Materials Today Chemistry 16 (2020) 100262

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Materials Today Chemistry

journal homepage: www.journals.elsevier.com/materials-today-chemistry/

Water treatment: functional nanomaterials and applications from

adsorption to photodegradation
Karim Khanmohammadi Chenab a, Beheshteh Sohrabi a, Amir Jafari b,
Seeram Ramakrishna c, *
a
Department of Chemistry, Surface Chemistry Research Laboratory, Iran University of Science and Technology, Tehran, Iran
b
Department of Medical Nanotechnology, Faculty of Advanced Technology in Medicine, Iran University of Medical Sciences, Tehran, Iran
c
Department of Mechanical Engineering, Center for Nanofibers and Nanotechnology, National University of Singapore, Singapore

a r t i c l e i n f o a b s t r a c t

Article history: Global efforts for engineering desired materials which are able to treat the water sources still are ongoing
Received 3 February 2020 in the bench level methods. Considering adsorbent and photocatalytic materials as the main reliable
Received in revised form candidates still are encountering with struggles because of many challenges that restrict their large-scale
19 February 2020
application. This review comprehensively considered the recent advanced materials water treatment
Accepted 21 February 2020
methods which involve to magnetic, activated carbon, carbon nanotubes (CNTs), graphene (G), graphene
oxide (GO), (Graphene) quantum dots, carbon nanorods, carbon nano-onions, and reduced graphene
oxide (RGO), zeolite, silica and clay-based nanomaterials. The adsorption and photocatalytic properties of
Keywords:
Photocatalyst
these nanomaterials introduced them as highly potent option for heavy metal ions and organic dyes
Carbon nanomaterials removal and photocatalytic degradation. High specific surface area in conjugation with presenting higher
Heavy metal kinetics of adsorption and decomposition are the main characteristics of these materials which make
Dye them appropriate to treat wastewater even in ultralow concentration of the pollutants. Considering the
Pollutants mechanistic aspects of the adsorption and photocatalytic decomposition process, challenges and op-
Environment portunities were other subjects that have been highlighted for the discussed nanomaterials. In term of
the adsorption approaches, the mechanism of adsorptions and their influence on the maximum
adsorption capacity were discussed and also for photocatalyst approach the radical active spices and
their role in kinetic and efficiency of the organic pollutant decomposition were provided a deep
discussion.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction
The paradigm shifts away from the bulky to the nanomaterials
in recent decades, which has been caused to the great advance-
ments of nanotechnology in developing of nanomaterials which
with their nanoscale sizes have opened a new horizon to their
many industrial and environmental applications such as water
treatment and pollutants removal. Researches attention toward the
nanotechnology originated from the many physicochemical prop-
erties of the materials which could not be obtained from the bulk
phase, and this issue makes many advantages to their usage in
many fields of sciences especially in dye and heavy metal ions
removal [1e5]. Unfortunately, plethora of reports that prove their
* Corresponding author.
E-mail address: seeram@nus.edu.sg (S. Ramakrishna).
dangerous effects on human health and their control still remained
as a challenge especially few diseases directly relate to the water
sources. Many studies showed that, dye pollutants significantly
enhance the risk of esthetic aspects of the water sources which
potentially compromise the aquatics and plants ecosystems [6,7].
Moreover, the human society encounters and also struggles with
massive volume of the pollutants that threat environment and
many ecosystems. Elimination of the biofouling film on various
marine surfaces remains as a challenge because of high cost of the
antifouling conventional coating materials [8,9]. Recent major
concerns concentrated on the facts that how we can solve the
environment pollutants using nanomaterials with taking into ac-
count the safety issues. Basically, the pollutants penetration in
freshwater sources could be as an environmental challenge that
many expensive conventional protocols should be carried out for
their eliminations. High cost, disability of the conventional refining
methods in removal of the heavy metals, elimination of biofouling,

https://doi.org/10.1016/j.mtchem.2020.100262
2468-5194/© 2020 Elsevier Ltd. All rights reserved.
2 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262
and dye-based pollutants are the main problems which
seem struggling, and it needs to be solved these challenges ur-
gently. Therefore, developing a green approach that solves the
potential toxicity of nanomaterial and also eliminates the pollut-
ants have been as an interesting field which attracted a lot of at-
tentions of researchers in all over of the world because the green
nanomaterials with numerous benefits not only are more efficient
(in that the conventional methods do not) but also implementation
of the green and available sources, good stability, low final cost of
the refining, and and so on could replace previous expensive/low-
efficient old methods [10,11]. Principally, green sources of the
nanomaterials (e. g. natural locust bean gum-based hydrogels) with
adsorption and photocatalytic properties make them safer and
their methods of preparation in the most cases are easy [12e14].
Many experimental results, showed the effect of the dispersion
degree of nanomaterials in their toxicity. For these reasons, in
recent years, many efforts have been carried out for synthesis and
developing the solid safe nanomaterials [15]. In this approach, re-
searchers have tried to overcome to the agglomeration issue and
degree of dispersion as parameters which control their physi-
ochemical properties and especially their cytotoxicity. The sepa-
ration of the nanomaterials after refining process of the pollutants
from the clean phase, could be carried out by using various
methods, but using a magnetic nanomaterial which supply the
possibility of induced external control of separation after refining
have been reported [16]. For instance, iron oxide nanomaterials and
their derivatives which could be prepared by microwave ultrasonic,
solvo/hydrothermal methods. In addition, many chemical synthesis
processes can be used for preparing the nanomaterials such as sol-
gel, reverse microemulsion, and coprecipitation [17,18]. The water
treatment process is the main aims of the refining process which
they suffer from the low efficiency, high energy and cost, and
complicated process of treatment convince many researchers to
develop nanomaterials-based treatment methods. Among
mentioned methods, the precipitation process could be performed
in large scalable method for removal of heavy metals, for example,
chromium and so on. [19]. Recently, natural environment and
ecosystem encounter with heavy metals and industrial dyes, and
their toxic and harmful effects do not cover for anyone. The heavy
metals which mainly consist on Cd, Pb, Zn, Cu, Ni, Hg, and Cr ions
vastly detected in different kinds of water and soil sources that
their presence thoroughly relate to many industrial activities of
humankind [20e22]. The results of studies implicated that the dyes
as other types of toxic materials which have extreme biotoxicity,
carcinogenic and mutagenic effects, threating the life of many types
of aquatics [22]. Therefore, the technology of absorbing or removal
process of heavy metals and dyes not only is urgent but also
changes the deplorable condition of many types of aquatic animals
in water sources. Based on the recent literature, it has been dis-
cussed that magnetic nanoparticles (MNPs) such as iron oxide and
their derivatives have potential capability in removal and absorp-
tion of the heavy metals from the water sources which their ability
about removal of the Pb, As, and other types of heavy metal ions are
very hopeful and satisfactory [19]. Carbon nanomaterials are other
types of adsorbents and photocatalysts which indicate high effi-
ciency of water treatments because of high specific surface area and
various morphologies. In despite of nanomaterials good ability in
absorption process, low absorption capacity restricts their large-
scale applications. For instance, dissolution in acidic media for
many years had been remained as an unsolved challenge but in
recent years using many polymeric derivatives of the iron oxide
nanoparticles which avoid their dissolution in acidic media and
increase their absorption capacity because of increasing in specific
surface area could eliminate this limitation. Because the high risk of
desorption in adsorption approach, the photocatalytic approach
has been developed to overcoming this hurdle. So, the photo-
degradation process as one of the mechanisms for water source
remediation recently attracted many attentions because of solving
ability of desorption problems, higher reaction efficiency, low risk
of toxicity, and high kinetics of photochemical reactions under
visible irradiation. Therefore, this review discusses comprehen-
sively the types of the nanomaterials and their interfacial modifi-
cation effect on specific parameters that play a vital role in removal,
absorption and degradation features, and focuses on their synthetic
and modification methods. Different factors could affect the ab-
sorption and photodegradation mechanism, capacity and stability
of these types of materials which should be mentioned to their
optimum condition of absorption. Finally, the future prospective
and conclusion which show the reliability of these types of mate-
rials were presented. Fig. 1 schematically represents the family of
materials which have been discussed in this review.
2. Adsorption approach
2.1. Magnetic iron oxideebased nanoparticles
As a non-toxic, recyclable, reusable and easy-to-synthesis
nanomaterials, the MNPs are pioneer in great physiochemical
properties for absorption and removal of pollutants in which the
easy separation after removal process using an external induced
magnetic field make them unique in comparison with other types
of nanomaterials [23,24]. MNPs recently have been widely used as a
potential catalytic support material because of their magnetic be-
haviors which allows them to separate from the reaction batch
without using any advance methods of the separation such as ex-
tractions centrifugation or filtration methods. For this reason, they
could reduce the cost of the removal and catalytic process signifi-
cantly and increase the efficiency of the process. Besides, there has
been argued that the possibility of MNPs covalent binding inter-
action between their surface and catalysts is another plausible
method. This issue which basically decrease the MNPs dispersibility
in the reaction environments and could influence indirectly on the
purity and efficacy of the reaction. In this regard, MNPs recently
have been widely used as supports materials for organic materials
synthesis [25]. In addition, with good controlling in MNPs and their
surface modification and chemistry they have potential of usage as
agents for bioimaging, delivery, therapy, and other biological and
biomedical applications [23,26]. Metal oxide nanostructures are
one of the most widely investigated MNPs. Metal oxide nano-
material and nanostructures with semiconductor, insulator and
metallic properties illustrated great potential of applications in vast
types of electronic usage. Materials such as Fe2O3, MnO3, NiO2,
Co3O4, and many broad types of magnetic materials characteriza-
tion reported using easy and simple methods. Among them Fe2O3
and its derivatives (a-Fe2O3 and g-Fe2O3) have wide usage and are
more common that other magnetic nanomaterials [27]. Fe3O4 types
of materials with spinel, fcc, and hcp structure show the super-
paramagnetism properties [28,29]. Even more than this, the low
cytotoxicity and biocompatibility make them as appropriate option
for biological applications such as tissue engineering, therapy, and
bioimaging applications [23,30e33]. The superparamagnetic
properties of the Fe2O3 and its derivatives make it possible to
develop a core-shell nanomaterial with unique capabilities. Hence
Fe2O3 have been selected as core of the core-shell approaches, and
the shell can be the arbitrary materials. Dar and Shivashankar [27]
and Radu [34] et al. evaluated the temperature effect on the for-
mation of Fe3O4, g-Fe2O3, and a-Fe2O3 nanoparticles through
annealing method from 200 to 600
C. The single crystalline anal-
ysis and size of the particles from 30 to 65 nm have been proved for
the particles using HRTEM images method. Two types of the
 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262 3

