Applied Surface Science Advances 16 (2023) 100431

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Applied Surface Science Advances

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Carbon nanotubes and graphene-based materials for adsorptive removal of

metal ions – A review on surface functionalization and related
adsorption mechanism
R. Hari Krishna a, b, *, M.N. Chandraprabha b, c, **, K Samrat c, T P Krishna Murthy c,
C Manjunatha d, S. Girish Kumar d, ***
a
Department of Chemistry, M. S. Ramaiah Institute of Technology, Bengaluru-560054, Karnataka, INDIA
b
Center for Bio and Energy Materials Innovation, M. S. Ramaiah Institute of Technology, Bengaluru-560054, Karnataka, India
c
Department of Biotechnology, M. S. Ramaiah Institute of Technology, Bengaluru-560054, Karnataka, India
d
Centre for Nanomaterials and Devices, Department of Chemistry, RV College of Engineering, Bengaluru 560059, Karnataka, India

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

Keywords: Enhanced use of heavy metals for commercial and non-commercial applications has resulted in industrial and
Carbon nanotubes domestic discharge loaded with toxic metal ions creating increased environmental concern. Owing to the wide
Heavy metal array of heavy metals that can be effectively removed, relatively low cost and economical process conditions,
Adsorption
removal of heavy metals by adsorption has attracted the scientific community over years. Search for novel ad­
Functionalization
sorbents which are cost-effective with higher adsorption affinity and reusability has been an area of active
research. Carbon based adsorbents, which offer enhanced surface area, higher surface to volume ratio and ease of
surface functionalization, have proven to be more effective than conventional adsorbents for removal of both
inorganic and organic contaminants. Among the various carbon based adsorbents, carbon nanotubes, graphene
and modified graphene oxide composites are gaining increasing importance as effective adsorbents for heavy
metal removal from waste waters. This paper presents a comprehensive review on use of these adsorbents for
adsorptive removal of various heavy metals. Optimal conditions for maximum removal of various metal ions are
highlighted. Case studies on approach to surface functionalization of adsorbents and the mechanism of metal ion
removal by the functionalized surface are discussed for practical application.

1. Introduction demographic trends show a continuous growth of the world population

Environment pollution has been very well perceived by the scientific
community around the world and delivering clean water, food, and
renewable energy is a major challenge in the present [1]. Water is an
extremely important resource required to sustain and develop the life on
this planet Earth [2]. Its unique physicochemical properties play a
central role in biochemical metabolism of living organisms [3].
Approximately, 1.4 billion km3 water is abundantly available on earth’s
surface but more than 97% of this water is stored in oceans, polar ice
caps and glaciers. A mere 1% of water resource on the Earth is available
or accessible as freshwater for consumption from lakes, rivers, ponds,
and wells [4]. Even if is slower than in the last decades the present
with expectations to reach 9.8 billion by 2050 [5,6]. The expected in­
crease in global population associated with rapid urbanization, indus­
trialization, and climatic changes will significantly impact the quality of
natural water source directly or indirectly [7]. We are currently in the
“Pollutant Removal Age,” and the treatment of wastewater has
expanded from an optional and voluntary approach into an essential
multistage operation applied to improve the quality of both potable
water and those released in the environment substantially. Strict regu­
lations for permissible limits of contaminants in discharged effluent
resulting in increased disposal costs has necessitated the need to search
for economical methods of treatment [8,9].
The pollutants are commonly classified as physical, chemical,

* Corresponding author at: Department of Chemistry, M S Ramaiah Institute of Technology, Bengaluru-560054, Karnataka, India.
** Corresponding author at: Department of Biotechnology, M S Ramaiah Institute of Technology, Bengaluru-560054, Karnataka, India.
*** Corresponding author at: Department of Chemistry, RV College of Engineering, Bengaluru-560059, Karnataka, India.
E-mail addresses: rhk.chem@gmail.com (R.H. Krishna), chandraprabhamn@yahoo.co.in (M.N. Chandraprabha), girichem@yahoo.co.in (S.G. Kumar).

