Journal of Cleaner Production 284 (2021) 124703

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Journal of Cleaner Production

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

Review

Recent advances on composite hydrogels designed for the remediation

of dye-contaminated water and wastewater: A review
Antonio G.B. Pereira a, **, Francisco H.A. Rodrigues b, Alexandre T. Paulino c,
Alessandro F. Martins d, e, ***, Andre

R. Fajardo f, *
a
Laborato
rio de Biopolímeros (LAPOL) Universidade Tecnolo
gica Federal Do Parana
(UTFPR), Campus Dois Vizinhos (DV), 85660-000, Engenharia de
Bioprocessos e Biotecnologia, Brazil
b
Centro de Ci^encias Exatas e Tecnologia, Universidade Estadual Vales Do Acaraú (UVA), Campus da CIDAO, 62042-030, Sobral, CE, Brazil
c
Laborato
rio de M
etodos Analíticos e Química Ambiental (LaMAQA), Universidade Do Estado de Santa Catarina (UDESC), Campus Oeste, Departamento de
Engenharia de Alimentos e Engenharia Química, 89870-000, Pinhalzinho, SC, Brazil
d
Laborato
rio de Materiais, Macromol

sitos (LaMMAC), Universidade Tecnolo
eculas e Compo
gica Federal Do Parana
(UTFPR), Campus Apucarana, 86812-
460, Apucarana, PR, Brazil
e
Grupo de Materiais Polim
ericos e Compo
sitos (GMPC), Universidade Estadual de Maringa
(UEM), 87020-900, Maringa
, PR, Brazil
f
rio de Tecnologia e Desenvolvimento de Compo
Laborato
sitos e Materiais Polim
~o Do
ericos (LaCoPol), Universidade Federal de Pelotas (UFPel), Campus Capa
Lea~o, 96010-900, Pelotas, RS, Brazil

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

Article history: Dye-contamination in water supplies, industrial effluents, and rivers is one of the major water pollution
Received 8 July 2020 issues. It has put at risk the drinking-water supplies around the globe. Various remediation approaches
Received in revised form have been extensively developed and tested to minimize this worrying scenery. In particular, adsorption
27 September 2020
techniques are often ranked as one of the most prominent strategies to treat dye-contaminated water
Accepted 14 October 2020
likely due to their attractive practical and economic advantages. Overall, the efficiency of adsorptive
Available online 17 October 2020
removal of dyes from water is closely related to the adsorbent material features, which has a critical role
Handling editor Prof. Jiri Jaromir Klemes in this process. Currently, thousands of materials (raw or processed) have been tested as adsorbents.
Otherwise, none of them have achieved the prominent status assigned to the hydrogels. Frequently
Keywords: labeled as an ideal adsorbent, the leading role of these soft materials towards the adsorptive removal of
Hydrogel dyes from the water was consolidated almost two decades ago, when the introduction of different
Composite materials into the hydrogel matrices resulted in composite materials with unique properties. In this
Nanomaterials paper, an entirely conceptual and critical review of literature is presented, focusing on the tremendous
Dye
potential of composite hydrogels to remediate dye-contaminated water. Specifically, the main advances
Adsorption
related to the use of composite hydrogels containing clay minerals, carbonaceous materials, organic fi-
Wastewater treatment
brils and whiskers, magnetic and metallic particles, and other inorganic fillers are reviewed in this paper.
Additionally, general methods to prepare composite hydrogels, the main effects ascribed to the com-
posite formation are addressed in this paper. Finally, the main drawbacks and challenges associated with
the application of these types of hydrogels are reviewed to understand the research gap and limitations
regarding their practical use. We believe that the information provided in this review paper may
contribute to enhance the scientific basis for the practical and efficient use of these fascinating adsorbent
materials.
© 2020 Elsevier Ltd. All rights reserved.

Contents

* Corresponding author.
** Corresponding author.
*** Corresponding author. Laborato
rio de Materiais, Macromole
culas e
Compo
sitos (LaMMAC), Universidade Tecnolo
gica Federal do Parana
(UTFPR),
Campus Apucarana, 86812-460, Apucarana, PR, Brazil.
E-mail addresses: antoniog@utfpr.edu.br (A.G.B. Pereira), afmartins@utfpr.edu.br
(A.F. Martins), andre.fajardo@pq.cnpq.br (A.R. Fajardo).

https://doi.org/10.1016/j.jclepro.2020.124703
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al. Journal of Cleaner Production 284 (2021) 124703

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Dyes - general aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. General methods to prepare composite hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
4. Dye adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.1. Composite hydrogels containing clay minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.2. Composite hydrogels containing carbon-based materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.3. Composite hydrogels containing metallic (nano)particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.4. Composite hydrogels containing nanowhiskers and nanofibrils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5. Overview and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

1. Introduction published with this thematic (i.e., composite hydrogels for dye
removal) overcomes the thousands and continues to focus on
Enormous efforts have been made to remediate the different cutting-edge research on the aqueous pollution management field.
earth environments affected by contaminants from human wastes To illustrate this trend, Fig. 1 displays a histogram showing the
and industrial activities. Removing or degrading harmful com- number of publications per year considering different searching
pounds, molecules, and elements that affect the environment’s terms in the ISI Web of Science© database. In summary, the number
safety and quality are required. Regarding the aquatic environment, of publications linked to “dye adsorption” has exponentially
one of the most promising remediation strategies consists of the increased in the past two decades. By including the terms “hydro-
utilization of adsorbent materials to remove contaminants gel” or “composite hydrogel” to the search, the number of publi-
(Malaviya and Singh, 2011). Adsorption can be an advantageous cations also shows a noticeable increase. It represents a
process over other approaches (coagulation, filtration, precipita- considerable fraction of all studies concerning dye adsorption,
tion, ion exchange, reverse osmosis, and oxidative processes), confirming the relevance of this research area. However, this figure
mainly as it is a simple design and low-cost method, as well as also highlights the need for further studies on the development and
effective towards a wide range of pollutants (Amin et al., 2014; application of composite hydrogels for dye adsorption.
Rashed, 2013). The possibility of adsorbent reuse is another desir- Some review articles have recently been published describing
able aspect (Lessa et al., 2017; Wang et al., 2012). Currently, several the use of composite hydrogels in some adsorptive processes (not
studies have been devoted to preparing adsorbent materials for limited to dye adsorption) (Du et al., 2020; Nangia et al., 2018;
wastewater treatment (Maqbool et al., 2016; Tajizadegan et al., Thakur et al., 2019). Overall, these articles focused on specific sys-
2016). Natural materials, agricultural, and industrial wastes have tems (in terms of composition or utilized filler) providing limited
been utilized as low-cost adsorbents (Bhatnagar and Sillanpaa, view regarding to a broad research field. Herein, we did not limit
2010; Bhatnagar et al., 2015). Also, advanced engineered mate- the discussion to a specific hydrogel matrix or hydrogel kind. For
rials such as activated charcoal, graphene, carbon nanotubes, silica- the first time, we provided a conceptual and critical discussion on
based materials, and hydrogels have found broad applicability in the use of the most common filler materials to the preparation of
this research field (Pillai and Kandasubramanian, 2020; Tibbetts this kind of composite. This review attempts to understand the
and Kostakis, 2020). In this case, it is important to mention that adsorption ability of these composite hydrogels considering their
the use of advanced and ultra-processed materials can suppress the conception and design. Throughout this paper, we try to answer
low-cost label often associated with adsorption.
Hydrogels show remarkable advantages over other adsorbent
materials once they have excellent water affinity, high porosity,
easy handling, varied morphology, and tunable dimensions.
Another great advantage lies in the fact that hydrogels are readily
prepared from natural and synthetic polymers (mixed or not)
(Muya et al., 2016). Moreover, the entrapment of different fillers
(e.g., clays, metals, carbon-based materials, organic fillers, among
others) in the hydrogel matrix creating composite materials with
excellent and enhanced properties in terms of thermal stability,
chemical resistance, mechanical properties, and adsorption ca-
pacity (Kabiri et al., 2011; Pavlyuchenko and Ivanchev, 2009). Due
to the intrinsic properties of fillers, such as large specific area and a
large number of functional groups, composite hydrogels may pre-
sent better adsorption selectivity and capacity than conventional
hydrogels (Thoniyot et al., 2015). In the last two decades, the
number of studies dealing with composite hydrogels’ design and
application for adsorption of various pollutants from aqueous me-
dia has increased considerably. Most specifically, the use of com-
posite hydrogels as adsorbent materials for the removal of dyes
from water has been widely investigated by various researchers
from different areas (chemists, physics, materials, and environ-
Fig. 1. Number of publications per year considering three different search terms in the
mental engineers, and others). As a result, the number of papers ISI Web of Science© database. (*Data collected in May 2020).

2
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al.
two fundamental questions: How does the filler nature affect the
physicochemical and morphological features of the composite
hydrogels? What is the impact of this combination
(hydrogel þ filler) on the entire adsorption process? To deal with
this goal, the first part of this review encompasses a general
description of synthetic dyes, and the main methods to prepare
composite hydrogels. Next, we review and discuss the main ad-
vances related to the use of composite hydrogels for removing dyes
from water. In the last part, some future perspectives of this
research field are postulated.
2. Dyes - general aspects
Synthetic dyes are one of the most important classes of chemical
compounds used in several industries (textile, leather, paper
printing, cosmetics, pharmaceutical, and food) and technological
applications (biological and chemical research, light-harvesting
arrays, and photo-electrochemical cells, among others). According
to Allied Market Research (2019) report, the global market of dyes is
expected to reach $ 15 billion by 2026. These colored substances
absorb electromagnetic radiation in the visible range of the spec-
trum (~400e800 nm) and, currently, there are more than 10,000
dyes available in the market. Among them, more than 70% are azo
(eN]Ne) derivatives. There are distinct classification systems of
dyes based on: (i) their chemical structure (chromophore/aux-
ochrome), and (ii) the method of applying these dyes on an in-
dustrial scale (acid, reactive, direct, basic, vat, disperse, metal
complex, and mordant, etc.) (Benkhaya et al., 2020). Due to their
considerable structural diversity, synthetic dyes can exhibit distinct
chemical, biological and physical properties.
The main issue related to the industrial use of dyes is their
remarkable loss rate throughout manufacturing processes. For
example, the textile industry lost about 10e15% of synthetic dyes
(Periyasamy and Militky, 2020). A fraction of this becomes part of
the industry effluents that without adequate treatment can be
released into waterways (rivers, lakes, etc.). Considering that some
of these dyes are non-biodegradable, they can pose a significant
threat to the environment and human health. The presence of a
minimal amount of synthetic dyes in water (<1 ppm) can affect the
transparency and gas solubility of water bodies (river, lakes, un-
derground water, etc.). Moreover, these colored substances absorb
and reflect the sunlight entering the water, interfering with the
aquatic species growth, and impairing photosynthesis. Several
studies confirm that synthetic dyes could exert acute and chronic
effects on living organisms, depending on their concentration and
extension of exposure. Table 1 summarizes some general infor-
mation concerning the synthetic dyes commonly used as models in
adsorption studies at the lab-scale. It is essential to inform the
reader that most of these cationic or basic dyes used as models in
adsorption studies constitute a small fraction of the world textile
dyes market. Also, some of them are old, which limits their use in
modern textile industries. The most important classes for the next
few years are reactive, disperse and direct (Allied Market Research,
2019).
Among the current literature, there is a consensus that colored
effluents must be efficiently treated to remove the entire dyestuff
before disposal. Fig. 2 summarizes the main processes used to treat
dye-contaminated water and wastewaters.
In summary, all the processes outlined in Fig. 2 have advantages
and disadvantages. High operational costs, low efficiency, limited
versatility, complicated handling, and secondary pollution are
frequently listed as the main drawbacks of some of those processes.
On the other hand, some researchers have considered adsorption as
a cost-effective and alternative method to remove dyes from water
and wastewater in a safer manner (Adegoke and Bello, 2015;
3
Journal of Cleaner Production 284 (2021) 124703
Katheresan et al., 2018). Adsorption, a surface phenomenon in
which a solute (atoms, ions, or molecules in a gas or liquid state)
adheres to a solid sorbent, has gained enormous attention due to its
low-cost, simplicity of design and ease of operation. The main ad-
vantages of adsorption regarding the removal of dyes from water
include: (i) the use of compact systems (specific containers or
equipment not necessary); (ii) low sensitivity to diurnal variation
(adsorption processes can be performed all day long); (iii) low ef-
fect of toxic chemicals on the process; (iv) greater flexibility in
design and operation; (v) high ability to the removal of organic
contaminants, and (vi) the absence of harmful by-products (Crini
and Lichtfouse, 2019; Katheresan et al., 2018). Furthermore, the
potential reuse of the adsorbent (solid used to adsorb the solutes)
and the recovery of the dye are additional relevant aspects asso-
ciated with the adsorption process. Although adsorption has many
interesting features, as above mentioned, one should be aware that
such process also presents some difficulties which include limited
number of adsorbent re-use as well as energy and chemical input to
regenerate the adsorbent. In certain textile industries, adsorption
processes have been used as a post-treatment strategy after using
preliminary methods (e.g., ozonation, coagulation, oxidative pro-
cesses, among others) (Yaseen and Scholz, 2019). Moreover, hybrid
methodologies of adsorption associated with electric discharge
plasma have been reported (Shang et al., 2019).
The attractive characteristics associated with adsorption have
also motivated (directly or indirectly) the development and appli-
cation of different adsorbent materials. Nowadays, a myriad of
papers has been published describing the use of different kinds of
materials as adsorbents to remove synthetic dyes from water. Also,
excellent review papers have covered the main advances of this
research area (Buruga et al., 2019; Zhou et al., 2019). To illustrate
this statement, Table 2 highlights the adsorption capacity (qm) of
different materials (such as waste biomass, carbonaceous materials,
hydrogels, polymeric or inorganic particles, and others) tested as
adsorbents for dye removal.
The small fraction of examples listed in Table 2 gives a clear idea
that the adsorption process is highly dependent on the nature of
the adsorbent, mainly when their adsorption capacities are
compared. Of course, it cannot be omitted that the experimental
conditions are also a relevant factor regarding the efficiency of this
physicochemical process. Considering the dye-contaminated wa-
ters, hydrophilic and functional materials appear to foster better
adsorption results. Due to this trend, the studies focused on pre-
paring of composite hydrogels for adsorption uses have grown in
the last decades since these materials usually show superior
properties compared to conventional hydrogels or other hydro-
philic materials. The most current methods and protocols to pre-
pare composite hydrogels are reviewed in the next section.
3. General methods to prepare composite hydrogels
A hydrogel is a porous three-dimensional, physically, or chem-
ically crosslinked polymer network of flexible chains and its unique
structure allows absorbing and retaining large amounts of water
without dissolving (Ahmed, 2015). The water inside the hydrogel
and its porous structure allow solute diffusion in or out the
hydrogel matrix (Bell and Peppas, 1995). This kind of soft-material
can be classified according to the origin of the polymers (synthetic,
natural or semi-synthetic); composition (homopolymer or copol-
ymer); the network type (semi-interpenetrating or full-
interpenetrating); the polymer charge (neutral, cationic, anionic
or ampholytic); structure (amorphous or crystalline), and durability
(durable or degradable), among others (Ahmed, 2015; Ullah et al.,
2015). Currently, stimuli-responsive behavior is also a criterion to
classify hydrogels. Stimuli-responsive hydrogels (or smart
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al. Journal of Cleaner Production 284 (2021) 124703

Table 1
Synthetic dyes commonly used as models in adsorption studies.