Fig. 1. The schematic illustration of water treatment two main approaches involve to adsorption and photodegradation. The magnetic Fe2O3, zeolites, silica, amorphous
carbon, and clay NPs are some of the main applicable materials for adsorption of heavy metals and organic dyes pollutants. The graphene, graphene oxide, carbon nanotubes, carbon
nanorods, carbon graphene quantum dots and nano-onions could be used as the photocatalysts to photodegradation process of organic dye contaminants under light irradiation.

crystalline planes (222) and (311) were detected to the particles
which were related to the crystal lattice sizes 2.4 and 2.5 Å. In
addition, for g-Fe2O3, results showed the 4.8 Å and 2.5 Å were
related to the (111) and (311) planes, respectively. For a-Fe2O3, the
single plane (012) appeared in 3.6 Å crystal lattice. Magnetic
behavior of the nanoparticles showed the ferrimagnetic properties
with saturation magnetization equal to ~70 emu/g for all of the
samples at 25
C. Their results indicated non-magnetic properties
for hematite with saturation magnetization equal to ~0.9 emu/g at
25
C [27]. In accordance with recent reports, the saturation
magnetization amount for ferrimagnetic Fe2O3 based on their
crystal phase is 74.1 emu/g and 64.7 emu/g for magnetite and
maghemite [35]. The magnetite was formed at 370
C for 30 min,
whereas the maghemite could be formed at a temperature higher
than 200
C [35]. And it should be noted that the hematite phase
can form at temperature highre than 400
C (see Fig. 2).
Adsorption of solute spices form the liquid phase is a technique
that can be controlled by phase transfer process. The phase transfer
process which depends on the enrichment of absorbate on the
surface of a solid can be changed in various microenvironmental
conditions. Many parameters can play a role in this process such as
the solid surface wettability [36], the viscosity of the liquid phase,
the net charge of the solid surface, the nature of the absorbate, the
mechanism of the absorption, and so on [37]. Using solid-state
absorbents with high absorption capacity have been as major
challenge of the researches for removal of the heavy metals and
dyes. In this context, many important parameters are that should be
discussed by researchers which they directly influence on the
mechanism of the absorption and subsequently the capacity of
absorbent. Therefore, the physical and chemical absorption as two
main and critical adsorption mechanisms influence on the removal
mechanism and amount of heavy metal ions, dyes as absorbates are
the core of this field which attracted much attentions. In chemical
mechanism model, many types of strong interactions are being
postulated which include the coordination interaction between
absorbent and solute spices, chemical covalent, and acid-base
bonding, whereas in physical approach, the electrostatic forces
between absorbent and absorbate or other weak interaction such as
Van der Waals interactions are the base of the separations [21].
Basically, although the nature of the heavy metal ions or dyes
directly influences on the absorption capacity gradually, and the
absorbent and their mechanism of absorption should be appro-
priately designed based on the absorbate physiochemical proper-
ties and provide the absorption optimum condition [38].
Adsorption process as a fundamental phenomenon plays a key role
in removal process of pollutants because of their superior
4 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262

Fig. 2. TEM images of Fe3O4 magnetic nanoparticles (a). The tunneling emission microscopy (TEM) images show PEG200 (b), maghemite (c) and for hematite (d) in resolution
100 nm. (B) Furier transfer-infra red (FT-IR) spectroscopy analysis of magnetite, maghemite, and hematite. X-ray diffraction analysis for magnetite, maghemite, and hematite. The X-
ray photoelectron spectroscopy (XPS) analysis which shows the Fe2p for the maghemite (dashed line), hematite (dash-dot line), and magnetite (solid line). The figures reproduced
with permission from study by Radu et al. [34]. Copyright 2017 Elsevier.

