Malatji Et Al 2021 Removal of Methylene Blue From Wastewater Using Hydrogel Nanocomposites A Review

Nanomaterials and Technologies for Environmental Applications - Review Article
Nanomaterials and Nanotechnology

Volume 11: 1–27
Removal of methylene blue from © The Author(s) 2021
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DOI: 10.1177/18479804211039425
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nanocomposites: A review
Nompumelelo Malatji1, Edwin Makhado1, Kwena D Modibane1 , Kabelo E Ramohlola1,

Thabiso C Maponya1, Gobeng R Monama1 and Mpitloane J Hato1
Abstract
Water pollution by organic dyes continues to pose a serious health and environmental threat to the ecosystem. Although
adsorption using biopolymer-based hydrogels has proven to be an ideal technique for the treatment of these dye
contaminants from aqueous solutions, these hydrogels suffer from lack of mechanical stability and recovery as compared to
synthetic polymers. Herein, we review the low-cost synthesis of hydrogel incorporated with inorganic components mainly
focusing on strategies to improve the mechanical stability and separation of the hydrogel in removing methylene blue (MB)
dye from aqueous solution. The literature shows that hydrogel nanocomposites are a class of materials that have flourished
significant consideration, especially concerning water treatment. In adsorption technology, hydrogel nanocomposites act as
absorbents, prominent to enhance their removal efficiency towards contaminants. This review highlights the preparation
and use of hydrogel nanocomposites as efficient adsorbents. In-depth discussions on adsorption and diverse synthetic
routes of hydrogels have been devoted to applications of these nanocomposites and are compared in this contribution to
the removal efficiency of MB dye from wastewater.
Keywords
Adsorption, hydrogel, inorganic components, methylene blue, nanocomposites
Date received: 8 March 2021; accepted: 21 July 2021
Topic Area: Polymer Nanocomposites and Nanostructured Materials

Topic Editor: Leander Tapfer
Associate Editor: Tao Zhu
1
Nanotechnology Research Lab, Department of Chemistry, School of
Introduction Physical and Mineral Sciences, University of Limpopo (Turfloop),
Polokwane, Sovenga 0727, South Africa
Water is very important for the survival of living things on
earth.1 Despite the need for this resource, water pollution Corresponding authors:
continues to be a problem in most countries including South Edwin Makhado, Department of Chemistry, University of Limpopo,
N-Block 1014, Private Bagx1106, Sovenga 0727, South Africa.
Africa, where the mainstream water supplies are under- Email: [email protected] or [email protected]
ground and surface water.2 Water pollution may be defined
Mpitloane J Hato, Department of Chemistry, University of Limpopo,
as any water that is unsafe for drinking by humans and N-Block 1012, Private Bagx1106, Sovenga 0727, South Africa.
animals.2 There are two classes of water contaminants, Email: [email protected]
namely, point sources and non-point sources in which they Kwena D Modibane, Department of Chemistry, University of Limpopo,
are defined as a source of pollution at a fixed location N-Block 1010, Private Bagx1106, Sovenga 0727, South Africa.
(mines, industries, power stations, water treatment station, Email: [email protected]
Creative Commons CC BY: This article is distributed under the terms of the Creative Commons Attribution 4.0 License
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further permission provided the original work is attributed as specified on the SAGE and Open Access pages (https://us.sagepub.com/
en-us/nam/open-access-at-sage).
2 Nanomaterials and Nanotechnology
etc.) and pollution from moving sources (cars, buses and removal capacity for dyes, but the major disadvantage is its
trains), respectively.3,4 In point source, water pollutants may inability to remove all dye types and high costs.13,16 The
be classified as either inorganic (fertilizers and toxic photochemical method uses UV light and most use Fenton
metals), organic (dyes) or microbial (viruses and bacteria).5 reagent.17 It offers the advantage of no sludge production
For example, dyes are organic complexes mostly used by and odour elimination.13,16 The main advantage of dye
textile industries to give colour to fabrics and contribute degradation using heterogeneous photocatalysts is the
largely to pollution.6 Other applications may include use in ability to use the sunlight in the production of hydroxyl
medical, pharmaceutical, paper, rubber, plastics, leather, radicals. Its drawback is the formation of by-products.18 The
food and cosmetics industries.7 Dyes contain aromatic rings electrochemical destruction method applies electrical cur-
in their structure and can be made up of either chromophores rent for the destruction of dye molecules.19,20 This method
or auxochromes.7,8 Chromophores are responsible for the does not generate sludge and does not require the addition of
production of colour (OH, NH2, NHR, NR2, Cl, COOH and any chemical reagent.13,19 However, it has the disadvantage
R =alkyl group), and auxochromes (NO2, NO and N = N) of high flow rates, which consequently reduce the removal
improve chromophores, make molecules soluble in water and efficiency of dyes, sludge production and causing a sec-
improve their affinity to bind materials.8 The discharging of ondary pollution problem.13,21 It is worth mentioning that
dye effluents into either surface and/or groundwater sources above-mentioned conventional methods are also applicable
leads to contamination which ultimately results in various for recovery of metals from wastewater. Apart from the
health and environmental problems.8,9 Consumption of aforementioned processes, cementation processes have been
contaminated water by humans can lead to vomiting, muta- well documented in the literature for recovering metals from
tion, cancer, breathing problems, diarrhoea, eyes burn, nausea wastewater. Several researchers have investigated this process
shock, cyanosis, jaundice and tissue necrosis.7,8–10 The en- in the recovery of copper (Cu), gold (Au), aluminium (Al) and
vironmental issues include the death of aquatic organisms, zinc (Zn) from wastewater.22 Anaerobic bioremediation in-
leading to the development of foul smell,11,12 hence the need volves degradation of organic contaminants under anaerobic
to eliminate dyes from waste effluents before discharging conditions in the presence of anaerobic microorganisms.23
them into rivers and other water streams. The advantage of this technique is that water-soluble dyes can
Conventional methods used to remove dyes from water be decolourized; however, this method results in the pro-
include adsorption, membrane filtration, ion-exchange, duction of sulphide and methane.24 Amongst these tech-
photochemical method, electrochemical destruction and niques, the adsorption technique is most favoured owing to its
anaerobic bioremediation systems (Table 1).13 The mem- cheap operation costs, easy design and fast removal of
brane filtration technique separates pollutants using a dye.25,26 During this process, dye molecules are attached on
physical barrier that allows permeability by water only such the surface of a solid material (adsorbent) through either
that contaminants are retained on the membrane surface. physical interactions (hydrogen bonding, weak Van der Waals
Factors influencing the separation behaviour of the mem- forces) or chemical bonding.27
brane filtration may include sieving, size of contaminants, The most used commercial adsorbent is activated
adsorption and electrostatic interactions.14 Its advantage is carbon (AC) (powder or granular).6,25 The application of
that it is fast with low space requirement and it removes all AC as an adsorbent is possible due to its high adsorption
dye types.13 However, the disadvantage is its limited life- capacity, high removal efficiency, large surface area and
time before fouling, high costs of the membrane and sludge high porosity.29 It effectively removes various types of
production.15 During ion-exchange for treatment of dye organic micropollutants as well as their secondary oxi-
effluents, the concentration of the dye is reduced through the dation products and inorganic compounds.29 The main
use of anionic or cationic resins whose ions exchange with disadvantage of this adsorbent, however, is the high cost
the dye molecules to form solid particles that are easy to and its regeneration problems.6 To reduce the cost of using
remove.16 The advantage of ion-exchange is that it has high commercial AC, agricultural by-products including shells
Table 1. Methods of removing dyes from water.
Adsorbent method Disadvantages References
Membrane filtration Membrane fouling and production of concentrated sludge 25