https://doi.org/10.1016/j.apsadv.2023.100431
Received 30 January 2023; Received in revised form 10 June 2023; Accepted 17 June 2023
Available online 29 June 2023
2666-5239/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
R.H. Krishna et al.
Table 1
Sources, limits, and toxicity of selected heavy metals [4,18,20,22–25]
Heavy Sources
Metal/metal
ions
Lead (Pb(II)) Coal combustion,
plumbing fixtures, cable
coverings, ceramic,
glass, batteries,
electroplating, paints
and pigments, mining,
jewelry
Cadmium Electroplating,
(Cd(II)) photographic and
engraving process,
metal smelting, paints,
pigments, batteries,
plastics, synthetic
rubber,
photoconductors and
photovoltaic cells,
fertilizer, mining,
pesticide, refining,
welding
Chromium Dyeing, textile, paints
(Cr(III) or production, leather
(Cr(VI)) industry, tanning,
electroplating, steel
fabrication,
Arsenic (As Volcanic activities,
(III) or As atmospheric deposition,
(V)) rock sedimentation,
smelting, dyes, paints,
drugs, pesticides,
fertilizers, the release of
untreated effluents,
groundwater
contamination
oxidation of pyrite (FeS)
and arsenopyrite
(FeAsS)
Mercury (Hg Volcanic and
(II)) geothermal activities,
coal combustion,
mining operations,
municipal solid waste
incineration, and
batteries, paint
industries, paper
industry, tanning and
electroplating industries
WHO Health impact
Limits
(mg/L)
0.05 Insomnia, anorexia,
chronic nephropathy, high
blood pressure,
hypertension, learning
deficits, affects the liver,
kidneys, central nervous
system, and
gastrointestinal tract,
reduced fertility, exposure
to high concentration
causes hypertension,
infertility, arthralgia and
coma, shortened attention
span, risk factor for
Alzheimer’s disease,
0.005 Osteomalacia,
osteoporosis, and
hyperuricemia,
emphysema, headache,
coughing, itai–itai, kidney
diseases, lymphocytosis,
microcytic hypochromic
anemia, lung and prostate
cancer, testicular atrophy,
vomiting,
neurodegenerative
diseases, renal toxicity,
hypertension, microcytic
hypochromic anemia,
lymphocytosis, weight loss,
fatigue, pulmonary fibrosis,
peripheral neuropathy,
atherosclerosis.
0.05 Bronchopneumonia,
chronic bronchitis, lung
cancer, dermatitis, skin
ulcers, reproductive
toxicity, embryotoxicity,
mutagenicity,
teratogenicity,
carcinogenicity,
perforation of septum and
irritant contact dermatitis,
diarrhea, vomiting,
emphysema, headache,
liver diseases, lung cancer,
nausea, renal failure
0.05 Effects peripheral nervous
system (PNS), central
nervous system (CNS),
gastrointestinal tract (GI),
cardiovascular, pulmonary
diseases, genitourinary
(GU), hemopoietic,
dermatologic, fetal and
teratogenic diseases,
anorexia, brown
pigmentation, hyper-
pigmentation, localized
edema, severe arsenicosis,
nausea and cancer of liver,
skin, lung, bladder and
kidney.
0.001 Minamata disease,
acrodynia, ataxia, impaired
neurologic development,
reduced immunity, loss of
memory, gastrointestinal
irritation, effects on
kidneys, lungs, skin and
eyes, increases salivation,
hypotonia, hypertension,
decrease rate of fertility,
2
Applied Surface Science Advances 16 (2023) 100431
biological and radiological pollutants. Physical pollutants, such as sed­
iments or suspended materials, majorly influence the physical properties
and appearance of the water. Chemical pollutants include man-made or
naturally occurring organic and inorganic chemicals. Biological pollut­
ants include viruses, bacteria, parasites and algae. Elements with un­
stable atoms that emit ionizing radiations (e.g. plutonium, caesium and
uranium) are grouped under radiological pollutants.
The major organic pollutants in water consist of organic dyes, per­
sonal care products, pharmaceuticals, pesticides, endocrine disruptors,
detergents, and common industrial organic wastes like halogenated
hydrocarbons and their derivatives, aromatics and phenolics. The
inorganic pollutants are majorly heavy metals such as lead, cadmium,
chromium, mercury, arsenic, etc. [10].
2. Heavy metals and their toxicity
Heavy metals are inorganic elements and natural components of the
earth’s crust with density more than 4-5 g/cm3 [11,12]. Heavy metals
are broadly categorized as toxic metal ions [Hg(II), Pb(II), Zn(II), Cr(III)
or Cr(VI), Ni(II), Cu(II), As(III) or As(V), Co(II), Cd(II), Sn(II), etc.],
precious metal ions [Pt(II) or Pt(IV), Pd(II), Au(III), Ag(I), Ru(III), etc.]
and radionuclides [U(VI), Ra(II), Th(IV), Am(III), etc.] [13–15]. Based
on the toxicity, heavy metals are classified as non-essential and essential.
Non-essential heavy metal ions such as Cd(II), Hg(II), As(III) or As(V)
and Cr(III) or Cr(VI) possess high toxicity even at low concentration.
Contrarily, essential heavy metal ions such as Zn(II), Cu(II), Fe(II) or or
Fe(III), and Co(II) are less harmful at a lower concentration. These
essential heavy metals are also cofactors in many biological processes
such as cell growth, oxygen utilization, biomolecular synthesis, enzy­
matic reactions, immunity of the cell [16]. Some of the heavy metals
ions (e.g. Fe(II) or Fe(III), Mn(II), Cu(II), Ni(II), and Zn(II)) in trace
concentrations are required as nutrients for the life process in micro­
organisms and plants but become toxic at higher concentrations [2,17].
Increased industrial and technological developments is creating a
burden on the environment by discharging large quantities of hazardous
heavy metals [18]. The ubiquitous nature of heavy metals allows them
to enter the human body from different sources through various routes
which include oral ingestion, inhalation, and dermal exposure. Heavy
metals have deleterious effects on the environment and human health by
entering into the food chain [19]. Unlike other pollutant molecules,
heavy metals are excreted slowly through kidney, liver and spleen and
the longer storage leads to the damage of the organs by altering the
cellular functioning. Concentration of heavy metal above the critical
values leads to serious health issues. Continuous exposure of heavy
metal may decrease the activity of the central nervous system, alter the
blood composition and damage the liver, lungs, kidneys and other
fundamental organs [20,21]. Among several heavy metal ions, lead (Pb
(II)), cadmium (Cd(II)), chromium (Cr(III) or Cr(VI)) mercury (Hg(II))
and arsenic (As(III) or As(V)) are the possible causes for most of the
heavy metal-related diseases [20]. The impact of these heavy metals on
living organisms along with their sources and recommended permissible
limits in water according to the World Health Organization (WHO) are
presented in Table 1.
3. Methods of heavy metal removal
Over the past few decades, wastewater treatment methods for
providing safe and clean water became increasingly required because of
the stringent and fast-growing demand for clean water. This has made it
obligatory to reduce efficiently noxious heavy metals from industrial
effluents below permissible limits before releasing them into the
ecosystem [23]. Thus, a better understanding of water treatment tech­
niques which mainly aim to reduce water pollution problems is of
utmost importance [26]. To overcome this problem, it is essential to find
suitable and sustainable techniques for water treatment with low cost,
less energy consumption and high removal efficiency. Each technology
R.H. Krishna et al.
Table 2
Common techniques used in heavy metal ion removal [28,34–37]
Technique Advantages
Ion exchange • High regeneration of
materials
• Selective metal removal
• Rapid kinetics
• High removal efficiency
• High treatment capacity
Electrochemical • No consumption of
method chemicals
• Metal selective
• Pure metals can be
achieved
• High separation
selectivity
Chemical • Simple
precipitation • Economical
• Apply for broad range of
metals
• Simple operating
conditions
Flocculation and • Sludge produced with
chemical good sludge settling and
coagulation dewatering
characteristics
• Turbidly removal along
with removal of heavy
metal
Membrane filtration • High selective separation
and efficiency
• Requires lesser space
• Low pressure
requirement
• Less generation of solid
waste
• Less chemical
consumption
Flotation • High metal selectivity
and removal efficiency
• Low detention periods
• High overflow rates
• Low operating cost
• Production of more
concentrated sludge
Photocatalysis • Generates less harmful
by-products
• Simultaneously removes
inorganic and organic
pollutants
Adsorption • Low capital cost
• Ease of process operation
• High metal binding
capacities
• Effective in wide range of
pH
• Regeneration of the
adsorbent materials
• High efficiency
• Most of heavy metals can
be removed
may be suitable for certain conditions, such as the treatment standards,
operation objectives and economics in terms of capital and operating
requirements of the wastewater treatment process [27,28]. Ion ex­
change, electrochemical method, chemical precipitation, flocculation
and chemical coagulation, membrane filtration, flotation, photo­
catalysis, and adsorption are the commonly employed techniques in
heavy metal ion removal from wastewater [29–33]. The corresponding
Disadvantages
• Synthetic resins costly
• Serious secondary
pollution due to
regeneration of the resins
• Less number of metal ions
removed
• High initial investment
and operating costs
because of membrane
fouling and high energy
consumption
• Serious disposal problem
due to large amount of
sludge generation
• Additional operating cost
for sludge disposal
• Ineffective for water with
low concentration of
heavy metals
• High cost
• High expenditure of
chemicals
• Flocculation and chemical
coagulation must be
coupled with other
treatment techniques for
the complete removal of
heavy metals.
• Increased sludge volume
generation
• High operational cost due
to membrane fouling
• Complex Process
• Low flow rates and
permeate flux
• High initial and running
cost
• Presence of other metals
decreases the removal
decreases efficiency
• High initial capital cost
• High maintenance and
operation costs
• Long process time
• Limited applications
• Low selectivity (depends
on adsorbent material)
• High cost (depends on
adsorbent material)
• Regeneration is
sometimes difficult
• Performance depends
upon adsorbent
3
Applied Surface Science Advances 16 (2023) 100431
advantages and disadvantages of these methods are presented in
Table 2.
Despite acceptable heavy metal removal efficiencies and discharge
standards, most of the above mentioned techniques generate secondary
waste and require sophisticated equipment to carry out further treat­
ment process. Adsorption process has been considered to be a promising
substitute for the removal of toxic heavy metals from wastewater
because of its easy operation, flexibility and high ability to remove
heavy metals [23,38]. It also has low initial costs, relatively simple
design and operation of the treatment equipment and produces less
secondary pollutants. The availability of a wide range of adsorbents
including green materials as adsorbents makes this technique a better
choice for wastewater treatment [8,39–45]. Besides, most adsorption
processes are of reversible nature and due to this adsorbents can be
regenerated by appropriate desorption processes for multiple uses.
[46–48]. The adsorption process is based on mass transfer phenomena
through which a solid material can selectively eliminate dissolved pol­
lutants from solution by attracting the dissolved pollutants to its surface
[49]. As a mass/phase transfer process, adsorption is extensively used to
eliminate pollutants from fluid phases (liquids or gases). Adsorption is
generally defined as an enrichment of chemical species/pollutants on
the solid or a liquid surface from a fluid phase. In the remediation of
wastewater, adsorption has demonstrated as an effective technique for
the removal of a diverse group of pollutants. Active and energy-rich sites
present on the solid surfaces can interact with the solutes in the nearby
aqueous phase owing to their specific electronic and special properties
[50,51].
The basic terms used in adsorption process is presented in Fig. 1. The
solid substance that offers the surface during adsorption is called
adsorbent; the species/pollutant that will be adsorbed is termed as the
adsorbate. By varying the liquid phase properties such as pH, tempera­
ture, and concentration, the adsorbed species can be released from the
solid surface and transferred back into the liquid phase. This phenom­
enon is known as desorption. Since the adsorption is a surface phe­
nomenon, the porosity and surface area are critical properties of the
adsorbent [52]. The adsorption can be monolayer or multilayer. In
monolayer adsorption, a single layer of adsorbate molecules is adsorbed
on the surface of the adsorbent. The adsorbent surface is homogenous
and adsorption energy is uniform for all the sites. There is no further
interaction between the adsorbed molecules. In the second type of
adsorption, adsorbate molecules can interact with other layers of
adsorbate molecules already adsorbed on the surface (multilayer) and
the theoretical adsorption capacity of the adsorbent increases beyond
that of the limited active sites due to the heterogeneous surfaces.
Generally, chemisorption is a monolayer adsorption process while
physisorption is a multilayer adsorption process [50,51].
4. Adsorbents
In the industrial scale, the adsorption of heavy metals is affected by
many process parameters viz., mode of adsorption, adsorbent nature,
adsorbent dose, nature of wastewater (pollutant types, concentration,
etc.), effluent pH, temperature, time, etc [54]. Among these parameters,
to attain and sustain the desired water quality, a careful selection of
adsorbent is of supreme importance. Adsorbents used in the removal of
pollutants from wastewater are of natural origin or obtained through the
activation process. An ideal adsorbent utilized should possess the
following characteristics [27,54–56]:
1) Environmentally friendly: adsorbents having the lowest impact on
the environment, biodegradable and non-toxic
2) Low-cost: available abundantly from a natural source or synthetic
adsorbent with lesser preparation cost.
3) Satisfactory adsorption properties: High surface area, porous struc­
ture, high adsorption efficiency, rapid removal of pollutants, easy
recovery of pollutants from adsorbent, reusability, highly selective
R.H. Krishna et al.
Fig. 1. Basic terms of adsorption process. Figure reproduced with permission from [53]
Fig. 2. different geometry of CNTs – (a) unrolled graphene sheet showing SWCNT geometry, (b) zig-zag, (c) armchair and (d) chiral (Figure reproduced with
permission from [65].)
toward the pollutants in wastewater at lower concentrations,
industrial-scale use, mechanical strength.
5. Carbon based materials as adsorbents
Demand for novel materials that can overcome the limitations of
conventional adsorbents has led to increased application of carbon-
based materials (ex. carbon nanotubes, graphene and its composites,
fullerene etc) for adsorptive removal of organic and inorganic pollutants
[7,57,58]. These materials have an advantage of excellent physical and
chemical properties with high surface area resulting in good adsorption
capability. Their unique chemically reactive structure enabling easy
functionalization coupled with ease of synthesis by various routes has
resulted in use of these materials as new generation adsorbents for the
removal of various organic compounds (Ex. phenol, antibiotics, benzene
4
Applied Surface Science Advances 16 (2023) 100431
compounds, bisphenol A, aromatic dyes, etc) and heavy metal ions (Ex.
As(III) or As(V), Pb(II), Cu(II), Cr(III) or Cr(VI), Co(II), Cd(II), Hg(II), U
(VI), Eu(III), Sr(II), etc) [59,60]. The following paragraphs highlight the
application of carbon nanotubes and graphene-based materials for
adsorptive removal of metal ions.
5.1. Carbon nanotubes (CNTs)
Carbon nanotubes (CNTs) are allotropic forms of carbon with tubular
nano- architecture that are made of cylindrical graphene sheets
composed from carbon atoms arranged in hexagonal beehive pattern
[61]. It was first detected in 1952 by Radushkevish and Lukyanovich,
but in recent history, the discovery is ascribed to S. Iijima who obtained
multi-walled carbon nanotubes from carbon soot during the fabrication
of C60 carbon molecule by arc evaporation process [62–64]. The
R.H. Krishna et al.
Fig. 3. Structure of (A) SWCNT and (B) MWCNT (Figure reproduced with
permission from [66].)
thickness of CNTs is of about 1/50000th of human hair. Depending on
the geometry, CNTs exist in three forms such as chiral, zig-zag and
armchair (Fig. 2). Further, CNTs are classified into two types based on
the number of layers, as single-walled carbon nanotubes (SWCNTs) and
multi-walled carbon nanotubes (MWCNTs) (Fig. 3). The diameter of
SWCNTs is about 0.4 to < 3 nm, whereas in case of MWCNTs diameter
ranges from 1.4 to 100 nm.
Numerous methods have been developed to synthesize CNTs with
different morphology and structure. But most commonly used methods
are chemical vapour deposition (CVD), laser ablation and arc discharge.
The elements required for synthesis of CNTs are carbon source, sufficient
energy and catalyst. The feature of all above methods is to provide en­
ergy to the source of carbon leading to production of carbon fragments
which undergo recombination, generating of CNTs. The source of energy
might be electricity, heat or high-intensity light from arc discharge,
furnace used in CVD and laser (laser ablation), respectively [67].
Due to their superior optical activity, electrical conductivity, thermal
properties, mechanical strength and chemical reactivity [61], CNTs have
been used in numerous applications such as energy storage and con­
version devices [68], sensors [69], hydrogen storage media [70],
nanosized semiconductor devices [71], field emission displays [72] and
radiation sources [73], probes [74], drug delivery systems [75] and
artificial implants [76], high strength composites [77] etc.
Apart from this, CNTs have been used in wastewater treatment as
well as for drinking water purification due to enhanced adsorption,
catalytic and electrochemical properties combined with high mechani­
cal strength, high specific surface area, superior water transport prop­
erty and excellent chemical inertness. Various water treatment
applications of CNTs includes oil-water separation, water desalination,
removal of emerging pollutants such as persistent organic pollutants,
pharmaceutical products etc. and removal of heavy metals from
Fig. 4. Bar graph showing the number of articles in year wise in last decade appeared in Scopus data base for the keywords “Functionalized carbon nanotubes”,
“Modified carbon nanotubes” and “Functionalized carbon nanotubes+ Adsorption”.
5
Applied Surface Science Advances 16 (2023) 100431
wastewater [78].
CNTs have shown promise as adsorbents for adsorption of various
metal ions such as Co(II), Ni(II), Pb(II), Sr(II), Zn(II), Cu(II), Cr(VI) and
Cd(II) from wastewater of many industries such as battery industries,
metal plating facilities, chemical manufacturing and mining operation
[79–81]. In addition, CNTs are used as promising adsorbents in textile
industries for removal of synthetic dyes from wastewater [82].
Based on the target contaminants chemical nature and intended
application, various functional groups are introduced on CNT surfaces,
at sidewalls and at the tips to remove environmental contaminants
especially from wastewater effectively. Functionalization or modifica­
tion is carried out to improve the affinity of CNTs towards hydrophilic
ions or molecules. The statistical data obtained from scopus data base for
the different terms given in Fig. 4 shows that the recent trend and
increased interest among the researchers for the functionalized carbon
nanotubes.
CNTs are commonly functionalized through chemical oxidation, in
which oxygen containing functional groups are incorporated (e.g.,
-COOH, -C=O and –OH) resulting in CNTs affinity to heavy metal cations
[80,83,84]. Surface oxidation is usually carried out under reflux con­
dition using single or combination of inorganic acids (e.g., H2SO4 and
HNO3) and oxidizing agent (e.g., NaOCl, KMnO4 and H2O2) via liquid
phase oxidation method [85]. Datsyuk et al., [86] observed higher de­
gree of functionalization of MWCNTs in the presence HNO3 than
H2SO4-H2O2 mixture treatments. Further, microwave irradiation can
accelerate acid functionalization by irradiating for 20 to 40 min
[87–89].
To overcome the problems of low surface area and formation of
mesoporous structure by aggregation of CNTs resulting in structural
alternations, alkali activation of CNTs are carried out. In this method,
powder form of MWCNTs are mixed with KOH and heated to 750◦ C for 1
h, sparged with argon gas followed by washing with concentrated HCl,
deionized water and dried. The CNTs activated by alkali treatment were
successful in adsorbing both cationic and anionic dyes, as well as m-
xylene, ethylbenzene and toluene found in aqueous solutions [90,91].
Separation of spent adsorbents after contaminants or heavy metal
removal from aqueous solutions or remediation treatment is one of the
critical aspects in adsorption process. Tiny nanoparticles may be sepa­
rated using centrifugation or filtration from aqueous solution, but cost
and energy involvement is high. Thus, developing cost-effective tech­
nology by providing magnetic properties to adsorbents has significantly
gained importance [85]. Incorporation of magnetic properties to
MWCNTs is usually obtained by grafting magnetic iron oxide nano­
particles (magnetite (Fe3O4) or maghemite (γFe2O3)) via multistep
sol-gel process. The obtained MWCNTs will have increased affinity to­
wards anionic dye compounds and heavy metals [92,93]. Further, alkali
precipitation method are also used to achieve incorporation of magne­
tite (Fe3O4) nanoparticles on oxidized MWCNTs [94–97]. It was found
R.H. Krishna et al. Applied Surface Science Advances 16 (2023) 100431