properties to make a condition of absorption to obtain a low energy
consumption, easy, and ability to scale-up progress. All of these
parameters are related to the reversibility of the adsorbents to
regeneration and reusing the process [20]. In this respect, the
specific surface area plays a significant role because that controls
the time of absorption and its kinetics to achieve adsorption
equilibrium. Therefore, the capacity of absorption as one of the
main factors should be calculated to the adsorbates. Based on
several reports, there are many models of absorption which in
proportion to the absorption condition could estimate the param-
eters of absorption. Among them, the Langmuir isotherm is one of
the reliable and successful models generally has been used for
calculating the capacity of adsorption and also the mechanism.
Another model is the Freundlich isotherm that commonly has been
used for gas absorption on the solid substrate, but many reports
proved reliability of this model for the liquid phase under specific
condition. In accordance with the Langmuir isotherm model, the
absorption process is monolayer and the surface saturates after
monolayer absorption process which comprised from first, pseudo
first- or pseudo second-order of the absorption kinetic. Funda-
mentally, the kinetics of adsorption which considers the amount of
adsorbate concentration during adsorption process in versus of
time and depends on many factors such as surface functional
groups, wettability state, specific surface area, and so on that have
been controlled by interaction between adsorbent and adsorbate.
Although the monolayer adsorption could potentially restrict the
maximum adsorption capacity, developing adsorbents which could
remove the heavy metals and dyes in multilayer adsorption
mechanism directly depends on isotherm of adsorption. Unfortu-
nately, for many types of materials the adsorption occurs mono-
layer. The only condition for overcoming this hurdle is increasing
the surface area of the adsorbent. On one hand, increasing in spe-
cific surface area could cause monolayer adsorption. On the other
hand, because of the high amount of adsorption sites dye molecules
and heavy metals ions could adsorb without limitation in adsorp-
tion [39]. As mentioned previously, high porosity and specific sur-
face area is one of the most important characteristics of the
adsorbent materials which up to now many types of materials and
composite have been reported with these properties. The reduced
graphene oxide (RGO) [40], synthetic zeolite [41], and active carbon
[42] are the groups of materials that can play as potent materials for
adsorbent applications because of high specific surface area.
Although, the mixture of these materials and MNPs can
decrease the specific surface area of the composite, whereas for the
 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262
combination of materials such as clay and zeolites with low surface
area MNPs would enhance that [40,42e47]. Therefore, considering
the specific surface area after composition with magnetic particles
is urgent and could reveal many points about the adsorption ca-
pacity [48e50]. The role of dispersion degree in specific surface
area is irrevocable and recently in many reports, this issue has
comprehensively been considered. For example, Mohebrad et al.
[51] considered the specific surface area effect of the microbial
electrochemical system of the whey cheese on protein removal
efficiency. Up to now, vast range of the nanomaterials which
composited with MNPs is used as substrates for removal of the blue
dye. The activated montmorillonite [52], carbon [53e55], silica
[56], rectorite [57], zeolite [58], graphene [59], graphene oxide (GO)
[60,61], carbon nanotubes (CNTs) [62], and halloysite nanotubes
[63] are the broad family of materials with high specific surface
area, and the high capability of application in dyes and heavy metal
ions removal. Mechanism of absorption on the zeolites is on the
base of the ion exchange ability between solid surface and liquid
phase. The superhydrophobic Fe2O3 nanorod is another magnetic
option which could be used for oil wastes from the water sources
removal [64].
2.2. Zeolites and silica-based nanomaterials
Zeolites are one of the highly porous materials which have
great potential of application as adsorbent of many types of
pollutants because of their capability in high absorption capacity
and efficient treatments of pollutants. Generally, zeolites can be
categorized to main synthetic and natural types which their
application in water treatment have been reported so far. Based
on many reports, natural zeolites (e. g. clinoptilolite) and syn-
thetic types did not show similar behavior in absorption of heavy
metals because of their difference in physiochemical properties
such as their surface porosity, purity, and their chemical stability
[65]. Meanwhile, for the zeolites which composited with Fe3O4
MNPs, the synthetic and natural types showed significant ab-
sorption [41,43,66]. The presence of the magnetic nanomaterials
makes it possible that the cytotoxicity of these types of materials
greatly have been decreased. Moreover, the biocompatibility is
other property of these materials that makes them suitable for
biological application [67]. The removal of the dye pollutants are
the other applications of the zeolites and Fe2O3 MNPs composites
which in accordance with the reports they have been tested to
removal of the malachite green dye from the water media which
is one of the most harmful type of the dye pollutants that its
presence in water sources can cause too many carcinogenesis and
other kind of the fractures in aquatics [68,69]. The recent study
about the removal of malachite green dye showed the strong pH
dependency (pH ¼ 8.0) of absorption. In this pH, the maximum
absorption capacity was obtained that was equal to 13.8 mg/g at
first dye concentration equal 80 mg/L, and in addition, the con-
tact time between dye and adsorbent was estimated equal one
hour at 6
C. It should be noted that, maximum adsorption from
water medium on adsorbent after reaching to the equilibrium of
adsorption and desorption. Typically, this unit defined as mg/g of
adsorbate over nanomaterial as adsorbent. Usually, many factors
such as specific surface area, wettability of the adsorbent, surface
functional group, size of nanomaterials and their morphology are
the associating things that play a role in the maximum amount of
nanomaterial adsorption capacity. The results indicated that the
process of adsorption not only is exothermic but also were car-
ried out spontaneously which relate to the fly ash zeolitic
structure [69]. Moreover, in another report, Jain et al. in
communication to the fly ash absorption potential abilities
5
studied magnetic nanocomposites with fly ash [69] in 3:1 wt
ratio. The composite saturation magnetization was analyzed
which was equal to 19.9 emu g-1. This composition indicated the
good capacity of absorption for heavy metal ions as
Zn2þ<Cd2þ<Pb2þ. More study about the mechanism of adsorp-
tion revealed that the capacity of adsorption could be affected by
ions electronegativity which for Pb2þ, Cd2þ, and Zn2þ was equal
with 2.33, 1.69, and 1.65, respectively. Another factor which plays
a role in adsorption process is the ions radii which were 1.21,
0.97, and 0.74 Å for Pb2þ, Cd2þ, and Zn2þ, respectively which
could be interpreted by hard soft acid-base theory [69,70].
Pizarro et al. [49] in a study which considered the composition of
nanomagnetite and zeolite reported high adsorption capacity for
removal of arsenic ions. Their results indicated that amount of
the adsorbed arsenic ions depends on average size of nano-
magnetite (50 nm) which composited by natural zeolite. They
noted that the monodentate and bidentate coordination binding
between arsenic ions and Fe atoms not only cause high absorp-
tion capacity but also make the complex highly stable against
desorption of the ions. In should be noted that the magnetic-
induced effect of the nanoparticles can be as other structural
parameter that can help to high adsorption capacity [49]. These
types of the magnetic zeolite composites were considered by
Yuan et al. [71] to removing the Pb2þ ions through 120 min were
obtained for the contact time and adsorption process to achieve
the equilibrium. The capacity of adsorption was determined
equal to 196.8 mg/g under the condition that Fe3O4 particles had
5% of the zeolitic adsorbent. The surface optimum physi-
ochemical properties can play a significant role in Pb2þ adsorp-
tion process which have been considered by magnetic
composition of chitosan/clinoptilolite zeolite [72]. Among many
parameters, pH, temperature, concentration of adsorbate, and
adsorbent are the main parameters that should be optimized for
obtaining maximum adsorption. For chitosan/clinoptilolite mag-
netic nanocomposite, the optimum of these parameters were
4.0e6.0 20
C-60
C, 10e90 mg/L 0.2e1.0 g/L, respectively. The
maximum amount for adsorption capacity of Pb2þ on chitosan/
clinoptilolite magnetic nanocomposite was 124.955 mg/g which
was obtained at 5.49, 60
C, 89.08 mg/L of adsorbate, 0.48 g/L of
adsorbent, respectively. Many reports indicated the presence of
the many types of heavy metal ions in water sources which
convince researcher to develop special adsorbents family with
capability of simultaneous adsorption. In this respect, in on
study, the simultaneous adsorption process of metal ions consists
of Pb2þ, Cu2þ, Cr6þ, and Cd2þ using magnetic Fe3O4/mesoporous
silica-based nanocomposite has been considered. Analysis of ki-
netics showed that adsorption cab be modeled with pseudo
second-order, whereas the ions were adsorbed monolayer in
which their isotherm of adsorption can be considered with
Langmuir model. Based on this model, the maximum adsorption
capacities were obtained equal to 127.24, 125.80, 115.60, and
114.08 mg.g1 for Pb2þ, Cu2þ, Cr6þ and Cd2þ, respectively (Fig. 3)
[73].
Metal organic frameworks (MOFs) recently have been the
major attention in various fields. These types of materials show
great reliability for being used in water remediation because the
high specific surface area, high surface free energy, ability to
provide broad range of the surface area, and ability to engage in
various functionalization based on their surface features for
removal applications. In this communication, the Fe3O4/SiO2/Zr
MOF magnetic adsorbent was applied to removal of the Pb2þ,
methyl orange, and methylene blue dyes. This adsorbent shows
the capacity of adsorption equal to 102.2, 219 and 128 mg/g,
respectively [74]. The presence of MOF has a significant effect on
6 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262

Fig. 3. (a) Scanning electron microscopy (SEM) and (b) tunneling emission microscopy (TEM) of image of magnetic Fe3O4/mesoporous silica-based nanocomposite. Contact time
versus uptake (left) and pH (right) of 4-chlorophenole and 4-bromophenole on magnetic Fe3O4/mesoporous silica-based nanocomposite. The adsorbate initial concentration was
50 mg/L, whereas agitation rate was set on 250 rpm, and also adsorbent dosage was 0.2 g/L at ambient temperature 25
C. The figures reproduced with permission from a study by
Anbia et al. [73]. Copyright 2015 Springer.

