals like chromium, lead, iron and
cobalt. From the table it was seen that the graphene in its form has been
reported having adsorption capacity of 22.42 and 370 mg−1 for lead and
cobalt. Graphene in its extended form and in mix with metals have showed
adsorption capacity of 367, 246 and 106.3 mg−1 for lead, zinc and
cadmium respectively. It was clear that upon coating of metal elements
onto the graphene has increased the adsorption property towards heavy
metal removal from aqueous solution. Coated graphene adsorbents have
favored Freundlich kinetic isotherm, as this is also independent of type of
pollutant and adsorbent material.
4. Application of graphene on heavy metal removal
4.1. Interaction and removal methods
Various mechanisms have been proposed to explain the interaction of
the adsorbent graphene or graphene oxides with heavy metals. Some of
those are precipitation, ion exchange methods or surface complications
(Liu et al., 2019). Other modes are electrostatic interactions, Lewis-base-
acid-mechanism can also be used to describe the interaction between the
adsorbate and the heavy metals. Table 2 provides the various interaction
mechanisms reported in literature. These mechanisms have been proposed
with the help of spectroscopic techniques like X- ray photoelectron spec-
troscopy, X-ray absorption fine spectroscopy and Fourier transform infrared
spectroscopy (Gao et al., 2018b; Zhao et al., 2018). The FT-IR results of
Graphene Oxide imply that interaction mechanism of heavy metals with
Graphene Oxide depends upon the functional groups attached with it. For in-
stance, if the functional groups present in graphene oxide are functional
N. Nirmala et al. Science of the Total Environment 840 (2022) 156564

Table 1
Literature collection on the articles reported the heavy metal removal efficiency by graphene-based adsorbents.
Adsorbent Targeted Contact Concentration Temperature pH Adsorption References
heavy time (h) (mg L−1) (K) capacity
metal (mg−1)

Graphene Lead (II) 15 40 303 4 22.42 (Wang and Peng, 2010)

Graphene Cobalt (II) 24 20 – 8 370 (Chang et al., 2013)
Graphene magnesium‑aluminum Chromium (VI) 24 50–250 – 2 183.82 (Yuan et al., 2013)
Graphene/Iron Chromium (VI) 4 25–125 293 4.25 162 (WooáLee et al., 2011)
Graphene oxide Lead (II) 24 5–300 298 6.8 367 (Madadrang et al., 2012)
Graphene oxide Zinc (II) – 10–100 293 7 246 (Wang et al., 2013a)
Graphene oxide–Titanium dioxide Zinc (II) – – – 5.6 88.9 (Lee and Yang, 2012)
Graphene oxide -iron oxide Lead (II) 48 – 303 6.5 588.24 (Yang et al., 2012)
(Ethane-1,2-diyldinitrilo) tetraacetic Lead (II) 24 5–300 298 6.8 525 (Madadrang et al., 2012)
acid modified Graphene oxide
Iron Graphene oxide Cadmium (II) – 303 6 106.3 (Zhao et al., 2011b;
Zhao et al., 2011a)
Graphene oxide/Chitosan Lead (II) – 50 Room – 99 (He et al., 2011)
temperature
Graphene oxide – Iron oxide/Ferrosoferric oxide Mercury (II) 1 2–6 298 7.0 22.0 (Bhunia et al., 2012)
Graphene oxide – Silver Mercury (II) – 1 303 – 9.53 (Sreeprasad et al., 2011)
Graphene oxide – Manganese oxide Mercury (II) – 1 303 – 9.5
Polypyrrole/Graphene oxide Chromium (VI) – – – – 9.56 (Li et al., 2012)
Polypyrrole-Graphene oxide Mercury (II) 3 50–250 293 3 979.54 (Chandra and Kim, 2011)