Table 3
Adsorptive capacity of carbon nanotubes modified with supports and different functionalization materials.
Adsorbent Metal pH Specific surface area of Sorption References
ion adsorbent efficiency/
(m2/g) sorption capacity
(mg/g)

MWCNTs-KOH@NiNPs Pb(II) 5.5 1242 481 [125]

As(V) 440.9
Cd(II) 415.8
MWCNT-SH Pb(II) 5 144.9 — [126]
MWCNTs5-15 nm Pb(II) 5 215.38 ± 0.03 1306 ± 5 [127]
Ni(II) 230.78 ± 0.01
MWCNTs16-25 nm Pb(II) 5 201.35 ± 0.02 1245 ± 4
Ni(II) 206.40 ± 0.02
Polyethylene (PE) - Lignin (LG) - CNTs - Ni/Al2O3 Pb(II) 6 52.12 146.08 [128]
HNO3 oxidized: MWCNTs 3h/ Cd(II) 5 277 10.5 [129]
HNO3 oxidized: MWCNTs 6h Pb(II) 273 23.4
Chitosan-modified magnetic carbon nanotubes (CS/MWCNTs/ Cr(VI) 4.0 ± — 1.54 [130]
Fe) 0.2
KMnO4 oxidized and DES (from (C4H9)4N+Br− (TBAB) + Glycerol) functionalized MWCNTs Ni(II) 7 103.18 115.8 [131]
(KTMWCNT)
Fe3O4/MWCNTs- Cu(II) 7 — 9.5 [132]
COOH
Multi-walled carbon nanotubes (MWCNTs) As(V) 6 200 1250 [133]
Mn(VII) 192 1250
Carboxylated multi-walled As(V) 250 1172
carbon nanotubes (MWCNTs-OCH2CO2H) Mn(VII) 236 1172
Carbon nanotube/poly-amidoaminedendrimer composite As(III) 7 — 432 [117]
(PAMAM/CNT) Co(II) 494
Zn(II) 470
Multi-walled carbon nanotubes (MWCNTs) Cd(II) 8-9 66.624 43.103 [120]
Carboxylated multi-walled carbon nanotubes (MWCNTs-COOH) 166.2 212.766
3-aminopyrazolemodified multi-walled carbon nanotubes (MWCNTs-f) 7.312 400
Carbon nanotubes (CNTs) Pb(II) 7 169.7 23.6 [134]
Lignin grafted carbon nanotubes (L-CNTs) 91.8 235
poly-amidoamine/ carbon nanotube dendrimers (PAMAM/CNT) Pb(II) 7 — 4870 [115]
Cu(II) 3333
Polyamine/carbon nanotubes composite (polyamine/CNT) Pb(II) 6 18 ~ 99% [113]
KMnO4 oxidized and DES (from allyltriphenylphosphonium bromide (ATPB) + Glycerol) Hg(II) 5.5 199.366 186.97 [122]
functionalized MWCNTs (KA-CNTs)
KMnO4 oxidized and DES (from methyltriphenylphosphonium bromide (MTPB) + Glycerol) As(III) 3 205.500 23.4 [135]
functionalized MWCNTs (KM-CNTs)
KMnO4 oxidized and DES (from benzyltriphenylphosphonium chloride (MTPC) + Glycerol) 6 174.772 14.23
functionalized MWCNTs (KB-CNTs)
MWCNTs Pb(II) 5 206 104.2 [136]

Fe-inserted MWCNTs (FCNT) As(III) 6.5 74 1.224 [118]

HNO3 oxidized CNTs (FCNT-OX) 129 1.897
N2 annealed then HNO3 oxidized CNTs (FCNT-HOX) 169 5.995
Fe-inserted MWCNTs (FCNT) As(V) 74 0.8826
HNO3 oxidized CNTs (FCNT-OX) 129 2.515
N2 annealed then HNO3 oxidized CNTs (FCNT-HOX) 169 6.371
Thiolated multi-walled carbon nanotubes (MWCNTs-SH) Hg(II) 6 234.89 204.64 [137]
189.61 61.10
Cd(II)
Fe3O4-nonoxidative As(III) 7 — 9.11 [138]
graphene/CNT composite (M-G/C) As(V) 5.21
Multiwall carbon nanotubes/thorium oxide composite (MWCNTs/ThO2) Pb(II) 5.5 — 95.5% [139]
CNTs (by CVD from CH4) Hg(II) 5 — 91 [140]
HNO3 oxidized CNTs (CNTs-COOH) 150
WCNTs (by CVD from CH4+ H2O vapors) 104
HNO3 oxidized WCNTs (WCNTs-COOH) 200
HNO3 oxidized CNTs (M-CNT) Cd(II) 7 170 2.02 [121]
HNO3 oxidized activated carbon (M-AC) 1420 1.98
HNO3 oxidized carbon nanofibers (M-CNFs) 35.1 1.22
HNO3 oxidized fly ash (M-FA) 3.35 1.58
Alumina-decorated multi-walled carbon nanotubes (Al2O3/MWCNTs) Cd(II) 8 109.82 27.21 [141]
Manganese oxide/carbon nanotube composite (MnO2/CNT) Hg(II) 7 110.38 58.8 [142]
Multi-walled carbon nanotubes (CNTs) Hg(II) 6 85.1 5.479 [143]

HNO3 Oxidized MWCNTs (CNT-OX) 152.5 27.32

Iodide incorporated MWCNT (CNT-I) (from CNT-OX + KI) 153.0 123.45
Sulphur incorporated MWCNT (CNT-S) (from CNT-OX + CS2) 155.3 151.51
Dodecyl-benzene-sulfonic-acid doped polyaniline/multi-walled carbon nanotubes (DP/ Cr(VI) 2 —- 55.55 [144]
MWCNTs)
Multi-walled carbon nanotube–hydroxyapatite composite (MWCNT–HAP) Co(II) 6 —- 16.26 [145]
Sulphur containing multi-walled carbon nanotubes (S-MWCNTs) Hg(II) 8 —- 0.0728 [123]
(continued on next page)

6
R.H. Krishna et al. Applied Surface Science Advances 16 (2023) 100431

Table 3 (continued )
Adsorbent Metal pH Specific surface area of Sorption References
ion adsorbent efficiency/
(m2/g) sorption capacity
(mg/g)

Sulphur containing activated carbon (S-AC) 0.0447

Poly(acrylic acid) grafted multiwall carbon nanotubes Co(II) 6.8 — 9.78 [119]
(MWCNT-g-PAA)
magnetic multi-walled carbon nanotube / iron oxide composites (magnetic MWCNT/IO) Co(II) 6.4 — 10.61 [98]
HNO3 Oxidized MWCNTs (OMWCNTs) Pb(II) 8 197 4.37 [116]
OMWCNTs + TX-100 (octylphenolpolyethoxylate) 8.57
OMWCNTs + BKC (benzalkonium chloride) 3.27
OMWCNTs + SDBS (sodium dodecylbenzensulfonate) 66.95
HNO3 oxidized Carbon nanotube sheets (mats) Cu(II) 7 — 64.93 [146]
Zn(II) 74.63
Pb(II) 117.65
Cd(II) 92.59
Co(II) 85.74
Al2O3/MWCNT composites Pb(II) 7 — ~100% [147]
MWCNT/nano-iron oxide composite Cr(III) 6 92 88% [148]
Carbon-encapsulated magnetic nanoparticles (CEMPs) HNO3 soaked Cu(II) 8 118.7 3.21 [149]
MWCNTs HNO3 soaked (CNTs) Co(II) 8 75 2.77
Activated carbon HNO3 soaked (AC) Co(II) 415 0.46
Aligned carbon nanotubes supported ceria nanoparticles (CeO2/ACNTs) Cr(VI) 7 — 30.2 [150]

that magnetic nanoparticle – CNTs composite effectively removed heavy
metals [98], dye compounds [99], atrazine [100] and arsenic [101]
form wastewater.
CNTs are also functionalized with different non-magnetic metal ox­
ides such as ZrO2, TiO2, Fe3O4, CeO2, as well as bimetallic Pd/Fe-Fe3O4
to achieve higher affinity towards contaminants. The metal oxide-CNTs
hybrids successfully adsorbed toxic metal ions such as Cd(II), Fe(II) or Fe
(III), Cu(II) and As(III) or As(V) from water [88,89,101–106]. Modifi­
cation of CNTs with metal oxides is carried out by functionalization of
CNTs by chemical oxidation method followed by alkali precipitation of
metal oxides on nanotubes surface [88,89].
In recent years, modification of CNTs with nano-zero-valent iron
(nZVI) has been successfully achieved for application in adsorptive
removal of azo dyes [107], hexavalent chromium [108], nitrobenzene
[109] and selenite [110] from wastewater.
Apart from this, to improve the adsorption affinity towards specific
compound or element, CNTs are also functionalized or modified with
polymers of different types such as poly(propyleneimine)dendrimers
[111], poly(methyl methacrylate) [112], polyamine [113] and natural
biopolymers (e.g., guar gum) [114]. MWCNTs modified with polymers
were efficient in adsorbing single and multicomponent organic dye so­
lutions as well as heavy metals. Other CNTs functionalization or

Fig. 5. Mechanism of adsorption of metal ions by PAMAM/CNT nanocomposite (Figure reproduced with permission from [115].)