the capacity of adsorption. By the mean that the maximum
adsorption capacity was rose up to 248 mg/g at pH 10 after
100 min at 25
C [56].
2.3. Clay-based nanomaterials
Most of the published records have been dedicated to applica-
tion of clay-based materials for removal of dyes, nutrients, and
heavy metal ions. There are broad range of the clays such as
montmorillonite, kaolinite, sepiolite, bentonite, and sericite which
are in the center of the researchers' attentions because of their low-
cost, high specific surface area, high chemical stability in broad
range of pH and so on; for example, the montmorillonite large
surface area potentially provides high capacity of adsorption in
comparison with other alike. Many reports attributed to the fact
that the heavy metal ions can be removed from liquid media using
montmorillonite during the ion exchange mechanism and also
adsorption process. The two main interactions are responsible to
the adsorption process which involve electrostatic attractions and
hydrogen bonding that could be formed between metal ions and
surface sites and also between edge of montmorillonite surface
[58,75]. For the talc (one another type of clay) surface, the
adsorption mechanism is different because basically the talc sur-
face divides into two non-polar ‘faces’ and polar ‘edges’ of the
structure. Therefore, metal ions can potentially adsorb on nega-
tively charged sites of the talc surface [76e78]. In this respect,
Kalantari et al. [77] evaluated the capability of the magnetic Fe3O4/
talc-based nanocomposites as highly potent option for removal
application of Cu2þ, Pb2þ, and Ni2þ. For these ions, although the
initial concentration was set at 100, 92, and 270 mg/L, the removal
of the ions time were 120 s and also the adsorption capacity was
determined equal to 74.62, 21.05, and 33.33 mg/g for Pb2þ, Cu2þ,
and Ni2þ, respectively. In another study, Dong et al. [79] studied a
novel nanocomposite which formed from hydroxyapatite/magne-
tite to evaluate its removal effect on Pb2þ ions (Fig. 4). They re-
ported the peak adsorption capacity for this nanocomposite was
598.8 mg/g, in which the adsorption isotherm followed the Lang-
muir model.
The simultaneous removal of the heavy metal ions was
considered by Yan et al. [44] for Pb2þ, Cd2þ, and Cu2þ using Fe3O4/
bentonite as adsorbent which combined each other in 1.44:1 ratio
of Fe3O4 to bentonite. They found that the equilibrium of adsorp-
tion process was achieved after 30 min, and the adsorption ca-
pacities measured and that were equal to 81.5, 21.7, and 19.6 mg/g
for Pb2þ, Cd2þ, and Cu2þ, respectively.
2.4. Carbon-based nanomaterials
2.4.1. Activated carbon
As a commercial adsorbent, the activated carbon has been
widely applied for many applications in various fields and also
the removal of the heavy metals, dyes, and harmful nutrients. In
recent years, the removal of contaminations in ppm and ppb
concentration attracted a lot of attentions because of the harmful
effect of the heavy metals even in the ppb level of concentrations
[19,80]. In this respect, Yao et al. [81] considered the removal
properties of the magnetic composition of the iron oxide/acti-
vated carbon for removal of Pb2þ ions. High specific surface area
 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262
Fig. 4. The scanning electron microscopy (SEM) for magnetic hydroxyapatite/Fe3O4: (a) before adsorption of Pb2þ and (b) after adsorption of Pb2þ; (c) Contacting time versus
removal efficiency for Pb2þ ions using hydroxyapatite/Fe3O4; (d) pH versus removal efficiency for Pb2þ ions using hydroxyapatite/Fe3O4 The figures reproduced with permission
from a study by Dong et al. [79]. Copyright 2010 Elsevier.
for iron oxide/activated carbon which was 678.3 m2/g of the
adsorbent and maximum adsorption capacity equal to 19.37 mg/g
obtained great removal at pH ¼ 6. The mesoporous Fe2O3@C has
another interesting encapsulate properties which makes it as
appropriate option for removal of the arsenic ions. Moreover, the
fast adsorption process of arsenic ions implies on the fact that the
rate of adsorption can be fitted to pseudo second-order kinetics.
In addition, the excellent reusability of this adsorbent proves its
great chemical stability in the whole range of pH [82]. Increasing
in temperature of the preparation of the composite causes great
enhancement in absorption and saturation equilibrium of
Fe2O3@C-300 and Fe2O3@C-500. For the samples, the reported
capacity of adsorption were equal to ~19.3 and 29.4 mg.g1 for
As3þ ions and 8.0 and 17.9 mg.g1 for As5þ ions [82]. The results
indicated the different interactions between adsorbents and
arsenic ions which rely on different absorption mechanism and
subsequently different adsorption capacity. Moreover, the fast
adsorption after 10 min of the 98% of As3þ which was in 5 ppm
shows the remarkable kinetics of this type of adsorbents. The
kinetics of adsorption was fitted on pseudo second-order model
(Fig. 5) [82]. The capability of matrix to eliminate As3þ ions from
the liquid media was considered which just in ~1.4 mg.g-1 at
25
C saturation capacity was measured. But the incorporation
process which involves loading 52 wt% iron oxides on carbon
during pyrolysis process at 300 and 500
C, significant adsorption
was obtained to the samples which were equal to ~27.7 and
18.1 mg.g1 for As3þ, respectively. The stable mono or/and
bidentate coordination between iron oxide and ions are the main
mechanism of the adsorption. The adsorption of As5þ on the
carbon matrix and the Fe2O3@C-T encapsulates also showed the
same results [82].
7
2.4.2. Carbon nanotubes
The remarkable electrical and thermal properties of the carbon-
based nanomaterial based on latest publications have introduced
them as highly potent candidates for many electronic and other
biological and biomedical applications [83]. Moreover, many other
useful properties of these nanomaterials increase their capability of
usage for water remediation because the large specific surface area,
great ability for their surface chemical and physical modification
and functionalization and so on. [84,85]. Most of the CNT's water
treatment application was reported for heavy metals elimination
[86]. In term of structural view, the CNTs can be found in two mains
categorize of the single-walled CNTs and the multiwalled CNTs
(MWCNTs) [87] which they differ on the number of the walls and
the diameters [88,89]. CNTs as materials with high specific surface
area exhibit significant adsorption capability of elimination many
types of the heavy metals such Mn7þ, Tlþ, Cu2þ, Pb2þ, Cr6þ, and so
on. [90e94]. The internal and external active sites of the CNTs
potentially enhance their ability for these applications. In order for
improving the capacity of adsorption for CNTs (removal of heavy
metals) plausibly functional groups can be made during the func-
tionalization process, in which they are carboxylic acids (eCOOH),
amines (eNH2), hydroxyl (eOH) and so on. The functionalization
process go through chemical and thermal methods and can be
found even in omnipresent literatures [95]. For instance, in this
process, the oxidant agents and materials can be used for
improving the number and types of functional groups [96]. In this
respect, recently, Mohamed et al. [97] demonstrated a functional-
ization method of CNTs for removal of Hg2þ. They reported allyl
triphenyl phosphonium bromide and glycerol as a preoxidized
agent in batch condition and pH of the adsorption of Hg2þ was set
in 5.5 in which after 28 min of contact time in the peak adsorption
8 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262

Fig. 5. Schematic representation of the Fe2O3@C encapsulates adsorbent and its synthesis process. Tunneling emission microscopy (a, b, e, f), High resolution tunneling emission
microscopy (c, d, insets in d and e), Selected area diffraction (SAED) patterns (insets in c and e), and dark-field scanning tunneling emission microscopy (TEM) image (g) of the
mesoporous Fe2O3@C-T encapsulates obtained at 300 (aed), 500 (e), and 600
C (f, g) respectively. Adsorption isotherms which was obtained at 25
C (A) for As3þ (aec) and for As5þ
(def) on the mesoporous carbon (a, d), Fe2O3@C-300 (c, f), and Fe2O3@C-500 (b, e). Time-dependent capture for As3þ (B) by the mesoporous Fe2O3@C-500 with a adsorbent dosage
equal to 1 mg mL1 and arsenic concentration equal to 5 (g,h) and 25 ppm (i,j). The figures reproduced with permission from Ref. [82]. Copyright 2012 Wiley.