Ion-exchange Ineffective for all dye types 6,13
Photochemical method Production of by-products 25
Electrochemical destruction Moderately high flow rates that decrease the amount of dye removed 25
Anaerobic bioremediation systems Lead to the production of methane and hydrogen sulphide which are harmful 13,28
Adsorbent using activated carbon The adsorbent is expensive 28
Malatji et al. 3
Figure 1. The total number of publications per year on hydrogel nanocomposites for removal of dyes during the period 2011–2021
(using science direct database). *Data collected in May 2021.
and seeds of fruits have been used for production of However, due to their lack of stability, most researchers
AC.30,31 For example, a study by Geçgel et al. (2012) have explored their application as hydrogels.7,10,39,40 For
generated AC from Pea Shells (Pisum sativum) and re- example, Zhou et al.40 prepared cellulose based hydrogels
moved 246.91 mg/g of methylene blue (MB) from water.32 and removed 2197 mg/g of MB.
Further, to improve regeneration of AC, a study by Park Hydrogels are a class of three-dimensional (3D) soft
et al. (2019) regenerated spent AC obtained from waste- polymeric materials, which can imbibe a substantial amount
water treatment plant through heat treatment and KOH of liquids.41 In this direction, their innate ability to absorb
chemical activation.33 The group reported an increased and hold a high volume of liquid qualifies them as ideal
specific surface area from 680 m2/g (spent AC) to 710 m2/g materials for the adsorption of aquatic pollutants.41 Hy-
(regenerated AC). Despite these improvements, AC still drogels attracted a great deal of attention in various fields
suffers the problem of separation from water bodies and (gas sensing,42 drug delivery43 and cosmetics44) owing to
that it produces secondary pollution.33 In an attempt to their non-toxicity, low cost, permeability and biocompati-
improve separation of AC from water bodies, many studies bility.10 However, the applicability of hydrogels has been
have introduced magnetic nanoparticles into the AC ma- overshadowed due to their weak mechanical properties and
terial, to enable recovery through exposure to an external partial adsorption capacity.10 The yearning for enhancing
magnetic field.29,34,35 Considering the evidence that bio- inherent shortcomings exhibited by hydrogels has instigated
logical materials could be used for dyes removal, many tremendous research interest in the development of hy-
researchers were prompted to investigate the use of bio- drogel nanocomposite, which is a robust process to improve
logical materials such as polysaccharides, agricultural the disadvantages without losing the advantage of hydrogels.
waste and fruit peels as cheap and effective adsorbents for In the past decades, the use of hydrogel nanocomposites for
MB removal.6 Compared to AC and other materials, the removal of MB dyes in aqueous environment has in-
polysaccharides (cellulose, chitin, chitosan, sodium algi- creased considerably. In the past 10 years, a developing trend
nate, etc.) offer greater advantages for use as adsorbents for of publications in hydrogel nanocomposites for removal of
removal of MB.7 The advantages include non-toxicity, MB dyes is shown in Figure 1. The literature survey statistics
cheap cost, and eco-friendliness, sustainability due to show an exponential increase in the number of publications
their abundant availability, high chemical reactivity, bio- per year considering hydrogel nanocomposites for the re-
degradability, polyfunctionality and biocompatibility.36–38 moval of MB dye.
This review summarizes the recent advances and de- Additionally, they provide information about the mechanisms
velopments of hydrogel nanocomposites as adsorbents for of adsorption, adsorption capacity and surface properties. This
wastewater treatment. This is realized by doing a detailed study employs the Langmuir, Freundlich and Temkin iso-
review of the reactions and mechanisms of adsorption in- therm models. Below are their brief descriptions including
cluding an overview of the adsorption of MB dye. Then, we their linear and non-linear equations.
introduce hydrogel nanocomposite as an adsorbent for MB
removal with great emphasis on the structure and synthetic Langmuir isotherm model. Irving Langmuir63 established
routes. the Langmuir isotherm in 1916. The model theory assumes
that the active sites on the solid surface have the same
energy, leading to homogeneous adsorption of adsorbate
Adsorption molecules (monolayer coverage).64 Graphically, adsorption
Background equilibrium is observed by a plateau, which is a point where
all active sites are fully occupied and no further adsorption
The attachment or adherence of molecules on the surface of can occur.65,66 The model is expressed as follows, non-
solid material is known as adsorption. The adsorbent material linear (equation (1)) and linear (equation (2)) forms
contains active adsorptive sites on its surface to which
molecules (gas or liquid) from the bulk solution (adsorbate qm bCe
qe ¼ (1)
solution) bind to.45,46 Adsorption of molecules may occur 1 þ bCe
either physically or chemically.47 The mass transfer process
may occur in the form of migration, diffusion or convection, ce 1 ce
¼ þ (2)
in which liquid or gaseous molecules are transferred to a solid qe qm KL qm
phase.48,49 Interactions such as Lewis acid-base, van der
where Ce is the equilibrium concentration (mg/L), qe is the
Waals and Columbic are characteristic of physisorption50,51
amount adsorbed at equilibrium (mg/g), KL (L/mg) is the
whereas chemisorption is distinguished through the devel-
adsorption equilibrium constants of Langmuir, the Lang-
opment of new adsorbate–adsorbent bonds.52 The adsorptive
muir constants qm (mg/g) represent the monolayer ad-
sites can have the same or different energy, depending on the
sorption capacity and b relates to the heat of adsorption. The
nature of the material.53 Owing to its principle, adsorption has
values of qm and KL can be determined from the linear plot
gained interest for application in hydrogen storage, sensing,
of Ce/qe against Ce. The essential features of the Langmuir
drug delivery, gas capture and water treatment.54–57
isotherm can be employed to predict the affinity between the
The recent interest in applying adsorption for the
sorbate and the sorbent using the dimensionless equilibrium
treatment of dyes from wastewater was attracted by its low
constant (RL).
operation costs, easy design, efficiency and fast removal of
The RL is a dimensionless constant denoted as the
dye.58,59 Before applying an adsorbent material on an in-
separation factor. RL is calculated using the following
dustrial scale (column adsorption), it is first optimized in
equation (3)
batch mode experiments; then if it possesses a high removal
efficiency, it can be employed for column adsorption 1
studies.60,61 Factors that affect the adsorption process in RL ¼ (3)
1 þ bCo
wastewater treatment include the following55,56,60:
If RL > 1, adsorption is not favoured. If RL = 1, adsorption
1. The adsorbent and adsorbate charges, is linear. If RL < 1, adsorption is favoured, and if RL = 0, the
2. the solution pH, reaction is irreversible.66
3. temperature,
4. dye concentration, Freundlich isotherm. The model assumes multilayer
5. adsorbent dose and coverage of the adsorbent. The model is expressed by the
6. the surface area of the solid material. following equations in a non-linear (equation (4)) and linear
(equation (5)) form
When an adsorption process reaches equilibrium, it means
the active sites of the adsorbent are saturated with adsorbate qe ¼ KF Ce1=n (4)
molecules and no further adsorption can take place.61 1
ln qe ¼ lnln KF þ lnln ce (5)
n
Adsorption parameters
where qe (mg/g) and Ce (mg/L) are the amounts adsorbed and
Adsorption isotherms. The isotherms of adsorption are sig- the solution concentration, respectively, at equilibrium. KF is
nificant for describing the adsorbate–adsorbent interactions.62 the sorption enthalpy and varies with temperature. KF and n
Malatji et al. 5
are the sorption capacity and sorption intensity.67 n deter- where K2 is the equilibrium rate constant of pseudo-second-
mines the non-linear relation between adsorption and the order adsorption (g/mmol min). K2 will be determined using
concentration of the solution.67 the slope and intercept of the plot of t/qt versus t.
Temkin isotherm. The Temkin isotherm theory ignores Thermodynamics. During the adsorption process, thermo-
the concentration values and assumes that the decrease in dynamic parameters such as enthalpy (ΔHo), entropy (ΔSo)
heat of adsorption concerning the temperature is linear and Gibbs free energy (ΔGo) are required to determine
instead of decreasing logarithmically as suggested in the spontaneity and heat change.72 Thermodynamics parame-
Freundlich equation. The non-linear (equation (6)) and ters may be calculated according to the formulas below
linear (equation (7)) forms of the Temkin model are ex- qe
pressed as follows below KD ¼ (12)
Ce
RT
qe ¼ lnln ðKT Ce Þ (6) ΔG° ¼ RTlnKD (13)
bT
RT RT ΔS ΔH
qe ¼ lnAT þ lnCe (7) lnKD ¼ (14)
bT bT R RT
where KD represents the distribution coefficient of the
where AT is the equilibrium binding constant corresponding