Dye Chemical Structure Information Contamination sources

Rhodamine B C28H31ClN2O3 Natural sources

CAS 81-88-9 Textile industry
Mw 472.09 g/mol Leather industry
Solubility in water 15 g/L Dyestuff industry
UVeVis (lmax) 558 nm Food industry
Molecular size ~16 Å Plastic industry
Cationic and Zwitterionic nature pKa z3.7 Laundry activity
Oral LD50 ¼ 887 m g/kg in mice
Potential health effects: Irritation of respiratory tract, skin, eyes. Cancer hazard due to
chronic exposure.
Methylene C16H18ClN3S Textile industry
blue CAS 61-73-4 Leather industry
Thiazine class Dyestuff industry
Mw 319.85 g/mol Paper industry
Solubility in water 44 g/L Plastic industry
UVeVis (lmax) 665 nm Pharmaceutical uses
Molecular size ~14 Å Laundry activity
Cationic nature pKa z3.14
Oral LD50 ¼ 3.5 g/kg in mice
Potential health effects: Mutagenic, reproductive disorders, abdominal pain, vomit, etc.
Brilliant C27H33N2.HO4S Pigments industry
green CAS 633-03-4 Dyestuff industry
Triphenylmethane class Chemical industry
Mw 482.64 g/mol Pharmaceutical uses
Solubility in water 100 g/L
UVevis (lmax) 625 nm
Molecular size ~17 Å
Cationic nature
Oral LD50 ¼ 313 mg/kg in rat
Potential health effects: Toxic by ingestion; may cause eye damage and blindness by
contact.
Methyl red C15H15N3O2 Textile industry
CAS 453-52-7 Leather industry
Azo class Dyestuff industry
Mw 269.30 g/mol Chemical industry Laundry
Almost insoluble in water activity
UVeVis (lmax) 410 nm
Molecular size not available
Cationic nature pKa z5.0
Oral LD50 ¼ not available
Potential health effects: Not available
Methyl C14H14N3O3S Textile industry
orange CAS 547-58-0 Foodstuffs industry
Azo class Paper industry
Mw 327.33 g/mol Leather industry
Solubility in water 50 g/L Lab activities Laundry
UVeVis (lmax) 464 nm activity
Molecular size ~26 Å
Anionic nature pKa z3.4
Oral LD50 ¼ 60 mg/kg in rat
Potential health effects: Irritant. Severe exposure may cause death. May damage genetic
material.
Crystal violet C25N3H30Cl Textile industry
CAS 548-62-9 Leather industry
Triphenylmethane class Dyestuff industry Laundry
Mw 407.99 g/mol activity
Solubility in water 50 g/L
UVeVis (lmax) 590 nm
Molecular size ~14 Å
Cationic nature pKa z3.29, 3.78 and 4.26
Oral LD50 ¼ 420 mg/kg in rat
Potential health effects: Serious eye damage. May cause cancer.
Malachite C23H25N2 Cl Textile industry
green CAS 562-64-2 Leather industry
Triphenylmethane class Dyestuff industry
Mw 364.91 g/mol Lab activities Laundry
Solubility in water 76 g/L activity
UVeVis (lmax) 617 nm
Molecular size not available
Cationic nature pKa z6.9
Oral LD50 ¼ 80 mg/kg in mouse
Potential health effects: Irritant to the eye, skin, gastrointestinal, and respiratory tract.

4
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al.
Table 1 (continued )
Dye Chemical Structure Information
Congo red C32H22N6Na2O6S2
CAS 573-58-0
Azo dye
Mw 696.66 g/mol
Soluble in water
UVeVis (lmax) 498 nm
Molecular size ~25 Å
Anionic nature pKa z4.0
Oral LD50 ¼ 143 mg/kg in human
Potential health effects: Carcinogenic and teratogenic.
Fig. 2. Processes commonly applied in the treatment of dye-contaminated water/wastewaters.
hydrogels) can exhibit drastic volume changes in response to spe-
cific external stimuli (e.g., pH, temperature, ionic strength, electric,
and magnetic field, and others) (Soppimath et al., 2002). This
noticeable volume change can occur continuously over a range of
stimulus levels, or, discontinuously at a critical stimulus level
depending on the hydrogel formulation (Shibayama and Tanaka,
1993).
Hydrogel properties are straightly related to experimental
conditions under which the hydrogels are formulated (e.g., the
chemistry of starting materials, the nature of crosslinking, cross-
linker concentration, and so on). Various studies are devoted to the
preparation of hydrogels with specific physicochemical and struc-
tural properties, considering that such properties can be engi-
neered from experimental conditions. Thus, hydrogels have found
utility in a huge range of applications (e.g., agriculture, biomedi-
cine, pharmaceutics, environmental uses, catalysis, separation/pu-
rification, and others) (Ahmed, 2015; Guilherme et al., 2015;
Varaprasad et al., 2017b). Detailed descriptions of the hydrogel
preparation and their potential applications have been extensively
reviewed by various authors (Hua et al., 2018; Nie et al., 2019;
Rodrigues et al., 2014). In general, hydrogels are of great scientific
and technological interest due to their large specific surface, unique
pore structure, low interfacial tension, tunable properties, and
morphology. All these features of hydrogels have attracted atten-
tion for adsorption purposes. Hydrogels can interact with specific
substances (e.g., atoms, ions, organic compounds, and biological
molecules), and efficiently separate them from a mixture (Paulino
et al., 2011; Zdanowicz et al., 2014). This ability can also be asso-
ciated with the presence of a variety of functional groups, such as
5
Journal of Cleaner Production 284 (2021) 124703
Contamination sources
Textile industry
Leather industry
Dyestuff industry
hydroxyl (OH), amine (NH2), carboxyl (COOH), sulfate
(SO3H), and others, and the 3D structure of interaction sites in the
case of the molecularly imprinted hydrogel. These groups define
the hydrogel adsorption selectivity and capacity (Khan and Lo,
2016; Si et al., 2019).
Hydrogels have emerged as effective adsorbents for removing a
wide range of water-soluble contaminants due to their high
adsorption capacity, permeability to small molecules, rapid
response, and simple design (Dragan and Apopei, 2011). Moreover,
recycling and recovering methods have allowed reusing these
adsorbent materials several times, which is very attractive,
considering economic and practical concerns (Du et al., 2020).
The adsorption ability of hydrogels through physical or chemical
interactions is comparable to activated carbon, which is the most
common adsorbent material used to treat aqueous pollutants (Gad
et al., 2011). Compared with other adsorbent materials, the struc-
ture of hydrogel can be flexibly designed, and the properties can be
adjusted by altering the type and number of functional groups
according to the required use. In this facet, various synthetic
monomers have been polymerized or copolymerized and cross-
linked, resulting in hydrogels with different functional groups
(Coskun and Delibas, 2012; de Azevedo et al., 2017). These synthetic
monomers have been gradually replaced or blended with natural
polymers, mainly polysaccharides, due to the growing environ-
mental concerns. Unlike many synthetic monomers, poly-
saccharides are biodegradable, non-toxic, cost-effective, abundant,
and renewable (Chang and Juang, 2004). Polysaccharide-based
hydrogels composed of sodium alginate, pectin, starch, chitosan,
carboxymethyl chitosan, and N-succinyl-chitosan, kappa-
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al. Journal of Cleaner Production 284 (2021) 124703

Table 2
Adsorption capacities (qm) of different materials tested as adsorbents for the removal of dyes from water.

Dye Adsorbent Main features qm Reference

(mg/g)

Rhodamine Zeolitic imidazole framework-67 BET surface area of 833 m2/g 46.2 (Li, Y.F. et al., 2019)
B Average pore diameter 2.71 nm
Magnetic properties
Up to 4 reuses
Organo-vermiculite Positively charged surface 283.0
Yu et al. (2019)
Ability to treat binary systems
Biochar Bamboo shoot shell as source 85.8
Hou et al. (2019)
BET surface area of 513 m2/g
Average pore diameter 2.09 nm
Positively charged surface
Low reusability
Graphene oxide BET surface area of 71.5 m2/g 578.0
Yin et al. (2019)
Banana peel Porous surface 9.53
Oyekanmi et al. (2019)
Highly functionalized surface
Chitosan-g-poly (acrylic acid-co-2-acrylamide-2-methyl propane Negatively charged surface 556.9
Tang et al. (2018)
sulfonic acid) hydrogel Up to 5 reuses
Methylene Maleylated-modified hydrochar BET surface area of 28.2 m2/g pHpzc (point of zero 1155.6 (Li, B. et al., 2019)
blue charge) ~2.3
Up to 4 reuses
Pyrolytic carbon Waste tires as source 71.6
Zhang et al. (2019)
BET surface area of 60 m2/g
Irregular pore distribution
Up to 3 reuses
Reduce graphene oxide/titanate nanotube BET surface area of 127.7 m2/g 26.5
Nguyen and Juang
Average pore diameter 19.6 nm
Photocatalytic activity (2019)
Up to 5 reuses
Modified apricot kernel shells Negatively charged surface 33.7
Namal and Kalipci
Low surface area
(2019)
Poly (acrylic acid) hydrogel pHpzc (point of zero charge) ~1.0 2100.0
Hu et al. (2018)
Total porosity ~80%
Up to 5 reuses
Brilliant Modified bambusa tulda pHpzc (point of zero charge) ~7.7 41.67
Laskar and Kumar
green Highly functionalized surface
High porosity (2019)
Modified tarap peel Oxidized surface pHpzc (point of zero charge) ~2.6 275.0
Dahri et al. (2017)
Biochar Rice straw as source 111.1
Ur Rehman et al. (2016)
BET surface area of 232.2 m2/g
Average pore diameter 5.2 nm pHpzc (point of zero
charge) ~6.2
Rice husk ash BET surface area of 228 m2/g 85.6
Tavlieva et al. (2013)
Particle size 15 mm
Red clay BET surface area of 100.3 m2/g 125.0
Rehman et al. (2013)
Average pore diameter 14.8 nm pHpzc (point of zero
charge) ~6.8
Methyl red Orange peels Porous surface 225.1
Trifi et al. (2019)
Highly functionalized surface
Biogenic Ag@Fe nanocomposites Particle size 5e40 nm 125.0
Zaheer et al. (2019)
Photocatalytic activity
Pd-nanoparticles loaded activated carbon BET surface area of 1340 m2/g 133.3
Ghaedi et al. (2016)
Average pore width 2 nm
Particle size 25e90 nm
Amorphous poly (azomethinethioamide) resin pHpzc (point of zero charge) ~4.5 90.9
Vidhyadevi et al. (2014)
High porosity
Low reusability
Methyl Mesoporous Cu2O/BiO3 composite BET surface area of 75.3 m2/g 1533.2
Tang et al. (2019)
orange Particle size 5 nm
Zeta potential þ40.7 mV
Low reusability
Functionalized carbon nanotubes BET surface area of 197.8 m2/g 310.2
Ibrahim et al. (2019)
Average pore size 241.3 nm
Zeta potential þ24.8 mV
Biochar Sheep manure as source 45.6
Lu et al. (2019)
BET surface area of 171.8 m2/g
Average pore size 11.9 nm
Irregular pore distribution
Magnetic lignin-based carbon nanoparticles BET surface area of 82.8 m2/g 113.0
Ma et al. (2018)
Average pore size 12 nm
Particle size ~77 nm pHpzc (point of zero charge)
~6.0

6
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Table 2 (continued )

Dye Adsorbent Main features qm Reference

(mg/g)