was observed also based on Freundlich isotherm model, and the
maximum adsorption capacity was 186.97 mg$g1. The adsorption
kinetics for this type of adsorbent followed the pseudo second-
order. Although, the comprehensive consideration of carbon-based
nanomaterial and their ability in removal application for heavy
metals were reviewed by Xu et al. [98]. In another argument, the
combination of the CNTs with other materials could also give great
composites with high ability of adsorption. In this communication,
Zhan et al. [99] developed an amino-functionalized Fe3O4/carbox-
ylic MWCNTs using solvothermal synthetic method. Observed
 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262
appropriate efficiency in removal of the Cu2þ ions were resulted for
the synergistic effect which originated from CNTs and the amino
groups simultaneous present. in addition, they reported the
adsorption capacity for Cu2þ was 30.49 mg$g1 in which the
isotherm of the adsorption satisfied by Langmuir model. In addi-
tion, the presence of the external induced magnetic field from the
magnetic iron oxide nanoparticles could play an helpful role to
increase the separation capacity. Despite of CNTs, successful
removal functionality of the heavy metals, their applications could
be limited because of some challenges that they encountered with.
The first issue related to the final cost of separation which CNTs
higher cost causes higher cost of separation. Second, dispersion
problem of the CNTs which still remain as an unsolved challenge.
Although many different methods been proposed for dispersion
such as using ultrasonic waves, surfactant agents, and polymeric
materials. But their dispersion in large-scale could restrict their
usage in this field. Moreover, the separation process of the CNTs
after adsorption process is another challenge which makes a risk of
their pollution in water media and most importantly, they are
potentially toxic and this aspect of the issue is under debate [95].
2.4.3. Graphene, graphene oxide, and reduced graphene oxide
Graphene is one of the most important and applicable 2D ma-
terials in which its great potential of application in water remedi-
ation, well understood at recent literatures through exceptional
features in that, can be found just in this category. Because of the
exceptional physiochemical properties such as mechanical, stiff-
ness, electrical, thermal, optical and more especially high specific
surface area are the characteristics of the G and its derivatives that
make them as pioneer of the many applications such as water
remediation and heavy metal adsorption from the wastewater
sources [95]. GO and RGO are the two main derivatives of the G
which is the base of many materials to obtain high capacity of
adsorption of heavy metals during the water remediation process.
The presence of the functional groups which mainly are the hy-
droxyl (-OH), carboxyl (-COOH), epoxide and carbonyl functional
groups not only make the G sheets more hydrophilic to disperse in
aqueous media but also make great potential for functionalization
and composition of these types of materials and the MNPs [100].
Similar to the G, the RGO with eOH, eCOOH functional groups
Fig. 6. The graphite, G and other allotropes of carbon with functional groups which can cause negative charge on their surfaces. Reproduced with permission from a study by

rez-Iglesias et al. [102]. Copyright 2017 Elsevier.
Sua
9
could be modified easier than GO because of the mild oxidation
condition and their easy dispersibility in water media [101]. The
structure of the G and RGO for many years have been considered
and finally their negative charges which could be related to the
presence of the oxygen-containing functional groups and also the
hydrophilic nature of the sheets are the main reasons for appro-
priate adsorption capacity of heavy metals (Fig. 6) [102].
The water remediation and heavy metal removal application of
the G-, GO-, and RGO-based materials recently have been reported
by many researchers. For example, Wang et al. [103] evaluated the
factors that can play a role in heavy metal removal. These param-
eters were pH, concentration of the adsorbent, contact time of
absorbate and adsorbent, temperature, and presence of the coex-
isting ions that may disrupt the removal process. Their results
demonstrated that the monolayer adsorption fitted suitably with
Langmuir isotherm and the kinetic of adsorption can be considered
by pseudo second-order model. In accordance with their results,
the capacity of adsorption for Zn2þ was more than 246 mg$g1,
which shows appropriate adsorption of Zn2þ by GO. In another
study, Zhao et al. [104] developed ultrathin layers of the GO
nanosheets using Hummers method. Their results indicated that
the great adsorption could be obtained for the heavy metal ions
removal such as Cd2þ and Co2þ. Interestingly, pH-dependent nature
of the oxygen-contained functional groups which regulates the net
charge of the GO sheets, the adsorption process extremely should
be depended on pH. The adsorption capacities less or more could be
affected by pH and for the Cd2þ and Co2þ were 106.3 and
68.2 mg$g1, respectively. As mentioned previously, after disper-
sion of the G, GO, and RGO in water media, their separation is so
difficult and needs many complicated separation processes which
ended up with expensive costs. In this respect, Arshad et al. [105]
developed as novel G-based adsorbent using calcium alginate
which was embedded to GO and was reduced by polyethylenimine,
and the adsorption capacity obtained for Pb2þ, Hg2þ, and Cd2þ were
602, 374, 181 mg$g1, respectively which could be fitted on the
Langmuir isotherm because of the monolayer adsorption of the
ions. Moreover, they considered the kinetics of adsorption and re-
sults showed that the pseudo second-order kinetics could explain
as well for this type of adsorbent. The functionalizing process of the
calcium alginate plays a significant role in adsorption process and
10 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262

Fig. 7. (a) Representation of G airgel fabrication which shows supercapacitor properties and has adsorption abilities. (b) low-resolution scanning electron microscopy (SEM)
micrograph for G airgel. High-resolution- X-ray photoelectron spectroscopy (HR-XPS) spectra of C 1s peak: for (c) Gas and (d) activated GAs. (e) Isotherms consideration (f) dis-
tribution of pore size (g) isotherms and (h) distribution of pore size for GAs after KOH activation process. The figures reproduced with permission from a study by Myung et al. [106].
Copyright 2019 ACS.
 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262 11

Table 1
The representative of the recent adsorption-based nanomaterials and their characteristics in heavy metals and organic dyes removal process.

Adsorbent Adsorbate Maximum capacity of Adsorption (mg.g-1) Contact time (minutes) Reference

Talc-Fe3O4 Cu2þ, Ni2þ, Pb2þ 21.05, 33.33, 74.62 2, 2, 2 [76e78]

Montmorillonite Fe3O4 Cu2þ, Ni2þ, Pb2þ 70.92 2, 2, 2 [75]
65.78
263.15
Montmorillonite-Fe3O4 Cr6þ 15.3 60 [107]
Activated montmorillonite Methylene blue 106.38 25.02 [52]
Fe3O4
Bentonite-Fe3O4 Pb2þ 81.5 30 [44]
Cd2þ 21.7 30
Cu2þ 19.6 30
Kaolinite- Fe3O4 Cu2þ 98 120 [108]
Pb2þ 106 120
Cd2þ 97 120
Cr5þ 100 120
Ni2þ 95.2 120
Bentonite-Fe3O4 Co2þ 18.76 15 [109]
Aluminosilicate nanotubes (Imogolite) As5þ 349.16 240 [110]
- Fe3O4
Mesoporous As5þ 74 1440 [111]
Silicate
- Fe3O4
Sepiolite- Fe3O4 Cr6þ 33.4 1440 [48]
Titanate nanotubes Pb2þ 382.3 240 [112]
- Fe3O4
Rectorite- Fe3O4 Methylene blue 18.6 480 [57]
Neutral red 16.0 480
Hydroxyapatite- Fe3O4 Pb2þ 598.98 1440 [79]
Layered double hydroxide Cr6þ 50.65 1440 [113]
- Fe3O4
Sericite Fe2O3 As5þ 5.78 900 [114]
Halloysite nanotubes Cd2þ 11.4 45 [115]
- Fe3O4
Halloysite nanotubes Methylene blue 18.44 480 [63]
- Fe3O4 Neutral red 13.62 480
Methyl orange 0.65 480
Carbon- Fe3O4 Cr6þ 61.69 240 [116]
Carbon- Fe3O4 As3þ 29.4 300 [82]
Carbon- Fe3O4 Methylene blue 117 180 [55]
Carbon-FexOy Methylene blue 60.84 250 [54]
Activated carbon Cd2þ 49.75 30 [42]
- Fe3O4 Pb2þ 86.21 24
Activated carbon Cu2þ N/A 10 [117]
- Fe3O4
Activated carbon As5þ 29.4 300 [82]
- Fe2O3
Carbon-Fe3O4 Methylene blue 117 180 [55]
Carbon-FexOy Methylene blue 60.84 250 [54]
Activated carbon Cd2þ 49.75 30 [42]
- Fe3O4 Pb2þ 86.21 24
Activated carbon Cd2þ N/A 10 [117]
- Fe3O4
Activated carbon As5þ 13.87e20.33 120 [118]
- Fe3O4
2þ
Activated carbon Pb 18.21e19.37 1440 [81]
- Fe3O4
Activated carbon Acid yellow 17 71.43e83.33 30 [119]
a-Fe2O3
Activated carbon Alizarin Red S 108.69 60 [120]
g-Fe2O3
Activated carbon Remazol 211.05 60 [121]
- Fe2O3 Brilliant Blue R
Activated carbon Bismarck 224.0 60 [122]
- Fe3O4 Brown
Activated carbon Procion red 278 50 [123]
- Fe3O4
Activated carbon Nylosan blue 223.82 120 [124]
- Fe3O4 Chromazurol S 114.68 120
Safranin T 286.91 120
Carbon nanotubes Cu2þ 8.148 600 [125]
- Fe3O4
Carbon nanotubes Cr4þ 47.98e83.54 30 [126]
- Fe3O4
(continued on next page)
12 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262