7
R.H. Krishna et al.
modification procedures include specific chemical derivatization, poly­
mers and coupling with other carbon based adsorbents (such as gra­
phene or biochars) [85].
In summary, CNTs have been explored for removal of various heavy
metal ions with modification by organic or inorganic groups. Adsorptive
capacity of carbon nanotubes modified with supports and different
functionalization materials is tabulated in table 3. CNTs modified with
poly(amidoamine) PAMAM dendrimer showed highest adsorption ca­
pacity of 4870 mg/g for Pb(II), while oxidized MWCNTs modified with
surfactant (benzalkonium) showed lowest adsorption capacity of 3.27
mg/g for Pb(II) [115,116]. Similarly, significantly high amount of As
(III) (432 mg/g) was adsorbed by CNTs modified with dendrimers while
poor adsorptive removal of 1.897 mg/g was exhibited by Fe-inserted
carbon nanotubes oxidized with nitric acid (FCNT-OX) [117,118]. In
case of adsorptive removal of Co(II), maximum capacity of adsorption
was observed in CNTs coated with poly(amidoamine) PAMAM den­
drimer (494 mg/g) while the lowest was obtained for bare CNTs (9.78
mg/g) [117,119]. Adsorption capacity of Cd(II) was highest in 3-amino­
pyrazole modified multi-walled carbon nanotubes (400 mg/g) and
lowest in unmodified CNTs (2.02 mg/g) [120,121]. In case of Hg(II), the
adsorptive capacity was highest for KMnO4 oxidized and Deep Eutectic
Solvent (DES) from Allyltriphenylphosphonium bromide (ATPB) -
Glycerol functionalized CNTs (186.97 mg/g) while Sulphur containing
multi-walled carbon nanotubes exhibited very poor adsorption (0.0728
mg/g) [122,123]. The adsorption of mercury onto sulphur containing
multi-walled carbon nanotubes was controlled due to chemisorption
process via Hg-S bond formation. Form the above results and literature
review it is clear that polymer and organic molecule modified CNTs are
more efficient in removal of heavy metals from aqueous solutions and
wastewater. The optimal pH for Pb(II), As(III), Co(II), Cd(II) and Hg(II)
removal is 5-7, 3-7, 6-7, 6-9 and 5-8, respectively for various modifi­
cation of CNTs. Hayatiet al., [115] reported that super adsorptive ca­
pacity of polymer (PAMAM dendrimer) modified CNTs is due to the high
surface area of composite and amino terminal groups leading to
adsorption of heavy metal ions by van der Waals, hydrogen, and elec­
trostatic force. The mechanism which plays an important role in removal
of Pb(II) and Cu(II) ions by PAMAM/CNT composite is based on van der
Waals, electrostatic, encapsulating and chelating interactions. Metal ion
encapsulation and chelating can be attributed to the transfer of charge of
ligand to the metal as well as coordination of metal ion with one or more
of the tertiary amine sites of the PAMAM’s as depicted in Fig. 5. In
addition to above, contaminants get encapsulated also due to the pres­
ence of nanopores in the composite sorbent structure [115,124].
5.2. Graphene based adsorbents
Graphene, owing to its advantages like availability from several
facile synthesis techniques, excellent mechanical, physical and chemical
properties, large surface area, possibility to form surface active sites
with ease of modification and functionalization, and characterized by
their delocalized π-electron systems has attracted immense attention as
an efficient adsorbent for removal of various contaminants like heavy
metals and complex organic pollutants like pharmaceuticals, dyes, an­
tibiotics etc. Graphene is a 2D material made of one atom thick layer of
hexagonally arranged sp2-hybridized carbon atoms with close-packed
honeycomb crystal lattice connected by σ and π bonds. It can be easily
modified by chemical reactions.
Graphene can be synthesized by bottom-up or top-down approaches.
Common bottom-up methods reported for the synthesis of graphene
include chemical vapour deposition, epitaxial growth while the top-
down methods used are mechanical and chemical (solution-assisted)
exfoliation of graphite. Top-down synthesis is considered most conve­
nient for large-scale production of graphene [151].
Graphene as an adsorptive material is used in various forms like
nanosheets, nanotubes, membranes, 3-D structures, hydrogels etc.
Graphene-based materials used for adsorptive removal of pollutants can
8
Applied Surface Science Advances 16 (2023) 100431
be broadly classified into two categories such as,
1 Graphene oxide (GO) and reduced graphene oxide (rGO)
2 Organic, inorganic, metallic and polymeric composites of GO and
rGO.
GO, which is obtained by chemical exfoliation of graphite, is an
oxidative form of graphene which contains a large number of oxygen
functional groups like hydroxyl, carbonyl, carboxyl, epoxy etc. [152].
Presence of these oxygen functional groups in the GO structure results in
increased interlayer separation compared to graphite. This leads to
changes in carbon hybridization resulting in a mixture of sp2 and sp3
hybridization in GO. The oxygen groups, due to their binding to inor­
ganic metal ions and organic molecules via electrostatic interaction and
coordination, makes GO an ideal adsorbent material for removal of
inorganic and organic pollutants [153].
Reduced GO (rGO) is obtained by chemical or thermal reduction of
GO resulting in removal of oxygen functional groups from GO. It has
properties similar to graphene, yet with altered structure, presenting
carbon vacancies and clustered pentagons and heptagons, as well as
some residual oxygenated groups [154,155]. Although GO has a
chemically reactive structure compared to rGO, the hydrophilic nature
of GO can lead to poor adsorption capability and difficulty in its removal
from the solution. Reduced GO is therefore explored extensively for
adsorption applications.
Selective and enhanced adsorption by graphene based materials
have been reported to be enhanced by suitable chemical modification
and functionalization of GO and rGO [156]. The widely utilized func­
tionalized graphene-based materials are organic, inorganic, metallic and
polymeric composites of GO and rGO. Some of the reported synthetic
routes of these composites include hydrothermal, co-precipitation, solid
state dispersion, solution combustion etc. Some of the functionalization
strategies include use of inorganic materials, organic molecules, metal
organic frameworks, polymers, zeolites and combinations of these.
Inorganic materials for functionalization of graphene include various
metals, metal oxides, ceramic materials. Magnetic inorganic materials
are most commonly considered due to their ease of separation after
adsorption. Nanoscale inorganic materials with enhanced magnetic
properties and catalytic adsorption have been used to obtain GO com­
posites with excellent adsorption capacity. Extensive studies have been
reported on Fe3O4 impregnated GO and rGO sheets for sustainable and
efficient removal of several metal ions [157]. Other inorganic materials
considered are MnO2, SiO2, TiO2, layered double hydroxides, semi­
conducting materials like CdS etc.
Functionalization with organic molecules is achieved by covalent
modification or non-covalent decoration. Ethylenediaminetetraacetic
acid (EDTA) is one of the commonly used organic molecules in GO
composites. Ethylenediaminetetraacetic acid (EDTA) decorated GO
shows enhanced adsorption of metal ions due to increased surface
functional groups. Cetyltrimethylammonium bromide (CTAB) prevents
agglomeration of GO and contributes to enhanced adsorption. Some of
the other organic molecules considered for GO composites used in
adsorption are triisopropanolamine, aminopyrazole etc.
Polymers are considered as functionalising molecules due to the
large functional groups present in them. Some of the polymers used for
GO and rGO composites are polypyrrole, polyaniline, poly(amido­
amine), poly(N-vinylcarbazole), chitosan, cellulose, epoxy resin. Poly­
mer impregnated GO composites have shown excellent improvement in
adsorption capacity for most of the metal ions. This is attributed to the
complexation between the polymer functional groups and the metal
ions. In addition, the polymer impregnated GO sheets have reduced
aggregation which results in enhanced adsorptive behaviour of the
composite.
The following paragraphs discusses on the application of bare and
functionalized graphene-based adsorbents for removal of heavy metal
ions.
R.H. Krishna et al. Applied Surface Science Advances 16 (2023) 100431

Table 4
Summary of Lead removal by graphene based adsorbents.
Adsorbent Metal ion pH Adsorption capacity (mg/g) Specific surface area of adsorbent Reference
(m2/g)

GO–Gd2O3 nanocomposite Pb(II) 4 158.73 2.757 [172]

Reduced graphene oxide hydrogel (rGOH) Pb(II) 4 2503.62 553.69 [173]

Tannin- reduced graphene oxide aerogel (TRGA) Pb(II) 4 803.84 122.2 [174]
Graphene oxide (GO) Pb(II) 4 55.80 59.98 [175]
Starch-graphene oxide architecture (SGO) Pb(II) 10 383.32 406.52 [176]
EDA functionalized MgO (EDA-MgO) Pb(II) 4 425.83 — [177]
GO-fullerenol hybrid GO-C60(OH)22 Pb(II) 5.5 1307 — [178]
MnFe2O4@SiO2/GO-Ion Imprinted Polymer (IIP) Pb(II) 6.5 58.82 — [179]
GO-La(OH)3 composite Pb(II) 4 71.42 — [180]
Amino-functionalized graphene oxide Pb(II) 7 71.89 — [171]
rGO-MnO2 Pb(II) 5 365.4 156 [161]
Fe3O4@Triisopropanolamine GO Pb(II) 5 461 15.43 [169]
Zeolitic Imidazolate-8@GO Pb(II) 5 356 946.5 [181]
nano FeS-Graphene Pb(II) 6 645 201.3 [182]
GO-SOxR Pb(II) - 285 102 [183]
GO-SOxR@SiO2 Pb(II) - 172 92 [183]
GO-SOxR@TiO2 Pb(II) - 312 208 [183]
GNPs (graphene nanoplates)/Fe-Mg-Cu oxide Pb(II) 7 251.3 104.908 [184]
Dithiocarbamate-GO Pb(II) 7 251.3 — [185]
Fe3S4/RGO Pb(II) 6 285.71 80.96 [186]
GO-cellulose Pb(II) 5 10 — [158]
GO sheets Pb(II) 5 765.7 — [160]
Layered Double Hydroxide Intercalated with MoS2−
4 Ions Pb(II) 5.1 288.9 — [187]
Graphene nanosheets Pb(II) < 6.5 460 625.8 [188]
GO-hyperbranched polyethylenimines Pb(II) 4-5.0 438.6 77.82 [189]
LS-GO-PANI Pb(II) 5 216.4 — [170]
GO-MnFe2O4 Pb(II) 4 673 196 [162]
CoFe2O4-rGO Pb(II) 5.3 299.4 169.9 [190]
Amino-functionalized Fe3O4/graphene composite Pb(II) 6.5 27.95 62.43 [191]
Amino siloxane oligomer-linked GO Pb(II) 5 312.5 53.7 [192]
GO Pb(II) 7 692.66 —- [167]
Poly(N-vinylcarbazole) -GO Pb(II) 7 982.86 —- [167]
RGO–iron oxide Pb(II) 6.5 454.55 —- [193]
RGO–Fe(0)/Fe3O4 Pb(II) 7 19.7 384.62 [194]
Poly(amidoamine) modified GO Pb(II) – 10.6 — [195]
Chitosan/GO Pb(II) – 216.92 4.232 [196]
GO–chitosan composite hydrogel Pb(II) 4.9 90 — [166]
Magnetic chitosan/GO Pb(II) 5 76.94 382.5 [165]
GO Pb(II) 5 1119 — [159]
GO Pb(II) 5.6 35.6 88.97 [197]
GO–TiO2 Pb(II) 5.6 65.6 132.74 [197]
Graphene/δ-MnO2 Pb(II) 6 164.29 — [163]
SiO2/graphene Pb(II) 6 113.6 252.5 [198]
Graphene/MWCNT Pb(II) – 44.5 435 [199]
GO–iron oxide Pb(II) 6.5 588.24 142.36 [200]
GO Pb(II) 6.8 367 430 [168]
EDTA modified GO Pb(II) 6.8 525 623 [168]
Graphene nanosheets Pb(II) 4 35.46 400 [201]
KPF6 functionalized graphene (GNSPF6) Pb(II) 5.1 406.4 — [202]
Few-layered GO nanosheets (FGO) Pb(II) 6 842 — [203]
GO/chitosan Pb(II) – 99 — [164]
Graphene nanosheets Pb(II) 4 22.42 400 [201]

