State of Arte2

Environmental Science and Pollution Research (2018) 25:24569–24599
https://doi.org/10.1007/s11356-018-2605-y
REVIEW ARTICLE
Hydrogel applications for adsorption of contaminants in water

and wastewater treatment
Vinh Van Tran 1 & Duckshin Park 2 & Young-Chul Lee 1
Received: 20 November 2017 / Accepted: 18 June 2018 / Published online: 14 July 2018
# Springer-Verlag GmbH Germany, part of Springer Nature 2018
Abstract
During the last decade, hydrogels have been used as potential adsorbents for removal of contaminants from aqueous solution. To
improve the adsorption efficiency, there are numerous different particles that can be chosen to encapsulate into hydrogels and
each particle has their respective advantages. Depending on the type of pollutants and approaching method, the particles will be
used to prepare hydrogels. The hydrogels commonly applied in water/wastewater treatment was mainly classified into three
classes according to their shape included hydrogel beads, hydrogel films, and hydrogel nanocomposites. In review of many
recently research papers, we take a closer look at hydrogels and their applications for removal of contaminants, such as heavy
metal ion, dyes, and radionuclides from water/wastewater in order to elucidate the reactions between contaminants and particles
and potential for recycling and regeneration of the post-treatment hydrogels.
Keywords Hydrogel . Heavy metal . Dye . Radioactive . Adsorption . Water/wastewater treatment
Introduction only on species living in water but also on the broader biolog-
ical community (Guo et al. 2015).
Water is the most essential substance to humans and other Yearly, heavy metals are released into environments from
living organisms. However, some harmful chemical com- various industrial production or auxiliary processes as well
pounds cause water pollution that exerts negative effects not as other human activities (Chen et al. 2010; Patel et al.
2010). There are more than 40 elements of greater-than
Highlights 5 g/cm 3 mass, which are regarded as heavy metals
• Unique particles entrapped in synthesis process of three types of
(Srivastav et al. 1994; Zenk 1996). Heavy metal ions are
hydrogels
• Adsorption kinetic models, adsorption isotherm models, and the among the main contaminants found in water. Due to their
mechanism of contaminants on hydrogels persistence and toxicity properties, such pollutants, heavy
• Impact factors on the adsorption capacity of hydrogels: pH, adsorbate metals, have attracted considerable-attention within the sci-
concentration, swelling degree, and other ions
entific, governmental, and community-activist communities.
• Recycle and recovery methods of used hydrogels and effect of
mechanical properties on the reusability of hydrogels Toxic metals are very dangerous to all biological organisms
• Applications of hydrogels on removal of metal ion, dye, and and the overall environment, especially when present above
radionuclides from water/wastewater the given tolerance levels (Abachi et al. 2013; Ali et al.
Responsible editor: Angeles Blanco 2011) and even at low concentrations. Even so, nearly
1 million t of dyes is annually used in the chemical industry
* Young-Chul Lee worldwide, more than 10% of which are discharged as ef-
dreamdbs@gachon.ac.kr fluents that seriously pollute the environment and affect
1
humans as well as aquatic organisms (Sethuraman and
Department of BioNano Technology, Gachon University, 1342 Raymahashay 1975; Yagub et al. 2014). Generally, the dyes
Seongnamdaero, Seongnam-si 13120, Gyeonggi-do, Republic of
Korea have complex and stable structures, and their degradation in
2 nature is usually very difficult and slow; consequently, they
Korea Railroad Research Institute (KRRI), 176
Cheoldobakmulkwan-ro, Uiwang-si 16105, Gyeonggi-do, Republic will accumulate (Fu and Viraraghavan 2001; Kadirvelua et
of Korea al. 2003; Zollinger 2003). Besides heavy metals and dyes,
Content courtesy of Springer Nature, terms of use apply. Rights reserved.