groups of oxygen, then the binding happens through surface complexation.
Whereas, if the functional groups present in the surface of graphene oxide
are aromatic, the interactions are cation-pi in nature (Gao et al., 2018b).
The interaction between graphene oxides with heavy metals dependents on
the density of states, i.e., partial and total, and that the binding of heavy
metals (copper) with graphene oxides is stronger when graphene oxides
have functional groups of oxygen rather than nitrogen (Wang et al., 2018).
This is because the functional groups of oxygen are negatively charged
which interact with the positively charged heavy metal ions and serve as
active sites for adsorption (Gao et al., 2018b). This describes the electrostatic
interaction mechanism. Ion exchange theory states that, for GO aerogels,
the hydronium ions present on the surface get liberated when the pH is
high, making active sites available for adsorption of heavy metals (Mi et al.,
2012).
Factors like the pH, temperature, contact time between the heavy
metals and the adsorbent, the dosage and concentration of heavy metals
and the adsorbent that play a significant role in controlling the interaction
mechanism. The pH of the aqueous solution should never be higher than 7,
thus a pH less than 7 will hinder the metal ion hydrolysis which yields metal
hydroxides hindering the adsorption process. At high pH, the H+ ions will
compete with the heavy metals for active sites in the adsorbent, adsorption
mechanism followed is ion exchange method, as both the types of ions are
positively charged (Liu et al., 2016). The adsorption capacity increases with
the increase in temperature mainly because the rate of diffusion, both inter-
nal and external, increases with the increase in temperature (Chen et al.,
2015a). The adsorption process initially takes place in a rapid manner
due to a large number of active sites available, however as time progresses
the number of active sites also start decreasing and the rate of adsorption
will also decrease and progresses slowly till equilibrium (Zhao et al., 2016).
Another parameter that influences the interaction mechanism is the
initial concentration of the metal ions. Before saturation is reached the
rate of adsorption is high when the concentration of metal ions is high
(Liu et al., 2016). The next parameter which affects the interaction and
the rate of adsorption is the adsorbent dosage, which when high will result
in higher adsorption rates due to large number of active sites available for
adsorption (Wu et al., 2017).
metals in this case are absorbed by using a suitable graphene or graphene-
based adsorbents. They are mainly used because they provide many advan-
tages like high efficiency, less maintenance, and low cost for operation
(Wang et al., 2019; Wang and Zhuang, 2017). With the help of adsorption
isotherm models, the interaction between the adsorbate and adsorbent and
the efficiency of the adsorbent can be determined at equilibrium and at a
constant temperature (Al-Ghouti and Daana, 2020). Table 2 provides the
adsorption isotherm models that are used in adsorption process. Adsorption
isotherms are curves that are drawn with adsorption parameters like the
concentration of the adsorbate accumulated on the surface of the adsorbent
and the equilibrium concentration of the adsorbate in a particular solution
at a constant time. Adsorption isotherms are also expressions relating the
concentration of the adsorbate adsorbed on the surface of the adsorbent
and the adsorbate's equilibrium concentration in a particular at a constant
temperature. Usually, the equilibrium concentration of the adsorbate is
represented as qe and the concentration of the adsorbate adsorbed on the
surface of the adsorbent is represented by Ce (Sahu and Singh, 2018).
Various adsorption isotherm models were proposed based on the
adsorption parameters considered. These adsorption isotherms are classi-
fied into various categories such as the one parameter isotherm model,
two parameter isotherm model, there parameter isotherm model and so
on up to five parameter isotherm model. The Henry's isotherm model is
an example for one parameter isotherm model, Freundlich, Langmuir,
Dubinin Radush kevich and Halsey isotherm models are a few examples
of the two-parameter isotherm models. Meanwhile Redlich-Peterson,
Weber -Van VlietFritz Schlunder isotherm models are a few examples of
three, four and five parameter isotherm models respectively (Al-Ghouti
and Daana, 2020). Chromium ions removal via graphene oxide coated
with chitosan and amine exhibited Freundlich and Langmuir models
(Zhao et al., 2016). Graphene oxides modified with chitosan aerosol micro-
spheres showed Freundlich isotherm model on removal of copper and lead
metals (Yu et al., 2017). In another scenario, graphene oxides coated with
chitosan magnetic particles showed Langmuir isotherm model during
removal of Mercury metal (Zhang et al., 2014).
4.3. Adsorption kinetic models

4.2. Adsorption isotherm models The adsorption rate and equilibrium time for adsorption can be deter-
mined with the help of kinetic models. These studies are done to determine
Adsorption, which is a mass transfer operation, is used widely in waste- if the reaction complies with pseudo, first order or second order reactions.
water treatment to remove various pollutants present in wastewater, heavy They are used to determine the dependence of adsorption capacity of the

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adsorbate on the adsorbent depending on the adsorption time (Tsibranska

(Chen et al., 2015b)

(Chen et al., 2015a)

(Zhang et al., 2014)

(Wang et al., 2014)

(Kang et al., 2017)

(Zhao et al., 2016)

(Fang et al., 2017)

(Jiao et al., 2016)
and Hristova, 2010). Adsorption kinetic models are used to find out the dif-

(Cui et al., 2015)

(Liu et al., 2016)

(Vu et al., 2017)
(Yu et al., 2017)

(Yu et al., 2017)

(Yu et al., 2017)

ferent mass transfer mechanisms followed during the adsorption process.
References They are also used to find the rate of adsorption and the efficiency of the
adsorption process. The adsorption rate can be determined by using differ-
ent kinetic models or adsorption reaction models that have been developed
over the years. Some of these models are pseudo-first, second order models,

qt ¼ 1b ln ð1 þ abt Þ
qt = qe(1 − e−k1t)
Non-linear form

mixed order models, nth order models and mass transfer models which
include models for internal and external diffusion (Wang et al., 2020).
qt ¼ 1þqe 2k2 t

qt ¼ 1þqe 2k2 t

qt ¼ 1þqe 2k2 t

qt ¼ 1þqe 2k2 t
q2 k t

q2 k t

q2 k t

q2 k t
e

e
Some of the diffusion like the Morris and Weber model and the Boyd
model should be incorporated while studying the kinetics of the reaction.
This is because these models account for the diffusion of solid particles
Pseudo second order
Pseudo second order
Pseudo second order
Pseudo second order

Pseudo second order

Pseudo second order

Pseudo second order

Pseudo second order
Pseudo second order

Pseudo second order

Pseudo second order
Pseudo second order
(the heavy metal ions in this case) into the layer of the adsorbent while
Pseudo first order

determining the rate constants. The Weber and Morris model is used to ac-
count for the intra-particle diffusion in liquids systems and the Boyd model
is used to account for intra-particle diffusion of spherical particles while
Elovich
Kinetic
model

– determining the kinetics of adsorption (Tsibranska and Hristova, 2010).