Magnetic properties
Low reusability
Chitosan microspheres Particle size ~440 mm 207.0
Zhai et al. (2018)
Positively charged surface
Up to 5 reuses
Crystal Calcinated mussel shells BET surface area of 7.6 m2/g 482.0
Dandil et al. (2019)
violet Particle size 2 mm
Negatively charged surface
Modified corncob Epichlorohydrin modified surface pHpzc (point of 71.4
Song et al. (2019)
zero charge) ~4.0
Graphene oxide intercalated montmorillonite composite BET surface area of 242.1 m2/g 746.7
Puri and Sumana
Average pore size 5.6 nm
Zeta potential 25.2 mV (2018)
Particle size 0.5e1.0 mm
Up to 5 reuses
Arabic gum-cl-poly (acrylamide) hydrogel Particle size ~28 nm 90.9
Sharma et al. (2018)
Negatively charged surface
Up to 6 reuses
Mesoporous ZSM-5 zeolite BET surface area of 330 m2/g 1217.3
Briao et al. (2017)
Average pore size 2.0 nm
Particle size ~5 mm
Negatively charged surface
Malachite Coconut activated carbon BET surface area of 1101 m2/g 83.1
Qu et al. (2019)
green Average pore size 5 nm pHpzc (point of zero charge)
~4.5
Large-sized graphene Lateral size of graphene sheet 5 mm 437.7
Xing et al. (2019)
Thickness below 10 layers
Negatively charged surface
Modified Luffa aegyptica peel Cellulose-rich material 78.8
Mashkoor and Nasar
BET surface area of 4.7 m2/g
Average pore size 3.6 nm pHpzc (point of zero (2019)
charge) ~6.7
Up to 4 reuses
Magnetic activated carbon Negatively charged surface 766.0
Rong et al. (2018)
Magnetic property
Up to 3 reuses
Starch sulfate resin Porous beads 173.9
Guo et al. (2017)
Up to 5 reuses
Congo red Magnetic resin BET surface area of 5.2 m2/g 354.3 (Li et al., 2019a, 2019b,
Average pore size 3 nm
2019c)
Particle size 100e150 mm
Positively charged surface
Chitosan/TiO2 composite Low porosity 32.0
Habiba et al. (2019)
Positively charged surface
Alumina-zirconia composite BET surface area of 8 m2/g pHpzc (point of zero 57.5
Adesina et al. (2019)
charge) ~8.0
High porosity
MOF@Fe2O3 nanocomposite Particle size 100 nm 458.0
Han et al. (2019)
Magnetic property
Positively charged surface
Shrimp shell powder BET surface area of 66.3 m2/g 288.2
Zhou et al. (2018)
Average pore size 5.6 nm
Particle size 105 mm
Positively charged surface

carrageenan, cellulose, lignocelluloses, hemicellulose, and carbox-
ymethyl cellulose have been tested as adsorbents for water
purification.
In contrast to the relevant properties presented by hydrogels,
their practical application in water treatment is limited due to its
fragile structure, particularly at high temperatures, and low
adsorption kinetics. Further, some disadvantages related to the
purely synthetic origin and high rate of degradation of these
hydrogels are reported (Ahmed, 2015). The association of conven-
tional hydrogel matrices with different materials (e.g., clays, metals,
inorganic compounds, etc.) can overcome such drawbacks. Com-
posite hydrogels often show superior properties compared to the
conventional hydrogels, even at reinforcement phase content as
low as 5 wt-% (Guilherme et al., 2015; Li et al., 2007). Moreover,
novel properties (catalytic activity, magnetization,
biodegradability, selectivity, among others) can be created while
incorporating different materials into the hydrogel matrix
(Guilherme et al., 2012; Zheng, Y. et al., 2015). Overall, these fea-
tures enable the efficient use of composite hydrogels as adsorbents
in wastewater treatment. Although the research has demonstrated
the potential of hydrogel and composite hydrogels in the waste-
water treatment, data on real effluent applications and industrial-
scale are still missing up to date.
Fig. 3 summarizes the three main strategies used in the syn-
thesis of hydrogels composites. In this figure, the term “fillers” was
used to simplify the description of the different materials utilized in
this finality. The first strategy (i) encompasses the fillers’ entrap-
ment into a pre-formed hydrogel matrix, which involves one or a
multistep approach. A hydrogel matrix can be put in contact with
the filler to interact (by sorption, for example). So, according to the

7
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al.
Fig. 3. Illustrative scheme summarizing the principal strategies used to synthesize composite hydrogels.
interaction forces established among them, the filler can remain
entrapped. This strategy has been widely assessed to synthesize in
situ metallic nanoparticles using the hydrogel matrix to reduce
metallic ions and stabilize the nanoparticles (Sahiner, 2013; Souza
et al., 2019; Silva et al., 2020). The second strategy (ii) includes
mixing fillers with polymer solutions, which are subsequently
crosslinked. In this case, the polymers can be physically or chemi-
cally crosslinked. Interestingly, in some cases, the filler can act as a
crosslinker (Dannert et al., 2019). The third strategy (iii) encom-
passes the simultaneous polymerization-crosslinking of monomers
(mainly acrylic monomers) in the presence of the fillers (which can
be reactive or not). Herein, the use of crosslinkers is mandatory. It is
important to note that all of these strategies can synthesize com-
posite hydrogels with one or more polymers. Generally, they allow
obtaining materials with different properties. Recently, Dannert
et al. (2019) detailed in a review paper the main particularities
associated with the synthesis of composite hydrogels, as well as the
final properties of these materials depending on the selected
strategy. The reading of this review can be an excellent guide to
researchers that deal with the application of composite hydrogels
in adsorption studies.
4. Dye adsorption
4.1. Composite hydrogels containing clay minerals
Natural clay minerals are earthy materials composed mainly of
fine particles of hydrous aluminosilicates and other minerals such
as quartz, carbonate, and metal oxides. Generally, clays compose
the colloid fraction of soil consisting of sediment, rocks, and water
(Pinnavaia, 1983). Their basic structures comprise tetrahedral layers
of Si and O and octahedral layers of Al(OH)x. Both structures are
arranged in a hexagonal pattern. Eventually, Al atoms can be
replaced by Fe3þ, Fe2þ, or Mg2þ ions (Guggenheim and Martin,
1995). Also, clay minerals are composed of small amounts of al-
kali and alkaline earth elements (K, Na, Li, Ca, and Mg) and ions
(NHþ 2 3
4 , SO4 , PO4 ). The presence of these elements/ions invariably
confers a charged surface to the clay, which potentize the use of
8
Journal of Cleaner Production 284 (2021) 124703
clay minerals in processes triggered by surface forces, such as
adsorption or ion exchanging (Adeyemo et al., 2017). Beyond the
physicochemical properties, the low-cost, natural abundance, and
environmentally friendly are other attractive properties of clays.
Generally, 1 kg of clay is about 10-fold cheaper than 1 kg of gra-
phene or 100-fold cheaper than 1 kg of carbon nanotubes, and its
obtention is indescribably easier. Due to these characteristics, the
utilization of clay mineral on environmental remediation has
increased considerably to adsorb inorganic ions and organic mol-
ecules (Adeyemo et al., 2017; Weng et al., 2018; Zou et al., 2019).
A broad scope of clay minerals has been introduced in hydrogel
matrices resulting in absorbent materials with enhanced proper-
ties. Either composite hydrogels or nanocomposites containing
montmorillonite, attapulgite, smectite, vermiculite, biotite, lapon-
ite, sepiolite, bentonite, and halloysite have been synthesized and
used to remove synthetic dyes from water/wastewater. The authors
claim that the composite hydrogels reinforced with clays are
characterized by exceptional mechanical properties, thermal con-
ductivity, higher heat capacity, and faster swelling-deswelling
properties than conventional hydrogels (Kabiri et al., 2011).
Table 3 compiles the adsorption capacities of composite hydrogels
containing different clay minerals for different synthetic dyes.
The nature and amount of clay within the hydrogel network and
the experimental conditions are critical factors for controlling the
composite’s adsorption capacity. It affects the clay dispersion
within the hydrogel matrix and dictates the interactions with dye
molecules (Dannert et al., 2019). Effective dispersion of the clay
particles within the hydrogel prevents issues related to phase
separation and poor mechanical properties. Most importantly, it
enhances the adsorption ability of the composite by increasing the
specific surface and the number of binding sites (Adeyemo et al.,
2017).
The clay particle’s dispersion mostly depends on the processing
methods used to prepare the composite material (physical mixture,
intercalation or exfoliation of the clay sheets, etc.) and the chemical
compatibility between the inorganic and organic phases. Hydro-
philic (or hydrophilized) clays can be dispersed easier in hydro-
philic environments like the hydrogel matrix than hydrophobic
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al. Journal of Cleaner Production 284 (2021) 124703

Table 3
Adsorption data of different composite hydrogels containing clays used for the removal of dyes from water.

Composite hydrogel C%a Db Dye ETc EMd qm (mg/g) Ke pH References

KG-g-PMETAC/MMT e 1.0 AB ~400 F 128.8 1st e Krishnappa and Badalamoole (2020)

PAAm-co-IA/MMT 3.0 1.0 BCB 30 L 457 2nd 3e8
Kaplan and Kasgoz (2011)
CTS/HLT 5.0 e BCG 24 e 6.0 e 6.0
Palantoken et al. (2016)
PAAc/KAO 1e2 10 BG ~200 F/L 25 2nd 7.0
Shirsath et al. (2013)
ALG/KAO 70 e CBG ~600 F 10.3 2nd 6.5
Bai et al. (2020)
Cellulose/BNT 30 e CR ~45 L 46 2nd 7.0
Santoso et al. (2019)
Cellulose/CTS/REC 5.0 2.0 CR ~500 F 57 2nd e Tu et al. (2017)
Magadiite-CTS e 0.5 CR e L 135.8 2nd 6.5
Mokhtar et al. (2020)
k-CARR-g-PAAc/KAO e 0.5 CV 180 T 3.0 2nd 6.0
Dargahi et al. (2018)
PAAm/KAO e 10 CV ~250 F/L 25 2nd 10.0
Shirsath et al. (2015)
PAAm/LPT e 6.0 CV ~2500 e e e e Li et al. (2008)
CTS-g-P (ACr-co-AAm)/MMT 5.0 2.5 CV e F/L 256 e 4e9
Nagarpita et al. (2017)
NG 221
SY 208
CMC-g-P (ACr-co-AAm)/MMT 5.0 2.5 CV e F/L 196 e 4e9
Nagarpita et al. (2017)
NG 263
SY 175
PAAm-co-maleic acid/MMT 5.0 e CV ~1000 e 20 2nd 7.0
Aref et al. (2017)
KG-g-PMETAC/MMT e 1.0 CV ~400 F 137.8 1st e Krishnappa and Badalamoole (2020)
AAm/Zn-ACr/XG/SEP e e JGB e e e e e Karadag et al. (2016)
ALG/PAAm/BNT e e LV e e e e e Karadag et al. (2017)
CMC/AAm/AMPS/MMT e e LV e e e e e Karadag et al. (2014b)
PMAA-g-Cellulose/BNT e 1.0 MB ~50 S 372 2nd 6.5
Anirudhan and Tharun (2012)
CMC/PVA/BNT e 1.5 MB ~50 F 164 2nd 8.0
Dai et al. (2018)
PVA/BNT 1.0 e MB 1440 e 27.9 e e Sanchez et al. (2019)
CTS-g-PAAc/PAAm/BNT e e MB ~500 F/L 3057 PD 7.0
Bhattacharyya and Ray (2014)
CTS-g-PAAc/BNT 10 5.0 MB 25 L 2126 2nd 7.0
Liu et al. (2011b)
ALG/BNT 80 1.0 MB 400 L 769 2nd 6.0
Belhouchat et al. (2017)
k-CARR-g-PAAm/BNT e 5.0 MB 60 L 156 e 6.0
Pourjavadi et al. (2016)
CTS-g-PAAc/BNT e 1.0 MB 60 L 2002 2nd 2e9
Bulut and Karaer (2015)
CTS-g-PAAm/VMT 10 5.0 MB ~25 L 1685 2nd 7.0
Liu et al. (2010a)
CTS-g-PAAc/HLT 50 5.0 MB e e 1336 e 6.1
Liu et al. (2010b)
PAAm/HLT 14.8 48 MB 15 e e e e Feng et al. (2019)
CTS-g-PAAc/ATP 30 1.0 MB 25 L 1848 2nd 5.0
Wang et al. (2011)
CMC-g-PAAc/ATP 20 0.5 MB 25 L 2095 2nd 2e9
Liu et al. (2011a)
NSCTS-g-PAAm/ATP e 4.0 MB 30 L 135 2nd 2e12
Li et al. (2011)
Hemicellulose/LPT e 1.0 MB 150 L 149 2nd 5.0
Cheng et al. (2016)
PVA/LPT 37.5 1.0 MB ~25 L 251 2nd 5.5
Mahdavinia et al. (2017)
SH/PAAm/LPT e e MB ~350 e 800 e e Yi and Zhang (2008)
CMC/k-CARR/MMT 0.4 2.0 MB ~350 L 11 2nd 6.0
Liu et al. (2018)
Cellulose/MMT 20 e MB e F 277 1st 7.0
Wang, Q.Y. et al. (2019)
CTS-g-PAAc/MMT 2.5 1.0 MB 50 L 1859 2nd 6.5
Wang et al. (2008)
Lignocellulose-g-PAAc/MMT 20 10 MB ~60 L 1994 2nd 2e12
Shi et al. (2013)
Cellulose/CMC/MMT 5e15 63 MB ~30 L 783 2nd 1e11
Peng et al. (2016)
PVA-ALG-CTS-MMT e 2.0 MB ~500 F/S 137 E e
(continued on next page)

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A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al. Journal of Cleaner Production 284 (2021) 124703

Table 3 (continued )

Composite hydrogel C%a Db Dye ETc EMd qm (mg/g) Ke pH References

Wang et al. (2018)