adsorbate, qe and Ce represent the equilibrium concentration
to the maximum binding energy (L/g), bT is the Temkin
(mg/g) and in the solution (mg/L). R represents the universal
constant related to the heat of adsorption (kJ/mol), R is the
gas constant (8.314 J/mol K), and T is the temperature (K).
universal gas constant (8.314 J/mol/K) and T is the absolute
ΔHo and ΔSo may be calculated from the slope and intercept
temperature (K).68
of the plot lnKD versus 1/T. Negative ΔG values at different
temperatures are an indication of a spontaneous adsorption
Kinetic isotherms. Adsorption is a process that involves the
process.71,73 If ΔG decreases when the temperature is in-
transfer of mass of a solute from the liquid phase to the
creased, it means there is a more efficient interface during
surface of the adsorbent.69 The mechanism of adsorption
adsorption. A positive ΔH value indicates an endothermic
can be researched using either Lagergren’s pseudo-first-
adsorption process.74
order equation or pseudo-second-order equation. The
amount of contaminant adsorbed with time can be analysed
provided an appropriate model is used.70 To identify which
Adsorbent materials for MB
model is appropriate, the correlation coefficient (R2) is Although the adsorption technique is effective for dye re-
measured and must be close or equal to 1. The model with a moval, the type of adsorbent used limits its efficiency.75
higher R2 is the most suitable model for the adsorption Various materials have been used for MB dye removal. For
kinetics of contaminants. example, AC is reported to be the most frequently used nano-
The non-linear (equation (8)) and linear (equation (9)) adsorbent for removing a variety of inorganic and organic
equations for the pseudo-first-order kinetic model are contaminants owing to its high surface area, porous structure,
thermal stability and amphoteric nature.76,77 However, AC has
qe ¼ qe ½1 expðK1 tÞ (8) some drawbacks such as intraparticle resistance in industrial
application, high production costs and regeneration costs.77–79
lnðqe qt Þ ¼ lnðqe Þ K1 t (9)
Recent research studies have attempted to find ways to im-
where qe and qt refer to the amount of dye adsorbed (mg/g) prove the regeneration of AC and produce it at a lower cost.77
at equilibrium and at any time, t (min). K1 is the equilibrium On the other hand, alternative adsorbents such as fly ash,
rate constant of pseudo-first-order sorption (1/min). K1 will graphene, clay, carbon nanotubes and polysaccharides were
be determined using the slope and intercept of the plot of ln reported for removal of MB.80–87 Among these adsorbents,
(qe qt) versus t.71 Mittal et al.80 reported that using polysaccharides-based ad-
The non-linear and linear equations for the pseudo- sorbents is a promising strategy for MB dye removal from
second-order kinetic model are aqueous solutions. This is due to their enhanced adsorption
capacity amongst other attractive properties.
K2 q2e t
qe ¼ (10)
1 þ K2 qe t Polysaccharides. Polysaccharides can be defined as highly
hydrophilic and non-toxic natural polymers made up of
t 1 t multiple small units of saccharides that are connected
¼ þ (11)
qe K2 q2e qe through glycosidic bonds.83–85 These biopolymers are
found and used in plants or animals for structural support Carboxymethyl cellulose. Cellulose is the main component
and energy storage.86 Examples of polysaccharides in- of most plants.6 Carboxymethyl cellulose is a highly re-
clude carboxymethyl cellulose (CMC), alginate, carra- active, hydrophilic, water-dissolving derivative of cellulose
geenan, chitosan, guar gum, starch and locust bean with many carboxyl groups on its surface.82 Commercially
gum.85–87 These natural polymers offer the advantages of it can be obtained as sodium CMC with different degrees of
high absorption capacity, biodegradability and cheap saturation (DS), which may range from 0.6–0.95 depending
synthesis.88 However, due to low solubility and other on how it was prepared, and the solvent used.91,92 Car-
physical drawbacks, synthetic polymers are incorporated boxymethyl cellulose is mostly used in paper, packaging,
into the biopolymeric backbone to improve their proper- textile, food, cosmetics and pharmaceuticals.85,93 Due to its
ties.89 Polysaccharides-based materials have recently at- sensitivity to pH, non-toxic nature, hydrophilicity, low cost
tracted use for adsorption of dyes and toxic metals because and ability to form gels, CMC has been applied on its own or
of their non-toxic nature, biodegradability, easy avail- in a composite form as an adsorbent for removing inorganic
ability and low-cost synthesis.90 Amongst other poly- and organic contaminants.92,94
saccharides, CMC and alginate offer more attractive Carboxymethyl cellulose (Figure 2) is a cellulose de-
properties for application as dye adsorbents. rivative with carboxymethyl groups at carbon 2, 3 and 6.95
Figure 2. Structure of sodium carboxymethyl cellulose.63
13
Figure 3. C NMR of CMC.75 CMC: carboxymethyl cellulose.
Malatji et al. 7
In a study conducted by Kono,96 the resonances of CMC report that the use of isopropanol as the solvent yields CMC
were determined using carbon-13 nuclear magnetic reso- with very high DS.101 Huang et al.102 synthesized CMC
nance (13C NMR) as shown in Figure 3. In the spectrum of from the pulp of six different plants; the conditions that
CMC, the carbonyl carbon (C1, C4), overlap of C2, C3, C5, yielded the best CMC were 20% NaOH concentration, the
the carboxymethyl groups, and C6 were assigned to broad temperature of 60°C and 3–5 g of MCA. The group reported
13
C resonances at 178, 104, 83, 75 and 63 ppm.96 The that CMC yield increased with increasing MCA content.
existence of carboxylic groups (COO) on the polymer The degree of saturation influences the application of
chains of CMC allows for interactions with multivalent CMC.102 The hydrophilicity of CMC increases with an
metal cations (Al3+ and Fe3+) which results in the for- increase in DS. When DS > 0.4 (higher), CMC becomes
mation of stabilized ionotropic hydrogels. Interactions soluble in water, has better viscosity, enhanced cationic
with metal ions through the hydroxyl groups of the CMC exchangeability and improved covalent crosslinking
may improve the water insolubility and stability of the through radiation. Whereas when DS < 0.4 (lower), CMC is
polymer aggregates.95,96 insoluble, and it swells in solution.102 For example, a study
The reaction of cellulose with monochloroacetic acid reported the degradation of a polymer with irradiation of
(MCA) or its sodium salt in the presence of an organic 10% CMC (0.7 DS), whereas irradiation of CMC of 1.32
solvent under basic conditions produces NaCMC.97 There DS resulted in outstanding crosslinking and high gel-
are various materials from which CMC can be derived; for fraction.103 For adsorption, the properties of CMC can be
example, Petri98 prepared CMC from pineapple peels, and modified by crosslinking to form a gel, which will improve
in another study, Begum et al.99 prepared CMC from the solubility and hydrophilicity of CMC.
sugarcane bagasse. The synthesis of CMC occurs in three
steps: (1) alkalization, (2) carboxymethylation and (3) Alginate. Alginate is a sentimental term used in the di-
neutralization as outlined in the steps below. etetic, cosmetic, pharmaceutical and biotechnological in-
dustries.104 The alginate can be found in salts of magnesium
Step 1. Cell-OH + NaOH → Cell-OH.NaOH (Mg), potassium (K), calcium (Ca) and sodium (Na).104
E.C.C Stanford who was a pharmacist105 discovered algi-
Step 2. Cell-OH.NaOH + ClCH2COONa → Cell-O- nates in 1929. SA is found in brown algae, marine algae and
CH2COO Na+ + NaCl + H2O produced by some bacteria, hence abundant in nature.106,107
Applications of sodium alginate include drug delivery,
Step 3. NaOH+ ClCH2COONa → HO-CH2COONa + thicker, gel-forming agent, binder during the production of
NaCl tablets, use as a stabilizer and mixing agent.105–108 The
During the synthesis process, carboxymethyl groups recent use of polysaccharides as adsorbents for dyes and
replace hydroxyl groups at positions 2, 3 and 6 of cellulose. other pollutants is mostly due to the attractive properties that
In the synthesis of CMC, it is important to consider the polysaccharides possess, such as high hydrophilic struc-
degree of substitution, which will govern the porosity, and tures, their non-toxic nature, biodegradability and cheap
adsorption capacity of CMC.99 Degree of Substitution (DS) synthesis.109–111
refers to the number of hydroxyl groups replaced by car- Sodium alginate (SA, Figure 4) is made up of poly-β-1,
boxymethyl groups. Each β-glucopyranose unit of cellulose 4-D- mannuronic acid and α-1, 4-L-guluronic acid.112 The
has three hydroxyl groups; therefore, hypothetically DS structure consists of carboxylic groups and hydroxyl
value will range between 0 and 3.0.100 Various factors may groups, which can react with metal ions or crosslinking
affect the DS of CMC such as the solvent, temperature and agents to form hydrogels.113 Alginate can be extracted from
the NaOH concentration.101 For example, most researchers its salt forms by ion-exchange methods.114 Because of the
Figure 4. Structure of sodium alginate.62