5.2.1. Lead
Lead is one of the commonly occurring pollutant and several studies
have been reported on the adsorptive for the removal of lead by
graphene-based materials. Adsorption studies of lead Pb(II) by GO, rGO
and their composites are listed in the Table 4. Removal capacity of Pb(II)
by graphene materials ranged from as low as 20 mg/g for GO-cellulose
composite [158] to as high as 1119 mg/g with unmodified GO sheets
[159]. The optimum pH for removal of Pb(II) is 5-7. Graphene and GO
sheets have shown excellent binding capacity to Pb(II). Sitko et al [159]
have obtained significant removal of Pb(II) (1119 mg/g) with GO sheets.
They also observed the change in the GO dispersivity in water after
adsorption. GO complexed with metal ion showed tendency to
agglomerate and precipitate, which is an essential step for removal of
complexed adsorbent. Peng et al [160] have also reported high
adsorption capacity of 766 mg/g for GO sheets.
GO modified with inorganic and organic groups have also been
explored for removal of Pb(II). GO functionalized with inorganic metal
ions have shown higher adsorptive removal of Pb(II) [161–163] while
GO and magnetic GO composites conjugated with chitosan and cellulose
have shown poor adsorption capacity [158,164–166]. Among the
various organic molecule conjugated GO composites, poly(N-vinyl­
carbazole)–GO has shown highest adsorption capacity of 983 mg/g
[167], which was attributed to improved availability of GO oxygen
groups. EDTA-GO, prepared via silylation process, enhanced the
adsorption capacity of GO from 328 mg/g to 525 mg/g because of in­
crease in surface functional groups [168]. Organic-inorganic hybrids of
GO have also been used for heavy metal removal. A typical example is
use of nano-Fe3O4/triisopropanolamine (TI) functionalized graphene
oxide composites for enhanced Pb(II) removal [169]. Maximum uptake
of 392.5 mg/g of Pb(II) was obtained at pH 5. The adsorption of Pb(II)
onto nano-Fe3O4/TI functionalized graphene oxide composites was
through complexation between the nitrogen groups of TI and Pb(II)

9
R.H. Krishna et al. Applied Surface Science Advances 16 (2023) 100431

Fig. 6. Schematic representation of adsorption mechanism of Pb(II) ions on nano-Fe3O4/triisopropanolamine (TI) functionalized graphene oxide composites
(Graphical abstract reproduced with permission from Cao et al, [169])

Fig. 7. Possible adsorption mechanism for Pb(II) on LS-GO-PANI (Reproduced with permission from Yang et al, [170])

10
R.H. Krishna et al. Applied Surface Science Advances 16 (2023) 100431

Table 5
Summary of Copper removal by graphene based adsorbents.
Adsorbent Metal pH Adsorption capacity (mg/ Specific surface area of Reference
ion g) adsorbent
(m2/g)

GO-EDTA-CS Cu(II) 4.5 130 ± 2.80 1.326 [209]

GO/Polyethyleneimine (PEI) sponge Cu(II) 5.5 150.9 — [210]
carboxylated graphene oxide (GO-COOH) Cu(II) 5 62.02 — [211]

reduced Graphene Oxide–Starch composite (rGO/WS) Cu(II) 8 542.01 406.40 [212]

Graphene oxide-titanium dioxide/sodium alginate (GO-TiO2/SA) composite Cu(II) 6 90.91 133.40 [213]
Few-Layered Magnetic Graphene Oxide (FLMGO) Cu(II) 8 1114.22 224.10 [214]
Amino-functionalized graphene oxide Cu(II) 7 26.25 — [171]
Amino-GO Cu(II) 7 194.08 — [215]
Amino-functionalized CNT graphene aerogel Cu(II) 6-7 318.5 117.3 [205]
Fe3O4/graphene oxide Cu(II) 7 32.5 167.9 [216]
Fe3O4/chitosan/graphene oxide Cu(II) 8 217.4 132.9 [217]
GO –COOH Cu(II) 6 357.1 39.79 [207]
Amino modified magnetic GO Cu(II) 5.5 578.1 — [204]
Diethylenetriaminepentaacetic acid-modified magnetic graphene oxide (DETP- Cu(II) 5 131.4 — [218]
MGO)
rGO-SDS (reduced graphene oxide - sodium dodecylsulfate) Cu(II) 5 369.2 242 [208]
GO/cellulose hydrogel Cu(II) 5- 88.5 45.12 [219]
6.5
Fe3O4/Graphene oxide supported 1,2-diaminocyclohexanetetraacetic acid Cu(II) 5 26.45 — [220]
(DCTA)
GO/CdS Cu(II) 5- 120 25.79 [221]
6.6
GO membrane Cu(II) 5.5 76.89 — [222]
Poly(amidoamine) modified GO Cu(II) – 8.69 — [195]
GO–chitosan composite hydrogel Cu(II) 5.1 70 — [166]
Sulfonated magnetic GO composite Cu(II) 5 50.68 92.79 [223]
Calcium alginate/GO Cu(II) – 60.24 — [224]
GO Cu(II) 5.3 117.5 — [225]
GO Cu(II) 5 294 — [159]
Graphene/MWCNT Cu(II) – 9.8 435 [199]
GO aerogel Cu(II) 6.3 17.73 — [206]
Graphene/δ-MnO2 Cu(II) 6 104.09 — [163]

coupled with electrostatic interactions between oxygen containing
functional groups of GO surface and Pb(II). The synthesis and adsorption
mechanism are depicted in Fig. 6 where the formed nitrilotriacetic acid
is also involved in Pb(II) complexation.
Thiol groups have also been considered for functionalization since
they offer high binding sites. Pirveysian et al. [160] functionalized GO
using Na2S when various sulfur-derived groups such as SH, CS, SO, SO3−
were generated by one pot facile method. Sulfur -derived groups func­
tionalized GO (GO-SOxR) was further coated with TiO2 and SiO2 and
were used as adsorbents for the removal of various metal ions (Zn(II), Cr
(III) or Cr(VI), Ni(II), Pb(II)). Thiol functionalized GO exhibited good
adsorption capacity for all the metal ions tested. Composites of thiol
functionalized GO with TiO2 (GO-SOxR-TiO2) and SiO2 (GO-SOxR-SiO2)
showed enhanced adsorption capacity for all the metal ions.
GO-SOxR-TiO2 (312 mg/g) composite showed increase in the adsorption
of Pb(II) when compared to GO-SOxR (285 mg/g). In case of Ni(II) the
adsorption capacity almost doubled for GO-SOxR-TiO2 (344 mg/g) when
compared to GO-SOxR (175 mg/g). Similar enhancement was observed
with respect to adsorption of Cd(II) and Zn(II). Higher adsorption by
GO-SOxR-TiO2 was attributed to the high surface area of the composite.
Electrostatic interaction coupled with hydrogen bonding between the
positive metal ions and the oxygen containing functional groups (hy­
droxyl, carbonyl, sulphonyl/sulphonate, etc) on the surface of the
adsorbent were the contributing factors for the adsorptive removal of
metal ions.
Lignosulfonate-GO-polyaniline (LS-GO-PANI) ternary nano­
composites have shown excellent adsorption for Pb(II) (216.4 mg/g at
pH 5) [170]. The adsorption process occurred due to the chemical
interaction between the binding sites of the functionalized adsorbate
and the adsorbent. Synergetic effect of the lignosulfonate and polyani­
line functional groups was evident by the enhanced order of uptake of Pb
(II) by the binary and ternary composites compared to GO. While the
abundant amine and imine functional groups on PANI fibres form strong
metal conjugates with Pb(II), electronegative sulfonic groups of LS chain
interact electrostatically with the Pb(II). LS chains also possess abundant
carboxyl and phenolic groups which can result in formation of com­
plexes with Pb(II). Amino groups of PANI fibres may enhance the
coordinative ability of carboxyl groups of GO nanosheets and sulfonic
groups of LS chains for lead ions. This synergistic effect of the functional
groups thus contributes to the enhanced adsorption capability of the
tertiary composite. Possible adsorption mechanisms for Pb(II) on
LS-GO-PANI is represented in Fig. 7.
Recently, Huang et al [171] have synthesized amino-functionalized
GO (GO-NH2) by grafting (3-aminopropyl) triethoxysilane on GO
sheets. The resultant composite with high surface area with numerous
active sites was used as an adsorbent for effective removal of various
metal ions like Pb(II), Cu(II), Cd(II) and Cr(II). Adsorption of the metal
ions onto GO-NH2 was shown to occur via chemical adsorption.
5.2.2. Copper
Copper finds extensive applications in microelectronics and the use
of graphene-based materials for removal of copper ions and copper
complexes from water has been attempted by various researchers
(Table 5). GO sheets/membranes, magnetic GO sheets and amine
functionalized GO are the commonly used graphene-based adsorbents
for the removal of Cu ions. Amongst these, composites of metallic GO are
widely used because of ease of separation and reuse. Amino modified GO
substrates (GO-NH2) are the other class of adsorbents researched for Cu
ion removal. Amino groups on the layered GO sheets provide additional
sorption sites for the heavy metal ions due to their ability to form
complexes with those ions. The adsorption of metal ions on amino
functionalized GO substrates occurs by ion exchange, surface complex­
ation and electrostatic attraction. Under acidic pH conditions, depro­
tonation of the functional groups on the GO-NH2 surface is inhibited

11
R.H. Krishna et al. Applied Surface Science Advances 16 (2023) 100431

Fig. 8. Complexation and chelation interaction of Pb(II) and Cu(II) adsorption on MWCNT-PDA hybrid aerogel (Reproduced with permission from Zhan et al [205].

resulting in the repulsion between positive ammonium groups from
substrate and metal cations. Also, H3O+ in solution compete for the
adsorption sites leading to poor uptake of metal ions by the GO-NH2
surface. With increase in pH, protonation of amino groups is decreased,
which results in availability of more NH2 groups on the surface,
increasing the uptake of the metal ions. Huang et al [171] used
amino-functionalized graphene oxide (GO-NH2) for removal of several
metal ions. The uptake capacity for Cu(II) was found to be 26.25 mg/g.
The highest copper uptake has been reported for amino modified
magnetic GO (578 mg/g) [204]. Copper uptake of the magnetic GO
sheets (MGO) were found to be almost doubled when functionalized
with amino groups (319 mg/g for MGO to 578 mg/g for amino-MGO) in
all pH conditions.
Amino-functionalized (via polydopamine) CNT partially reduced
graphene oxide aerogels (prGO-MWCNT-PDA) for the uptake of Cu has
been reported by Zhan et al [205]. These hybrid aerogels have highly
porous structure coupled with unique adsorption properties of CNTs and
3D architecture of graphene. Incorporation of CNTs not only improved