PAAc-co-AAm/MMT e 0.5 MB 20 S 718 1st/2nd 8.0
Wang et al. (2020)
ALG-g-P (AA-co-St)/organo-I/S) e 0.5 MB 30 L 1843 2nd 2e10
Wang et al. (2013)
PAAc-co-AAm/MMT 2.0 1.0 MB 25 L 1964 2nd 5.0
Wei et al. (2018)
PAM/ALG-MMT 20 1.0 MB 200 L 2639 2nd e Qiu et al. (2014)
ALG/HEC 2.0 2.0 MB 660 F 785 1st 6.0
Pawar et al. (2018)
CTS-g-PAAc/VMT 10 0.5 MB 30 L 1682 2nd 7.0
Liu et al. (2010a)
LNR-g-MaH/AAc/MMT e e MB e F 9.7 2nd 6.5
Ahmad et al. (2020)
ALG/KAO 70 1.0 MB e F 504 e 6.5
Bai et al. (2020)
Magadiite-CTS e 0.5 MB 75 L 42.3 2nd 4.5
Mokhtar et al. (2020)
KG-g-PMETAC/MMT e 1.0 MB ~400 F 155.8 1st e Krishnappa and Badalamoole (2020)
CTS/MMT e 1.0 MB 900 L 530 2nd e Kang et al. (2018)
CTS-g-PAAc/PAAm/BNT 4.0 e MG 600 F 2714 1st 7.0
Bhattacharyya and Ray (2014)
CTS-g-P (AAc-co-IA)/ATP 5.0 0.5 MG 120 L 2433 2nd 2e11
Zheng et al. (2014)
GE-g-PAAc/ATP 5.0 1.0 MG e e 1190 e 2e10
Zheng, Y.A. et al. (2015)
PAAc-co-PAAm/ATP 30 1.0 MV 10 L 1194 2nd 3e12
Wang et al. (2010)
CTS/HLT 3.0 e NB e e ~7.0 e 6.0
Palantoken et al. (2016)
ALG/KAO 70 1.0 NR ~250 F 592.4 2nd 6.5
Bai et al. (2020)
PMOA/ATP 3.0 e RhB ~450 F 1.7 2nd 4.6
Yuan et al. (2015)
CTS-g-NVP/MMT 0.2 0.9 RhB e F 37 2nd 10.0
Vanamudan et al. (2014)
AAm/SMA/MMT 05e2 e ST e e e e e Karadag et al. (2014a)
St-g-PAAc/MMT 1.0 0.5 ST ~30 F 2237 e e Al et al. (2008)
KG-g-PMETAC/MMT e 1.0 TB ~400 F 149.6 1st e Krishnappa and Badalamoole (2020)

Abbreviations: AAc ¼ Acrylic acid; AAm ¼ Acrylamide; ACr ¼ Acrylate; ALG ¼ Alginate; ALG-g-P(AAc-co-St)/organo-I/S) ¼ Alginate-g-poly(acrylic acid-co-organo-illite)/
smectite; AMPS ¼ 2-acrylamido-2-methyl-1-propanesulfonic acid; ATP ¼ Attapulgite; BNT ¼ Bentonite; CMC ¼ Carboxymethyl cellulose; CTS ¼ Chitosan; CMCTS ¼ Car-
boxymethyl chitosan; GE ¼ Gelatin; HLT ¼ Halloysite; IA ¼ Itaconic acid sodium salt; KAO ¼ Kaoline; k-CARR ¼ Kappa-carrageenan; KG ¼ Karaya gum; LPT ¼ Laponite; LNR-
g-MaH ¼ Maleated liquid natural rubber; MMT ¼ montmorillonite; NSCTS ¼ N-succinyl chitosan; NVP ¼ N-vinyl pyrrolidone; PAAc ¼ Polyacrylic acid;
PAAm ¼ Polyacrylamide; P(ACr-co-AAm) ¼ Poly(acrylate-co-acrlylamide); PMAA ¼ Poly(methacrylic acid); PMETAC ¼ Poly(2-methacryloyloxy ethyl)trimethyl ammonium
chloride; PMOA ¼ Poly(2-(2-methoxyethoxy) ethyl methacrylate-co-oligo(ethylene glycol) methacrylate-co-acrylic acid); PVA ¼ Poly(vinyl alcohol); REC ¼ Rectorite; SEP ¼
Sepiolite; SH ¼ Sodium humate; SMA ¼ Sodium methacrylate; St ¼ Starch; VMT ¼ Vermiculite; XG ¼ Xanthan gum.
Dyes: AB ¼ Azure B; BCB ¼ Brilliant cresyl blue; BCG ¼ Bromocresol green; BG ¼ Brilliant green; CBG ¼ Coomassie brilliant blue G250; CR ¼ Congo red; CV ¼ Crystal violet;
JGB ¼ Janus green B; LV ¼ Lauths violet; MB ¼ Methylene blue; MG ¼ Malachite green; MV ¼ Methyl violet; NB ¼ Nile blue; NG ¼ Napthol green; NR ¼ Neutral red; RhB ¼
Rhodamine B; ST ¼ Safranine T; SY ¼ Sunset yellow; TB ¼ Toluidine blue.
a
C% ¼ Content of clay (wt-%) into the composite hydrogel.
b
D ¼ Adsorbent dosage (g/L).
c
ET ¼ Time necessary to achieve the equilibrium condition (min).
d
EM ¼ Equilibrium mechanism (Isotherms: F ¼ Freundlich; L ¼ Langmuir; S ¼ Sips; T ¼ Temkin).
e
K ¼ Kinetic mechanism (1st ¼ Pseudo-first-order; 2nd ¼ Pseudo-second-order; PD ¼ Pore diffusion; E ¼ Elovich).

clays (Murugesan and Scheibel, 2020). Also, the ratio between
organic and inorganic phases must be modulated to ensure
adequate mechanical and swelling properties. Overall, high
amounts of clay can result in materials with low adsorption ability
because interactions between clays and polymer chains (electro-
static interactions, H-bonds, van der Waals forces, etc.) crosslink
the composites. This behavior reduces the composite flexibility and
the number of hydrophilic groups available to bind aqueous pol-
lutants (Du et al., 2020).
The ideal inorganic/organic phase ratio in a composite hydrogel
embedded with clays particles must be determined individually.
This is not a simple task considering the particularities associated
with the polymer and hydrogel types. Table 3 illustrates this chal-
lenge. As can be seen, adsorption capacity (consequently the pro-
cess efficiency) concerning a specific dye varies drastically
according to the prepared composite type. The adsorption effi-
ciency depends on adsorbent and adsorbate types and their affin-
ities. For example, an alginate/bentonite composite containing
50 wt-% of clay imparted a methylene blue adsorption of 769 mg/g
(Belhouchat et al., 2017), while at the same clay content (50 wt-%), a
chitosan-g-poly (acrylic acid)/halloysite composite exhibited an
adsorption capacity of 1336 mg/g for the same dye (Liu et al.,
2010b). Of course, this comparison is not fair if we do not
consider other important aspects of the composite hydrogels and
experimental conditions.
It is necessary to examine some aspects to understand the real
effect of clay minerals on the adsorption ability of the composite
hydrogels. How do clays affect the surface properties of the
hydrogels and their swelling behavior? These two crucial aspects
are straightly related to the nature and amount of clays used to

10
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al.
prepare composite hydrogels. Considering that in the majority of
protocols describing the preparation of composites with clays, the
addition of these fillers occurs during the pre-crosslinking step.
Thus, it is reasonable to conclude that clays influence the hydrogel
crosslinking density. The influence (desired or not) drives a series of
secondary effects that alter (drastically or not) the final properties
of the composite hydrogel.
Ahmad et al. (2020) showed a noticeable change in the
morphology of liquid natural rubber/acrylic acid hydrogel after
incorporating montmorillonite. Similarly, incorporating this clay
into a hydrogel matrix based on poly (acrylic acid-co-acrylamide)
has also promoted changes in the composite morphology
compared to the pristine hydrogel (Wei et al., 2018). Overall, many
authors reported that the presence of clays into the hydrogel net-
works made the composite surface rough and porous, increasing
the surface area of the formed composites compared to the con-
ventional hydrogels (Leitao et al., 2015; Rodrigues et al., 2013).
Concerning the porosity, the introduction of clays usually affects
the pore distribution and the average pore size of the composite
hydrogels. Currently, there is no consensus on the effect of clays on
the porosity of the final hydrogel. A study showed that the intro-
duction of clays could increase the pore size and total porosity of
composite hydrogels (Hosseinzadeh et al., 2015). At the same time,
opposite results have also been reported (Zhang et al., 2009).
Overall, changes in the surface morphology of hydrogels affect their
interactions with the aqueous medium. This interaction plays an
essential role in the adsorption process because the water mediates
the contact between dye molecules and the surface of the com-
posite. In this way, the interactions between water and hydrogel are
guided by the material hydrophilicity and morphology. The
hydrogel hydrophilicity is mainly associated with the polar groups
available in its network. Hydrophilic groups such as hydroxyl, car-
boxylic, and amines can support efficient interactions with water
molecules and polymer chains, enhancing the liquid uptake. As a
result, dye molecules dissolved in water are put in contact with
adsorption sites on the hydrogel more easily. The hydrogel
morphology contributes to the swelling process. Generally, a highly
porous structure with randomly distributed and interconnected
pores improves the swelling process (Rodrigues et al., 2013). In
most of the studies focused on hydrogels as adsorbent materials, a
high swelling ability is often associated with a high adsorption
Fig. 4. Illustrative scheme showing the adsorption of methylene blue (MB) on chitosan-based hydrogel containing montmorillonite nanosheets. MMTNS ¼ montmorillonite
nanosheets; HG-45 ¼ hydrogel sample with MMTNS at 45 g/L; and LG-15 ¼ hydrogel sample with MMTNS at 15 g/L. Reproduced with permission of Elsevier (Kang et al., 2018). (For
interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)
11
Journal of Cleaner Production 284 (2021) 124703
capacity. Some review papers have highlighted the advantages
offered by superabsorbent hydrogels (hydrogels that can absorb
more than 100-fold their weight in water (Cipriano et al., 2014))
toward the adsorption of some water-pollutants (Ma and Wen,
2020).
In summary, the introduction of clay minerals in hydrogel
formulation also may affect the morphology and general hydro-
philicity of the resulting composites simultaneously (Vanoss and
Giese, 1995). The presence of SieOH groups and charged atom
moieties in certain clays favors the liquid uptake capacity of the
composite hydrogels. Kundakci et al. (2008) demonstrated that the
introduction of bentonite on hydrogels based on acrylamide with 2-
acrylamide-2-methyl-1-propanesulfonic acid significantly
improved their swelling capacities. These enhanced properties
were paramount to increase the adsorption capacity towards the
cationic Lauths violet (thionine).
Despite being common sense to associate the higher swelling
with the higher dye adsorption capacity, some systems do not
follow such rule. Santoso et al. (2019) showed the introduction of
bentonite in a cellulose-based hydrogel reduced the swelling ca-
pacity, increasing the adsorption of Congo red (10%) compared to
the pristine hydrogel. The introduction of bentonite increased the
crosslinking density, leading the hydrogel matrix to be more
compact, thereby, diminishing the swelling and adsorption capac-
ities. On the other hand, incorporating bentonite in a cellulose-
based network increased the composite surface area, raising the
number of active sites to interact with dye molecules. In this case,
the adsorption was improved (Santoso et al., 2019).
Clays can increase the number of active sites of composite
hydrogels to hold the dye molecules during the adsorption process.
Overall, the main interactions between clays and dye molecules
occur via hydrophobic, electrostatic, dipolar, and H-bond. Dipolar
and H-bond interactions occur between electronegative atoms on
dye molecules and SieOH groups on clays (Fang et al., 2018). In
contrast, hydrophobic effects involve the aromatic dye rings and
SieOeSi clay moieties. On the other hand, electrostatic interactions
can be expected between chargeable groups of dyes (such as
carboxylate, sulfate, amine, etc.) and the clay structure, which can
be positively or negatively charged (Ghadiri et al., 2015). Based on
their charge, ionic clays can be classified into two main groups;
cationic or anionic. Cationic clays possess a negative charge and are
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al.
Fig. 5. Synthesis schemes of cellulose-clay nanocomposite hydrogel. (a) Hydrogel network containing unmodified clay. (b) Epoxidized clay (chemical modified) crosslinked in the
hydrogel network.
widespread (e.g., smectite). Conversely, the anionic clays maintain
a positive charge and are relatively uncommonly found, but rather
economical and straightforward to synthesize (Ghadiri et al., 2015).
It is important to note that non-ionic clays are also found in nature
and do not have an ion exchange capacity (Mulligan et al., 2001).
Examples include kaolinite, serpentine, talc, and others.
The use of charged clay minerals (cationic or anionic) to prepare
adsorbent materials is highly attractive, as demonstrated else-
where. Composite hydrogels prepared with montmorillonite and
kaolinite (which has moderate negative surface charges) presented
outstanding adsorption capacities towards cationic dyes like
methylene blue and crystal violet (Table 3). In some cases, a syn-
ergistic effect between the functional groups of the hydrogel matrix
and charged clay enhances the adsorption capacity of the com-
posite material. Liu et al. (2010a) reported the use of a chitosan-g-
poly (acrylic acid) hydrogel to remove methylene blue with an
adsorption capacity of 1571.3 mg/g, due to the carboxylate-rich
structure of poly (acrylic acid). The introduction of vermiculite
(10 wt-%) in this hydrogel allowed increasing the adsorption ca-
pacity to 1612.3 mg/g. Vermiculite, a negatively charged clay, is
quickly ionized and dispersed into a chitosan-g-poly (acrylic acid)
network, increasing the negative charge density, favoring the
adsorption of cationic methylene blue.
The electrically charged clays can also increase the adsorption
capacity due to complementary interaction forces between the dye
molecules and the hydrogel matrix. As aforementioned, the
adsorption process is mainly driven by H-bonds and dipole-dipole
interactions between the organic dye backbones and the hydro-
philic hydrogels. So, the introduction of charged clays renders
composites with extra ability to interact with dyes electrostatically.
For instance, anionic aluminosilicates such as montmorillonite (a
clay with cation exchange capacity) allow the electrostatic inter-
action with cationic dyes like methylene blue, enhancing the
adsorption capacity of the composite compared to the pristine
hydrogel (Fig. 4) (Kang et al., 2018). In practical terms, the main
forces (as well as the mechanism) that drive the adsorption process
can be assessed by analytical techniques (e.g., FTIR, XPS, UVeVis,
etc.) and/or by theoretical analyses (e.g., isotherm models, ther-
modynamic parameters, etc.).
Beyond the improvements in adsorption capacity, most parts of
the studies focused on the use of composite hydrogels containing
clay minerals in dye removal and report improvements in the
adsorption rate due to the clay presence. The permanent charges on
the surface of clays layers can accelerate the adsorption process of
electro-charged dyes molecules. Long-range electrostatic in-
teractions take place between the adsorbent and the adsorbate
(Momina et al., 2018). This effect is pronounced for clays exfoliated
12
Journal of Cleaner Production 284 (2021) 124703
to nanolayers before the composite preparation because the exfo-
liation increases the specific area, exposing the adsorption sites to
interact with dye molecules. Mahdavinia et al. (2017) prepared
composite hydrogels of poly (sodium acrylate)-g-carrageenan filled
with Na-montmorillonite for the removal of crystal violet from
water. At 8 wt-% of Na-montmorillonite, the clay was fully exfoli-
ated (determined by XRD analysis), increasing the absorption rate
of the composite about 5-fold than the kinetic rate calculated for
the pristine hydrogel using a pseudo-first-order kinetic model
(Madhavinia and Zhalebaghy, 2011). In practical terms, these re-
sults stand out that the composite hydrogels achieve their
maximum adsorption capacity faster than the pristine hydrogel.
Given that time is a crucial variable in real applications, this result is
attractive since it allows optimizing the duration of the adsorption
process. Other experimental parameters including initial dye con-
centration, pH of the aqueous medium, and temperature, should
also be assessed to obtain the optimal experimental conditions.
Despite the encouraging results, criticism regarding the com-
posite hydrogels containing clay minerals has also been raised,
mostly because of the high energy input, and water and chemical
agents required in the preparation (Karadag et al., 2017). This
shortcoming occurs when there is low compatibility (in terms of
structure or chemical nature) between the hydrogel matrix and the
clay requiring additional chemical modification steps (Fig. 5). Peng
et al. (2016) fabricated a series of cellulose-clay nanocomposite
hydrogels through the chemical crosslinking of cellulose/carbox-
ymethyl cellulose and montmorillonite (at 5, 10, and 15 wt-%) for
the adsorption of methylene blue. In this case, the clay layers were
efficiently intercalated within the cellulose matrix only after the
chemical modification of the clay structure, as illustrated in Fig. 5.
According to the authors, the insertion of epoxy groups on the clay
layers allowed the reaction with hydroxyl groups of cellulose/car-
boxymethyl cellulose, enabling the entering of polysaccharide
chains into the galleries, but stacking the clay nanosheets (Peng
et al., 2016). Further than the chemical modification of clays,
other options include compatibilizing chemical agents or cross-
linking agents (such as glutaraldehyde and epichlorohydrin) to
provide stability to the synthesized composites. However, some
studies warn that the use of these chemicals may prevent biodeg-
radation and can often enhance the toxicity of these composites.
4.2. Composite hydrogels containing carbon-based materials
Carbon-based materials (graphite, graphene oxide, graphene,
carbon nanotubes, and others) have been associated with hydrogels
due to their great versatility and because they can be chemically or
physically combined with hydrogel matrices. Carbon-based
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al. Journal of Cleaner Production 284 (2021) 124703