Figure 5. Classification of hydrogels.
presence of divalent ions, monovalent, water-soluble salts a. Homopolymeric hydrogels: they are hydrogels
of alginates can transform into water-insoluble salts. The consisting of the same type of monomer.
COO and -OH functional groups on the alginate backbone b. Copolymeric hydrogels: these hydrogels comprise
will allow adsorption of cationic dye pollutants.115 How- two or more different kinds of monomers such that
ever, sodium alginate just like other polysaccharides suffers the network would have at least one hydrophilic
from a lack of stability.111 To enhance the stability of SA and component on the polymer network chain.
its adsorption capacity, the biopolymer may be cross-linked c. Multipolymer interpenetrating polymeric hydrogel
with synthetic polymers into forming a hydrogel.116,117 This (IPN): the hydrogel network consists of two com-
will allow their use as adsorbents without them dissolving in ponents (natural and/or a synthetic polymer) that are
the adsorbate solution. The major disadvantage of poly- independently cross-linked.
saccharides as adsorbents is that they dissolve in water and
have low mechanical stability.116,117 To resolve this prob- It was also demonstrated that hydrogels can be cate-
lem, polysaccharides are cross-linked to form hydrogels, gorized based on whether they are120
which do not dissolve in water.
a. crystalline,
Hydrogels b. amorphous or
c. semi-crystalline: showing properties of both crys-
Background talline and amorphous phases.
Hydrogels are hydrophilic polymer chains that are cross-
linked to form gel structures that swell in aqueous solution The other classification is based on whether the cross-
and trap fluids for a long period without dissolving.83,84 linking of hydrogels occurs via chemical or physical means.
Hydrogels may contain carboxylic, amine, imide, hydroxyl Briefly,
and sulfonyl groups in their 3D structure that are responsible
for the hydrophilicity and swelling capacity.118 Depending a. physical crosslinking in hydrogels may be through
on the nature of the hydrogel, it can be classified based on (1) formation of a hydrogen bond, (2) hydrophobic
various properties. Classification of hydrogels (Figure 5) interactions between chains, in which the dissipation
can be based on whether they are synthetic (involves the use energy of the bond prevents breakage and improves
of synthetic monomers), natural (involves using biopoly- the hydrogel strength, and (3) crystallization where
mers) or a combination of synthetic and natural monomers gels are subjected to freeze and thaw process in PVA/
resulting in a hybrid hydrogel.119 The polymeric composite PVP solution 10 h at 15°C and then placed at room
classification can be based on the method used to synthesize temperature for 2 h. Lastly (4) between oppositely
the hydrogel119: charged groups.84
Malatji et al. 9
Table 2. Physical and chemical stimuli classifications. trapping water.11,48,49 The ideal properties of a hydrogel
depend on its specific application. For application in water
Physical stimuli Chemical stimuli
treatment, the hydrogel must have the following properties
Light Composition of solvent below98:
Magnetic field pH
Temperature Molecular species 1. High absorption capacity;
Sound Ionic strength 2. low residue monomer and soluble content;
Electric field 3. cost-effective;
Pressure — 4. reusable;
5. high biodegradability and not produce harmful by-
products;
b. Chemical crosslinking can be achieved by (1) using 6. must retain neutral pH after swelling in water and
aldehydes such as acetaldehyde, glutaraldehyde 7. easy recoverability.
(GA) and formaldehyde and (2) radiation using an
electron beam, gamma rays or ultraviolet rays at The swelling capacity of hydrogels is indicative of their
room temperature in which a free radical is formed, absorptive capacity which may be affected by factors such
monomers are added to the chain for growth and the as the intermolecular spaces in the 3D network, the exis-
gel forms at the critical gelling point. Lastly (3) free- tence of hydrophilic groups on the hydrogel polymer
radical polymerization using a cross-linker, for ex- backbone and the pore size of the hydrogel surface.10
ample, MBA. In this method, an initiator such as Hence, parameters such as the amount of initiator, cross-
potassium persulfate (KPS) generates free radicals, linker, polymer, monomer and solvent volume are opti-
the radicals react with other monomers and then mized during the preparation of the hydrogel to obtain
MBA is added to the polymer chain to form the optimum conditions for preparing an ideal hydrogel.122
hydrogel.84,121
In addition, the hydrogels may be classified based on the Preparation methods