Table 6
Summary of Chromium removal by graphene based adsorbents
Adsorbent Metal ion pH Adsorption capacity (mg/ Specific surface area of Reference
g) adsorbent
(m2/g)

GO–Gd2O3 nanocomposite Cr(III) 4 29.155 2.757 [172]

Graphene oxide-zinc oxide nanohybrid (ZnO-GO) Cr(VI) 8.02 3.69 32.95 [235]
RGO - β-cyclodextrin epichlorohydrin (RGO-βCD-ECH) composite Cr(VI) 1 1321.0 12.207 [236]
GO-NH2-AHMT (4-amino-3-hydrazino-5-mercapto-1,2,4-triazole) Cr(VI) 2 734.2 85.8 [237]
graphene oxide-dicationic (bisimidazolium) ionic liquid composite (GO- Cr(VI) 3 260.92 10.46 [238]
DIL)
Amino-functionalized graphene oxide Cr(VI) 7 280.11 — [171]
EDTA-GO composite Cr(VI) 3 36.59 100.93 [228]
Epoxy-GNP NC Cr(IV) - 85 47.63 [239]
GO/Chitosan Cr(VI) 2 86.17 – [240]
Amine modified GO-Chitosan composite Cr(VI) 2 219.5 11.69 [241]
Polypyrrole/GO Cr(III) 2 625 59.92 [233]
Graphene nanosheets Cr(VI) - 1.66 594.7 [242]
Exfoliated graphene oxide impregnated with Aliquat-336 Cr(IV) 2.5- 37.08 —- [226]
3.5
Poly(amidoamine) modified GO Cr(VI) – 4.15 — [195]
GO/Polyaniline Cr(VI) 2-3 1149.4 —- [230]
Magnetic cyclodextrin–chitosan/GO Cr(VI) 3 61.31 445.6 [243]
Graphene/MgAl-layered double hydroxide Cr(VI) 2 183.82 34.97 [234]
CTAB modified graphene Cr(VI) 2 21.57 —- [232]
Graphene/Fe@Fe2O3@Si\S\O Cr(VI) 7 1.03 42.1 [229]
Polypyrrole/GO Cr(VI) – 495 84.8 [244]
RGO–Fe(0)/Fe3O4 Cr(VI) 7 31.1 384.62 [194]
Graphene/Fe Cr(VI) 4.25 162 56 [227]

12
R.H. Krishna et al.
Fig. 9. (A) Illustration of interaction between IL and EGO. (B) Illustration of interaction between EGO, IL and chromium(VI). (Reproduced with permission from
Kumar et al, [226]).
the mechanical strength and stability of the graphene sheet, but also
prevented restacking of the graphene sheets. CNTs in the graphene
nanosheets enhanced the surface area for adsorption. Further, conju­
gation with polydopamine (PDA) provided abundant catechol and
amine functional groups on the CNT-graphene surface resulting in
enhanced uptake of Cu(II). Complexation and chelation were proposed
to be the major interactions between these functional groups and the
metal ions (Fig. 8). The aerogel produced was sponge-like which facil­
itated easy removal and recycle. The hybrid aerogel showed excellent
adsorption capacity of 318.5 mg/g for Cu(II) and 350.9 mg/g for Pb(II).
The uptake for the MWCNT-PDA hybrid aerogel was much higher
compared to that reported for GO aerogels (17.73 mg/g) [206].
Higher uptake of Cu(II) has been reported for other graphene based
composites like carboxylated graphene oxide, GO-COOH (357.1 mg/g)
[207]; reduced graphene oxide - sodium dodecylsulfate (rGO-SDS -
369.2 mg/g) [208]; plain GO (294 mg/g) [159].
5.2.3. Chromium
Removal of chromium (Cr(III) and Cr(VI)) by graphene and its
composites has been attempted by several researchers as listed in
Table 6. Protonation and deprotonation of the functional groups on the
surface of the adsorbent dictates the removal efficiency of the metal ion.
Chromium ions exist as various oxo anions depending on the pH of the
solution. Adsorbent medium pH therefore plays a very important role on
Fig. 10. Schematic adsorption mechanisms on graphene and MGNCs (Reproduced with permission from Zhu et al, [229]).
13
Applied Surface Science Advances 16 (2023) 100431
the removal of chromium from a solution. The dominant forms of
chromium anions at various pH are Cr2O2− 7 at pH<2, HCrO4 in the pH
−
2−
range 2-5 and CrO4 at pH >5. This necessitates understanding the
interaction mechanism between the adsorbent and Cr(VI) with respect
to pH for optimal removal of Cr(VI). Interaction between exfoliated GO
impregnated with Aliquat-336, a quaternary ammonium halide with
three long saturated chains and one methyl group and Cr(VI) was
studied extensively by Kumar et al [226].In the pH range studied,
Chromium exists as HCrO−4 . Methyltrioctylammonium cation can
therefore be involved in ion-pair electrostatic interactions with the
HCrO−4 anion. The overall mechanism of interaction is depicted in Fig. 9.
The pH for optimal removal of Cr(VI) was found to be 2.5-3.5. pH of zero
point of charge (pHZPC) for the ionic liquid-GO conjugate was 3.5.
Above pH 3.5, the surface charge of ionic liquid-GO conjugate is posi­
tive. Below pH 3.5, electrostatic interaction favours chromium adsorp­
tion. With increase in pH above 3.5 the removal efficiency decreased.
This was attributed to two factors, (i) deprotonation of surface hydroxyl
groups of GO resulting in the repulsion between ionic liquid conjugated
GO and hexavalent chromium oxy anion (ii) hydroxyl ions would
compete for the active sites on the ionic liquid conjugated GO. The au­
thors also studied the interference of several anions and cations on the
removal efficiency of Cr(VI). Anions like sulphate, chloride and phos­
phate can compete with HCrO−4 for the active sites on the adsorbent
R.H. Krishna et al. Applied Surface Science Advances 16 (2023) 100431

Table 7
Summary of Arsenic removal by graphene based adsorbents.
Adsorbent Metal pH Adsorption capacity (mg/ Specific surface area of Reference
ion g) adsorbent
(m2/g)

GO–Gd2O3 nanocomposite As(V) 4 36.765 2.757 [172]

Chitosan-magnetic GO grafted polyaniline doped with cobalt oxide (CSMGOP- As(V) 7 90.91 — [251]
Co3O4)
Carboxymethylcellulose incorporated Fe-Al layered double hydroxide - rGO (FAH- As(V) 7 258.39 156.24 [252]
rGO/CE)
Magnetic chitosan modified with Graphene oxide and Polyethyleneimine (MCS/GO- As 7 220.26 — [253]
PEI) (III)
Nitrile functionalized calix [4]arene grafted onto magnetic As 6 67.12 68.2 [254]
graphene oxide (N-Calix-MgO) (III)
Graphene oxide - Fe3+-modified clinoptilolite zeolite composite (GOFeZA) As(V) 7- 557.86 — [255]
8
Graphene oxide iron nanohybrid (GFeN) As 7 306 159.62 [256]
(III)
As(V) 431
Chitosan-graphene oxide-gadolinium oxide (CS-GO-Gd2O3) nanocomposite As(V) 6 252.12 61.28 [257]
Epoxy resin - Graphene nanoplates nanocomposite (Epoxy-GNP NC) As - 98 47.63 [239]
(III)
Graphene - Spinel CuFe2O4 composite As(V) 4 172.3 —- [246]
EDTA-Magnetic Chitosan/GO (EDTA-MCS/GO) As 7 42.8 81.36 [258]
(III)
Aminopyrazole-f-GO As 7.6 131.6 —- [259]
(III)
Fe3O4@SiO2/GO As 4 7.51 —- [260]
(III)
Fe3O4@SiO2/GO As(V) 4 11.46 —- [260]
Fe3O4–GO composite As 4 7.57 —- [245]
(III)
Fe3O4–GO composite As(V) 6 4.9 —- [245]
Fe3O4–RGO composite As 6 5.79 —- [245]
(III)
Fe3O4–RGO composite As(V) 7 4.23 —- [245]
RGO–Fe3O4/TiO2 As 7 99.5 275.23 [247]
(III)
RGO–Fe3O4/TiO2 As(V) 7 77.7 275.23 [247]
nZVI-RGO As 6.5 35.83 100.65 [261]
(III)
nZVI-RGO As(V) 4 29.04 100.65 [261]
GO-MnFe2O4 As 7 146 196 [162]
(III)
GO-MnFe2O4 As(V) 7 207 196 [162]
GO–FeOOH As(V) 7 73.42 117 [262]
GO–ZrO(OH)2 As 7 95.15 420.9 [263]
(III)
GO–ZrO(OH)2 As(V) 7 84.89 420.9 [263]
RGO–Fe(0) As 7 37.3 124.34 [194]
(III)
RGO–Fe3O4 As 7 21.2 140.70 [194]
(III)
RGO–Fe(0)/Fe3O4 As 7 44.4 384.62 [194]
(III)
Graphene/Mn2+ 3+ 2−
x Fe2-x O4 nanocomposite As 7 14.42 280 [264]
(III)
Fe3O4-RGO As 7 10.2 148 [265]
(III)
Fe3O4-RGO As(V) 7 13.1 117 [265]
GO/ferric hydroxide As(V) 6 23.78 — [266]

surface, thereby reducing the adsorption efficiency if Cr(VI). Cations like
Zn(II), Cd(II), Pb(II), Co(II) and Ni(II) did not interfere with the
adsorption of Cr(VI). However, Mn(II) and Fe(II) could interfere with the
adsorption of Cr(VI) by reducing it to Cr(III).
Optimal removal of chromium by iron nanoparticle decorated gra­
phene was reported as pH 2-3 by Jabeen et al [227]. Recent studies by
amino-functionalized graphene have also shown similar pH related
interaction between chromium ions and the adsorbent [171]. Optimal
removal of hexavalent chromium was therefore obtained below pH 3.
Similar behaviour is exhibited by EDTA-GO composite, which contains
oxygenic and amine groups, that can be protonated under acidic con­
ditions resulting in maximum interaction between the negatively
charged HCrO−4 anion and the adsorbent at acidic pH conditions [228].
Dependence of chromium removal efficiency on temperature is also
studied by several researchers. Adsorption of Cr(VI) in general is fav­
oured by lower temperature indicating the exothermic nature of the
process. Contrary to this, Jabeen et al [227], using iron nanoparticle
decorated graphene, have shown adsorption was favoured by high
temperature. This was attributed to pore size enlargement and/or acti­
vation of the adsorbent surface.
Zhu et al [229] have studied removal of chromium ions by magnetic
graphene nanocomposite (MGNC). Nanoparticles dispersed on the gra­
phene sheet comprised of iron core, inner Fe2O3 shell, and the outmost
amorphous Si− S− O compound shell. They observed significant increase