The Bangham model is used to account for diffusion through pores
qe ¼ K f Ce 1n

qe ¼ K f Ce 1n

qe ¼ K f Ce 1n

K f Ce 1n

qe ¼ K f Ce 1n

qe ¼ K f Ce 1n (Chakrapani et al., 2010). Amine coated graphene oxide adsorbent showed

Non-linear

e KL

e KL

e KL

e KL

1þCe K L
K L Qu C e

K L Qu C e

K L Qu C e

K L Qu C e

K L Qu C e
qe ¼ 1þC

qe ¼ 1þC

qe ¼ 1þC

qe ¼ 1þC

Pseudo second order upon removal of uranium and chromium metal from
form

qe ¼

qe ¼
wastewater (Zhao et al., 2016). In a study, graphene oxide coated with
glycol and aerogel exhibited Elovich kinetic model on removal of lead
Freundlich (high temperature),

metal (Fang et al., 2017).

Langmuir (low temperature)

5. Regeneration ability of graphene/desorption studies

Adsorption isotherm

Regeneration of spent adsorbent is the major factor that is considered in

Freundlich

Freundlich

Freundlich

Freundlich

Freundlich

achieving sustainable process in industrial scale. This helps in economy,

Langmuir

Langmuir

Langmuir

Langmuir
Langmuir
Langmuir
Langmuir
Langmuir

Langmuir

reduced new material need, time and workforce. Thus the regeneration
process ensures that the adsorbent is used up to its full potential before
being disposed in to the environment (Lai et al., 2019). It is very evident
Complexation coordination, electrostatic interaction

that different types of adsorbents have different regenerative abilities.

Usually, methods like desorption and thermal treatments are commonly
Surface complexation electrostatic interaction

employed for regeneration. During desorption, the exhausted adsorbent is

brought in contact with highly concentrated acid or alkali or an organic
solvent (Guo et al., 2011). The choice of solvent depends on the nature of
Chelation, electrostatic interaction

Chelation, electrostatic interaction

the heavy metal adsorbed and the nature of both, the adsorbate and the
adsorbent (Liu et al., 2019). Similarly, an experiment was performed to
determine the rate of desorption of Cu (II) ion from spent graphene oxide
Electrostatic interaction

electrostatic interaction
Interaction mechanism

Surface complexation

and the desorption rate was found to be 95 % during the first five cycles
and 90 % after ten cycles (Wu et al., 2013). Similarly, EDTA and thiourea
Chemisorption
Chemisorption
List of heavy metals studies that has reported the fitted isotherm and kinetic models.

can also be used as solvents for the desorption process respectively (Liu
et al., 2013; Leng et al., 2012). Similarly, experiments conducted to achieve
desorption of Cu (II) from Graphene oxide/cellulose hydrogel by using the
solvents 0.1 mol/L HCl and 0.1 mol/L NaOH (Chen et al., 2016). In a study,
–
–

–
–
–

the nitrogen, sulfur-graphene nanoplatelets (NS-GrNPs) has shown the

Triethylenetetramine-magnetite reduced Graphene oxide

exalted heavy metal ions adsorption and desorption of up to 99.706,

94.558, 78.62 % for 60 min and 72.62, 56.54, 80.38 %, receptively (Yuan
Graphene oxide/Chitosan aerosol microspheres

Graphene oxide/Chitosan aerosol microspheres

Graphene oxide/Chitosan aerosol microspheres

et al., 2013). Initially when the exhausted adsorbent was brought in contact
with an acidic environment, due to a surge in the number of H+ ions,
Polystyrene - Magnesium Graphene oxide
Sodium alginate/Graphene oxide aerogel

there would be a competition for active sites, the heavy metal ions on the
Chitosan- Magnetic Graphene oxide
Chitosan/Graphene oxide monolith

surface of the adsorbent would be replaced by the H+ ions. Next when

Activated carbon Graphene oxide
Glycol - Graphene oxide -aerogel
Amino modified Graphene oxide

the adsorbent is treated in an alkaline medium, the COO- groups would

Magnesium Graphene oxide

be obtained from the carboxyl groups. It was found that the adsorbent
Types of graphene based

Amine - Graphene oxide

was able to retain its capacity after five cycles of adsorption and desorption
(Chen et al., 2016).

6. Challenges and future research perspectives

adsorbent

Xanthate
Alginate

Chemical exfoliation Hummer method was mostly preferred for synthe-

sis of graphene oxide-based nanomaterials. The preparation of graphene-
Chromium (VI)

based nanomaterials itself consumes lots of time though the complicity of

Name of the

Mercury (II)
heavy metal

Arsenic (III)