Table 4
Adsorption data of different composite hydrogels containing graphene oxide (and derivatives) used for the removal of dyes from water.

Composite hydrogel C%a Db Dye ETc EMd qm (mg/g) Ke pH References

PMPTC/GO 0.3 e MB ~150 e 13 2nd e Wang, R. et al. (2019)

PAAm/GO 50 0.2 MB 20 F/L 293 2nd e Yang, Y.Y. et al. (2017)
CMC/AAm/GO ~10 4.0 AB 720 e 185 e 6.0
Varaprasad et al. (2017a)
WG/GO e e CD e e e e Yu et al. (2015)
Chitin/TA/GO 7.0 e CR ~400 L 231 2nd 7.0
Liu et al. (2020)
CTS/GO e e CR ~4000 e 10 2nd e Zhao et al. (2015)
CTS/amino-functionalized-GO 20 e CR 5.0 L 385 2nd 7.0
Omidi and Kakanejadifard (2018)
PVP/AAc/GO 0.2 5.0 CR 40 F 78 2nd 7.0
Atyaa et al. (2019)
Double ALG/GO network e 1.0 MB 1200 F/L 2300 2nd 8.0
Zhuang et al. (2016)
Single ALG/GO network e 1.0 MB 1200 F/L 1800 2nd 8.0
Zhuang et al. (2016)
Double ALG/PVA/GO network 5.0 0.1 MB 480 L 1437 2nd 6.0
Kong et al. (2019)
Single ALG/PVA/GO network 5.0 0.1 MB 480 L 1256 2nd 6.0
Kong et al. (2019)
ALG/immobilized GO network 5.0 0.2 MB 200 F/L 181 2nd 5.4
Li et al. (2013a)
ALG/GO e 5.0 MB 60 F 122 2nd 5.3
Balkız et al. (2018)
CTA/PAAc/GO 0.5 1.0 MB 2250 297 E 7.0
Chang et al. (2020)
CTS/GO 50 0.13 MB 70 e 390 e 6.5
Chen et al. (2013)
CTS/GO e e MB 50 e 3.5 2nd e Zhao et al. (2015)
PVA/sulfonated-GO 1.0 80 MB 720 L 5.1 2nd 6.2
Li et al. (2015)
Cellulose/GO 0.5 20 MB ~20 e 123 2nd 7.0
Soleimani et al. (2018)
Cellulose/GO 10 2.0 MB ~70 e 46 2nd e Liu, Z.J. et al. (2017)
CMC/PVA/GO 0.7 1.5 MB 80 L 89 2nd 8.0
Dai et al. (2018)
k-CARR/GO ~30 e MB 6.0 L 658 2nd 5.3
Yang, M.L. et al. (2017)
PEGDMA-rGO 1.0 2.5 MB 720 L 60 2nd 7.4
Halouane et al. (2017)
PAMm/GO 5.0 e MB 75 e 26 2nd e Cui et al. (2015)
PMMA/GO MB e e Thompson et al. (2018)
PEGD/thiolated-GO 17 e MB ~75 e 6.0 2nd e Liu, J.M. et al. (2017)
PAAc-g-XG/GO 0.1e1.0 0.25 MB e e e E/ID 7.0
Hosseini et al. (2020)
PEI/GO e e MB 240 e 334 2nd e Guo et al. (2015)
PVA/sulfonated-GO 1.0 80 MG e L 4.4 2nd 6.2
Li et al. (2015)
ALG/PAAc/Graphite e e MG 60 L 629 2nd 7.0
Verma et al. (2020)
XG-g-PAAc/rGO 5.0 0.5 MV 30 L 1052 2nd 6.0
Makhado et al. (2018)
PAMm/GO 50 0.025 Rh6G 20 F/L 288 2nd e Yang, Y.Y. et al. (2017)
CTS/GO e e RhB 250 e 1.9 2nd e Zhao et al. (2015)
PMPTC/GO 0.3 e RhB ~150 e 12 1st e Wang, R. et al. (2019)
Cellulose/GO 0.5 20 RhB ~40 e 62 2nd 7.0
Soleimani et al. (2018)
PEI/GO e e RhB 240 e 132 2nd e Guo et al. (2015)
ALG-Fe3þ/rGO 50 e RhB 360 L 18.4 2nd e (Xiao et al., 2020)

Abbreviations: AAc ¼ Acrylic acid; AAm ¼ Acrylamide; ALG ¼ Alginate; CMC ¼ Carboxymethyl cellulose; CTS ¼ Chitosan; GO ¼ Graphene oxide; k-CARR ¼ kappa-Carra-
geenan; PAAc ¼ Poly(acrylic acid); PAAm ¼ Poly(acrylamide); PEI ¼ Poly(ethyleneimine); PEGDMA ¼ Polyethylene glycol dimethacrylate; PMPTC ¼ Poly(3-(meth-
acryloylamino)propyl-trimethylammonium chloride); PVA ¼ Poly(vinyl alcohol); PVP ¼ Poly(vinyl pyrrolidone); rGO ¼ Reduced graphene oxide; TA ¼ Tannic acid; WG ¼
Welan gum, XG ¼ Xanthan gum.
Dyes: AB ¼ Acid blue 133; CR ¼ Congo red; CV ¼ Crystal violet; MB ¼ Methylene blue; MG ¼ Malachite green; MV ¼ Methyl violet; RhB ¼ Rhodamine B; Rh6G ¼ Rhodamine
6G; CD ¼ Cationic dyes mixture (methylene blue, rhodamine 6G, methyl violet, and chrome azurol S).
a
C% ¼ Content of graphene oxide (and derivatives) (wt-%) into the composite hydrogel.
b
D ¼ Adsorbent dosage (g/L).
c
ET ¼ Time necessary to achieve the equilibrium condition (min).
d
EM ¼ Equilibrium mechanism (Isotherms: F ¼ Freundlich; L ¼ Langmuir).
e
K ¼ Kinetic mechanism (1st ¼ Pseudo-first-order; 2nd ¼ Pseudo-second-order; ID ¼ Intraparticle diffusion; E ¼ Elovich).
13
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al.
materials display excellent features such as high density, high
strength, and high hardness (Papageorgiou et al., 2017), which
encourage their use in several fields to solve environmental and
energy issues. We observed uses in CO2 reduction, H2 photoelec-
tron generation, batteries, production of clean energy from oxygen
reduction reaction, development of sensors, and materials for
treatment of wastewater and water (for degradation of organic
pollutants and adsorption purposes) (Dutta et al., 2019; Siwal et al.,
2020).
More recently, graphene-based composite hydrogels have
received considerable attention to be applied as adsorbent mate-
rials for dyes (Zhuang et al., 2016). They are often prepared by
combining graphene oxide to polymer matrices. The graphene
oxide synthesis is easily performed from conventional chemical
and micro-mechanical exfoliation processes compared to the
chemical vapor deposition approach that produces graphene with
high structural homogeneity (Kumar et al., 2015). Conventional
methods support graphene oxides with defects in their sheets;
however, these processes are cheaper than the chemical vapor
deposition method. The graphene oxide structure is highly disor-
dered compared to the graphene (both materials comprise carbon
chains with hexagonal structures) (Kusiak-Nejman and Morawski,
2019).
Graphene oxide presents hydrophilic moieties (OH,
eCeOeC, and eCOOH) in its structure, which can bind dyes.
Above pH 5.0, the carboxylic groups on graphene oxide ionize,
providing high negative charge density to the material. In addition,
graphene oxide can be chemically reduced to remove oxygen-based
sites (OH and eCeOeC) to impart the reduced graphene.
However, the chemical reduction is not complete and often pro-
duces materials with low aqueous solubility and low dispersibility
in polymer systems (Johnson et al., 2015). Due to these features, the
graphene oxide is principally used to prepare reinforced composite
hydrogels, aiming to produce adsorbents economically viable for
the removal of dyes (Cui et al., 2015). The association of hydrogels
with graphene oxide produces composite materials with renewable
mechanical, optical, thermal stability, high surface area, high
negative charge density, and recyclability properties (Liu et al.,
2020). These traits can be tuned by modulating graphene oxide
content into the hydrogel structure.
The higher dispersibility of the graphene oxide in polymer
systems is ascribed to anionic and hydrophilic moieties in its
structure. Graphene oxide is usually combined with hydrogels
formulated with anionic polymers to produce adsorbent materials
with strong anionic behavior for removing cationic dyes (Zhuang
et al., 2016). Table 4 compares the adsorption capacities of com-
posite hydrogels containing graphene oxide or its derivatives
applied to remove dyes from water.
Physical composite hydrogels based on single and double algi-
nate/poly (vinyl alcohol)/graphene oxide networks have demon-
strated high sorption capacities upon cation dyes in aqueous
environments (Table 4) (Kong et al., 2019). However, the removal
capacity principally depends on the experimental procedure used
to prepare the composites. For instance, a double network of algi-
nate/poly (vinyl alcohol) composite hydrogel (beads) crosslinked
with Ca2þ ions embedded with graphene oxide showed higher
adsorption capacity (qm ¼ 1437 mg/g) compared to the single
network alginate/poly (vinyl alcohol)/graphene oxide-based com-
posite hydrogel (qm ¼ 1256 mg/g) toward methylene blue (Table 4).
Another double network based on alginate/graphene oxide com-
posite ionically crosslinked with Ca2þ ions to (without poly (vinyl
alcohol) reached qm of 2300 mg/g toward methylene blue, whereas
a single crosslinked alginate/graphene oxide composite (Table 4)
and pristine graphene oxide composite imparted qm of 1800 and
600 mg/g, respectively (Zhuang et al., 2016). Beads of Ca2þ-alginate
14
Journal of Cleaner Production 284 (2021) 124703
and Ca2þ-kappa-carrageenan containing graphene oxide showed
qm of only 122 and 658 mg/g toward methylene blue as well (Balkız
et al., 2018; Yang, M.L. et al., 2017). These results highlight the
interdependency concerning the type of hydrogel network and the
filler in terms of adsorption capacity. Nevertheless, an advantage
often attributes to these composite beads lies in the fact that they
can easily be separated from aqueous solutions after adsorption
using a simple filtration method (Yang, M.L. et al., 2017).
Another study reported physical alginate/reduced graphene
oxide composite hydrogels prepared with different divalent
crosslinker cations (Ca2þ, Ba2þ, and Cu2þ), and Fe3þ (Xiao et al.,
2020). Due to the size, both Ca2þ and Fe3þ ions can crosslink two
and three macromolecular alginate chains. The crosslinking process
carried out with these ions improved the mechanical properties
and durability of the double network structures compared to the
single network structures. However, the higher compression
strength and lower swelling ratio of the composite crosslinked with
Fe3þ promoted low qm (18.4 mg/g) towards rhodamine B.
As noticed in the literature, composite hydrogels containing
graphene oxide are generally prepared using physical crosslinking
approaches, mainly when polysaccharides are utilized (by them-
selves or blended with synthetic polymers) (Liu et al., 2020). In this
case, the absence of chemical crosslink agents (e.g., glutaraldehyde
and epichlorohydrin) (Crini et al., 2019) reduces potential risks
associated with toxicity. Physical crosslinking seems to be more
eco-friendly than some chemicals used to reduce graphene oxide
(e.g., hydrazine). These toxic chemistries may harm the benign
advantage from the prepared composites with fillers (Pei and
Cheng, 2012).
Physical composites based on polysaccharides and graphene
oxide are prepared from the assembling of graphene oxide sheets
and polysaccharide chains, generally guided by electrostatic forces
(Chen et al., 2013). A physical chitosan/graphene oxide composite
hydrogel formed by the interaction of the positively charged chi-
tosan and the negatively charged graphene oxide showed a
remarkable capacity for removing methylene blue, rhodamine B,
methylene orange, and Congo red. Moreover, the post-used
adsorbent samples could be regenerated and recycled, using suc-
cessive adsorption and washing cycles (Vo et al., 2020). Similarly,
physical composite hydrogels based on chitosan/poly (acrylic acid)/
graphene oxide and chitosan/poly (acrylate)/graphene oxide sup-
ported the adsorption of methylene blue and food yellow 3,
respectively (Chang et al., 2020). Besides enhancing the adsorption
capacity, in this case, the graphene oxide exerted a leading role in to
reinforce of the hydrogel network. The authors also highlighted the
synergistic effect between poly (acrylic acid) and graphene oxide,
which significantly enhanced the swelling and adsorption capac-
ities of the composite hydrogel. To the composite, the maximum
adsorption capacities for methylene blue and food yellow 3 reached
297 mg/g and 288 mg/g (Chang et al., 2020). Chen et al. (2013) and
Dai et al. (2018) prepared physically crosslinked hydrogels of chi-
tosan/graphene oxide and carboxymethyl cellulose/poly (vinyl
alcohol)/graphene oxide and tested them as adsorbents of methy-
lene blue. As found, these composites exhibited discrepant
adsorption capacities (390 and 89 mg/g, respectively). According to
the authors, electrostatic interactions between adsorbent-
adsorbate pairs had driven the adsorption mechanism in both
hydrogels. The greater availability of negative charge on the com-
posites based on the chitosan/graphene oxide samples explains the
better performance of this sample.
On the other hand, physical alginate/graphene oxide-based and
gum/graphene oxide-based composites promoted better sorption
capacities upon cationic dyes than the chitosan/graphene oxide-
based and cellulose/graphene oxide-based composites (Table 4).
Alginate and gums are natural polysaccharides with anionic
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al. Journal of Cleaner Production 284 (2021) 124703