24570 Environ Sci Pollut Res (2018) 25:24569–24599
radioactive waste, a waste product containing radioactive Application of hydrogel beads for adsorption
materials usually produced in a nuclear process such as of contaminants
nuclear fission, is also one of the common contaminants
significantly affecting water resource. Although the radioac- Particles entrapped in hydrogel beads
tivity of such waste will decrease over time, it will do so for heavy-metal ion removal
only at a very slow rate; therefore, it can seriously affect
human health and the environment over very long duration Cellulose is known as the most abundant renewable material
(Jing et al. 2013). In addition, in modern agriculture, pesti- in the world. However, its derivatives have usually received
cides have been widely used for protecting crops and live- more interest in synthesizing hydrogels because they have a
stock, which have also led to a lot of serious health impli- better solubility in water than cellulose. One of the most com-
cations. According to experts, these pesticides have been mon derivatives is carboxylmethyl cellulose (CMC), which is
discharged through direct agricultural runoff, leaching, and known as a water-soluble cellulose derivative that has been
improper disposal of empty containers (Dwivedi et al. available on the market. A method commonly used to prepare
2014). Besides, the discharge of nitrogen components CMC-based hydrogels is crosslinking method by using the
(nitrate) in the water source is currently harmful for both crosslinking agents like polycarboxylic acids, epichlorohydrin
human and animal health. Nitrates may cause several seri- (ECH), and N,N′-methylene-bisacrylamide (Fekete et al.
ous problems when dispersed in water, since they cause the 2017). In 2010, typical hydrogel beads were successfully pre-
groundwater pollution and the eutrophication of rivers pared based on CMC by inverse suspension crosslinking
(Rossi et al. 2015). Therefore, the pesticides and nitrate using ECH as cross-linker (Fig. 1) (Yang et al. 2010). The
remediation from aqueous solution has been a worldwide adsorption capacity of these hydrogels was evaluated with
problem and challenge. model wastewater including heavy-metal ions, Pb2+, Ni2+,
The investigation and application of various methods to and Cu2+. The results confirmed that a new bond, CAOAC,
remove these contaminants from water is absolutely essen- was formed by the reaction between ECH and CMC.
tial for protection of the environment. Compared with chem- Compared with pure CMC, the hydrogel beads had lower
ical and physical methods commonly used to remove dyes, crystallinity. The hydrogel beads’ adsorption of Pb2+, Ni2+,
heavy metal ions, and others, currently, the adsorption and Cu2+ were based on the formation of coordination bonds
methods stand out as one of the most effective and friendly with the oxygen atoms in their carboxyl groups. The formed
methods for dye removal from aqueous solution (Azbar et hydrogel beads thus exhibited a high adsorption capacity for
al. 2004; Mohan et al. 1998). Hydrogel is a three- heavy-metal ions.
dimensional polymer that can be synthesized by the reaction Recently, a biopolymer based on chitosan (CS) has attracted
between one or more monomers. Hydrogel’s three- great interest in various fields, especially environmental bio-
dimensional network and porous structure typically endows technology, because of its very high adsorption capacity of
them with a hydrophilic property and corresponding capac- heavy-metal ions and low cost (Jin and Bai 2002; Yoshida
ity to adsorb large amounts of water or biological fluids and Takemori 1997). Moreover, CS can be easily synthesized
(Ahmed 2015). Hydrogels’ high water retention and low at the industrial level by a simple method based on chitin. CS
cost have attracted great attention as effective adsorbents. hydrogel beads are regarded as a potential adsorbent for effec-
The hydrogels commonly applied in water/wastewater treat- tive removal of heavy metals in industrial wastewater treatment
ment were mainly classified into three classes including hy- (Chatterjee et al. 2005; Chatterjee et al. 2007; Ngah et al. 2002).
drogel beads, hydrogel films, and hydrogel nanocomposites CS has also shown a great material in the production process of
according to their shape and physicochemical properties hydrogel due to the combination ability with various materials.
(Table 1). By blending CS with a high concentration of CMC solution, a
In order to improve adsorption efficiency, there are novel CS-based hydrogel called CM(carboxymethylated)-cel-
many different and unique nanoparticles utilized for en- lulose/CS in the form of physical hydrogels was successfully
trapment in hydrogel beads, hydrogel films, or hydrogel synthesized by irradiation-based crosslinking (Zhao and
nanocomposite as hybrids (Jing et al. 2013). This study Mitomo 2008). Due to adding CS, the hydrogel’s adsorption
will provide an overview of the recent literature’s results capacity for divalent heavy-metal ions and crosslinking extent
obtained in the treatment of wastewater utilizing hydrogels had been improved. Also, CS could combine with PVA to form
for the removal of heavy-metal ion, dyes, radionuclides, a CS/poly(vinyl alcohol) (PVA) hydrogel bead for adsorption of
and other pollutants from aqueous solution as well as in lead ion from an aqueous solution (Jin and Bai 2002). The Pb2+
the recovery and recycling of used hydrogels. It is evident ion adsorption on these hydrogel beads showed a strong depen-
from the literature survey that nanoparticles into hybrid dence on pH, and the mechanism of the adsorption process is
hydrogels have shown good potential applicability for re- based on complexation, ion exchange, and electrostatic interac-
moval of various aquatic pollutants. tion. For the electrostatic interaction, the hydrogels possessed a

Environ Sci Pollut Res (2018) 25:24569–24599 24571
Table 1 The physiochemical properties of three types of hydrogel
Physiochemical Morphology Swelling Mechanical properties Thermal Reference