Arsenic (III)
Arsenic (V)

experiment is comparatively less. Therefore, either the replacement or

Uranium
Lead (II)

removal of chemicals in order to shorten the process for the preparation

Copper
Table 2

Cu(II)

of graphene-based adsorbents should be a future perspective. It is also

responsible enough to look further in reduction of chemical usage or in

7
N. Nirmala et al.
Fig. 5. Future perspectives of graphene-based composites in photocatalysis and adsorption process.
replacement of cheaper chemicals would also results in achieving the cost-
effective process and applicable to industries is considered an important
focus.
The future perspectives and wide range of applying graphene-based
materials are highlighted in Fig. 5. Graphene based Nano adsorbents are
also capable to recover the adsorbents as well as the adsorbate even after
the number of cycles of heavy metal removal process performed is its
unique advantages. Though, GO based Nano adsorbents are in demand
due to its large surface area and pore size, which is an added advantage
for the adsorption of heavy metal ions from the wastewater. Whereas,
graphene-based Nano adsorbents are proved adsorbents due to their
potential adsorption capabilities towards the environment.
Different graphene-based adsorbents like PAMAMs/GO, EDTA/mGO,
chitosan/SH/GO and Chitosan/GO are guaranteed to remove either one
or two of the following heavy metal Cd (II), Pb (II), Cu (II) and Cr (VI).
Graphene based nanocomposites, graphene oxide coated composites,
graphene oxide-based aerogels need to be tested with heavy metals for
enhanced removal and commercialization. Graphene-based nanomaterials
can serve as an effective candidate for efficient removal of heavy metals
from the due to their higher regeneration and higher reusability capacities
as per the lab scale studies. However, further studies need to be assessed
with respect to the real time conditions of wastewater from the industries
for removal of heavy metals. Only then the worst situations of its can be
detectable to evaluate the effectiveness and usability of the graphene-
based nanomaterial adsorbents. It is also recommended to conduct heavy
metal removal experimental process using the prepared graphene-based
nanomaterial adsorbents for longer durations will help us in assessing the
actual dosage requirement, worst and best conditions detectability and
guaranteed heavy metal recovery. It will be useful to compare between
the lab-scale and industries site studies which are also a support to recom-
mend for the implementation of these prepared graphene-based nanomate-
rials for treating the wastewater for the longer duration. Henceforth, the
8
Science of the Total Environment 840 (2022) 156564
development of these graphene-based nanomaterial adsorbents for
most of the wastewater treatment plant can also be achieved successfully
for the effective heavy metal recovery which also helps to maintain the
healthier environment.
7. Conclusion
In summary, graphene-based adsorbents comprised excellent applica-
tions towards removal of heavy metal from aqueous system. In recent
literatures, it was clear that researchers mainly adopt both top-down and
bottom-up approach for synthesis of graphene adsorbents. Mainly
graphene-based adsorbents were used for decontaminating water polluted
with heavy metal, dyes, solvents, oil, drugs, emerging contaminants. The
contaminants were removed via interactions like electrostatic, hydropho-
bic, π - π complexation and H-bond. Currently many research were reported
on removal of conventional pollutants like heavy metals, dyes, solvents
within controlled conditions. Many studies need to be directed towards
removal of such pollutants from real time industrial wastewater. This is
the right time to push ourselves from laboratory to outside world to work
on real time environment.
CRediT authorship contribution statement
N. Nirmala: Conceptualization, Writing - Original draft preparation. V.
Shriniti: Methodology, Writing - Original draft preparation. K. Aasresha:
Writing, Reviewing and Editing. K. P. Gopinath: Supervision, Project ad-
ministration. S. S. Dawn: Writing, Reviewing and Editing. A. Sheeladevi:
Writing, Reviewing and Editing. P. Priyadharsini: Investigation, Writing -
Original draft preparation. J. Arun: Supervision, Project administration.
Kathirvel Brindhadevi: Writing, Reviewing and Editing. Nguyen Thuy
Lan Chi: Writing, Reviewing and Editing. Arivalagan Pugazhendhi: Su-
pervision, Project administration.
N. Nirmala et al.
Declaration of competing interest