Fig. 6. Illustrative scheme regarding the formation of polyethyleneimine (PEI)/graphene oxide (GO) composite hydrogel. (A) Graphene oxide sheet, (B) branched polyethyleneimine,
(C) composition of the tested hydrogels, and (D) photographic images of the hydrogel formation. Reproduced with permission of Springer (Guo et al., 2015).

behavior in aqueous solutions above pH 5.0. Cationic chitosan
(pKa z 6.0e6.5) is often synthesized from partial chitin deacety-
lation. Chitosan is soluble in dilute acid solutions, and cellulose is a
neutral polysaccharide used to produce synthetic carboxymethyl
cellulose with different degrees of substitution (Dai et al., 2018;
Facchi et al., 2017). Due to the active anionic behavior, polyanionic
materials should foster better results for removing cationic dyes
from aqueous environments than the chitosan and cellulose
(Table 4).
A physical composite based on cellulose/graphene oxide
prepared by mixing cellulose and graphene oxide in 1-allyl-3-
methylimidazolium chloride (ionic liquid) removed 46 mg/g of
methylene blue (Table 4) (Liu, Z.J. et al., 2017). Imidazolium-based
ionic liquids have high cytotoxicity, and it is challenging to
remove them from the hydrogel structure completely (Ramin et al.,
2019). Overall, strategies using ionic liquids should be avoided to
produce composite hydrogels because they are expensive, and their
syntheses are complicated. The removal capacity promoted by a
cellulose/graphene oxide composite for methylene blue was low
compared to the sorption results supported by alginate, xanthan

Table 5
Adsorption data of different composite hydrogels containing carbon nanotubes used for the removal of dyes from water.

Composite hydrogel C%a Db Dye ETc EMd qm (mg/g) Ke pH References

PMPTC/MWCNT 0.3 e MB 200 e 8 2nd e Wang, R. et al. (2019)

RF/Co3O4/MWCNT 0.2 e RhB e e e 1st e Shafiee et al. (2019)
PMPTC/MWCNT 0.3 e RhB 150 e 2 2nd e Wang, R. et al. (2019)
PHB/ALG/CMWCNT 5.0 1.0 BB 300 F 24 2nd e Guo et al. (2016)
PHB/ALG/CMWCNT 0e2 1.0 BB e e e e e Cai et al. (2018b)
PMMAc-g-hemicellulose/MWCNT 10 7.0 MB e F 222 2nd e Sun et al. (2014)
CTS/cellulose-g-MWCNT 50 e MB e e e e e Cai et al. (2018a)
ALG/MWCNT 25 0.1 MO 80 L 14 e 7.0
Li et al. (2012)

Abbreviations: ALG ¼ Alginate; CTS ¼ Chitosan; MWCNTs ¼ Multi-walled carbon nanotubes; PMPTC ¼ Poly(3-(methacryloylamino)propyl-trimethylammonium chloride);
PHB ¼ Poly(hydroxybutyrate); PMMAc ¼ Poly(methacrylic acid); PVA ¼ Poly(vinyl alcohol); PVP ¼ Poly(vinyl pyrrolidone); RF ¼ Resorcinol formaldehyde; SWCNTs ¼ Single-
walled carbon nanotubes; TA ¼ Tannic acid; WG ¼ Welan gum, XG ¼ Xanthan gum.
Dyes: BB ¼ Brilliant blue; MB ¼ Methylene blue; MO ¼ Methyl orange; RhB ¼ Rhodamine B.
a
C% ¼ Content of carbon nanotubes (wt-%) into the composite hydrogel.
b
D ¼ Adsorbent dosage (g/L).
c
ET ¼ Time necessary to achieve the equilibrium condition (min).
d
EM ¼ Equilibrium mechanism (Isotherms: F ¼ Freundlich; L ¼ Langmuir).
e
K ¼ Kinetic mechanism (1st ¼ Pseudo-first-order; 2nd ¼ Pseudo-second-order).

15
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al.
gum, and chitosan-based composites (Omidi and Kakanejadifard,
2018), and still lesser than the sorption capacity imparted by
native graphene oxide (Li et al., 2013a).
Physical composite hydrogels are also prepared by combining
synthetic polymers and graphene oxide. For example, poly (vinyl
alcohol)/sulfonated graphene oxide composites containing 1.0 wt-%
of modified graphene oxide produced from a freezing-thawing
process fostered qm of only 5.1 mg/g for methylene blue, whereas
the raw poly (vinyl alcohol) hydrogel imparted only 1.2 mg/g (Li
et al., 2015). It is essential to mention that freezing-thawing pro-
cesses usually produce hydrogels with high crosslinking densities,
which may explain these discreet results. Otherwise, composite
hydrogels of poly (acrylamide)/graphene oxide exhibited encour-
aging results towards the adsorption of methylene blue (qm ¼ 26
and 293 mg/g, Table 4) (Cui et al., 2015) and rhodamine 6G
(qm ¼ 288 mg/g, Table 4) (Yang, Y.Y. et al., 2017). Moreover, ac-
cording to the authors, the prepared composite showed remarkable
durability, which can be explained by Coulombic, H-bonds, hy-
drophobic forces, and p-p stacking of graphene oxide sheets that
support their structures. Guo et al. (2015) reported the preparation
of branched polyethyleneimine/graphene oxide composites via
physical crosslinking supported by H-bonds and electrostatic in-
teractions between amine-rich polyethyleneimine and graphene
oxide sheets at room temperature. Fig. 6 shows the chemical
structures of the polyethyleneimine, graphene oxide, and com-
posite hydrogel, as well as the experimental conditions used to
create the composites, and digital images of the polyethyleneimine/
graphene oxide mixtures. The gelation process occurs as the poly-
cationic polyethyleneimine, and polyanionic graphene oxide con-
tents are adjusted in the final mixture at room temperature. The
composite stiffness can increase as the graphene oxide composite
concentration rises, highlighting the reinforcement ability of this
filler. The composite properties showed to be straightly dependent
on the polyethyleneimine/graphene oxide ratio. The authors esti-
mate an adsorption capacity of 334 mg/g for methylene blue and
132 mg/g for rhodamine B.
Composite hydrogels containing graphene oxide have also been
prepared via chemical crosslinking approaches and tested for ad-
sorbents for dye removal. A chemical composite hydrogel consist-
ing of poly (acrylic acid), xanthan gum, and reduced graphene oxide
was prepared by Makhado et al. (2018) using microwave radiation.
Herein, the amount of reduced graphene oxide introduced in the
hydrogel matrix exerted a noticeable effect on the swelling ability
of the composites, which also affected their adsorption capacity. At
the highest amount of reduced graphene oxide (80 mg), the
maximum adsorption capacity assessed for methyl violet was
around 1052 mg/g (Table 4). The negatively charged groups of
reduced graphene enhanced the composite and cationic methyl
violet interactions. According to the authors, the high surface area
of the reduced graphene oxide also contributes to this enhanced
performance.
Overall, the composite hydrogels based on negatively charged
polymers and graphene oxide usually show a remarkable adsorp-
tion capacity towards cationic dyes. In this sense, the use of poly-
saccharides such as alginate, xanthan gum, and kappa-carrageenan,
which have high contents of carboxylate and sulfate anions in the
molecular structure at pH below 5.0, has been widely investigated.
Verma et al. (2020) demonstrated that alginate/poly (acrylic acid)/
graphite composite hydrogel prepared via chemical crosslinking is
highly efficient for malachite green removal (qm ¼ 629 mg/g).
Instead of graphene oxide, the authors’ utilized graphene, which
comprises a tridimensional layered structure based on sheets
stacked together and supported by weak van der Waals forces
(Verma et al., 2020). Optimization studies allowed increasing the
composite adsorption capacity from 76 to 89% as the graphite
16
Journal of Cleaner Production 284 (2021) 124703
content increased from 0.01 to 0.1 g. The maximum removal per-
centage was achieved at 0.05 g graphite content, respectively.
Composites based on either chitosan/graphene oxide ore
chitosan/amino-functionalized graphene oxide are useful for
removing of Congo red. Because of the cationic behavior, chitosan-
based composites can often promote low sorption capacities for
cationic dyes (Table 4). As the graphene oxide content plays an
essential role in the adsorption process, its concentration must be
modulated into the hydrogel to provide composites with high
water uptake, mechanical reinforcement, and thereby great sorp-
tion capacities (Makhado et al., 2018). Materials with suitable
recyclability and reusability are produced; however, there is no
mention of issues concerning the graphene oxide synthesis and its
structural heterogeneity (Makhado et al., 2018). The adsorption
tests are often performed in weak acid or alkaline conditions
because both graphene oxide and hydrogel networks must have
their chemical sites (anionic moieties) ionized to remove cationic
dyes mainly by establishing electrostatic interactions (Liu, J.M.
et al., 2017). Unfortunately, during the literature review, it was
observed that many papers do not report the surface areas of the
composite hydrogel used as adsorbents, as well as the pH condi-
tions and temperatures used in the adsorption assays.
Another concern lies in the fact that in many cases, the results of
dye removal promoted by the raw graphene oxide are quite similar
to those assessed to the respective composite hydrogels (Li et al.,
2013a). Also, the conventional chemical process used to synthe-
size graphene oxide from graphite (an inexpensive feedstock) is
accomplished from many and longer steps, which often generates
residual wastes containing water, sulfuric and chloride acids, and
manganese ions (Chen et al., 2013). The adsorption results pro-
moted by the native graphene oxides synthesized from the same
experimental procedure (conventional Hummers-based method)
are quite different, even when similar strategies are used in the
adsorption processes (Li et al., 2013a). It is challenging to obtain
graphene oxide with reproducibility by following a more viable
(conventional) technique. There is often no comparison between
the adsorption results imparted by hydrogels and their composites
(Li et al., 2015).
In addition to graphene oxide, carbon nanotubes are also rele-
vant carbonaceous-derivatives often used to prepare composite
hydrogels for adsorption uses. Carbon nanotubes are allotropic
forms of carbon-related to the fullerene family. Their exceptional
thermal, mechanical, and electronic properties together with their
tubular shape, offering a high surface area and enabling adsorption
or conjugation of a wide variety of pollutant compounds, make
carbon nanotubes attractive platforms for the development of
composite adsorbent materials (Gao et al., 2013; Saber-Samandari
et al., 2017). Two types of carbon nanotubes are commonly
found: (i) single-walled and (ii) multi-walled (Yu et al., 2014). Up to
date, only multi-walled carbon nanotubes have been introduced
into hydrogels matrices aiming to obtain adsorbent materials for
dyes removal. Overall, multi-walled carbon nanotubes are easier
dispersed into polymer solutions compared to the single-walled
carbon nanotubes, which may explain this trend. Table 5 com-
piles adsorption data and examples of composite hydrogels con-
taining carbon nanotubes used to remove dyes from aqueous
systems.
The use of carbon nanotubes as adsorbents for treating dye-
contaminated water is dated after 2004 (Santhosh et al., 2016).
More recently, these nanomaterials have been introduced in the
hydrogel matrix resulting in composite materials. Probably, the
chemical nature of the nanotubes, which is rich in oxygen-based
groups (OH, eCeOeC, and eC]O on the basal planes and
edges), had motivated the formulation of this kind of composite
(Zhou et al., 2019). From a critic viewpoint, the potential benefits
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al. Journal of Cleaner Production 284 (2021) 124703

Table 6
Adsorption data of different composite hydrogels containing metal (nano)particles used for the removal of dyes from water.