properties stability
Hydrogel beads - Spherical beads; rough - High swelling ratio; - Great mechanical strength - Stable up (Dwivedi et al. 2015;
surface. - pH-dependence - Quite tensile elasticity: to 260 °C Ma et al. 2017;
- Outer surface: quite Young’s modulus Mohammed et al. 2015;
rough, smooth or pores (0.93–2.14 MPa) Pathak et al. 2016; Pour
- Size: uniform, diameter: and Ghaemy 2015;
20 nm–5 mm Yu et al. 2015a;
Zhuang et al. 2016)
Hydrogel films - Thin film: thickness Degree of swelling - High elongation at break – (Al-Mubaddel et al. 2015;
10–300 μm (245% - 2400%); - High tensile elasticity: Baruah et al. 2016;
- Homogenous texture - pH-dependence Young’s modulus Gogoi et al. 2015;
~ 15 MPa Mirabedini et al. 2017;
Nguyen and Liu 2014)
Hydrogel - Soft, and elastic with a - Degree of swelling - Good mechanical Stable up (Heydari and Sheibani 2015;
nanocomposite slippery surface; (350–7300%) properties: elongation to 300 °C Kasgoz and Durmus 2008;
- Highly porous network - Swelling ratio increases near 1000% Pourjavadi et al. 2015;
structure with time; - Low tensile elasticity: Zhao et al. 2015;
- pH-dependence Young’s modulus: Zhou et al. 2011)
~ 453 kPa
ζ-potential. In the case of pH < 6.3, the ζ-potentials of the CS/ mechanical strength and recyclability (Ma et al. 2017). The
PVA hydrogels were positive, and for pH > 6.3, negative. hydrogel preparation process was conducted with a two-step
Therefore, the heavy metal ion adsorption occurs even though method by which EDTA is cross-linked with CS and MBA is
the interaction between the metal ions and the hydrogels is cross-linked with PAM to form a double-network hydrogel
electrostatically repulsive at pH < 6.3. In an attempt to improve (Fig. 2). The hydrogel showed a high adsorption capacity for
the efficiency of CS-hydrogel beads in metal ion removal ap- Cd2+, Cu2+, and Pb2+ ion based on the mechanism of the ion
plications, a glutamic-CS hydrogel beads (GCS) was synthe- exchange interactions between metal ions and carboxylate
sized by reactions between CS and different concentrations of groups. This hydrogel was effectively demonstrated for treating
glutamic acid (Abdelwahab et al. 2016). It is the presence of practical wastewater with various kinds of heavy metal ions,
glutamic acid in the structure that affected the treatment effi- with an adsorption efficiency of 98%.
ciency of the hydrogels in removing Cu2+ and Ni2+ ion. It is In preparing a high-strength hydrogel for adsorption of
found that when the concentration of glutamic acid increased, metal ions from industrial lean solvents and reusability, a se-
the adsorption of the hydrogels decreased. This phenomenon ries of PAM hydrogel beads was successfully synthesized by
was explained that the increase of the crosslinking degree using three components with different functions (Pal and
caused a decrease in the hydrogel pore size. Especially, it is Banat 2015). To fabricate these hydrogel beads, acrylamide
notable that a combination of CS with ethylenediaminetetra- as a monomer was polymerized with ammonium
acetic acid (EDTA), N,N-methylenebis(acrylamide) (MBA), peroxodisulphate as initiator. The acrylamide monomer was
and polyacrylamide (PAM) formed an exceptional type of hy- then cross-linked to form PAM hydrogels using N,N′-
drogel beads which its outstanding properties are a remarkable methylenebisacrylamide as the cross-linker. The fabricated
Fig. 1 Preparation of CMC

hydrogel particles with ECH as
crosslinker

Fig. 2 Schematic representation of CTS/PAM gel synthesis (reprinted (adapted) with permission from Ma et al. 2017. Copyright (2017) American
Chemical Society)
hydrogel beads with an entangled 3D network were effective- solution (Yu et al. 2015a). Due to PDopa-PAH PEC loaded
ly demonstrated for removal of metal ions. Moreover, the inside the hydrogel matrix, this type of hydrogel beads can
hydrogel beads also showed good reusability: the adsorption effectively and efficiently remove various ionic pollutants,
capacity had only slightly dropped even after 15 cycles of both heavy metal ions and ionic organic dyes, from aqueous
desorption and reuse. In addition, the hydrogel could easily solution. Because the chemical structure of PDopa contains
be desorbed by sodium chloride and the hydrogel beads can be three types of functional group (catechol group, carboxyl
excellent adsorbents offering operation costs and good group, and amino group), the formed PDopa-PAH PECs
reusability. hydrogels possess a larger adsorption capacity of heavy metal
The interaction between two oppositely charged polymers ions compared to other adsorbents. Moreover, because both
results in the formation of polyelectrolyte complexes (PECs) PDopa and PAH are pH-sensitive, the hydrogel beads can be
(Philipp et al. 1989). Recently, PECs have been widely ap- easily recovered for reuse by adjusting the pH in the surround-
plied as potential flocculent materials to precipitate metal ions ing media. In addition, given the ease and appropriateness of
in the wastewater treatment industry, owing to their relative synthesizing hydrogel beads for large-scale production with
cheapness and ease of use. Especially, after simply mixing little raw material loss and byproduct generation, the synthesis
with other oppositely charged polyelectrolytes according to can be extended to various polyelectrolytes.
each experiment condition, PECs will be formed as precipi- Pectin (Pec) is a natural chemical compound with a hetero-
tates or thin films, or dispersed colloids in water, which makes geneous structure that is basically formed by smooth and hairy
them excellent materials for water treatment (Petzold and regions having various unit of polymers, such as the poly(1 →
Schwarz 2014; Thünemann et al. 2004; Zhang and Sun 4) α-D-galacturonic acid (Pérez et al. 2000; Reis et al. 2009).
2009). Based on PECs’ interaction between positively Pec has been generally found in citric fruits, principally the
charged poly(allylamine hydrochloride) (PAH) and negatively lemon. This particular polysaccharide has been commonly
charged poly(L-3,4-dihydroxyphenylalanine) (PDopa), new used in feed compositions (Willats et al. 2006) and the phar-
hydrogel beads, namely PDopa-PAH PEC hydrogel beads, maceutical industry. Its structure includes large numbers of
were introduced for removal of ionic pollutants in aqueous ionic groups, making it an excellent polymer matrix for