Table 1 (continued )

Adsorbent Adsorbate Maximum capacity of Adsorption (mg.g-1) Contact time (minutes) Reference

Carbon nanotubes Methylene blue 48.1 15 [62]

- Fe3O4 Thionine 36.4 15
Janus green B 250.0 15
Carbon nanotubes Methyl orange 10.54e10.89 70 [127]
- Fe3O4
6þ
Carbon nanosphere Cr 200 720 [128]
- Fe2O3
2þ
Multi walled carbon Pb 41.77 N/A [129]
nanotubes
- Fe3O4
Multi walled carbon Methyl violet 666.7 41 [130]
nanotubes
- Fe3O4
Graphene oxide - Fe3O4 Hg2þ 91.29 120 [131]
Graphene oxide - Fe3O4 Cd2þ 91.29 1440 [60]
Graphene oxide foam Cr6þ 258.6 20 [132]
- Fe3O4
Polypyrolle graphene oxide Hg2þ 400e769 600 [133]
- Fe3O4
3þ
Silica-graphene oxide Cr 4.7 5 [134]
- Fe3O4
Graphene oxide - Fe3O4 Reactive Blue 62.54 70 [135]
19
Graphene oxide - Fe3O4 Reactive 164 & 188 120e1440 [136]
Black 5
Graphene oxide - Fe3O4 Methylene blue 172.6 70 [61]
Graphene oxide - Fe3O4 Malachite green 27.9 1 [137]
Graphene oxide - Fe3O4 Methylene Blue 64.23 1440 [60]
Orange G 20.85 1440
Reduced graphene oxide (RGO) Pb2þ 1666.66 60 [138]
- Fe3O4
Reduced graphene oxide Pb2þ 30.68 600 [139]
- Fe3O4
5þ
Reduced graphene oxide As 58.48 170 [140]
- Fe3O4 Pb2þ 65.79 170
Ni2þ 76.34 170
Reduced graphene oxide Rhodamine 93.37 120 [136]
- Fe3O4 6G
Re59duced graphene oxide Methyl violet 196 45 [141]
- Fe3O4
3þ
Graphene Iron oxide As 11.34 120 [73]
Calcium silicate graphene oxide (MGSi) Acridine orange 193.05 480 [142]
- Fe3O4
Graphene - Fe3O4 Fuchsine 89.4 60 [143]
Graphene - Fe3O4 Rhodamine B 186.4 30 [144]
Graphene - Fe3O4 Rhodamine B 67.43e82.41 30 [145]
Graphene Fe2O Methylene Blue 45.27 30 [59]
Congo red 33.66 30

has a synergetic effect for removal process. Other great properties
of this adsorbent were high reusability which after five-time
adsorption process still showed high efficiency for Pb2þ that was
about 75e80%. Dye adsorption using G airgel recently was intro-
duced by Myung et al. [106] for removal of MB, Rh B, MO, and BG1.
They reported complete adsorption for G airgel after 12 h (Fig. 7).
Table 1 shows a great comparison between characteristics of
different materials for removal of the heavy metals and organic
dyes. The time of adsorption as one of the most important factors in
commercialization process plays a significant role which is in order
of the ~0.5e2.0 h. This time is too long, and it could limit the in-
dustrial and large-scale application of the nanomaterials in removal
process. Therefore, increasing in kinetics of adsorption could be
urgent.
four main interfacial and molecular mechanism. First, is contami-
nant (dyes, pigments, or other types of the organic molecules)
diffusion process from the aqueous phase to the the photocatalyst
interface; second, adsorption of dye molecules on the surface;
third, oxidation of absorbed contaminants with radical spices;
forth, desorption of the reaction products. In contrast to the
adsorption approach that uses the adsorption mechanisms for
removal of the dyes and heavy metals, pollutants have been
degraded during some radical types of the reactions in presence of
the photocatalysts in the photocatalytic approach. In this section,
the types and mechanism of the photodegradation process
comprehensively were discussed.
3.1. Mechanism of photodegradation and regeneration

3. Degradation approach
Implementation of light source for photocatalytic degradation of
the pollutants in water sources has recently been an efficient
approach which could solve many restrictions that researchers
struggle. The photocatalytic treatment mechanistically involves
Basically, in this process, the highly active radical spices such as
hydroxyl radicals (OH) during a photocatalytic condition were
generated and under the condition that the organic pollutants are
in direct contact with these spices, they were degraded efficiently
[146,147]. In accordance with the photocatalytic degradation phe-
nomenon, this process has several benefits in comparison with the
 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262 13

Fig. 8. The scanning electron microscopy (SEM) image of silver-ZnO-MWCNT photocatalyst and the dye photodegradation process. The figures reproduced with permission from a
study by Moradi et al. [146]. Copyright 2017 Elsevier.

adsorption approach. First, it is about the concentration of the
pollutants, in which these types of removal can significantly carry
out, whereas in adsorption approach, removal in ultralow con-
centration removal of the heavy metals of dyes still remained as a
challenge [148]. Enhanced adsorption and consecutive photo-
catalytic degradation phenomenon of dyes possibly encountered
with several problem. Photocatalyst deactivation (i.e. loss of pho-
tocatalyst active sites) is a gradual process which associated with
considerable decline in the removal efficiency of dyes and get
worse as by-products increased just because of partial oxidation of
organic compounds. In this context, one of the problems is that
simply related to intermediate products accumulation on the
nanomaterial surface which through physical blocking of active
sites put limitation on photon accessibility to the catalyst surface.
When this process is repeated several times, nanomaterial loses
their efficiency and functionality [149]. Even in the case of the
wide-gap semiconductors (e. g. TiO2), it had been revealed that
presence of some functional groups such as surface hydroxyl
groups, for the formation of the photo-induced oxygen vacancies
resulted in higher regeneration in comparison with photocatalysts
with low hydroxyl group. Interestingly, for regeneration of active
sites in semiconductors, it would be enough to expose nano-
materials to UV light and H2O(g)-rich atmosphere simultaneously
[150]. Keeping the humidity content for stabilizing efficacy of
photodegradation in the reactor possibly would be enough to
continuously rehydrate the photocatalyst surface [151]. Another

Fig. 9. Scanning electron microscopy (SEM) of CNTs in various diameter (a) 10e20 nm, (b) 20e40 nm and (c) 40e60 nm; UV-Vis Absorption of methyl orange dye after microwave
degradation (25 mg/L methyl orange, 450 W of microwave degradation, 3.0 min time of contact in microwave degradation condition, 1.2 g/L CNTs under pH ¼ 6.0 condition);
influence of microwave irradiation versus time (a) and the kinetics of degradation (b). The figures reproduced with permission from a study by Chen et al.[159]. Copyright 2016
Elsevier. CNTs, carbon nanotubes.
14 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262

Fig. 10. Tunneling emission microscopy (TEM) of CdS and CdS/RGO nanocomposites prepared under different conditions. (a) CdS (xC%, xO%, xCd%, xS%, and wCdwt% ¼ 26.7, 10.4,
32.6, 30.3 and 90.5), (b) NCP-I (xC%, xO%, xCd%, xS%, and wCdwt% ¼ 38.5, 14.4, 24.2, 22.8, and 83.4), (c) NCP-II (xC%, xO%, xCd%, xS%, and wCdwt% ¼ 44.6, 15.9, 20.3, 19.2, and 78.6),
(d) NCP-III (xC%, xO%, xCd%, xS%, and wCdwt% ¼ 65.3, 21.1, 6.9, 6.7, and 46.9), (e) NCP-IV (xC%, xO%, xCd%, xS%, and wCdwt% ¼ 46.3, 15.6, 20.9, 17.2, and 78.3); (a) X-ray photoelectron
spectroscopy (XPS) analysis for CdS/RGO photocatalysts (NCP-I). (b), (c) XPS C 1s spectrum of CdS/RGO photocatalysts (NCP-IV, NCP-II); (a) Decomposition process of Rh.B, (b)
Decomposition of Rh.B in presence CdS and CdS/RGO photocatalyst. The figures reproduced with permission from a study by Fu et al. [166]. Copyright 2016 Elsevier. RGO, reduced
graphene oxide.