The authors declare that they have no known competing financial inter-
ests or personal relationships that could have appeared to influence the
work reported in this paper.
Acknowledgement
Author wish to thank Sathyabama Institute of Science and Technology
for support. Authors wish to thank freepik for source of diagrams. The
authors would like to thank Van Lang University, Vietnam for funding this
work.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2022.156564.
References
Abu-Nada, A., McKay, G., Abdala, A., 2020. Recent advances in applications of hybrid
graphene materials for metals removal from wastewater. Nanomaterials 10, 595.
Aghaei, E., Alorro, R.D., Tadesse, B., Browner, R., 2019. A review on current practices and
emerging technologies for sustainable management, sequestration and stabilization of
mercury from gold processing streams. J. Environ. Manag. 249, 109367.
Ahmad, S.Z.N., Salleh, W.N.W., Ismail, A.F., Yusof, N., Yusop, M.Z.M., Aziz, F., 2020. Adsorp-
tive removal of heavy metal ions using graphene-based nanomaterials: toxicity, roles of
functional groups and mechanisms. Chemosphere 248, 126008.
Ajiboye, T.O., Oyewo, O.A., Onwudiwe, D.C., 2020. Simultaneous removal of organics and
heavy metals from industrial wastewater: a review. Chemosphere 128379.
Al-Ghouti, M.A., Daana, D.A., 2020. Guidelines for the use and interpretation of adsorption
isotherm models: a review. J. Hazard. Mater. 393, 122383. https://doi.org/10.1016/j.
jhazmat.2020.122383.
Ali, I., Mbianda, X.Y., Burakov, A., Galunin, E., Burakova, I., Mkrtchyan, E., Tkachev, A.,
Grachev, V., 2019. Graphene based adsorbents for remediation of noxious pollutants
from wastewater. Environ. Int. 127, 160–180.
Baby, R., Saifullah, B., Hussein, M.Z., 2019. Carbon nanomaterials for the treatment of heavy
metal-contaminated water and environmental remediation. Nanoscale Res. Lett. 14, 341.
Bhunia, P., Kim, G., Baik, C., Lee, H., 2012. A strategically designed porous iron–iron oxide
matrix on graphene for heavy metal adsorption. Chem. Commun. https://doi.org/10.
1039/c2cc35120j.
Chakrapani, C., Babu, C.S., Vani, K.N.K., Rao, K.S., 2010. Adsorption kinetics for the removal
of fluoride from aqueous solution by activated carbon adsorbents derived from the peels
of selected citrus fruits. E-J.Chem. https://doi.org/10.1155/2010/582150.
Chandra, V., Kim, K.S., 2011. Highly selective adsorption of Hg2+ by a polypyrrole–
reduced graphene oxide composite. Chem. Commun. https://doi.org/10.1039/
c1cc00005e.
Chang, C.F., Truong, Q.D., Chen, J.R., 2013. Graphene sheets synthesized by ionic-liquid-
assisted electrolysis for application in water purification. Appl. Surf. Sci. https://doi.
org/10.1016/j.apsusc.2012.10.022.
Chaste, J., Saadani, A., Jaffre, A., Madouri, A., Alvarez, J., Pierucci, D., Aziza, Z.Ben, Ouerghi,
A., 2017. Nanostructures in suspended mono-and bilayer epitaxial graphene. Carbon N.
Y. 125, 162–167.
Chen, J., Yao, B., Li, C., Shi, G., 2013. An improved hummers method for eco-friendly synthe-
sis of graphene oxide. Carbon N. Y. 64, 225–229.
Chen, J.H., Xing, H.T., Sun, X., Su, Z.B., Huang, Y.H., Weng, W., Hu, S.R., Guo, H.X., Wu, W.B.,
He, Y.S., 2015. Highly effective removal of Cu(II) by triethylenetetramine-magnetic re-
duced graphene oxide composite. Appl. Surf. Sci. https://doi.org/10.1016/j.apsusc.
2015.08.076.
Chen, M.L., Sun, Y., Huo, C.B., Liu, C., Wang, J.H., 2015. Akaganeite decorated graphene
oxide composite for arsenic adsorption/removal and its proconcentration at ultra-trace
level. Chemosphere. https://doi.org/10.1016/j.chemosphere.2015.02.046.
Chen, X., Zhou, S., Zhang, L., You, T., Xu, F., 2016. Adsorption of heavy metals by graphene
oxide/cellulose hydrogel prepared from NaOH/urea aqueous solution. Materials (Basel).
https://doi.org/10.3390/MA9070582.
Chen, Z., Wei, D., Li, Q., Wang, Xiangxue, Yu, S., Liu, L., Liu, B., Xie, S., Wang, J., Chen, D.,
Hayat, T., Wang, Xiangke, 2018. Macroscopic and microscopic investigation of Cr(VI) im-
mobilization by nanoscaled zero-valent iron supported zeolite MCM-41 via batch, visual,
XPS and EXAFS techniques. J. Clean. Prod. https://doi.org/10.1016/j.jclepro.2018.01.
231.
Ci, L., Song, L., Jariwala, D., Elias, A.L., Gao, W., Terrones, M., Ajayan, P.M., 2009. Graphene
shape control by multistage cutting and transfer. Adv. Mater. 21, 4487–4491.
Cui, L., Guo, X., Wei, Q., Wang, Y., Gao, L., Yan, L., Yan, T., Du, B., 2015. Removal of mercury
and methylene blue from aqueous solution by xanthate functionalized magnetic
graphene oxide: sorption kinetic and uptake mechanism. J. Colloid Interface Sci.