Composite hydrogel C%a Db Dye ETc EMd qm (mg/g) Ke pH References

CTS@Fe3O4 e 1.0 AB ~400 L 142 2nd 7.0

Xu et al. (2019)
ALG@Yttrium e 2.0 ABB 30 L 1087 2nd 2e10 (Liu et al., 2020)
Collagen-g-PAAc-co-NVP/Fe3O4@SiO2 e 0.05 BG ~150 L 199 2nd 7.0
Nakhjiri et al. (2019)
PAAm-co-AAc/TiO2 20 1.0 CR e e 2.2 1st e Kangwansupamonkon et al. (2018)
ALG@Yttrium e 2.0 CR 30 L 1567 2nd 2e10 (Li and Yin, 2020)
PAAm/TiO2 0.5 e CV 600 F 132 2nd 6.5
Raj et al. (2018)
St-g-PAAc/ZnSe e 1.0 CV 30 F 189 2nd 6.0
Abdolahi et al. (2020)
PAAc/Co3O4 e 0.5 MB 30 F 837 e e Ansari et al. (2019)
PEGDMA-rGO/Fe3O4@cellulose 30 2.5 MB 720 L 112 2nd 7.4
Halouane et al. (2017)
CTS/Fe3O4@k-CARR e 2.0 MB 30 L 123 2nd 5.5
Mandavinia and Mosallanezhad (2016)
CTS/MMT/gFe2O3 e 100 MB 180 e 82 e e Bee et al. (2017)
Collagen-g-PAAc-co-NVP/Fe3O4@SiO2 e 0.05 MB ~125 L 202 2nd 7.0
Nakhjiri et al. (2019)
PVPA/Fe3O4@SiO2 e 1.4 MB e e 14 e e Sengel and Sahiner (2016)
AMPS/NIPAAm/Fe3O4 e 1.0 MB 10 F/L 833 2nd 7.0
Atta et al. (2018)
AMPS/NIPAAm/Cu2O e 1.0 MB 35 F 341 2nd 7.0
Atta et al. (2018)
AMPS/NIPAM/Fe3O4.Cu2O e 1.0 MB 5 F/L 746 2nd 7.0
Atta et al. (2018)
Cellulose/k-CARR/TiO2 0.7 e MB e e 115 e 7.0
Jo et al. (2017)
ALG/AgNPs e 1.0 MB 120 S 214 1st e Devi et al. (2016)
CMSt/PVA/Fe3O4 e 10 MB 600 F 24 2nd 7.0
Gong et al. (2015)
PAAm/CTS/Fe3O4 e 0.1 MB ~125 L 1603 1st 7.0
Zhang et al. (2020)
Cellulose/Fe3O4-diatomite e 0.7 MB 30 L 102 2nd 10
Dai et al. (2019)
HPG@Fe3O4 e 4.0 MB 30 L 459 2nd 8.0
Song et al. (2018)
PAAc-co-AAm/Co3O4.Cu2O e 0.5 MG ~40 L 238 2nd 7.0
Naseer et al. (2018)
PAAc-g-ALG/TiO2 e 0.6 MV e L 1157 e 7.0
Thakur and Arotiba (2018)
HPG@Fe3O4 e 4.0 MV 30 L 400 2nd 7.0
Song et al. (2018)
PMOA/ATP/Fe3O4 3.0 e RhB 400 F 1.7 2nd 4.6
Yuan et al. (2015)
PAAc-g-salep/AgNPs e 1.0 RhB 20 F 93 2nd 2.0
Bardajee et al. (2016)
PVPA/Fe3O4@SiO2 e 1.4 Rh6G e e 16 e e Sengel and Sahiner (2016)

Abbreviations: AAc ¼ Acrylic acid; AAm ¼ Acrylamide; ALG ¼ Alginate; AgNPs ¼ Silver nanoparticles; AMPS ¼ 2-acrylamido-2-methyl-1-propanesulfonic acid;
ATP ¼ Attapulgite; BNT ¼ Bentonite; CMC ¼ Carboxymethyl cellulose; CTS ¼ Chitosan; CMSt ¼ Carboxymethyl starch; HPG ¼ Hyperbranched polyglycerol; k-CARR ¼ kappa-
Carrageenan; MMT ¼ montmorillonite; NVP ¼ N-vinyl pyrrolidone; PAAc ¼ Poly(acrylic acid); PAAm ¼ Polyacrylamide; PEGDMA ¼ Polyethylene glycol dimethacrylate;
PMAA ¼ Poly(methacrylic acid); PMOA ¼ Poly(2-(2-methoxyethoxy) ethyl methacrylate-co-oligo(ethylene glycol) methacrylate-co-acrylic acid); PVA ¼ Poly(vinyl alcohol);
PVPA ¼ Poly(vinyl phosphonic acid); rGO ¼ Reduced graphene oxide; St ¼ Starch.
Dyes: AB ¼ Acid blue; ABB ¼ Acid brilliant blue; BG ¼ Brilliant green; CR ¼ Congo red; CV ¼ Crystal violet; MB ¼ Methylene blue; MG ¼ Malachite green; MV ¼ Methyl violet;
RhB ¼ Rhodamine 6G.
a
C% ¼ Content of metal (nano)particles (wt-%) into the composite hydrogel.
b
D ¼ Adsorbent dosage (g/L).
c
Equilibrium condition (min).
d
EM ¼ Equilibrium mechanism (Isotherms: F ¼ Freundlich; L ¼ Langmuir).
e
K ¼ Kinetic mechanism (1st ¼ Pseudo-first-order; 2nd ¼ Pseudo-second-order).

associated with the introduction of carbon nanotubes in hydrogels
matrices seem to be hidden by numerous limitations. For instance,
the adsorption capacities assessed from these composites (when
reported) appear to be unsatisfactory and do not match the oper-
ational costs associated with the preparation of these composites
(see Table 5). Considering the most successful example listed in
Table 5, the composite based on methacrylic acid-g-hemicellulose/
multi-walled carbon nanotubes, it should be considered that it
needs to be washed for 2 days to remove impurities generated
throughout the synthesis (Sun et al., 2014). Also, the high cost
associated with the synthesis of these nanotubes is a considerable
limitation concerning the preparation of this kind of composite.
Carbon nanotubes can be synthesized from different methods
(Prasek et al., 2011), including (i) chemical vapor deposition to
provide high-density self-aligned carbon nanotubes, (ii) arc
discharge method at high temperatures (above 1700  C) that sup-
ports carbon nanotubes with fewer defects, (iii) laser ablation
technique that differently of the arc discharge method, produces
carbon nanotubes by hitting graphite pellets with lasers, and (iv)
flame pyrolysis producing carbon nanotubes with fewer impurities

17
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al. Journal of Cleaner Production 284 (2021) 124703

Fig. 7. Schematic illustration of the preparation of hyperbranched polyglycerol (HPG)-based multi-carboxylic magnetic gel (MMG) adsorbent and the photograph of dried HPG-
based MMG after placement of a magnet. Reproduced with permission of Elsevier (Song et al., 2018).

Fig. 8. Schematic illustration of Fe3O4 nanoparticles and their functionalization with 3-aminopropyl) triethoxysilane (top) and the preparation of carboxymethyl cellulose based
hydrogel with functionalized Fe3O4 nanoparticles as crosslinker (bottom).

Table 7
Properties of some polysaccharide nanoparticles.

Cellulose Starch nanocrystals (StNCs) Chitin nanowhiskers (CtNWs)

Nanofibrils (CNFs) Nanowhiskers (CNWs)

Fibrillar shape Rod-like shape Platelet-like shape Rod-like shape

5e50 nm in diameter Few nm in diameter 10e30 nm in width 10e50 nm in diameter
1e3 mm in length 10e500 nm in length 20e150 nm in length 0.15e2 mm in length
High aspect ratio High aspect ratio Low aspect ratio High aspect ratio
Crystallinity <60% Crystallinity >70% Crystallinity <45% Crystallinity <70%
Thermally stable up to 260  C Thermally stable up to 230  C Thermally stable 150e200  C Thermally stable up to 280  C

*Data collected from (Barikani et al., 2014; Eichhorn et al., 2010; Kargarzadeh et al., 2018; Le Corre et al., 2010; Lin et al., 2011; Zeng et al., 2012).