superabsorbent hydrogel synthesis. Recently, Pec also was formed in the hydrogel matrix, which may be favorable for
applied in synthesis of materials for wastewater treatment CV adsorption.
through a novel Pec-based hydrogel that can be used to re- In the past decade, graphene oxide (GO) sheets, given their
move Cu2+ and Pb2+ ions (Guilherme et al. 2010). This hy- outstanding structure, have become a target of numerous stud-
drogel showed a high adsorption capacity and efficiency for ies for dye removal from wastewater. Due to its two-
removal of Cu2+ and Pb2+ from water: 120-mg Cu2+ and 130- dimensional structure, GO possesses a high adsorption capac-
mg Pb2+ per g hydrogel at pH 5.5 with 0.10-g mL−1 adsorbent ity for different dye molecules through π-π stacking interac-
concentration. tions (Singh et al. 2011). Moreover, GO also has negative
Fly ash (FA) is a waste product produced from thermal charges due to the presence of various oxygen-rich functional
power plants, steel mills, and other facilities. Due to its low- groups, such as carboxyl, carbonyl, and hydroxyl groups,
cost and abundance, it has been utilized as an adsorbent in which enhance electrostatic interactions with dye cations.
many fields (Wang &Wu 2006). With a new approach for Therefore, GO has been used as a potential adsorbent in var-
preparation of hydrogels, a novel magnetic attapulgite/fly ious applications, especially industrial wastewater treatment.
ash/poly(acrylic acid) (ATP/FA/PAA) ternary hydrogel beads By combining GO and polyethylenimine (PEI), a novel hy-
was synthesized for removal of Pb2+ ion (Jiang and Liu 2014). drogel bead as an efficient dye adsorbent was produced, which
In this method, magnetic FA particles were used as new cross- they named GO/PEI hydrogel (Guo et al. 2015). As for the
linkers (instead of the traditional cross-linkers) via an inverse preparation process, the hydrogel could be simply formed
suspension polymerization process. In this process, acrylic through a combination of amine-rich PEI and GO sheets
acid (AA) is attached onto an inorganic skeleton obtained by achieved by hydrogen bonding and electrostatic interactions.
the functionalized ATP and FA to form ternary hydrogel Figure 3 shows that GO sheets possess numerous functional
beads. By using inorganic materials, FA, the production cost groups (▬COOH and ▬OH) that can form hydrogen bonds
of the hydrogel beads is significantly lower and the mechan- with amine molecules of PEI under appropriate conditions.
ical strength, thermal stability, chemical resistance, and di- For this type of hydrogel, PEI is added in solution to facilitate
mensional stability also are improved. These hydrogel beads the gelation process of GO sheets, as GO sheets are regarded
showed effective treatment efficiency for removal of Pb2+ ion as the most important hydrogel ingredient for maintenance of
via a high adsorption capacity of 38 mg g−1 in 100-mg/L Pb2+ dye adsorption capacity. Moreover, it is demonstrated that this
solution at pH 5. Besides, the Pb2+ ion adsorbed in the hydro- hydrogel will be a new potential material for the organic dye
gel beads could be completely desorbed in 0.10-mol/L HCl removal with the high efficiency.
aqueous solution within 90 min. Halloysite is known as an aluminosilicate clay mineral pro-
duced by hydrothermal alteration and deposition (Joussein et
Particles entrapped in hydrogel beads for dye al. 2005; Levis and Deasy 2002). As halloysite can effectively
removal adsorb both cations and anions, it can be applied in various
fields including ceramic raw materials, catalysis, and polymer
Crystal violet (CV) is a typical cationic dye commonly used in nanofillers. In its structure, halloysite naturally appears as
coloring paper, temporary hair colorant, dyeing cottons, and small cylinders (nanotubes) with a high aspect ratio, for which
wools. When discharged into receiving environments, it can reason it usually is referred to as BHalloysite nanotubes
pollute the water source and cause some negative effects on (HNTs)^ (Lvov et al. 2008). Compared with other tubular
human health such as accelerated pulse, vomiting, shock, cy- nanomaterials (such as carbon nanotubes) used in wastewater
anosis, jaundice, quadriplegia, and others (Kunz et al. 2002). treatment, natural HNTs are more environmentally friendly
Hence the removal of CV from industrial effluent has attracted and cheaper (Du et al. 2010; Zhixin et al. 2014). By combin-
the attentions of numerous scientists and researchers. ing the two cheap materials, CS and HNTs, Peng and co-
Recently, a semi-IPN (interpenetrating polymer networks) hy- workers fabricated novel hydrogel beads that can be applied
drogel bead constituted of poly(acrylic acid-acrylamide meth- for removal of MB and malachite green (MG) from wastewa-
acrylate) and amylose was introduced for adsorption of CV ter (Peng et al. 2015). CS–HNTs hydrogel beads were obtain-
with high adsorption efficiency (Li 2010). However, its ad- ed by the dropping and pH-precipitation method. It is found
sorption capacity was found to be highly dependent on the that CS and HNTs are compatible in the preparation of hydro-
amylose content and pH of the solution. As for adsorption gel adsorbents: (i) HNTs can be immobilized by CS hydrogel
mechanism, the results indicated that the CV dye adsorption and completely incorporated into the hydrogel beads’ struc-
of hydrogel occurs via swelling combined with electrostatic ture and (ii) the thermal stability of the hydrogel beads is
and hydrophobic interactions. And as for the morphology of remarkably enhanced by HNTs. The appearance of hydrogel
the hydrogel, hydrophilic amylose was dispersed in continu- beads is shown in both wet and dry form (Fig. 4). The average
ous phases of poly(acrylic acid-acrylamide-methacrylate) hy- diameter of the hydrogel beads is changed from 2.29 to
drogel, and many open pores of 100-μm diameter were 2.75 mm in the wet form. It is found that HNTs have an