14
R.H. Krishna et al. Applied Surface Science Advances 16 (2023) 100431

Table 8 and from a minimum of 4.23 mg/g [245] to maximum of 207 mg/g
Summary of Cadmium removal by graphene based adsorbents. [162] for As(V). Adsorptive removal of arsenic ions was found to be
Adsorbent Metal pH Adsorption Specific Reference maximum with metal oxide modified GO followed by organic molecule
ion capacity surface area modified GO. Inorganic composites of GO showed relatively lower
(mg/g) of adsorption of arsenic ions. Maximum arsenic removal of 207 mg/g has
adsorbent
been reported for GO-MnFe2O4 [162]. Recently, La et al [246] have used
(m2/g)
graphene-spinel CuFe2O4 and have shown excellent adsorptive capacity
Reduced graphene Cd(II) 4 1185.27 553.69 [173] of 172 mg/g for As(V). Chitosan GO nanocomposite functionalized by
oxide hydrogel
(rGOH)
EDTA exhibited moderate adsorptive capacity of 42.8 mg/g for As(III).
Tannin- reduced Cd(II) 4 395.80 122.2 [174] Apart from good adsorption capacity, an ideal adsorbent is one which
graphene oxide can be retrieved and reused several times with high capacity. Among the
aerogel (TRGA) various composites used for arsenic removal, we observe that magnetic
Graphene oxide Cd(II) 6-7 108.70 510.59 [270]
graphene composite materials have been extensively explored to obtain
aerogel (GOA)
FLMGO Cd(II) 8 401.14 224.10 [214] enhanced adsorption coupled with effective retrieval and regeneration
Amino- Cd(II) 7 10.04 — [171] of the adsorbent. Reduced GO supported core shell Fe- Fe2O3 exhibited
functionalized excellent magnetic properties and high binding capacity for As(III) and
graphene oxide Cr(VI) [229]. Few papers have reported use of magnetic Go and rGO
GO/Calcium Cd(II) 7 181 [271]
further modified with organic, inorganic and metallic materials. Babu et
—
alginate-PEI
rGO Cd(II) 4 433.2 — [268] al [247] have used rGO supported mesoporous Fe2O3/TiO2 with
rGO/Fe3O4 Cd(II) 4 292.8 — [268] adsorptive efficiency of 99.5 mg/g and 77.7 mg/g for As(III) and As(V)
rGO/Ag Cd(II) 4 372.8 — [268] respectively. It is noteworthy to mention that the adsorptive capacity of
rGO/ Fe3O4/Ag Cd(II) 4 386.7 [268]
—
most of the GO and rGO composites used for arsenic removal is higher
GO-SOxR Cd(II) - 217 102 [183]
GO-SOxR@SiO2 Cd(II) - 277 92 [183] than some of the conventional adsorbents like functionalized cellulose
GO-SOxR@TiO2 Cd(II) - 384 208 [183] (~75 mg/g) [248], nano-chitosan (~97 mg/g) [249], rice husk (~28
Aminopyrazole-f- Cd(II) 7.6 285.7 — [259] mg/g) [250].
GO
GO Cd(II) 6-7 23.9 [267]
5.2.5. Cadmium
—
Graphene Cd(II) < 72.39 625.8 [188]
nanosheets 6.5 Removal of cadmium, another toxic metal ion, using various gra­
GO membrane Cd(II) 5.5 90.72 — [222] phene based materials has been reported by several researchers
GO Cd(II) 5 530 — [159] (Table 8). Compared to conventional adsorbents, GO and rGO based
RGO–Fe(0)/Fe3O4 Cd(II) 7 1.91 384.62 [194]
adsorbents have shown better adsorption of Cd(II) with adsorption ca­
GO–TiO2 Cd(II) 5.6 72.8 132.74 [197]
FGO Cd(II) 6 106.3 — [203] pacity as high as 530 mg/g [159]. Majority of the adsorbents used for Cd
C8mim+PF−6 ionic Cd(II) 6.2 30.05 — (II) removal are GO and rGO composites with inorganic materials.
[202]
liquid Composites with magnetic Fe3O4 are extensively used because of ease of
functionalized separation and retrieval of the adsorbent.
graphene
The effect of oxygen containing functional groups on the surface of
(GNSC8P)
GO on adsorption of Cd(II) has been investigated by Bian et al [267].
FTIR and XPS studies confirmed the role of the phenolic hydroxyl and
in adsorption of chromium on MGNC compared to plain graphene. This carboxyl group on the surface of GO to be responsible for adsorption of
was attributed to the difference in the adsorption mechanism with Cd(II). The optimum pH for maximum adsorption was found to be 6-7,
respect to MGNC and graphene. While the adsorption is single layer type with electrostatic interactions leading to binding of Cd(II) with the
on graphene, adsorption on MGNC occurs by surface complexation be­ negatively charged surface groups of GO. Higher pH resulted in repul­
tween Cr(VI) and sulphur on the outer shell of MGNC coupled with sion and reduced adsorption.
single layer adsorption on bare graphene (Fig. 10). The kinetics of Contrary to most of the reported work on enhanced adsorption ca­
removal was very fast with complete removal of Cr(VI) achieved within pacity of graphene composites, functionalization by metal nanoparticles
5 min at a dose of 3 g/L. have also shown decreased adsorption capacity of GO nanosheets [268].
Highest adsorption capacity for hexavalent chromium ions has been Park et al. [268] synthesized rGO nanosheets conjugated by either silver
reported by Zhang et al [230] using polyanaline (PANI) nanorods or magnetic iron oxide (rGO/Fe3O4, rGO/Ag, rGO/Fe3O4/Ag) and
decorated GO nanosheets. The adsorbent was highly acid resistant with evaluated the adsorption capacity of the nano composites for removal of
maximum adsorption capacity of 1149.4 mg/g in the optimal pH range Cd(II). Adsorption capacity of the composites for Cd(II) was in the order
of 2-3. XPS studies indicated that chromium removal occurred by Cr(VI) rGO (433.2 mg/g) > rGO/ Fe3O4/Ag (386.7 mg/g) > rGO/Ag (372.8
adsorption coupled with reduction to Cr(III). TiO2-rGO composite was mg/g > rGO/Fe3O4 (292.7 mg/g). Although functionalization resulted
used for photocatalytic reduction of Cr(VI) [231]. The chemical reduc­ in decreased adsorption capacity, the adsorption capacity was higher
tion of Cr(VI) using EDTA-rGO composite and CTAB modified GO has than most of the other sorbents reported for Cd(II) removal.
been reported by [228,232]. Polymer-based and carbon-based magnetic The authors have reported extensive studies towards understanding
nanocomposites have also been explored [229,233]. Optimal pH for the mechanism of adsorption and the observed decrease in the adsorp­
chromium removal with these nanocomposites was found to be pH 2-4. tion capacity of rGO composites. XPS studies indicated binding of Cd(II)
Yuan et al [195] have reported poly-amidoamine conjugated graphene was mediated by complexation with deprotonated sites on rGO and
for improved removal of Cr(III). Graphene@MgAl- double layered cation exchange of Na+/H3O+ by Cd(II). Competitive adsorption of
hybrid nanomaterial exhibited good adsorption capacity of 172.55 mg/g multi metal ion system was examined and the order of adsorption was
[234]. found to be Cu(II), Zn(II) > Ni(II) > Co(II) > Pb(II), Cd(II). Average
hydrodynamic diameters of the composites were examined and it was
5.2.4. Arsenic observed that the order of adsorption matched with the ionic radii of the
Adsorption of arsenic (As(III) and As(V)) by GO, rGO and their metal ions. Similar behavior was observed for GO sheets decorated with
composites is listed in Table 7. Adsorption of arsenic ranged from a Fe/Cu bimetallic nanoparticles [269] and it was attributed to the
minimum of 5.79 mg/g [245] to maximum of 146 mg/g [162] for As(III) decrease in the specific area and adsorption sites of inorganic material

15
R.H. Krishna et al. Applied Surface Science Advances 16 (2023) 100431

Table 9 (GO/2-PTSC) ligand exhibited high uptake capacity for Hg(II) ranging
Summary of Mercury removal by graphene based adsorbents. from 309 to 555 mg/g [273] under ultrasonic assisted conditions. Apart
Adsorbent Metal pH Adsorption Specific Reference from the surface oxygen groups of graphene, 2-PTSC, a
ion capacity surface tridentate-chelating ligand, also contributes to uptake of metal ion by
(mg/g) area of complexation and chelation mechanism. Sulphur and nitrogen atoms in
adsorbent
2-PTSC, having lower electronegativity than oxygen atoms, are actively
(m2/g)
involved in the complexation and chelation of Hg(II) via electron
rGO/PEI Hg(II) 4.5 219 227 [275] pair-sharing forming metal complexes. pH has a significant influence on
rGO Hg(II) 6.4 110.21 [276]
the removal of mercury ions by GO/2-PTSC. Under acidic pH conditions,
—-
GO-EDTA-CS Hg(II) 4.5 324 ± 3.30 1.326 [209]
poly- Hg(II) 5 174.7 — [277] protonation of 2-PTSC results in weak affinity to mercury ions. With
cyanoguanidine/ increase in pH to 4, more mercury ions are removed via complexation
graphene oxide and chelation. Additionally, ionization of the graphene surface func­
composite (DCDA-
tional groups containing oxygen results in electrostatic adsorption of
GO
MCS/GO-PEI Hg(II) 9 124.84 — [253] mercury ions on the graphene adsorbent. At pH>5, mercury exist as
GO-NH2-AHMT Hg(II) 2 1091.1 85.8 [237] divalent ions resulting in surface complexation with heteroatoms. pH 5
Polyamine modified Hg(II) 5 63.8 63 ± 8 [274] was therefore found to be optimum for removal of Hg(II) by GO/2-PTSC.
rGO Polyamine functionalized rGO prepared by hydrothermal/chemical
Selenocarrageenan- Hg(II) 3 331 [278]
reduction for removal of Hg(II) from real systems (river and sea water)
—
GO hydrogel
Tourmaline/GO Hg(II) 5 294 — [279] has been attempted by Yap et al [274]. Mechanism of Hg(II) removal is
GO/Calcium Hg(II) 7 374 — [271] depicted in Fig. 11. Hg(II) uptake by the prepared polyamine/rGO
alginate-PEI adsorbent was >85% as against ~16% reported for commercial acti­
dithiocarbamate Hg(II) 6 181.8 194.8 [280]
vated carbon. Zeta potential studies indicated positive charge on the
(DTC)-magnetic
rGO adsorbents up to pH 6 resulting in repulsion and poor removal of mer­
Graphene-MoS2 Hg(II) - 719 - 1245 — [272] cury ions. At pH 5 drastic increase in adsorption was observed. The
hybrid aerogels optimum pH for mercury uptake was found to be 5. The adsorbent also
Aminopyrazole-f-GO Hg(II) 7.6 227.3 — [259] exhibited high selectivity towards Hg(II) (>70%) in multimetallic so­
GO/2-PTSC Hg(II) 5 309 - 555 [273]
lution containing Hg(II), Pb(II), Co(II), Cd(II) and Cu(II). The Hg(II)
—
CoFe2O4-rGO Hg(II) 4.6 157.9 169.9 [190]
RGO–Fe(0)/Fe3O4 Hg(II) 7 22 384.62 [194] uptake efficiency of the adsorbent in real water system was ~74% for
Graphene/c-MWCNT Hg(II) 5 93.3 435 [199] river water and ~56.5% for sea water. The reduction in the uptake of
Polypyrrole–RGO Hg(II) 3 979.54 166 [281] mercury in sea water was attributed to the existence of mercury as
RGO–MnO2 Hg(II) 9.5 [282]
– —
chloro complexes (HgCl2− 4 and HgCl3 ) due to the presence of large
−
RGO–Ag Hg(II) – 9.53 — [282]
amount of chloride ions.

modified GO. Presence of functionalized group is not only required for
good adsorption but also for effective separation of the adsorbent and
hence is desirable even when it inhibits the adsorption capacity of the
graphene material. For instance, the functionalisation of magnetic ox­
ides helps in the magnetic separation and followed by the regeneration
of the adsorbents.
5.2.6. Mercury
Various graphene based adsorbents have been used for removal of Hg
(II) as listed in Table 9. Highest values for Hg(II) sorption ranging from
719 to1245 mg/g were reported or Graphene-MoS2 hybrid aerogels
[272]. Graphene composites modified with organic compounds are the
commonly used adsorbents for removal of Hg(II). Graphene oxide
modified chemically with 2-pyridinecarboxaldehyde thiosemicarbazone
5.2.7. Other metals
The other metal ions remediated using graphene based materials are
Co(II), Ni (II), Zn(II), Fe(III), Ag(I), Au(III), Mn(II), etc. Table 10 lists few
of the reported studies on removal of these metal ions by graphene based
adsorbents.
5.2.8. Radioactive metal ions
Ore mining, processing of spent nuclear fuels and other related ac­
tivities has resulted in release of various radioactive elements to the
environment necessitating the need for effective remediation of these
metal ions. Uranium exists commonly as U(VI) and is one of the widely
studied radioactive metal ion for remediation. Several graphene based
materials have been reported for removal of Uranium and other radio­
active metal ions (Table 11).