charge on their cross-linked polymer network.122,123 The As stated previously, biopolymers suffer poor mechanical,
charge may be thermal stability and they dissolve in water.89 Most re-
searchers have reported that crosslinking, grafting and
a. ionic (cationic/anionic), modification with inorganic constituents such as metal
b. non-ionic (neutral), oxides and clay improves solubility and stability problems
c. amphoteric (comprising both basic and acidic associated with biopolymers.3,121 The type of method used
groups) and to prepare the hydrogel, therefore, affects its structural
d. zwitterionic (contains anionic and cationic compo- make-up or physical properties. Amongst several physical
nents on each repeating structural unit). The net and chemical techniques used for hydrogel synthesis, the
charge of the gel is zero. most widely used methods are discussed below.
Lastly, hydrogels can also be categorized according to Grafting. Grafting is the modification of the polymer back-
what stimulates their response. These hydrogels are bone using synthetic polymers such as acrylamide, acrylic
sometimes called smart hydrogels.119,121 There are two acid, methacrylamide and vinyl alcohol as support mate-
categories of stimulus, namely, physical stimuli and rials.123 During grafting, an initiator creates a free radical site,
chemical stimuli as stipulated in Table 2. The swelling or de- and then a monomer unit is added to the generated free radical
swelling of hydrogels caused by changes in the environment site.124 Grafting can occur via either a chemical or radiation.
can be too much to a point that the hydrogel changes phase Chemical grafting involves using chemical reagents such as
(volume collapse). ammonium persulfate, KPS or other chemical initiators.125
Radiation grafting involves initiating free radicals using UV
visible or microwave radiation.126
Application of hydrogels It was shown in the literature that using a microwave
Hydrogels have gained much attention for use in various radiation method for synthesizing hydrogels produces
applications owing to their outstanding qualities; these sterilized hydrogels.126 Naturally, polysaccharides suffer
include use in the making of disposable diapers, absorbent from poor chemical and physical stability.89 Grafting has
pads, use in hydrogen storage, sensing, CO2 capture, bio- been reported to solve these issues including enhancing the
medical field (drug and cell delivery systems), immobili- performance of hydrogels through the introduction of new
zation of enzymes, wastewater treatment and agriculture for functionalities from grafted monomers.127 For example, in a
Figure 6. Thermogravimetric analysis of (a) SA and (b) SA-g-P (AA-co-AM)/PVP semi-IPN SAP.62 SA: sodium alginate; PVP:
polyvinylpyrrolidone; SAP: semi-IPN.
study conducted by Tally and Atassi,86 it could be observed irreversible and include electrostatic interactions, hydrogen
from the thermogravimetric analysis (TGA) curves of (a) bonding and the van der Waals forces.128 Chemical cross-
SA and (b) SA-g-P (AA-co-AM)/PVP semi-IPN SAP linking involves forming irreversible covalent bonds in the
(Figure 6) that grafting with synthetic polymers enhanced hydrogel polymer chain usually through the reaction of
the thermal stability of hydrogels by more than 20% weight complementary groups.129 Chemically cross-linked hy-
loss at above 200°C. drogels are mostly used in medical applications. For ex-
A study of the modification of CMC by grafting with poly ample, Liu et al.130 synthesized chitosan-based hydrogels
(3-sulfopropyl methacrylate), P (SPMA), in the presence of from PEG for application in drug delivery. In another study
KPS initiator for MB removal was carried out.93 The main by Kumar et al.,131 cross-linked hydrogels were produced
vibrational peaks at C =O (1718 cm1), S =O (1085 cm1) from GA as a covalent cross-linker (Scheme 1).
and S-O (626 cm1) were observed in Figure 7(a) of the The most commonly used chemical cross-linkers include
Fourier transform infrared (FTIR) of the CMC-g-P (SPMA) ethylene glycol dimethyl-acrylate, N, N-methylene-bis-
hydrogel.93 The scanning electron microscopy (SEM) image acrylamide (MBA), tetra-ethylene glycol dimethyl-acrylate
showed the well-defined pores and 3D interconnections of (EGDMA) or tri-propyleneglycol diacrylate (TPGDA).132
CMC-g-P (SPMA) hydrogel, for which the hydrogel could However, these cross-linkers are usually toxic and result in
allow easy penetration of dye molecules in solution through its non-biodegradable hydrogels.133 In addition, because of
pores as observed in Figure 7(b).93 The adsorption of MB by the the lack of internal structural homogeneity and an effective
hydrogel was characterized by an absorption peak at 664 nm mechanism for energy dissipation, chemically cross-linked
corresponding to the characteristic absorption band of MB hydrogels are very brittle.134 This prompted many re-
(Figure 7(c)). From the X-ray diffraction (XRD) (Figure 7(d)), searchers to consider introducing nanocomposites, ionic
the partially crystalline structure of CMC was characterized by interactions, hydrogen bonding and hybrid hydrogel
sharp peaks at 2θ = 9.4 and 20.1° resulting from the inter- systems to improve the hydrogel properties.135–137 A
molecular and intramolecular hydrogen bonding between hybrid system consists of physical interactions that will aid
carboxylic groups and hydroxyl groups of the biopolymer. in energy dissipation and chemical interaction, which will
Upon grafting on the CMC-g-P (SPMA), it could be observed mainly improve structural properties.138 Figure 8 illus-
that the peaks were broader, indicating the hydrogen bonds trates the preparation of hydrogel beads through ionic
were destructed, allowing grafting to take place.93 interactions by Rahmani et al.139 Briefly, a mixture con-
taining gum tragacanth (GT), graphene oxide (GO) and
Crosslinking. The process of crosslinking can occur through calcium carbonate (CaCO3) was added dropwise into a
physical or chemical interactions. Physical interactions are concentrated solution of Ca2+ which interacted with -OH
Malatji et al. 11
Figure 7. FTIR (a), SEM (b), UV-vis (c) and XRD (d) of CMC-g-P (SPMA).68 FTIR: Fourier transform infrared; SEM: scanning electron
microscopy; P (SPMA): poly (3-sulfopropyl methacrylate); CMS: carboxymethyl cellulose; XRD: X-ray diffraction.
and COO groups on the GT and GO to form hydrogel For example, the XRD patterns in Figure 10(a) showed a
beads. Ionic crosslinking offers the advantage of less successful hybridization and a uniform dispersion of the
toxicity.133 cross-linker as confirmed by the disappearance of charac-
In a study by Eftekhari-sis et al.,140 hybrid hydrogels teristic crystalline diffraction peaks of OV-POSS at 2θ = 9.8,
constructed from poly (N-isopropyl acrylamide-co-itaconic 23.1 and 23.9°.140 The TGA thermogram (Figure 10(b))
acid) and non-toxic octa-vinyl polyhedral oligomeric sil- showed that the crosslinking with POSS in the hybrid
sesquioxane (OV-POSS) cross-linker were prepared. Their hydrogels increased the thermal stability, wherein the
obtained SEM (Figure 9), XRD and TGA (Figure 10) weight loss at temperatures 340–500°C was less than
results are discussed. The rough non-homogeneous surface weight loss obtained for poly (NIPAM-co-IA) at the
was observed on the SEM image (a) of poly (NIPAM-co- same temperature. 140 From the obtained literature, it
IA). Upon hybridization with 8% POSS (b), 12% POSS (c) could be observed that the chemical and physical
and 12% POSS (d), the morphology changed to a honey- properties of the hydrogels were improved, including
comb like structure with homogeneous pores of varying creating porous structures that enable penetration of
pore sizes as POSS content was increased. The study adsorbate molecules.
reported that at 12% POSS the honey-comb pattern was
disrupted, indicating that the degree of uniformity in the Free-radical polymerization. Free-radical polymerization is a
hydrogel hybrid can be controlled by changing the technique in which polymerization is achieved by gener-
crosslinking content.140 ating free radicals to which chain growth occurs in
Figure 8. Scheme showing the preparation of gum tragacanth–based hydrogel beads.117
succession.141 This method involves a combination of mechanically and thermally stable for application especially
grafting and crosslinking. The decomposition of the initiator for removing effluents from industries that utilize water for
may occur using temperature, light or photon, which then cooling reactions,146,147 wherein the contaminants may be
forms a free radical.142 Decomposition by photon offers introduced at that point. In addition, the hydrogels must be
advantages such as low costs; it allows better spatial and easy to recover. Many recent studies have incorporated
time-based control of the reaction process and does not use nanofillers such as clay-based materials, carbon-based
chemical solvent.143 Scheme 2 shows a schematic repre- materials and metal oxides into the hydrogel matrix dur-
sentation of an overview of free-radical polymerization for ing the polymerization process to improve stability and
synthesizing hydrogels. Firstly, there is the generation of recoverability. The blended product is then called a hy-
free radicals by an initiator (initiation). Secondly, the free drogel nanocomposite.
radicals react with the monomer to generate vacant active
sites (propagation) and lastly, the formation of a polymer Carbon-based. Carbon-based hydrogel nanocomposites
network through crosslinking (termination).144 are hydrogels synthesized by incorporating materials such
Free-radical polymerization is the most frequently used as graphene oxide (GO), biochar, AC and carbon
procedure in the polymer industry.1 The advantages of using nanotubes.148,149 GO is a carbon material prepared by
free-radical polymerization are that it is easy to carry out, oxidizing graphene through chemical or thermal reduction
convenient, it is not easily affected by impurities and it is processes. It contains highly hydrophilic groups such as
suitable for designing and preparing polymers that can be hydroxyl, carboxylic and epoxy groups that are essential for
used for a variety of applications. Free-radical polymeri- adsorbing dyes and toxic metals.150 GO may interact with
zation allows well-characterized reaction kinetics and contaminants through pi-to-pi interactions, electrostatic
achievement of in situ properties.145 interactions or hydrogen bonding.151 Owing to its out-
standing mechanical, electrical and thermal properties, GO
Modification with inorganic materials. Depending on the in- has attracted its use in the biomedical, energy and envi-
tended application of the hydrogels, their physical prop- ronmental field.152
erties can be further enhanced through the incorporation of Carbon nanotubes are simply graphene sheets rolled up
inorganic materials. For example, for use in removing in cylinders of 1 nm in diameter.153 As a result of their
contaminants from aqueous solutions, the hydrogel must be porous structure, large surface area, high tensile strength
Malatji et al. 13
Figure 9. SEM images of poly (NIPAM-co-IA) hydrogel (a) and hybrid poly (NIPAM-co-IA)/OV-POSS (8%, 10% and 12% POSS) (b–d).118
SEM: scanning electron microscopy; OV-POSS: octa-vinyl polyhedral oligomeric silsesquioxane.
Figure 10. X-ray diffraction and thermogravimetric analysis.118