Fig. 3 Schematic depiction of formation of GO/PEI gels. a GO and b amine-rich PEI were combined to yield c GO/PEI hydrogels. (Reprinted (adapted)
with permission from Guo et al. 2015. Copyright (2017) Springer Open)
influence on the appearance, diameter, and microstructures. CS-based hydrogels, certain modification methods, such as
Via the adsorption behavior of the hydrogel beads with MB cross-linking (Vieira &Beppu 2006) and the addition of other
and MG, it is found that HNTs affected the adsorption capac- functional groups (Suna et al. 2006), were conducted. By
ity of hydrogel beads. It is the presence of HNTs that can using cetyl trimethyl ammonium bromide (CTAB), a cationic
considerably increase the adsorption effect of hydrogel beads surfactant, CTAB-impregnated CS hydrogel beads were pre-
for both pollutants. Besides, these hydrogel beads can be pared successfully for adsorption of CR (Chatterjee et al.
regarded as an excellent adsorbent, as they can be simply 2009). The addition of CTAB to CS hydrogel beads signifi-
recycled and reused by NaOH solution and acetone. cantly improved the adsorption capacity of the hydrogel. It is
Especially, the high removal ratio of dyes is maintained above found that the increase of the CTAB concentration led to a
92.0% in all hydrogel beads at the second adsorption. significant increase of CR adsorption capacity of the hydrogel
Congo red (CR) has been known as one of the dyes that beads. Additionally, using cationic surfactant to impregnate
causes an allergic reaction. It is metabolized to benzidine, a CS can enhance the adsorption capacity of hydrogels for CR
human carcinogen, and it is very difficult to biodegrade due to relative to other materials, and this approach will produce
a complex aromatic structure that provides physico-chemical, hydrogel adsorbents having a high adsorption efficiency for
thermal, and optical stability (Han et al. 2008). Recently, CS removal of anionic dyes.
has been regarded as an excellent material for wastewater Recently, the development of new adsorbents from feed-
treatment due to the large number of active amine (▬NH2) stock materials, such as starch, cellulose, and lignin, has been
groups in its structure. Accordingly, there have been many of interest to scientists due to the fact that the adsorbents
studies using CS to prepare hydrogel for anionic dyes and produced form these materials have many unique advantages
heavy metal removal. To enhance adsorption capacity of including low-cost, biodegradability, non-toxicity, and high
efficiency (Li and Bai 2006). Lignin is a class of complex
organic polymer that is synthesized by the chemical polymer-
ization method from three type of alcohol (Ralph et al. 2004).
Offering the outstanding advantages noted above, lignin is
regarded as a potential material for preparation of excellent
adsorbents. Recently, a type of lignin, lignosulfonate (LS), has
been used in the synthesis process of a typical Lignosulfonate-
g-acrylic acid (LS-g-AA) hydrogel bead with superabsorbent
capacity (Yu et al. 2016). In this preparation method, AA
Fig. 4 Appearance of chitosan and chitosan–HNTs hydrogel beads in wet
molecules were grafted onto the backbone LS in the presence
and dry state (reprinted (adapted) with permission from Peng et al. 2015. of N,N′-methylene-bis-acrylamide (MBA) as the cross-linker
Copyright (2017) Elsevier) and laccase/t-BHP as the initiator (Fig. 5). It was found that

Fig. 5 Schematic of LS-g-AA hydrogel synthesis catalyzed by laccase in presence of hydrogen peroxide (reprinted (adapted) with permission from Yu et
al. 2016. Copyright (2017) Elsevier)
the hydrogel shows a high adsorption efficiency for MB after other cations (Babu et al. 2007). When sodium alginate is
2 h and its adsorption capacity depends on the mass ratio of dissolved in a neutral and alkaline solution, the carboxylate-
AA, the pH of solution, and the initial pollutant concentration. functional group has a negative charge, which affects a greater
Moreover, the LS-g-AA hydrogel also showed that with its affinity to cations (Rocher et al. 2008). Yet, it has been sug-
desorption and reuse capacities, it is an excellent adsorbent. gested that anionic hydrogels produced from polysaccharide
The hydrogel could be desorbed by using a weak acid solution like alginate have inadequate efficiency for adsorption of an-
(pH of 4.0) and reused at least four times but still maintained ionic dyes from aqueous solution (Blackburn 2004).
high MB-adsorption levels. Employing a similar method, using However, by combining PVP with sodium alginate, that prob-
another feedstock material (cellulose), a novel amphoteric lem was overcome in preparing novel NaAlg/PVP-blend hy-
hydrogels was introduced for removing three anionic dyes, drogel beads (Inal and Erduran 2015). The hydrogel beads
namely acid red 9 (AR9), acid red 13 (AR13), and acid blue were fabricated by the gelation method in CaCl2 solution.
92 (AB92) (Kono 2015). To prepare the hydrogel, a series of They have been effectively demonstrated for adsorption of
cellulose ampholytes (CAms) was produced by a cationization different dyes such as reactive red-120 (RR), cibacron brilliant
reaction between sodium carboxymethylcellulose and 2,3- red 3B-A (CBR), and remazol brilliant blue R (RBB).
epoxypropyltrimethylammonium chloride. Then, the hydrogels Titanium dioxide (TiO2) is a flexible semiconductor that
were formed by a crosslinking method according to which has attracted great interest in the wastewater treatment field.
CAms is cross-linked by ethyleneglycoldiglycidylether It has many advantages, such as strong oxidizing power,
(EGDE). The adsorption capacity of the fabricated hydrogel superhydrophilicity, chemical stability, long-term durability,
was revealed to be a function of two factors: the pH of the non-toxicity, low cost, and transparency to visible light.
adsorption solution and the proportions of the cationic groups. Therefore, TiO2 has seen many applications in water splitting,
The highest adsorption capacity of the anionic dyes could be energy storage, dye-sensitized solar cells, and decomposition
reached at pH < 3 and with high proportions of cationic groups. of various pollutants. Using TiO2 as a photocatalyst is
Poly(N-vinyl-2-pyrrolidone) (PVP) is a water-soluble poly- regarded one of the most promising applications in terms of
mer that is quite friendly to the environment and to humans the removal of hazardous organic substances, because it
due to its non-toxic, biodegradable, and biocompatible prop- shows high photocatalytic activity under UV light irradiation
erties. Owing to these advantages, PVP is totally suitable for (Nakata and Fujishima 2012; Schneider et al. 2014).
synthesize hydrogel materials. Hydrogels based on the inter- According to this approach, a recyclable, recoverable, and
action of PVP and other component for removing anionic dyes reformable hydrogel-based photocatalyst was successfully
and metal ions (Lu et al. 2011; Senkal et al. 2006; Wang and synthesized (Mai et al. 2017). In the preparation process, the
Wang 2010) have been successfully prepared. Sodium algi- main observations were well-distributed TiO2 nanoparticles in
nate (NaAlg), a natural polysaccharide derived from brown the agarose hydrogel matrix and the gelation of the agarose in
seaweeds, also possesses the same friendly properties as hot water. The study used methyl blue (MB) to examine the
PVP. Hydrogel beads can be fabricated from NaAlg by photocatalytic activity of the hydrogel and the contents of
cross-linking the guluronic acid component of NaAlg with TiO2 and agarose in hydrogels as well as hydrogel size, shape,