18
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al.
and high yields (Prasek et al., 2011). Each of these approaches has
its specificity and can yield high-quality carbon nanotubes without
impurities following expensive strategies.
All papers listed in Table 5 concerns the production of hydrogel/
multi-walled carbon nanotube composites by acquiring carbon
nanotubes in companies (i.e., the carbon nanotubes are purchased,
not synthesized). By now, we believe that the use of carbon
nanotubes should be avoided to produce adsorbents. The strategies
used to yield them are expensive, and even at low contents (0.2 and
0.3 wt-%) into the hydrogel matrices can make the adsorption
process expensive.
Alternatively, other strategies have been investigated to over-
come the aforementioned limitations. Guo et al. (2016) prepared
physical polyhydroxybutyrate/alginate/carboxyl multi-walled car-
bon nanotubes composite membranes from a synchronized elec-
trospinning device. Compared to the raw polyhydroxybutyrate/
alginate membrane (qm ¼ 11 mg/g), the presence of the carboxyl
multi-walled carbon nanotube improved the tensile stretch and
enhanced the sorption capacity upon brilliant blue (qm ¼ 24 mg/g,
Table 5). However, the electrospinning approach is still unsuitable
for a real application because it does not produce materials on an
industrial scale. Also, after the crosslinking process, no nanofibers
are observed on the composite surface.
4.3. Composite hydrogels containing metallic (nano)particles
In the last decade, the number of studies devoted to the prep-
aration of composite hydrogels containing metallic (nano)particles
has increased considerably since such materials have found appli-
cation in different areas including environmental remediation.
Particular attention is given to the use of these composites to treat
dye-contaminated water, as highlighted in Table 6.
Metallic (nano)particles (pure or their compounds) have been
used not only to improve mechanical, electrical, and thermal
properties of hydrogels but also to provide catalytic activity in the
degradation of pollutant species and allow remote control of
swelling and adsorption/desorption of analytes by adjusting the
external magnetic field. This feature is available to metallic species
with measurable magnetic properties. Literature reports indicate
successful adsorbents with saturation magnetization ranging from
4 to 60 emu/g (Frachini and Petri, 2019). In particular, composite
hydrogels containing magnetic compounds can be quickly recov-
ered from the treated media with a magnet instead of the use of
more onerous processes such as filtration, sedimentation, or
centrifugation (Zhang et al., 2016; Zhao et al., 2016). This charac-
teristic increases the separation efficiency and decreases opera-
tional costs. Song et al. (2018) synthesized a magnetic hydrogel
based on a hyperbranched polyglycerol embedded with decorated
Fe3O4 nanoparticles using an elegant thiol-ene click chemistry
approach (Fig. 7). The composite was tested towards the removal of
methylene blue and methyl violet (Table 6). The post-used hydro-
gels were also conveniently recovered using a magnet, which
allowed the recycling of these hydrogels and their reuse in cyclic
adsorption runs.
Composite hydrogels containing magnetic (nano)particles also
can respond to external magnetic fields with reversible changes in
their shape and volume (Peng and Wang, 2018). The embedded
magnetic nanoparticles’ movements guide contraction and
distention of the polymeric chains because an external magnetic
field imposed attractive/repulsive forces (Shankar et al., 2017).
Consequently, the diffusion of liquids (inward and outward the
hydrogel matrix) can be tailored, affecting the adsorption/desorp-
tion of target solutes such as dyes molecules. Also, magnetic
nanoparticles associated with hydrogel matrices can support
composites with other magnetic-responsive properties, such as
19
Journal of Cleaner Production 284 (2021) 124703
magnetic induction heating (Thevenot et al., 2013). In this case, the
bulk phase of the composite hydrogel can be heated up via mag-
netic induction, causing a thermal transition that can favor the
adsorption process. Notoriously, up to date, few studies have been
conducted to investigate the effect of external magnetic field or
magnetic induction on hydrogels used as dye adsorbents. Given
that the adsorption is often classified as a simple, cost-effective, and
easy process, the utilization of most refined techniques is not
encouraged by the researchers, which may explain the lack of
studies in this area.
Metallic compounds can affect the surface area and adsorption
capacity of the composite hydrogels (Thoniyot et al., 2015). The
effect of these fillers on the hydrogel adsorption capacity has not
been fully understood yet. The presence of iron oxides, as fillers,
tends to decrease the adsorption capacity (Dannert et al., 2019),
likely due to the reduction of interaction sites on the adsorbent’s
surface because metallic nanoparticles are stabilized by functional
groups available along with the hydrogel matrices (Cho et al., 2015).
In practice, excess addition of metallic nanoparticles can increase
the crosslinking density of the hydrogel matrix, hampering its
swelling ability and, consequently, adsorption capacity. Therefore,
the amount of metallic nanoparticles in the hydrogel is paramount
to develop an adsorbent with desired properties.
Dai et al. (2019) showed that cellulose-based hydrogels’
adsorption ability towards methylene blue changes according to
the amount of Fe3O4-diatomite into the hydrogel. An increment
(z40%) in the methylene blue adsorption was noticed at low Fe3O4-
diatomite concentration (200 mg). Otherwise, adsorption capacity
decreased (z10%) at a high Fe3O4-diatomite dose (600 mg)
compared to the pristine hydrogel.
Although the use of this kind of composite as adsorbent seems
to be promising their syntheses are still challenging and raise some
other concerns. The natural tendency to aggregate, reduces the
metallic nanoparticle surface area/energy, causing inappropriate
dispersion of metal/magnetic nanoparticles in the hydrogel net-
works. Therefore, it can occur phase separation and limited in-
teractions between the polymers chains and fillers (Li et al., 2013b).
Moreover, oxidation of the metal nanoparticles, mainly under
acidic conditions, may cause their leaching from the composite
resulting in secondary pollution. This concern has been barely
addressed by studies focused on the development of composite
hydrogel containing metal nanoparticles for adsorption of dyes.
An alternative to overcome these issues is to use capping agents
(silicates, polymers, hydrogel matrices, and others) to protect the
metallic nanoparticles against aggregation (Facchi et al., 2018;
Nakhjiri et al., 2019). Carboxymethyl cellulose composite hydrogels
crosslinked by Fe3O4 nanoparticles functionalized with 3-
aminopropyl triethoxysilane, as illustrated in Fig. 8 (Uva et al.,
2017). The composite hydrogels were tested as adsorbents for the
removal of methylene blue and the adsorption capacity assessed
was around 620 mg/g. Interestingly, the authors also investigated
the adsorption of methylene blue in seawater. The adsorption was
strongly impaired because the seawater ions reduced the electro-
static attraction between the carboxylate groups on carboxymethyl
cellulose and cationic methylene blue.
The use of photoactive metallic compounds (TiO2, CuS, MoS2,
among others) to prepare composite hydrogels seems to be a recent
trend followed by various researchers. It allows simultaneous
adsorption and degradation in situ of adsorbed dyes. Chen et al.
prepared a composite hydrogel based on hydroxypropyl cellulose/
MoS2 (Chen et al., 2017). To promote a homogeneous dispersion of
MoS2 nanosheets, they were functionalized with hydroxypropyl
cellulose through an esterification reaction. Composite hydrogels
containing MoS2 nanosheets adsorbed more methylene blue than
the conventional hydroxypropyl cellulose hydrogels under similar
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al.
Fig. 9. Illustrative scheme of methylene blue adsorption using a composite hydrogel based on chitosan-g-poly (acrylic acid) containing 5 wt-% of CNWs. Reproduced with
permission of Elsevier (Melo et al., 2018). (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)
conditions likely due to the action of anionic groups in MoS2-
polymer structure and its large specific surface area. The adsorbed
dye molecules could be degraded by exposing the composite
hydrogel to sunlight, enabling recycling the adsorbents for further
reuse (Chen et al., 2017). The photo-recycled composite’s adsorp-
tion capacity was minimally affected after 3 cyclic runs (adsorption/
desorption). The use of combined adsorption/photodegradation
processes seems a promising approach to remove or eliminate dye
from water. However, additional studies must be carried out to
identify the secondary products generated from photodegradation.
Recent literature reports that this is the main drawback of oxidative
techniques as the secondary waste products may be toxic (Reza
et al., 2017). In parallel, studies concerning the entrapment and
binding of metallic species (ions and nanoparticles) into hydrogels
matrices appear as an alternative to control the leaching of these
materials to the environment. As a secondary advantage, this
approach contributes to preserving the stability of the metallic
species in terms of oxidation state, reducing potential toxicity and
inactivation issues.
4.4. Composite hydrogels containing nanowhiskers and nanofibrils
Polysaccharide nanoparticles refer primarily to cellulose nano-
fibrils, nanowhiskers and hairy cellulose nanocrystalloids, starch
nanocrystals, and chitin nanowhiskers generally obtained by acid
hydrolysis, mechano-chemical treatments, among various other
procedures (Rodrigues et al., 2014). These nanoparticles have
received significant attention from scientists and industry due to
their specific physicochemical properties (chemical inertness,
modifiable surfaces, low density, high strength, flexibility, renew-
ability, etc.) (Kargarzadeh et al., 2018). Some properties of these
nanoparticles are listed in Table 7. It is important to mention that
these properties depend on the polysaccharide origin and
20
Journal of Cleaner Production 284 (2021) 124703
extraction method used.
The term fibrils is employed to denote long, flexible nano-
particles consisting of alternating crystalline and amorphous re-
gions, whereas the term whiskers to highly crystalline rod-like
nanoparticles (Khalil et al., 2012). More recently, a new class of
nanocellulose has been developed, hairy cellulose nanocrystalloids
(HCNC), similar to whiskers but with losing chains (hair) coming
out from the ends of the crystalline rods (Yang and van de Ven,
2016). These materials are mainly investigated as fillers in the
composites formulation because they are isolated from abundant
renewable sources, are readily prepared, provide high surface area
and high density of functional groups accessible for chemical
modification or physical interaction with polymer matrices (Pereira
et al., 2020). Also, the growing interest in the study of more envi-
ronmentally friendly materials has stimulated the use of this kind
of material to prepare composites. Due to an eco-design philoso-
phy, that has increasingly been applied in various research fields,
the development of composites with the “sustainable” and “eco-
friendly” labels has been grown in a vertiginous way.
Despite this trend, only a few studies on composite hydrogel
containing nanofibrils, nanowhiskers, and hairy nanocrystals are
available. Most parts of studies focused on composite hydrogels
containing these fillers are devoted to investigating the effect of the
hydrogel/filler mass ratio on the composite properties. Overall, by
adjusting the hydrogel/filler mass ratio is possible to tailor the
mechanical properties, water uptake capability, and adsorption
features of such materials.
Cellulose nanoparticles (CNFs and CNWs) have been preferred
over other polysaccharide nanoparticles to prepare composite
hydrogels for the adsorption of pollutants. The small number of
studies concerning the use of other nanoparticles may be due to the
absence of standard processing methods to obtain such nanofillers,
which impairs large-scale production of StNCs and CtNWs. In a
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al.
recent review paper, De France et al. (2017) stated that the larger-
scale use of CNFs and CNWs could be associated with the stan-
dardization of extraction, purification, and characterization pro-
tocols used to obtain these nanofillers. This is a crucial advantage
since, beyond the botanical source; the extraction and purification
protocols have a straight influence on the final surface and bulk
properties of CNFs and CNWs. For example, CNWs are isolated from
both plant and bacterial sources mainly by acid hydrolysis. When
this reaction is carried out using sulfuric acid, sulfonated-CNWs are
obtained. The high negative surface charge (zeta potential up
to 50 mV) of these nanoparticles can enhance the colloidal sta-
bility of such suspensions and the ability of composite hydrogels to
adsorb cationic dyes (Vasconcelos et al., 2017).
Mohammed et al. investigated the adsorption behavior of a
composite hydrogel based on sodium alginate and CNWs towards
methylene blue (Mohammed et al., 2015, 2016). Hydrogel beads
were prepared by ionotropic gelation dropping aqueous alginate/
CNWs (100 nm long, 5 nm wide, and surface area of 500 m2/g)
suspension into a Ca2þsolution. The dye adsorption was improved
by a factor of 3, reaching around 60% dye removal at 1 wt-% CNWs
against 20% for the hydrogel without CNWs. The regeneration of
the post-used hydrogel beads was evaluated by desorbing the dye
using an eluent HCl-ethanol (1:1) mixture. At least five regenera-
tion and reuse cycles could be performed without efficiency loss.
The same composite beads were used as an adsorbent in a fixed bed
column (Mohammed et al., 2016). Methylene blue adsorption was
evaluated in a continuous flow, altering the parameters (i) dye
concentration, (ii) flow rate, and (iii) bed depth. The best adsorption
capacity was 255.5 mg/g, similar to that found in the batch ex-
periments. On the other hand, the preparation of composite beads
based on alginate and hairy cellulose nanocrystals (1:1 mass
composition) showed an outstanding adsorption capacity towards
methylene blue (1200 mg/g); 20% higher in comparison to pure
alginate beads (Yang and van de Ven, 2016). Hairy cellulose nano-
crystals present, in general, higher charge density than CNWs and
CNFs, promoting better adsorption results for cationic dyes.
Alternatively, combining CNWs with chemically crosslinked
hydrogel matrices can also lead to increased hydrophobicity or
absorption capacities of the resulting composites. For example,
Melo et al. (2018) investigated the effect of CNWs content on the
adsorption capacity of a composite hydrogel based on chitosan-g-
poly (acrylic acid). Outstanding adsorption capacity (qm ¼ 1968 mg/
g) was registered to the composite at 5 wt-% CNWs (Fig. 9). The
maximum methylene blue removal was promptly achieved
(60 min) under mild experimental conditions (room temperature
and pH 6.0), which is of interest from a practical viewpoint. Com-
posites with CNWs contents above 5.0 wt-% exhibited low
adsorption capacities due to the interactions between the polymer
chains and the filler restricting the network expansion and limiting
the liquid diffusion. Moreover, the number of adsorption sites
available on the adsorbent surface decreased as more
dipolaredipolar interactions between the hydroxyl groups of CNWs
and carboxyl groups of the hydrogel matrix were established.
Partially hydrolyzed poly (acrylamide)/CNWs composites con-
taining CNWs (up to 20 wt-%) have improved swelling and
adsorption properties compared to the pure hydrogel (Zhou et al.,
2014). Under optimal conditions (pH 5.0 and 20 wt-% CNWs), the
composite hydrogel adsorbed 326 mg/g of methylene blue,
achieving a removal efficiency of 90%. The same authors also re-
ported the use of electrospun mat composites based on hydrolyzed
poly (acrylamide) and CNWs (average width: 10 nm, lengths
40e120 nm, derived from H2SO4 hydrolysis of cotton fibers) for
adsorptive removal of methylene blue (Zhou et al., 2013). The
electrospun mats were submitted to a heat treatment (150  C, 1 h,
N2 atmosphere) to render insoluble fibers (crosslinking process).
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Journal of Cleaner Production 284 (2021) 124703
CNWs acted as both filler and crosslinker through ester linkages
between the hydroxyl groups of CNWs and carboxyl groups of
hydrolyzed poly (acrylamide). The fibrous mats with 10 wt-% CNWs
presented an average fiber diameter of 210 nm, with pore size from
2 to 20 nm, BET surface area of 9.8 m2/g, and an average porosity of
54%. Unfortunately, adsorption data concerning the pristine fibrous
mats (without CNWs) were not assessed in this study. Therefore, it
is not feasible to evaluate the effect of CNWs on the methylene blue
adsorption.
StNCs and CtNWs have been tested as adsorbents directly from
their colloidal suspensions. Despite the exciting results reported,
two crucial aspects related to their use must be considered: (i) the
onerous and multi-step recovery and regeneration processes of the
post-used adsorbent and (ii) the instability of the colloidal sus-
pension may impair the adsorption process. The first drawback can
be solved (partially or totally) by immobilizing the nanoparticles on
hydrogel matrices. Additional studies should be carried out to
determine the effect of this procedure on the adsorption capacity of
both components (the hydrogel and nanoparticles) and the exis-
tence of synergic outputs.
The low dispersion of the filler or its high interaction with the
hydrogel matrix can drastically affect the composite’s adsorption
capacity Alternatively, polysaccharide nanoparticles’ stability can
be enhanced by adjusting the pH, ionic strength, and grafting them
to ionized molecules. Cheng et al. modified the surface of StNCs by
grafting succinic anhydride (a negatively charged molecule at
specific pH), which generated promising results regarding methy-
lene blue adsorption. Polysaccharide nanoparticles usually possess
reactive functional groups on their surfaces, enabling their modi-
fication via chemical reactions (Khalil et al., 2016; Pereira et al.,
2014; Tao et al., 2020). Chemical modification drives colloidal sta-
bility, dispersion in hydrogel matrices, and dye adsorption capacity.
Therefore, advanced and cost-effective adsorbent materials for
water/wastewater purification can be developed.
5. Overview and future perspectives
The extraordinary number of papers published in the last two
decades describing the preparation and use of composite hydrogels
as adsorbents show the relevance of such advanced materials in the
technological and environmental fields. This review demonstrated
that composite hydrogels based on different polymers (synthetic
and natural) and fillers (proceeding from organic and inorganic
sources) are easy and straightforward prepared, showing enormous
potential to be applied in treating dye-contaminated wastewaters.
Also, exciting features such as fast adsorption kinetics, easy
handling, and reusability have helped increase the interest in this
kind of material.
From a comprehensive and critical viewpoint, the use of com-
posite hydrogels as ideal adsorbents still needs further develop-
ment. The scientific research that has been conducted points out
the following aspects and challenges for developing composite
hydrogels: (i) the improvement of specificity for key targets (i.e.,
selectivity according to the dye chemical nature); (ii) improvement
of the recyclability of the post-used hydrogels; (iii) improvement of
mechanical properties to allow more cycles of sorption/desorption;
(iv) assessment of adsorption process on real industrial wastes and
contaminated waters (including adsorption studies using non-ionic
and reactive dyes, which are massively used in industrial coloring
processes); (v) a better understanding of the effects of degradation
and release of the fillers in the environment and living organisms;
(vi) research and development of hydrogel adsorbent columns to
become affordable industrial and commercial products; (vii)
development of composite hydrogels able to remove coexistent-
contaminants (with organic and inorganic nature); and (viii) the
A.G.B. Pereira, F.H.A. Rodrigues, A.T. Paulino et al.
use of computational chemistry to simulate and predict the in-
teractions between composites with the targeted dye molecules.
Furthermore, studies focusing on understanding how the filler
material affects the resulting composite hydrogel properties
(intrinsic and adsorption properties) are required. These compos-
ites’ general safety must also be assessed since the use of novel filler
materials (mainly nanosized materials) can increase potential
environmental health risks. Up to date, there is scarce literature
evaluating how the leaching of these fillers affects the environ-
ment. Hence, the lack of information regarding these aspects
hampers the obtention of high performance, cost-effective, and
safe materials. Finally, we believe that a dialogue between re-
searchers of different areas (chemistry, physics, environmental and
materials engineering, and so on) is crucial to developing more
efficient adsorbent materials to remediate water/wastewater
contaminated by synthetic dyes or other organic/inorganic
contaminants.
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.
Acknowledgments
The authors are grateful for the financial support from the
Brazilian agencies CNPq (Grant. number 305974/2016-5), CAPES
(Finance code 001), FUNCAP (Process BP3-0139-00257.01.00/18),
and FAPESC (Grant number: 2019/TR672). A.T.P. and A.R.F. thank
CNPq for their PQ fellowships (Grant. numbers 312467/2019-2 and
303872/2019-5).
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