https://doi.org/10.1016/j.jcis.2014.10.019.
Fang, Q., Zhou, X., Deng, W., Liu, Z., 2017. Hydroxyl-containing organic molecule induced self-
assembly of porous graphene monoliths with high structural stability and recycle perfor-
mance for heavy metal removal. Chem. Eng. J. https://doi.org/10.1016/j.cej.2016.09.139.
9
Science of the Total Environment 840 (2022) 156564
Gao, Y., Chen, K., Ren, X., Alsaedi, A., Hayat, T., Chen, C., 2018a. Exploring the aggregation
mechanism of graphene oxide in the presence of radioactive elements: experimental and
theoretical studies. Environ. Sci. Technol. https://doi.org/10.1021/acs.est.8b02234.
Gao, Y., Ren, X., Wu, J., Hayat, T., Alsaedi, A., Cheng, C., Chen, C., 2018. Graphene oxide in-
teractions with co-existing heavy metal cations: adsorption, colloidal properties and joint
toxicity. Environ. Sci. Nano. https://doi.org/10.1039/c7en01012e.
Guo, D., Shi, Q., He, B., Yuan, X., 2011. Different solvents for the regeneration of the
exhausted activated carbon used in the treatment of coking wastewater. J. Hazard.
Mater. https://doi.org/10.1016/j.jhazmat.2010.12.068.
He, Y.Q., Zhang, N.N., Wang, X.D., 2011. Adsorption of graphene oxide/chitosan porous
materials for metal ions. Chin.Chem. Lett. https://doi.org/10.1016/j.cclet.2010.12.
049.
Jiao, C., Xiong, J., Tao, J., Xu, S., Zhang, D., Lin, H., Chen, Y., 2016. Sodium alginate/
graphene oxide aerogel with enhanced strength-toughness and its heavy metal adsorp-
tion study. Int. J. Biol. Macromol. https://doi.org/10.1016/j.ijbiomac.2015.11.061.
Joseph, L., Jun, B.-M., Flora, J.R.V., Park, C.M., Yoon, Y., 2019. Removal of heavy metals from
water sources in the developing world using low-cost materials: a review. Chemosphere
229, 142–159.
Kang, B.K., Lim, B.S., Yoon, Y., Kwag, S.H., Park, W.K., Song, Y.H., Yang, W.S., Ahn, Y.T.,
Kang, J.W., Yoon, D.H., 2017. Efficient removal of arsenic by strategically designed and
layer-by-layer assembled PS@+rGO@GO@Fe3O4 composites. J. Environ. Manag.
https://doi.org/10.1016/j.jenvman.2017.05.066.
Kostelli, G., Kourea, K., Ikonomidis, I., 2020. Effects of combustible tobacco smoking and
novel tobacco products on oxidative stress: different sides of the same coin? Curr. Opin.
Toxicol. 20-21, 41–47. https://doi.org/10.1016/j.cotox.2020.05.001.
Kumar, A.S.K., Kakan, S.S., Rajesh, N., 2013. A novel amine impregnated graphene oxide ad-
sorbent for the removal of hexavalent chromium. Chem. Eng. J. https://doi.org/10.
1016/j.cej.2013.06.089.
Kumar, M., Chung, J.S., Hur, S.H., 2019. Graphene composites for lead ions removal from
aqueous solutions. Appl. Sci. 9, 2925.
Kumar, V., Parihar, R.D., Sharma, A., Bakshi, P., Sidhu, G.P.S., Bali, A.S., Karaouzas, I.,
Bhardwaj, R., Thukral, A.K., Gyasi-Agyei, Y., 2019. Global evaluation of heavy metal con-
tent in surface water bodies: a meta-analysis using heavy metal pollution indices and mul-
tivariate statistical analyses. Chemosphere 236, 124364.
Lai, K.C., Lee, L.Y., Hiew, B.Y.Z., Thangalazhy-Gopakumar, S., Gan, S., 2019. Environmental
application of three-dimensional graphene materials as adsorbents for dyes and heavy
metals: review on ice-templating method and adsorption mechanisms. J. Environ. Sci.
(China). https://doi.org/10.1016/j.jes.2018.11.023.
Lee, Y.C., Yang, J.W., 2012. Self-assembled flower-like TiO 2 on exfoliated graphite
oxide for heavy metal removal. J. Ind. Eng. Chem. https://doi.org/10.1016/j.jiec.
2012.01.005.
Leng, Y., Guo, W., Su, S., Yi, C., Xing, L., 2012. Removal of antimony(III) from aqueous solution
by graphene as an adsorbent. Chem. Eng. J. https://doi.org/10.1016/j.cej.2012.09.078.
Levin, R., Vieira, C.L.Z., Mordarski, D.C., Rosenbaum, M.H., 2020. Lead seasonality in
humans, animals, and the natural environment. Environ. Res. 180, 108797.
Li, S., Lu, X., Xue, Y., Lei, J., Zheng, T., Wang, C., 2012. Fabrication of polypyrrole/graphene
oxide composite nanosheets and their applications for Cr(VI) removal in aqueous solu-
tion. PLoS One https://doi.org/10.1371/journal.pone.0043328.
Li, J., Wang, Xiangxue, Zhao, G., Chen, C., Chai, Z., Alsaedi, A., Hayat, T., Wang, Xiangke,
2018. Metal–organic framework-based materials: superior adsorbents for the capture of
toxic and radioactive metal ions. Chem. Soc. Rev. 47, 2322–2356.
Lim, J.Y., Mubarak, N.M., Abdullah, E.C., Nizamuddin, S., Khalid, M., 2018. Recent trends in
the synthesis of graphene and graphene oxide based nanomaterials for removal of heavy
metals—a review. J. Ind. Eng. Chem. 66, 29–44.
Liu, H., Qiu, H., 2020. Recent advances of 3D graphene-based adsorbents for sample prepara-