and concentration of a hydrogel are main factors that signifi- inorganic ion exchanger (Dwivedi et al. 2015). The hydrogel
cantly influenced the photodegradation efficiency. beads were found to have a high hydrophilicity and a high
Furthermore, the additional excellent features of this type of surface area. The optical microscope (OM) image of the swol-
hydrogel are its recyclability and the simplicity of the regen- len hydrogel beads shown in Fig. 6a reveals a round shape and
eration of pure TiO2 NPs. a relatively uniform size of 2 mm. Figure 6b shows the SEM
images of the outer surface of a dried hydrogel bead. As is
Particles entrapped in hydrogel beads for radioactive apparent, it is quite rough and has some large pores. The ad-
waste removal sorption of cesium ions onto the KNiHCF particles of the hy-
drogel beads happens by ion exchange between a potassium
With the rapid development of nuclear power application ion of KNiHCF and a cesium ion. Also, the hydrogel beads
around the world, radioactive wastes containing enormous could be effectively applied to adsorb radioactive cesium ions
amounts of radionuclides have become a focus of concern, within a wide range of pH (1–12), for a maximum capacity of
posing serious chemical and radiological toxicity threats to about ~ 64 mg per g of dry beads. The KNiHCF hydrogel beads
the environment. Among the common radioactive nuclides, are an excellent material for use in cesium removal from low
60
Co is one of the most harmful owning to its strong γ- level radioactive waste.
emission and relatively long half-life of 5.3 years (Wang et Taking a similar approach but using another type of inor-
al. 2013). The adsorption method is of great interest for re- ganic ion exchanger, new hydrogel beads for recovery or re-
moval of 60Co, owing to advantages including high efficiency, moval of cesium from low-level nuclear waste streams were
low cost and operation convenience compared with the alter- fabricated by encapsulating an inorganic sorbent, potassium
native methods (chemical precipitation, reverse osmosis, ion zinc hexacyanoferrate (KZnHCF) in hydrogel beads (Pathak
exchange, solvent extraction, coagulation, and membrane sep- et al. 2016). The preparation process of the hydrogel beads is
aration) (Thakura and Thakurb 2015). By using PVA and shown in Fig. 7. The KZnHCF-gel beads were prepared using
poly(acrylic acid-co-acrylic amide) P(AA-co-AM), novel sodium alginate stabilizing PVA to form a binding matrix. The
PVA-P (AA-co-AM) semi-IPN hydrogels were successfully reaction of ZnSO4 and KHCF will make KZnHCF sol in the
synthesized via free radical polymerization under the presence of PVA. The size of the KZnHCF particles formed
ultrasound-assisted condition for Co2+ ion removal (Wang et can be controlled by the PVA. An aqueous solution of 4%
al. 2016). As for the adsorption capacity of the hydrogel for sodium alginate was added to stabilize the KZnHCF sol.
Co2+ ions, it showed an excellent capability, compared with Then, hydrogel beads can be formed by dropping this mixture
other adsorbents. However, its adsorption efficiency was also into an aqueous bath containing 4-wt% CaCl2. The adsorption
influenced by various parameters, such as pH, temperature, process of the hydrogel beads was found to be quite efficient
adsorption time, and the initial concentration of pollutants. in the pH range from 3 to 10 and the adsorption capacity of the
In addition, the hydrogel was also used as an adsorbent owing hydrogel beads for cesium can approximately reach 95%.
to the merits of low material cost and operational convenience. Especially, the cesium adsorption efficiency of these hydrogel
Cesium (137Cs) is known as an important radioactive con- beads under the pH neutral condition was not affected signif-
taminant that can cause serious radiological hazards that affect icantly by the interfering ions (Na+, Ca2+, and Ba2+). This
human health and the environment due to its long half-life and mean that practical applications of such hydrogel beads for
high mobility in aquatic environments (Howard et al. 1991). treatment of cesium in aqueous nuclear wastes is completely
For the past many decades, development of efficient materials possible.
for removal of radioactive cesium from aqueous solutions has
been the focus of great attention from researchers worldwide. Particles entrapped in hydrogel beads for other
Inorganic ion exchangers possess many special properties in- contaminant removal
cluding selectivity, radiation, and thermal stabilities as well as
good compatibility with various matrices. Currently, a popular As has been noted, CS hydrogel beads are commonly used in
and important inorganic ion exchanger is transition metal contaminant removal applications due to their high adsorption
hexacyanoferrates, which can be applied in the nuclear industry capacity. In 2009, a CS hydrogel beads was introduced by
for removal of cesium. Generally, inorganic ion exchangers can Chatterjee and HanWoo 2009 for removal of nitrate. The ni-
be used to remove cesium in two different ways: (i) co- trate adsorption capacity of the hydrogel beads was identified
precipitation of cesium ions and (ii) preparation of metal increasing along with decreasing the pH of the solution.
hexacyanoferrate slurry. In 2015, a new method for synthesis Besides, the adsorption process also depends on the tempera-
of spherical potassium nickel hexacyanoferrate hydrogel beads ture: the optimum activity is achieved at 30 °C and the ad-
that binds the slurry of potassium nickel hexacyanoferrate sorption capacity will decrease with increases in temperature
(KNiHCF) particles in a alginate and polyvinyl alcohol over 30 °C. The maximum adsorption capacity of this hydro-
(PVA) matrix was introduced by utilizing KNiHCF as an gel could reach 92.1 mg g−1 at 30 °C. It is found that the