(0.15 TPa) and elastic modulus (0.91 TPa), CNTs have Clay-based hydrogels. Natural clays and their improved
attracted interests in use for adsorption of pollutants such as forms have recently been used for removing pollutants from
dyes, dichlorobenzene, ethylbenzene and some heavy water.161 The most commonly used clays, especially for
metals.154,155 CNTs can be categorized into two forms, treating toxic metals and dyes, are modified kaolinite and
namely, single-walled carbon nanotubes (SWCNTs), which montmorillonite.162 However, these clays are difficult to
are made up of single layers of graphene sheets, and multi- regenerate and reuse because of their colloidal dimen-
walled carbon nanotubes (MWCNTs), which are made up of sions.163 This prompted the functionalization of these clays,
multiple layers of concentric cylinders.153,156 For example, for example, the modification of montmorillonite to form
the incorporation of CNTs in gels improves the mechanical Cloisite 30B clay. In a study where C30B clay was in-
properties; however, the rate of degradation decreases. This corporated onto polypropylene grafted with maleic anhy-
is because carbon-based materials have high hydrothermal dride (PP-g-MA) and thermoplastic starch (TPS), it was
stability, which makes them resistant to harsh environ- reported that the biodegradability of the materials was
ments.154 Scheme 3 shows various interactions or appli- improved.164 Modification of adsorbents by introducing
cations that carbon-based materials can take part in such as functionalized clay components may improve both the
surface complexation, physical adsorption through its physical and chemical properties of adsorbents.163,164 Other
surfaces and electrostatic interactions.157 Amongst recent modifications with clay results improve the number of
studies that have used carbon-based materials to modify adsorbing active sites, enhanced porosity and low levels of
properties of the hydrogel, the incorporation of MWCNTs mineral impurities.164 In a recent study, C30B was mixed
into XG/PAA hydrogel improved the surface hydrophilicity with a culture obtained from an anaerobic sludge to remove
and specific area of xanthan gum.10 Makhado et al.119 hexavalent chromium, where the removal capacity of nearly
conducted studies on xanthan gum polymer cross-linked 100% was obtained.165 Peng et al.166 prepared cellulose-
with polyacrylic acid and incorporated with reduced gra- MMT hydrogels for removing MB. The hydrogels had a
phene oxide (rGO); the successful synthesis was confirmed maximum removal capacity of 1065 mg/g (Table 4). Their
by FTIR. Various carbon-based nanocomposite hydrogels viscoelasticity studies from the sweep measurements
and their adsorption properties for removing contaminants (Figure 11(a)) showed that when G0 < G00 the cellulose-
from aqueous solutions are listed in Table 3. MMT systems were in a viscous liquid form; however with
Table 3. Carbon-based adsorbent hydrogels and their adsorption properties in removing contaminants from aqueous solution.
Adsorption parameter
Dosage
Adsorbent Cross-linker Dye qe (mg/g) pH (mg) Isotherm Kinetics Reference
CMC-AAm-GO MBA Acid black- 185.45 6 100 — — 9