approach to regenerate photocatalysts for repeated use go through the photocatalytic process of the organic pollutants' degradation on
atmospheric oxygen injection during photocatalysis. Oxygen in- the silver-ZnO-MWCNT as a photoactive catalyst was depicted in
jection causes production of more radicals for the degradation of Fig. 8. In this process, the hole-electron formation after incident the
toxic hydrocarbon species [152]. The schematic representation of light photons could generate a charge transfer in photocatalyst
 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262
Fig. 11. Tunneling emission microscopy (TEM) of magnetic photocatalytic samples (A) CuFe2O4 (B) CuFe2O4 with 30 wt%GO (C) CuFe2O4 with 20 wt%GO (D) CuFe2O4 with 10 wt%GO
which have been used for acid orange 7 degradation. Chart of dye concentration (a) and ln(C0/C) (b) versus time. Influence of GO on photocatalytic reaction on CuFe2O4/GO. The
decomposition efficiency for the sample was 95% which has been obtained in presence of 0.8 g/L after 50 min of contact time. Adapted with permission from a study by Chen et al.
[169]. Copyright 2016 Elsevier.
which facilitates the formation of the O2- radicals. The generated
radicals could degrade the organic pollutants.
The advanced oxidation process of the organic pollutants refers
to the procedures that uses from the sunlight and ultra-violet ir-
radiations. In addition, the ozonation process on wet aqueous
media are the other categories of the chemical degradation of the
pollutants [153].
3.2. CNT-based photocatalysts
In recent years, the CNT-based composites showed great reli-
ability to use as photocatalysts for removal of the organic pollutants
because of their potential ability to functionalize and develope
composites with better physiochemical properties. The function-
alization not only could enhance the specific surface area for CNTs
with increasing in dispersibility, but also make it possible for dyes
to interact more efficiently with photocatalytic sites [154e157]. For
example, Si/Al@Fe/MWCNT which coated with ferrocene groups
showed appropriate photocatalytic activity for photodegradation
process of methyl orange, methyl blue orange G, and acid orange 7.
All parameters that can play a role in photocatalytic degradation
were evaluated, and the pH, time of reaction, concentration of
H2O2, amount of catalyst, and temperature were the parameters
which potentially control the efficiency of photodegradation pro-
cess [158]. In this respect, recent development of novel type of
CNTs/TiO2/AgNPs/surfactant photocatalyst was synthesized and
was applied for removal of the methyl blue dye contamination. In
accordance with results, the presence of the CNT in nanocomposite
could increase the electronic behavior of TiO2, and the presence of
AgNPs could increase the stability of photocatalyst during the for-
mation of the hole-electron pairs and reduce the band gap of the
photocatalyst (<2.25 eV). Another effect of AgNPs is enhancement
of the specific surface area of the photocatalyst which could facil-
itate the degradation process. The results proved the presence of
the OH radical which plays an important role in degradation. The
maximum photorefraction efficiency for each dye was calculated as
15
follows: 32.9%, 63.7%, 75.6%, and 99.9% for acid orange 7, orange G,
methyl blue, and methyl orange, respectively after exposure time
equal to 140 min [155]. The influence of the CNTs diameter on the
photocatalytic activity was evaluated for enhancing the photo-
catalytic degradation of organic pollutants under microwave con-
dition. CNTs with various diameters. The different size range of
CNTs (10e20, 20e40 and 40e60 nm). The results showed that after
just seven minutes 100% of the methyl orange dye was degraded by
CNTs with 10e20 nm in diameter under the 25 mg/L of dye con-
centration and also 1.2 g/L of the CNT dosage. The smaller diameter
not only increases the specific surface area but also can increase the
gap of the CNTs (Fig. 9) [159].
3.3. Carbon nanorodebased photocatalysts
Carbon nanorods with high specific surface area recently
attracted a lot of attention in photodegradation of dye pollutants
removal. Reports showed the facts that the superoxide pathway of
the dye degradation under sunlight condition has sufficiently done.
Recently Bhati et al. [160] developed water-soluble graphitic hol-
low carbon nanorods for MB degradation which their results
showed rapid dye degradation after 120 min.
3.4. GO and RGO and quantum dotebased photocatalysts
As one of the reliable catalysts, the GO and RGO-based mate-
rials and their derivatives show great potential application in
removal of the organic contaminants with photodegradation
process. From mechanistic view of the issue, the G and RGO-based
photocatalysts have the same mechanism of the degradation
which discussed for the CNTs [161e164]. This part of the review
discusses the materials and mechanism of decomposition of dye
contaminates in water media. Recently, Mohamed et al. [165]
developed an MnFe2O4/GO with sol-gel synthesis method. They
reported a spindle-like nanostructure which showed appropriate
photocatalytic activity to degrade methylene blue dye in water
16 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262

Fig. 12. Synthesis and mechanistic illustration of graphene quantum dot. Scanning electron microscopy (SEM) of graphene quantum dot/TiO2 with 1.0 wt % doping. (a) Photo-
catalytic degradation rates of MO dye with different contents of in composite. (b) UV-vis absorption spectra of MO in the presence of 1.0 wt % graphene quantum dot/TiO2
photocatalyst for 0e120 min, (c) Degradation rate curves of MO using graphene quantum dot, TiO2, and graphene quantum dot/TiO2. The figures reproduced with permission from a
study by Pan [172]. Copyright 2015 ACS.

media under visible light condition. In accoradnce with the re-
sults, this type of photocatalyst could decompose the methylene
blue in 1 g/L of dosage in lesser than 30 min under the condition
that the concentration of the dye was 10 mg/L. They estimated
that the rate constant of photodegradation process was
0.037 min1. Another semiconductor which shows great potential
of photodegradation if it combines with RGO is CdS. Using
gamma-ray radiation method, the CdS/RGO photocatalyst was
synthesized for removal of the Rhodamine B. The results show
more than 93% of degradation efficiency under visible light con-
dition (Fig. 10) [166].
The combination of TiO2 and CdS with RGO and also ZnO
microwires and nanowires are another strategy for obtaining
better photodegradation efficiency of organic dyes [167]. In this
communication, TiO2-CdS/RGO which prepared in solvothermal
method has been applied for photocatalytic degradation of
methylene blue. Because of high specific surface area of TiO2-CdS/
RGO (109.7 m2/g) in comparison with bare TiO2-CdS with 67 m2/g
and also 53 m2/g for CdS photocatalytic degradation reaction
progress had higher rate which the more kinetic of removal could
be related to the presence of RGO. The kinetic measurements of
photocatalyst showed the 97.5%, 94.0%, and 78.5% of reaction ef-
ficiency for TiO2-CdS/RGO, TiO2-CdS and bare CdS, respectively,
which run in 20 min under visible light. The synergetic influence
of RGO has been as the main reason for increasing in reaction
efficiency [168]. The magnetic photocatalysts could decompose
the organic pollutants as well as the magnetic adsorbents.
Therefore, CuFe2O4/GO which is prepared by hydrothermal syn-
thetic method indicated great capability in photodegradation of
dyes. Considering more details through mechanistic events
showed that the presence of O$2 spices which were generated
from the hole-electron separation could be as the main reason for
dye decomposition even after five times of reusability test (Fig. 11)
[169].
Recently the quantum dots provide many biological applications
because of their photoluminescence properties and also their
ability for surface functionalization is another advantage for them.
Their photocatalytic capabilities would be good because if their
green nature. In this respect, Das et al. [170] reported that this type
of materials has ability for using in label-free detection of the Fe3þ
and ascorbic acid detection and also highly efficient (~99.5%) pho-
tocatalytic degradation of MB dye after 130 min.
 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262 17

Table 2
Representative of photocatalyst materials for photodegradation process of the organic dyes.