Fig. 6 a OM image and b SEM

images of outer surface (reprinted
(adapted) with permission from
Dwivedi et al. 2015. Copyright
(2017) Royal Society of
Chemistry)
adsorption process of nitrate is a spontaneous, exothermic wt% gold nanoparticles on hydrogel beads is good enough to
process that has positive entropy, and that when increasing improve the adsorption capacity of the beads by more than
the pH of the solution to the alkaline condition, desorption twofold compared with pure beads.
of nitrate from hydrogel beads will be accomplished for a
desorption ratio of 87% at around pH 12.0.
Methyl parathion (MP) is one of the many types of organ- Application of hydrogel films for adsorption
ophosphorus pesticides used on cotton, soybeans, vegetables, of contaminants
and other crops. When discharged into living systems, the
toxic compounds from pesticides will prevent the action of Particles entrapped in hydrogel films for metal ion
acetyl cholinesterase, which can lead to great harm to living removal
creatures, such as loss of muscle control, paralysis, convul-
sions, coma, and even death (Agrawal et al. 2010). Therefore, The presence of Ca2+ and Mg2+ ions in liquid increases water
MP’s removal from the water is crucial. A novel hydrogel hardness, which is one of the main problems in the water-
beads for removal of MP from waste water were introduced treatment field. In 2016, a hybrid hydrogel film was success-
by developing a new method for one-pot synthesis of gold fully prepared by using conjugation of oxidized carbon dots
nanoparticle-loaded hydrogel beads by using a composite ma- (CDs) produced from 11-mercaptoundecanoic acid with CS
trix of CS (Dwivedi et al. 2014). These hydrogel beads are a (Baruah et al. 2016). Ca2+ and Mg2+ ions from the solution
strongly hydrophilic material that can contain up to 96% water were removed by using the hydrogel film as a potential plat-
and remain stable up to 200 °C. Their high water capacity also form based on the principles of ion exchange. The removing
enhances the interaction between the MP’s compounds and efficiency of Ca2+ and Mg2+ ions from pond water by the
the active sites of the hydrogel, leading to a higher adsorption hydrogel film was 68.01 and 56.35%, respectively. Figure 8
efficiency. The study also reveals that a loading of at least 0.5- shows the method of synthesis of CS-MUA-SO3Na-CDs
Fig. 7 Illustration of procedure

for preparation of KZnHCF-gel
beads (reprinted (adapted) with
permission from Pathak et al.
2016. Copyright (2017) Asian
Journal of Materials Chemistry).
a Preparation of formulation of
ZnSO4 and KHCF in presence of
PVA. b Drop wise addition of
formulation to CaCl2 aqueous
solution. c Curing of beads for
4 h. d Separation and washing of
prepared beads. e Optical
microscopy (OM) image of the
swollen beads

Fig. 8 Schema showing synthesis protocol of thiol functionalized carbon conjugation of sulphonated CDs with biopolymer chitosan (reprinted
dots (CDs) from MUA followed by their oxidation to form sulphonated (adapted) with permission from Baruah et al. 2016. Copyright (2017)
CDs and subsequent fabrication of polymeric nanocomposite films via Royal Society of Chemistry)
hydrogel thin film. The presence of ▬SH functionalities on hydrogel film is also suitable for use as an efficient filtration
the CDs surface was superseded by SO3Na after oxidizing. membrane for removal of the above-noted heavy metal ions.
Then the hydrogel was formed by mixing the oxidized CDs Especially, the removal of the quintet of heavy-metal ions of
and CS solution (dissolved in a 3:2 mixture of acetic acid and the Agr/CD hydrogel was more effective than that of the only-
glycerol). This hydrogel was then spread onto glass slides and Agr hydrogel. The removal percentage of the Agr/CD hydro-
dried at 60 °C for 2 h. Typically, the films were of a thickness gel for Cr6+, Cu2+, Fe3+, Mn2+, and Pb2+ ion was found to be
of ∼ 0.07 mm and the sulphonated CDs–CS hybrid hydrogel 27.75, 54.85, 38.48, 35.41, and 83.97%, respectively.
nanocomposite film can replace toxic conventional polysty- CS has many advantages for preparation of adsorbents for
rene crosslinked with divinylbenzene generally used for ion removal of pollutants from wastewater. However, pure CS ma-
exchange because it is a green material for water-softening terials have several drawbacks, such as low mechanical
applications. strength and difficult recovery (Wang and Wang 2008).
Agarose (Agr) is one of the most promising candidates for Moreover, CS is dissolved in acidic solution, which a lot of
generation of thermal reversible hydrogels. It is a linear poly- metal ions are preferentially adsorbed. To improve the mechan-
mer that is a disaccharide of D-galactose and 3,6-anhydro-L- ical and chemical features of hydrogels synthesized from CS as
galactopyranose and is extracted from seaweeds well as to enhance its stability under acidic conditions, several
(Golmohamadi et al. 2012). With combination of Agr, CS, cross-linking agents (ECH, glutaraldehyde, and others) are
and CDs, an Agr/CD hydrogel film as a solid sensing platform combined with CS in the hydrogel-preparation process. Using
was introduced for detection and adsorption of heavy metal glyoxal (an organic compound with the chemical formula
(Gogoi et al. 2015). The fabrication of the solid-sensing plat- OCHCHO) as a crosslinked agent, Mirabedini and co-
form was illustrated in Fig. 9. The generation of the platform is workers formulated a novel magnetic hydrogel via combina-
mainly based on a simple electrostatic interaction between the tion of CS and magnetic nanoparticles (Fe3O4) (Mirabedini et
OH− groups present in agarose and the NH3+ group present in al. 2017). The outstanding properties of this hydrogel are its
the CDs. This hydrogel can detect many different metal ions, easy reusability and high Cr6+ ion removal rate (80–90%) in
specifically Cr6+, Cu2+, Fe3+, Pb2+, and Mn2+. Besides, the water solution with a maximum adsorption capacity of