133
XG-cl-pAA/o- MBA MB 521 6 30 Langmuir Pseudo-first-order 10
MWCNTs
XG-cl-pAA/rGO MBA MV 1052.63 5 10 Langmuir Pseudo-second- 119
MB 793.65 order
CS/CNTs beads Alkaline CR 450.4 5 20 Langmuir Psedo-first-order 158
mixture
p (AAm)-CB MBA Phenol 1112 10 50 Langmuir Pseudo-first-order 159
p (AAm)-WB
k-C-g-pAA/CNT MBA CV 118 5–8 200 Langmuir — 160
Table 4. Clay-based adsorbent hydrogels and their adsorption properties in removing contaminants from aqueous solution.
Adsorbent Cross-linker Dye qe (mg/g) pH Dosage (mg) Isotherm Kinetics Reference
CMC-MMT ECH MB 1065 1–10 500 Langmuir Pseudo-second-order 166

K-Carra-AAm-MMT APS MB 49.52 7 50 Langmuir Pseudo-second-order 167
P (AA-co-AMPS)/MMT MBA MB 192 10 — Redlich–Peterson Pseudo-second-order 168
CS-g-IA/BT MBA MB 500 6 30 Langmuir Pseudo-second-order 169
Malatji et al. 15
Figure 11. ‘Properties of celluloseclay nanocomposite hydrogels. (a) Time dependence of storage modulus (G0 ) and loss modulus
(G00 ) for different gelation systems at 60°C. The data are shifted along the y-axis to avoid overlapping. (b) Gelation time. (c) Storage
modulus at 1 h. (d) Compressive-strain curves. (e) Photographs of M-5. (f) The swelling ratio in distilled water’.144
increasing time when G0 > G00 , the materials were in a gel from 0.3 KPa to 4.7 KPa as shown in Figure 11(d) and (e),
form. Figure 11(b) in this case revealed that increasing clay which was approximately 16 times higher. Furthermore, the
content decreased the gel formation. Figure 11(c) revealed study reported that an increase in clay content from 10–15
that the storage moduli (G0 ) of hydrogels containing clay wt.% reduced the swelling capacity of the hydrogel (Figure
was higher than that of unmodified hydrogel and was 9(f)), reportedly due to a high degree of crosslinking. In-
proportional to the clay content from 10 to 15 wt.%. The creasing the crosslinking density of the hydrogel enhanced
incorporation of clay, however, increased the gel strength mechanical properties.166
Figure 12. The inverse spinel structure of magnetite Fe3O4.155
Metal oxide–based hydrogels. Metal oxide–based nano- osmotic pressure and the attraction of the gel for the liq-
particles have been reported to have a high density and uid.180 When the crosslinking density is high, the space
restricted size, which are responsible for their very inter- between the polymer chains decreases making the gel to be
esting and unique chemical and physical properties.170,171 stiff due to small nonexpendable pores.180 Additionally, an
Examples of metal oxides include titanium dioxide (TiO2), increase for MNPs increases the thermal properties but
iron oxide (Fe3O4), magnesium oxide (MgO) and alu- consequently reduces the swelling capacity as the Fe3+ from
minium oxide (Al2O3). Owing to their non-toxic nature, the incorporated MNPs may act as a physical crosslinking
high surface area, high chemical stability and economical agent.179 The greatest advantage of incorporating MNPs
friendliness, Fe3O4 nanoparticles are widely used for the into the hydrogel matrix is the improved stability and easy
removal of toxic metals and organic pollutants from recovery of the material after application.181
water.170,171,172,173 Ion-oxide and zinc oxide nanoparticles
are some of the most frequently used metal oxides in Zinc oxide–based hydrogels. Zinc oxide (ZnO) can be
treating dyes from aqueous solutions.174 found in nature as a zincite mineral; however, the majority
of it is prepared synthetically. Its crystal structure can be
Magnetic (Fe3O4) nanocomposite hydrogels. Magnetite found in a hexagonal wurtzite form or cubic zinc blende
(Fe3O4) also known as black iron oxide amongst other form (Figure 13). The form that is most stable and com-
transition metals has the strongest magnetism and is stable at monly found at ambient temperature is the wurtzite struc-
ambient temperatures.175 Magnetite is prepared from the co- ture.188 ZnO is commonly used for treating skin-related
precipitation of iron oxide salts that result in an inverse problems such as nappy rash, dandruff and incorporation in
spinel crystal structure consisting of half of the Fe3+ in ointments used in wound dressing.188 Other applications of
tetrahedral coordination and the other half Fe2+ ions in ZnO include use in catalysis, batteries, sensors and ad-
octahedral coordination (Figure 12).176,177 The co-precipitation sorption of contaminants.189–192 Khan et al.193 reported
method is the most useful and suitable technique in preparing their application as adsorbent material in a study, where a
magnetite at both lab-scale and industrial scale.178 guar gum adsorbent hydrogel incorporated with ZnO
Due to their cheap synthesis costs, susceptibility, sta- nanoparticles was used for removing chromium (VI) from
bility, high porosity, magnetic properties, biocompatibility water. The group reported that incorporating ZnO nano-
and easy chemical modification, MNPs have attracted much particles improved the recovery of the adsorbent from the
use in the wastewater treatment field.173–177 The intro- aqueous solution after the removal of Cr (VI). In another
duction of MNPs into polymer structures to produce study, CMC hydrogel was modified with ZnO for antimi-
nanocomposite hydrogels leads to a hybrid hydrogel with crobial activity, which was influenced by their inexpen-
advantages of both components, thus improving chemical siveness and lacks colour.194 Therefore, looking at these
and physical properties. An example of such hybridized properties, the ZnO would be ideal for preparing hydrogels
hydrogel is Fe3O4-g-pAA hydrogel synthesized via radical for adsorbing dyes.
polymerization in the presence of MBA cross-linker, which
resulted in a highly adsorptive hydrogel of 507.7 mg/g Titanium dioxide–based hydrogels. Titanium dioxide is
removal capacity for MB179 as shown in Table 5. However, a naturally occurring oxide of titanium. It exists in three
according to Flory’s theory, the swelling degree of a hy- crystalline phases, namely, brookite, anatase and rutile.195
drogel depends on the density of crosslinking, the ionic The rutile phase is thermodynamically stable compared to
Malatji et al. 17
Table 5. Metal oxide–based adsorbents for organic dyes removal.
Cross- Dosage
Adsorbent linker Dye qe (mg/g) pH (mg) Isotherm Kinetics References
PAA-grafted MNPs MBA MB 507.7 4 20 Langmuir Pseudo-second- 179

order
Fe3O4-CS-Clay Clay MB 82 9–12 500 — — 181
SA-PAAc/ZnO MBA MB 1530 6–9 10 Langmuir Pseudo-second- 182
order
Fe3O4/p (Am-co-Na Ac) MBA MB 641 7 50 Langmuir Pseudo-second- 170
order
CMC coated Fe3O4@SiO2 — MB 22.7 11 30 Langmuir Pseudo-second- 183
nanocomposite order
Fe3O4/CA gel beads CaCl2 MV 713 — 20–40 modified Langmuir– Pseudo-second- 184
Freundlich order
ZnO–clay–alginate hydrogel Clay CR 546.89 5–7 200 Temkin Pseudo-first- 185
beads order
ZnO-PPy nanocomposite — BG 140.8 — 50–200 Langmuir Pseudo-second- 186
order
chitosan/silica/ZnO NC — MB 293.3 — — Langmuir Pseudo-second- 187
order
the anatase and brookite phases, which are metastable.195