tion of water pollutants: a review. Chem. Eng. J. 393, 124691. https://doi.org/10.1016/j.
cej.2020.124691.
Liu, L., Liu, S., Zhang, Q., Li, C., Bao, C., Liu, X., Xiao, P., 2013. Adsorption of Au(III), Pd(II),
and Pt(IV) from aqueous solution onto graphene oxide. J. Chem. Eng. Data. https://doi.
org/10.1021/je300551c.
Liu, J., Ge, X., Ye, X., Wang, G., Zhang, H., Zhou, H., Zhang, Y., Zhao, H., 2016. 3D graphene/
δ-MnO2 aerogels for highly efficient and reversible removal of heavy metal ions.
J. Mater. Chem. A. https://doi.org/10.1039/c5ta08106h.
Liu, X., Ma, R., Wang, Xiangxue, Ma, Y., Yang, Y., Zhuang, L., Zhang, S., Jehan, R., Chen, J.,
Wang, Xiangke, 2019. Graphene oxide-based materials for efficient removal of heavy
metal ions from aqueous solution: a review. Environ. Pollut. 252, 62–73. https://doi.
org/10.1016/j.envpol.2019.05.050.
Ma, J., Ullah, S., Niu, A., Liao, Z., Qin, Q., Xu, S., Lin, C., 2020. Heavy metal pollution in-
creases CH4 and decreases CO2 emissions due to soil microbial changes in a mangrove
wetland: microcosm experiment and field examination. Chemosphere 128735.
Madadrang, C.J., Kim, H.Y., Gao, G., Wang, N., Zhu, J., Feng, H., Gorring, M., Kasner, M.L.,
Hou, S., 2012. Adsorption behavior of EDTA-graphene oxide for Pb (II) removal. ACS
Appl. Mater. Interfaces. https://doi.org/10.1021/am201645g.
Mahmoud, M.E., Osman, M.M., Hafez, O.F., Elmelegy, E., 2010. Removal and
preconcentration of lead (II), copper (II), chromium (III) and iron (III) from wastewaters
by surface developed alumina adsorbents with immobilized 1-nitroso-2-naphthol.
J. Hazard. Mater. 173, 349–357.
Mi, X., Huang, G., Xie, W., Wang, W., Liu, Y., Gao, J., 2012. Preparation of graphene oxide
aerogel and its adsorption for Cu 2+ ions. Carbon N. Y. https://doi.org/10.1016/j.car-
bon.2012.06.013.
Nizamuddin, S., Siddiqui, M.T.H., Mubarak, N.M., Baloch, H.A., Abdullah, E.C., Mazari, S.A.,
Griffin, G.J., Srinivasan, M.P., Tanksale, A., 2018. Iron oxide nanomaterials for the re-
moval of heavy metals and dyes from wastewater. Nanoscale Materials in Water Purifica-
tion. https://doi.org/10.1016/B978-0-12-813926-4.00023-9.
Peng, W., Li, H., Liu, Y., Song, S., 2017. A review on heavy metal ions adsorption from water
by graphene oxide and its composites. J. Mol. Liq. 230, 496–504.
N. Nirmala et al.
Sahu, O., Singh, N., 2018. Significance of bioadsorption process on textile industry wastewa-
ter. The Impact and Prospects of Green Chemistry for Textile Technology. https://doi.
org/10.1016/B978-0-08-102491-1.00013-7.
Shukla, S.R., Pai, R.S., Shendarkar, A.D., 2006. Adsorption of Ni (II), Zn (II) and Fe (II) on
modified coir fibres. Sep. Purif. Technol. 47, 141–147.
Somani, P.R., Somani, S.P., Umeno, M., 2006. Planer nano-graphenes from camphor by CVD.
Chem. Phys. Lett. 430, 56–59.
Sreeprasad, T.S., Maliyekkal, S.M., Lisha, K.P., Pradeep, T., 2011. Reduced graphene oxide-
metal/metal oxide composites: facile synthesis and application in water purification.
J. Hazard. Mater. https://doi.org/10.1016/j.jhazmat.2010.11.100.
Staudenmaier, L., 1898. Verfahren zur darstellung der graphitsäure. Berichte der Dtsch.
Chem. Gesellschaft 31, 1481–1487.
Tetlow, H., De Boer, J.P., Ford, I.J., Vvedensky, D.D., Coraux, J., Kantorovich, L., 2014.
Growth of epitaxial graphene: theory and experiment. Phys. Rep. 542, 195–295.
Tsibranska, I., Hristova, E., 2010. Modelling of heavy metal adsorption into activated carbon
from apricot stones in fluidized bed. Chem. Eng. Process. Process Intensif. https://doi.
org/10.1016/j.cep.2010.08.003.
Vu, H.C., Dwivedi, A.D., Le, T.T., Seo, S.H., Kim, E.J., Chang, Y.S., 2017. Magnetite graphene
oxide encapsulated in alginate beads for enhanced adsorption of Cr(VI) and As(V) from
aqueous solutions: role of crosslinking metal cations in pH control. Chem. Eng. J.
https://doi.org/10.1016/j.cej.2016.08.058.
Wang, S., Peng, Y., 2010. Natural zeolites as effective adsorbents in water and wastewater
treatment. Chem. Eng. J. https://doi.org/10.1016/j.cej.2009.10.029.
Wang, J., Zhuang, S., 2017. Removal of various pollutants from water and wastewater by
modified chitosan adsorbents. Crit. Rev. Environ. Sci. Technol. https://doi.org/10.
1080/10643389.2017.1421845.
Wang, H., Yuan, X., Wu, Y., Huang, H., Zeng, G., Liu, Y., Wang, X., Lin, N., Qi, Y., 2013. Ad-
sorption characteristics and behaviors of graphene oxide for Zn(II) removal from aqueous
solution. Appl. Surf. Sci. https://doi.org/10.1016/j.apsusc.2013.04.133.
Wang, Q., Wang, X., Chai, Z., Hu, W., 2013. Low-temperature plasma synthesis of carbon