Fig. 11. Schematic mechanism of Hg(II) removal by Polyamine functionalized rGO (Graphical abstract reproduced with permission from Yap et al, [274]).

16
R.H. Krishna et al. Applied Surface Science Advances 16 (2023) 100431

Table 10 and electrostatic interaction. Formation of highly stable carbonate

Summary of other metal ions removal by graphene based adsorbents. complexes of uranium at solution pH >8 suppresses the uptake of ura­
Adsorbent Metal pH Adsorption Specific Reference nium by the adsorbent. On the other hand, rhenium exists as [ReO4]‾ in
ion capacity surface aqueous solutions. Maximum removal of rhenium was obtained in the
(mg/g) area of pH range 2.0 to 3.5 and the uptake was significantly suppressed at
adsorbent
pH>3.5. Electrostatic attraction between the protonated amine groups
(m2/g)
and [ReO4]‾ coupled with hydrogen bonding was the dominant
GO based hybrid Co(II) 9 691.004 — [283] adsorption mechanism for
materials (HMs)
Citrate modified Co(II) 8 145.35 — [284]
[ReO4] ‾while complexation with free amine groups dominated
Graphene Oxide uranium removal (Fig. 12). The authors thus observed “compensation”
(GO-C) phenomenon, wherein uranium and rhenium utilized free and proton­
GO/PVA/Fe3O4 Co(II) 5.2 373.37 122.328 ± [285] ated amine groups respectively, for adsorption (Fig. 11). Similar
nanocomposite 3.367
chemical affinity of uranium ions to nitrogen containing groups of GO-
Polyvinyl alcohol/ Co(II) 9.56 62.30 12.6 [286]
graphene oxide/ polyaniline composite, which was much stronger than that with oxygen
MnO2 composite containing surface functional groups of GO, was reported by Sun et al
Amino-GO Co(II) 7 180.19 — [215] [302]. On the other hand, Gao et al [303] demonstrated high [ReO4]−
nZVI-RGO Co(II) 5.7 131.58 17.9 [287] uptake via electrostatic attraction on polyaniline/titanium phosphate
GO Co(II) 5-8 21.28 2.8 [288]
Aminated GO (GO- Co(II) 6-7 116.35 120 [289]
adsorbent.
NH2) Besides uranium and rhenium, radioactive wastewater generally
FGO Co(II) 6 68.2 — [203] contains Sr(II), Cs(I) etc.
Magnetite/GO Co(II) 6.8 12.98 — [290] Sun et al [302] have demonstrated uptake of radionuclides on
rGO Ni(II) 6 69 [291]
—
GO-polyaniline composite. Maximum uptake of 245 mg/g for U(VI),
Graphene oxide Ni(II) 6-7 91.74 510.59 [270]
aerogel (GOA) 250.8 mg/g for Eu(III), 147.2 mg/g for Sr(II) and 184.7 mg/g for Cs(I).
Magnetic Ni(II) 6 97.44 263.19 [292]
fungal hyphal/ 6. Challenges, limitations and scope of CNTs and GO as
graphene oxide adsorbents for heavy metals
nanofibers
(MFHGs
Amino-GO Ni(II) 7 191.99 — [215] Despite these efforts that have been made, there is still a need for
GO-SOxR Ni(II) - 175 102 [183] continued development of novel adsorbents with high adsorption per­
GO-SoxR@SiO2 Ni(II) - 144 92 [183] formance and selectivity, low-cost and easy separation. CNTs have
GO-SoxR@TiO2 Ni(II) - 344 208 [183]
shown great potential as nanoadsorbents in removal of heavy metals
SDS functionalized Ni(II) 6 55.16 — [293]
GO from wastewater. But further studies need to be carried to assess the
EDTA-amine Ni(II) 7 103 — [294] ability of CNTs performance in the treatment of real and industrial
functionalized wastewater samples in the long-term operational conditions. The major
GO problem that limits the use of CNTs, is their high cost for full-scale water
GO membrane Ni(II) 5.5 63.72 [222]
treatment applications compared to conventional adsorbents [323].
—
Graphene/δ-MnO2 Ni(II) 6 46.55 — [295]
GO based hybrid Zn(II) 9 627.963 — [283] Apart from this, optimized and cost effective synthesis approaches for
materials (HMs) modification and functionalization of CNT materials for large-scale
GO Zn(II) 5 345 — [159] production has to be carried out. Integration of conventional and CNT
Poly(amidoamine) Zn(II) 6 13.23 [195]
—
enabled advanced technologies needs to be developed for wastewater
modified GO
GO Zn(II) 7 246 — [296] treatment system by undertaking future research [324].
GO–TiO2 Zn(II) 5.6 88.9 132.74 [197] The synthesis of graphene-based materials is still in lab-scale, and the
GO Zn(II) 5.6 30.1 88.97 [197] relevant study is at a preliminary stage at present, which limits their
Poly(amidoamine) Fe(III) - 29.74 — [195] application in industrial wastewater treatment. More attention should
modified GO
Graphene/c- Ag(I) – 64 435 [199]
be focused on the potential of graphene-based materials for practical
MWCNT wastewater containing multiple pollutants, and adsorption experiments
Chitosan/GO Au – 1076.65 4.232 [196] should be optimized accordingly.
(III)
Graphene-SDS Mn(II) 6 223.67 242 [208]
7. Conclusions
S-nZVI@GO Sb(III) 7 311.75 — [297]
GO- Zr-based Sb(III) 7 61.07 — [298]
metal-organic The review presented analyzes and summarizes the literature of
framework heavy metal ions removal from aqueous solutions by modified multi­
(GO@UiO-66- walled carbon nanotubes and the functionalized graphene-based mate­
NH2) composite
RGO/Mn3O4 Sb(III) 6.8 151.8 44 [299]
rials using the adsorption process. Removal of various metals such as Pb
RGO/Mn3O4 Sb(V) 6.8 105.5 44 [299] (II), Cd (II), Hg(II), As(VI) and Cr(VI) by adsorption mechanism using
GO- Sb(V) 7 158.6 287.6 [300] functionalized CNTs and their related compositions are critically sum­
Schwertmannite marized. Different chemical functionalization of CNTs by chemical
techniques with their procedure and mechanism are discussed. In gen­
eral, the adsorption of metal ions by CNTs is governed by various pa­
Huang et al [301] have studied the simultaneous removal of uranium
rameters such as surface chemistry, surface charge, nature of the
and rhenium by GO-PEI aerogels. Maximum uptake of U(VI) and Re(VII)
functional groups, pore characteristics of the surfactant and the modi­
was found to be 629.5 mg/g (at pH 5) and 262.6 mg/g (at pH 3.5),
fied chemical structure. Furthermore, the efficiency of the metal
respectively. Extensive protonation of amine groups of PEI results in
adsorption is also affected by experimental conditions such as temper­
poor complexation and thus inhibits effective uptake of uranium ions
ature, pH and concentration of the adsorbate/ adsorbent. Most of the
under acidic pH conditions. Availability of free amine groups at higher
literature showed that the functionalization has always enhanced the
pH results in complete removal of uranium due to both complexation
metal ion adsorption capacities of CNTs compared to the

17
R.H. Krishna et al. Applied Surface Science Advances 16 (2023) 100431

Table 11
Summary of radioactive metal ions removal by graphene-based adsorbents.
Adsorbent Metal pH Adsorption capacity Specific surface area of Reference
ion (mg/g) adsorbent
(m2/g)

MXene/graphene oxide nanocomposite (MGN) U(VI) 6 1003.5 465.9 [304]

Poly(amidoxime)/graphene oxide nanoribbons (PAO/GONRs) aerogel U(VI) 4.5 216 494.9 [305]
GO - poly(acrylamide) reticulated with N,N′-methylenebisacrylamide (GO-pAM- U(VI) 4 589.1 — [306]
MBA) composite
GO/FeS U(VI) 5 347.2 — [307]
GO-La(OH)3 composite U(VI) 4 78.82 — [180]
GO-PEI aerosol U(VI) 5 629.5 — [301]
Magnetic cucurbit[6]uril/GO U(VI) 5 66.81 — [308]
Phosphate-functionalized GO U(VI) 4 251.7 120 [309]
GO U(VI) 5 97.5 — [310]
Layered double hydroxide/graphene U(VI) 4 277.8 256.80 [311]
Graphene oxide-activated carbon felt (GO-ACF) U(VI) 5.5 298 — [312]
GO@sepiolite clay composite U(VI) 5 161.29 — [313]
GO-PANI U(VI) 6- 245 140.8 [302]
7
PVA-alginate/GO hydrogel Cs(I) 7 164.5 — [314]
Pectin stabilized magnetic GO Cs(I) 7 224 368.73 [315]
NH2 and N-derived groups functionalized GO (GO-N) composite Sr(II) 3.5 475 — [316]
PVA/GO aerogel Sr(II) 7 20.07 — [317]
Polyvinyl alcohol/graphene oxide/MnO2 composite Sr(II) 7 26.85 12.6 [286]
Polymer based GO Sr(II) 6 145.77 — [318]
Fe3O4–GO composite Sr(II) 6- 38.4 — [319]
7
GO-PANI Sr(II) 7- 147.2 140.8 [302]
8
Magnetic FeNi/RGO Eu(III) 6 16.61 — [320]
GO Th(IV) 1.4 58.59 — [321]
GO/CS/Cu-PBA (KCu hexacyanoferrate (II)) Cs(I) 6 64.7 — [322]
Fe3O4–GO composite Cs(I) >8 15.8 — [319]
GO-PANI Cs(I) 7 184.7 140.8 [302]

Declaration of Competing Interest

The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to influence
the work reported in this paper.

Data availability

No data was used for the research described in the article.

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