The advantages of TiO2 are that it is non-toxic, chemically
stable, highly reactive, biocompatible, cost-effective, con-
tains electrochemical properties and is safe to
produce.195,196 In addition, TiO2 possesses antimicrobial
and UV-protection properties.196 Applications of titanium
dioxide include the use of a photocatalyst for water-dye
degradation, in food and pharmaceuticals as a white col-
ourant, in sensors, ceramic industries, inorganic membranes
and biological implants.195,196 For example in a study by
Kangwansupamonkon et al., 197 TiO 2 /poly [acrylamide-
co-(acrylic acid)] hydrogel was reported to have 91.6%
removal for MB using 5% TiO2 as an inorganic initiator.
Another study by Ari et al.195 used P (AMPS)-TiO2
composite hydrogel for photocatalytic degradation of MB
and reported high catalytic performance and high thermal
stability due to the incorporated TiO2 nanoparticles. The
group also reported over 80% removal capacity for MB after
repeated cycles of more than five, hence improved reus-
ability and regeneration. Another study by Han et al.198 also
reported excellent performance in terms of regeneration,
self-cleaning and recovery of the prepared hydroxyethyl-
titanium dioxide-CMC (HEC-TiO2-CMC) hydrogel cage
for the removal of MB.198 Adsorption of MB onto
polyacrylamide-grafted gum ghatti (PAAm-g-Gg)/TiO2
hydrogel nanocomposite prepared by Mittal and Ray was
Figure 13. Crystal structure of zinc oxide.162 reported to be greatly dependent on the adsorbent dose, the
ionic strength, pH and temperature of the solution.199 The clay/magnetic hydrogel nanocomposites via free-radical
pair reported a removal capacity of 1305.5 mg g1 domi- polymerization method; their material exhibited improved
nated by pseudo-second-order rate model and Langmuir thermal stability and mechanical strength in comparison to
adsorption isotherm.199 The incorporation of TiO2 NPs onto the pure hydrogel. However, their adsorption studies
sodium alginate cross-linked polyacrylic acid (SA-cl-poly showed that the incorporation of Fe3O4 and Cloisite 30B in
(AA) hydrogel) was reported to have improved removal the polymeric hydrogel networks reduced the adsorption
capacity from 80% using hydrogel with no TiO2 to 94.1% capacity. The prepared clay/magnetic hydrogel nano-
and 99.4% for nanocomposites containing 0.05 and 0.2 g of composites exhibited an adsorption capacity of 1081.60 mg/
TiO2 NPs, respectively.200 XRD patterns from this study g, which is low when compared to the adsorption capacity
showed the disappearance of some TiO2 peaks after MB (1109.55 mg/g) of pure hydrogel.201 Surprisingly, Zhang
absorption indicating a reduction in the crystallinity of the et al.202 prepared PAAm/CS/Fe3O4 composite hydrogel via
nanocomposite that is said to be caused by the trapping of in situ polymerization for the removal of MB dye from
dye molecules within the micropores and macropores of the aqueous solution, and the obtained results demonstrated that
absorbent.200 the incorporation of Fe3O4 magnetic nanoparticles in the
In recent years, efforts have been made to confirm the hydrogel matrices improved both swelling and adsorption
effectiveness of using NCHs as adsorbent for wastewater capacity.202 Another study by Makhado et al.,182 synthe-
treatment. In this context, Malatji and co-workers fabricated sized sodium alginate/ZnO hydrogel nanocomposites by the
Table 6. Advantages and disadvantages of several hydrogel nanocomposites for the removal of methylene blue from aqueous solution.
Adsorbent Filler Advantages Disadvantages References
(PAAm-g-Gg)/TiO2 hydrogels TiO2 NPs Recyclability, adsorption capacity — 199

nanocomposite
SA-cl-poly (AA)-TiO2 O/I- TiO2 NPs Mechanical properties and adsorption Swelling capacity 200
hydrogels nanocomposite capacity
CMC-p (AA)/Fe3O4 hydrogels Fe3O4 NPs Mechanical properties and thermal stability Swelling and adsorption 201
nanocomposite capacity
Poly (acrylamide-chitosan)/Fe3O4 Fe3O4 NPs Adsorption capacity, low cost and swelling — 202
hydrogels capacity
Sodium alginate/ZnO hydrogel ZnO NPs Thermal stability, swelling and adsorption Mechanical properties 182
SA/p (AAc)/o-MWCNTs hydrogels o-MWCNTs Thermal stability, swelling and adsorption Mechanical properties 203
GK-cl-P (AA-cl-AAM)/SiO2 SiO2 NPs Surface area, adsorption capacity Pore size 204
nanocomposite
GumT-cl-HEMA/TiO2 hydrogel TiO2 NPs Adsorption capacity, surface area, thermal Swelling capacity 205
stability and regeneration
Scheme 1. Crosslinking using glutaraldehyde to produce hydrogel.109

Malatji et al. 19
Scheme 2. An overview of thermal free-radical polymerization and crosslinking.122
Scheme 3. Showing possible interactions of carbon-based materials.135
in situ free-radical polymerization method. They applied the adsorption capacity (1129.0 mg/g) exhibited by the pure
as-prepared material as an adsorbent for MB dye removal hydrogel. In addition, sodium alginate/ZnO hydrogel
from the aqueous phase. According to their results, sodium nanocomposites displayed relatively high thermal stability
alginate/ZnO hydrogel nanocomposites showed high ad- and excellent recycling performance than pure hydrogel.
sorption capacity (1529.6 mg/g) for MB in contrast to Nonetheless, the incorporation of ZnO NPs in the SA-poly
(AA) hydrogel matrix increased the swelling capacity, ORCID iD

which sequentially led to a decrease in the mechanical Kwena D Modibane  https://orcid.org/0000-0003-4502-122X
strength.182 Table 6 shows the advantages and disadvan-
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Nanomaterials and Technologies for Environmental Applications - Review Article

Nanomaterials and Nanotechnology

Nompumelelo Malatji1, Edwin Makhado1, Kwena D Modibane1 , Kabelo E Ramohlola1,

Date received: 8 March 2021; accepted: 21 July 2021

Topic Area: Polymer Nanocomposites and Nanostructured Materials

Table 1. Methods of removing dyes from water.

Adsorbent method Disadvantages References

Membrane ﬁltration Membrane fouling and production of concentrated sludge 25

Figure 2. Structure of sodium carboxymethyl cellulose.63

Figure 4. Structure of sodium alginate.62

Figure 5. Classiﬁcation of hydrogels.

In addition, the hydrogels may be classiﬁed based on the Preparation methods

Figure 8. Scheme showing the preparation of gum tragacanth–based hydrogel beads.117

Figure 10. X-ray diffraction and thermogravimetric analysis.118

CMC-AAm-GO MBA Acid black- 185.45 6 100 — — 9

Adsorbent Cross-linker Dye qe (mg/g) pH Dosage (mg) Isotherm Kinetics Reference

CMC-MMT ECH MB 1065 1–10 500 Langmuir Pseudo-second-order 166

Figure 12. The inverse spinel structure of magnetite Fe3O4.155

Table 5. Metal oxide–based adsorbents for organic dyes removal.

PAA-grafted MNPs MBA MB 507.7 4 20 Langmuir Pseudo-second- 179

the anatase and brookite phases, which are metastable.195

Adsorbent Filler Advantages Disadvantages References

(PAAm-g-Gg)/TiO2 hydrogels TiO2 NPs Recyclability, adsorption capacity — 199

Scheme 1. Crosslinking using glutaraldehyde to produce hydrogel.109

Scheme 2. An overview of thermal free-radical polymerization and crosslinking.122

Scheme 3. Showing possible interactions of carbon-based materials.135

(AA) hydrogel matrix increased the swelling capacity, ORCID iD

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