Photocatalyst Dye Time of reaction (minutes) Reaction efficiency (%) Reference

TiO2-CdS/RGO Methylene blue 20 97.5 [173]

RGO- TiO2 Methylene blue 120 92 [138]
RGO- TiO2 Methylene blue 60 93 [134]
TiO2/Graphene Methylene blue 150 96 [53]
TiO2-CdS/RGO Methylene blue 20 83 [45]
Graphene-CuO nanocomposite Methylene blue 20 99.44 [115]
CdS/RGO Rhodamine B 80 93 [117]
TiO2-CdS/RGO Rhodamine B 20 93.5 [173]
RGO/CuPc Rhodamine B 210 96.2 [130]
CeO2-RGA Rhodamine B 120 85 [57]
Fe/Fe3C@Fe/N-Graphene Rhodamine 6 G 40 95 [140]
CuFe2O4/GO Acid Orange 7 50 95 [135]
AgBr@Ag/N- RGO phenols 40 60e100 [108]
Ag-Ag2O-ZnO/GO Acid Blue 74 210 90 [116]
SiO2/Cu2O-graphene Synthetic organic dye 180 80.91 [174]
SiO2/Cu2O-graphene tert-Butyl alcohol 180 98.76 [174]
TiO2-GO Phenol 480 99.3 [49]
MnO2@CNT-G 4-nitrophenol 240 96 [42]

3.5. Carbon nano-onions
Better interfacial interactions between pollution and photo-
catalyst are critical to improve the response to light. In this respect,
the photocatalytic performance of a 3D composite based on carbon
nano-onion which is functionalized with ZnO was considered by
Seung to study the photocatalytic degradation of 2,4-dinitrophenol.
Their results showed 92% efficiency of photodegradation after
140 min under visible light. High charge-separation efficiency is the
main reason for great photocatalytic activity [171].
3.6. Graphene dotebased photocatalysts
Graphene quantum dots have recently presented wide range of
applications, for eaxmple, bioimaging, light-emitting devices, and
photocatalysis because of high active area and great optical and
physiochemical properties. They are environmentally friendly and
highly robust for using in harsh UV and visible light irradiation
condition. Recent reports showed evidences that proves the gra-
phene dots photocatalytic capabilities. For example, Dengyu et al.
[172] developed a heterojunction composite of the graphene dot
and TiO2 nanoparticles for removal of the MO dye. Their results
indicated that quantum dotebased heterojunctions can remarkably
represent the fast recombination of electron-hole pairs which make
their photocatalytic activities more possible (Fig. 12).
A brief comparison between carbon-based photocatalysts
shows that the morphology could be as one of the main criterions
for obtaining an efficient photocatalyst. The size and morphology of
the carbon-based photocatalysts directly influence on efficiency of
hole-electron pairs and subsequently on photocatalytic efficiency
and kinetics. These types of the photocatalysts have several ad-
vantages in comparison with other nanomaterials for photo-
catalytic applications. First, they are green and environmentally
safe. Therefore, the photocatalysts separation process does not
require, whereas adsorption approaches essentially requires to
adsorbent separation because of their toxic nature. Second, they
have greater specific surface area which makes it possible to better
interaction between dye molecules and the photocatalyst interface.
Third, their light absorption area depends on nanoparticles size.
Therefore, combining these nanomaterials in various sizes could
enhance their light absorption and quantum yield and subse-
quently the efficiency of electron-hole separation. In contrast to
these facts, they have some disadvantages. One of the most
important problems that this photocatalysts are struggling with, is
their low stability against harsh chemical medium which was
produced during photodegradation. Production the radical spices
could potentially change the photocatalyst surface and subse-
quently their photocatalytic activity. Table 2 obviously shows that
although the reaction efficiency of the photodegradation is high,
the longtime of the reaction could restrict their applications.
Moreover, this approach could not be used for removal of heavy
metals. A brief comparison between photocatalyst and adsorption
approach shows that these approaches suffer from low kinetics of
adsorption and photodegradation. According to this fact, devel-
oping materials with high kinetics of removal could be valuable.
4. Conclusion and prospective
In this review, broad summary advanced materials with
adsorption and photocatalytic application of water treatment were
discussed in detail. Still, there are abundant efforts for finding
materials which be able to treat the water sources are ongoing, and
many researchers are developing new types of the materials with
high specific surface area and photocatalytic properties. Magnetic,
carbon based (G, GO, RGO, CNTs, QDs), silica, zeolites and other
types of the materials recently were showed great potential of
application in these field. On the other hand, the adsorbent and
photocatalytic materials are the main reliable candidates still
struggling with many challenges that restrict their large-scale
application. High specific surface area and kinetics of adsorption
and decomposition are the main characteristics of these materials
which make them suitable to treat wastewater even in ultralow
concentration of the pollutants. The interfacial and morphological
properties of the adsorbents during adsorption heavy metals and
organic dyes are the key parameters for the adsorption approach,
whereas for photodegradation approach goes beyond the
mentioned points like the kinetic of photocatalytic reaction, hole-
electron separation efficiency, active radical spices formation and
light absorption ability of the photocatalysts play important roles.
As far as we know, the adsorption approach encounters with risk of
desorption of adsorbate spices during removal process which this
challenge has mostly been observed to nonmagnetic nanomaterials
because of the long-time adsorption. For Fe2O3-based magnetic
adsorbents because the possibility of short-time external induced
separation processes the risk of desorption is low, whereas for clay,
zeolite, silica and carbon nanomaterials, the risk of desorption is
higher than the standards. In addition, in one hand, short time of
hole-electron pairs of photocatalyst limits the concentration of the
18 K.K. Chenab et al. / Materials Today Chemistry 16 (2020) 100262
radical spices. On the other hand, low kinetic of photocatalytic re-
action which mainly relates to low concentration of the radical
spices increases the time of photodegradation. Because of
mentioned challenges that these types of the materials are strag-
gling with, designing a family of materials with dual adsorption and
photocatalytic properties would be facilitate and still it is remained
under debates. QDs with great optical and morphological proper-
ties could be as reliable options in large-scale water treatment
applications because they can represent dual adsorption and pho-
tocatalytic features. These capabilities which mainly result from
their ultralow size of the particles, represent great absorption ca-
pacity as an adsorbent and visible light sensitive property for
photocatalytic degradation. The time of treating that refers to the
contact time between contaminants and adsorbent (photocatalyst)
is an important and characteristic parameter which influences on
the commercialization process of these novel methods of water
remediation. The surface area, surface wettability state which re-
lates to the surface free energy and morphology, functional groups,
methods of modification are the parameters could potentially in-
fluence on the treating time. In fact, the surface wettability state
could play a significant role; likewise mentioned previously the
superhydrophobic photocatalysts were developed for increasing
the efficiency of photodegradation reactions. These types of the
surfaces and materials not only could increase the adsorption
capacity but also can facilitate the enrichment process of the
organic dyes or pollutants on the surface. The superhydrophobic
materials with localizing effect on dye molecules which facilitates
their diffusion from the medium to the substrate could decrease the
time of adsorption and photodegradation significantly. Many types
of the self-cleaning superhydrophobic surfaces recently were re-
ported in literatures which have mentioned to this fact that the
organic, hydrophobic and lipid molecules could be self-cleaned on
TiO2-based superhydrophobic surfaces because of the light sensi-
tive properties of the TiO2. This subject turn on many thoughts in
the minds by the mean that superhydrophobic materials not only
could increase the rate of adsorption of organic materials at the
interface but also during photodegradation process could remove
them efficiently. Moreover, photocatalytic materials essentially
need to bestow on the condition which the electron-hole separa-
tion was carried out significantly. The doping, functionalization,
composing with other photocatalyst materials and changing in
their crystallinity are the main strategies for this aim. Low solubility
in harsh chemical condition under irradiation is another desired
property that controls the photocatalytic activity. Another one is
the band gap of the semiconductor materials which may improve
their light absorption and quantum efficiency. Therefore, consid-
ering the types of the nanomaterials and their physiochemical
properties effect on adsorption and photocatalytic decomposition
process could help us to design better materials for water treat-
ment applications.
Declaration of Competing Interest
There is no conflict to declare.
Acknowledgements
The authors warmly acknowledge the Iran University of Science
and Technology (IUST) with funder ID 10.13039/501100006766. The
authors thank from National University of Singapore (NUS) and Iran
University of Medical Science (IUMS).
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