nanotubes and graphene based materials and their fuel cell applications. Chem. Soc.
Rev. 42, 8821–8834.
Wang, Y., Liu, X., Wang, H., Xia, G., Huang, W., Song, R., 2014. Microporous spongy chitosan
monoliths doped with graphene oxide as highly effective adsorbent for methyl orange
and copper nitrate (Cu(NO3)2) ions. J. Colloid Interface Sci. https://doi.org/10.1016/j.
jcis.2013.11.012.
Wang, Xiangxue, Liu, Y., Pang, H., Yu, S., Ai, Y., Ma, X., Song, G., Hayat, T., Alsaedi, A., Wang,
Xiangke, 2018. Effect of graphene oxide surface modification on the elimination of Co(II)
from aqueous solutions. Chem. Eng. J. https://doi.org/10.1016/j.cej.2018.03.107.
Wang, B., Gao, B., Wan, Y., 2019. Comparative study of calcium alginate, ball-milled biochar,
and their composites on aqueous methylene blue adsorption. Environ. Sci. Pollut. Res.
https://doi.org/10.1007/s11356-018-1497-1.
Wang, Y., Li, A., Cui, C., 2020. Remediation of heavy metal-contaminated soils by electroki-
netic technology: mechanisms and applicability. Chemosphere 129071.
WooáLee, J., BináKim, S., et al., 2011. Enhanced Cr (VI) removal using iron nanoparticle dec-
orated graphene. Nanoscale 3, 3583–3585.
10
Science of the Total Environment 840 (2022) 156564
Wu, H., Liu, C., Dai, Y., 2013. Adaptive pattern nulling design of linear array antenna by phase
perturbations using invasive weed optimization algorithm. 2013 IEEE 3rd International
Conference on Information Science and Technology, ICIST 2013. https://doi.org/10.
1109/ICIST.2013.6747792.
Wu, T., Mao, L., Wang, H., 2017. Adsorption of fluoride from aqueous solution by using hy-
brid adsorbent fabricated with Mg/Fe composite oxide and alginate via a facile method.
J. Fluor. Chem. https://doi.org/10.1016/j.jfluchem.2017.05.005.
Yang, X., Chen, C., Li, J., Zhao, G., Ren, X., Wang, X., 2012. Graphene oxide-iron oxide and
reduced graphene oxide-iron oxide hybrid materials for the removal of organic and inor-
ganic pollutants. RSC Adv. https://doi.org/10.1039/c2ra20885g.
Yang, J., Hou, B., Wang, J., Tian, B., Bi, J., Wang, N., Li, X., Huang, X., 2019. Nanomaterials
for the removal of heavy metals from wastewater. Nanomaterials 9, 424.
Ye, S., Chen, Y., Yao, X., Zhang, J., 2020. Simultaneous removal of organic pollutants and
heavy metals in wastewater by photoelectrocatalysis: a review. Chemosphere 128503.
Yu, R., Shi, Y., Yang, D., Liu, Y., Qu, J., Yu, Z.Z., 2017. Graphene oxide/chitosan aerogel mi-
crospheres with honeycomb-cobweb and radially oriented microchannel structures for
broad-Spectrum and rapid adsorption of water contaminants. ACS Appl. Mater. Inter-
faces. https://doi.org/10.1021/acsami.7b04655.
Yuan, X., Wang, Y., Wang, J., Zhou, C., Tang, Q., Rao, X., 2013. Calcined graphene/MgAl-
layered double hydroxides for enhanced Cr(VI) removal. Chem. Eng. J. https://doi.org/
10.1016/j.cej.2013.01.090.
Zhang, Y., Liu, Y., Wang, X., Sun, Z., Ma, J., Wu, T., Xing, F., Gao, J., 2014. Porous graphene
oxide/carboxymethyl cellulose monoliths, with high metal ion adsorption. Carbohydr.
Polym. https://doi.org/10.1016/j.carbpol.2013.09.066.
Zhang, Q., Hou, Q., Huang, G., Fan, Q., 2020. Removal of heavy metals in aquatic environ-
ment by graphene oxide composites: a review. Environ. Sci. Pollut. Res. 1–20.
Zhao, G., Jiang, L., He, Y., Li, J., Dong, H., Wang, X., Hu, W., 2011a. Sulfonated graphene for
persistent aromatic pollutant management. Adv. Mater. https://doi.org/10.1002/adma.
201101007.
Zhao, G., Li, J., Wang, X., 2011b. Kinetic and thermodynamic study of 1-naphthol adsorption
from aqueous solution to sulfonated graphene nanosheets. Chem. Eng. J. https://doi.org/
10.1016/j.cej.2011.07.072.
Zhao, G., Ren, X., Gao, X., Tan, X., Li, J., Chen, C., Huang, Y., Wang, X., 2011. Removal of Pb
(ii) ions from aqueous solutions on few-layered graphene oxide nanosheets. Dalt. Trans.
https://doi.org/10.1039/c1dt11005e.
Zhao, D., Gao, X., Wu, C., Xie, R., Feng, S., Chen, C., 2016. Facile preparation of amino func-
tionalized graphene oxide decorated with Fe 3 O 4 nanoparticles for the adsorption of Cr
(VI). Appl. Surf. Sci. https://doi.org/10.1016/j.apsusc.2016.05.022.
Zhao, G., Huang, X., Tang, Z., Huang, Q., Niu, F., Wang, X., 2018. Polymer-based nanocom-
posites for heavy metal ions removal from aqueous solution: a review. Polym. Chem.
https://doi.org/10.1039/c8py00484f.
Zong, E., Wei, D., Wan, H., Zheng, S., Xu, Z., Zhu, D., 2013. Adsorptive removal of phosphate
ions from aqueous solution using zirconia-functionalized graphite oxide. Chem. Eng. J.
https://doi.org/10.1016/j.cej.2013.01.088.