Fig. 9 Schematic illustration of preparation of Agarose/CD (Agr/CD) hydrogel film and its application for removal of heavy metal ions (reprinted
(adapted) with permission from Gogoi et al. 2015. Copyright (2017) American Chemical Society)
27.25 mg g−1. Moreover, it can be recycled for at least three nanosheets consisting of carboxyl and hydroxyl groups are linked
adsorption cycles. But most especially, it can be easily desorbed into the surface of the cellulose hydrogel, while the gel structure
by 0.1-M HCl solution without dissolving CS in the hydrogel. and its nanoporous property are maintained. Due to the linking
This means that the structure of CS can be significantly en- with GO, the GO/cellulose hydrogel films possess good com-
hanced by strong cross-linking with glyoxal. pressive strength. Increasing the GO/cellulose ratio, furthermore,
In recent decades, many studies have begun considering significantly improved the adsorption capacity for Cu2+ ions in
the effective and economic aspect of heavy-metal ion removal. aqueous solution. The GO/cellulose hydrogel showed a high
The biosorption method, a common approach, uses the syn- adsorption capacity, compared with the pure cellulose hydrogels.
thesis of raw materials, such as cellulose, starch, or CS for The GO/cellulose hydrogel also showed other distinguishing fea-
metal ion adsorption; they are abundant, low-cost, biodegrad- tures, such as high-efficiency regeneration and high adsorption
able, and environmentally friendly (Zhou et al. 2012). capacities for other metal ions (Zn2+, Fe3+, and Pb2+).
Cellulose, abundant natural polymer with excellent bio- Starch (St) is a raw material that is abundant, easy to pro-
compatibility properties, is one of the most commonly duce, recoverable, and naturally biodegradable. Many pub-
employed adsorption materials in wastewater treatment. lished studies have used chemically modified starch via vinyl
However, it still has not reached its potential applications in graft copolymerization to enhance the properties of starch,
many areas because it is difficult to process in common solu- expand the range of its application (Khalil et al. 1993;
tions (Zhou et al. 2004). Several efficient solvents have been Mostafa and El-Sanabary 2003), and provide for the biode-
studied and applied for the development of the production of gradability and biocompatibility of corresponding hydrogels.
cellulose-based adsorbents such as lithium chloride/N,N- Combining starch with sodium humates in a polymer hydro-
dimethylacetamide (Zhou et al. 2004), N-methylmorpholine- gel made possible a series of starch-g-poly(acrylic acid)/sodi-
N-oxide (Cai et al. 2004), and ionic liquid (Zhu et al. 2006). um humate (St-g-PAA/SH) hydrogels that were tested for their
By using phosphoric acid as an efficient solvent for cellulose, Cu2+ ion adsorption capacity in aqueous solution (Zheng et al.
several recent studies successfully developed a potential hy- 2010). This hydrogel displayed an excellent ability in
drogel, cellulose-graft-acrylic acid (C-g-AA) hydrogel, adsorbing Cu2+ within a wide pH range in an acidic environ-
through the free-radical polymerization method (Zhou et al. ment (2.7–5.0). Moreover, the most remarkable point respect-
2011; Zhou et al. 2012). This type of hydrogel showed out- ing the hydrogel was that it could be regenerated by using
standing adsorption behavior for both dyes MB and metal ions NaOH solution as the regenerating agent, and it was found
(Cd2+, Pb2+, and Ni2+) in aqueous solutions. In case of that the regeneration ability depends on the ratio of sodium
adsorbing metal ions, the adsorption capacity of C-g-AA hy- humates to hydrogel.
drogel depends on the pH of adsorbent solution, the most
effective value being reached at pH 5.0. Particles entrapped in hydrogel films for dye removal
By combining cellulose and GO, a simple and novel GO/
cellulose hydrogel as a potential material was introduced for ad- For removal of dyes from aqueous solutions, various tech-
sorption of metal ions (Chen et al. 2016). In this method, GO niques have been investigated and developed, among which

adsorption is a widely used process within the field of ad- its hydrophilicity, porosity, and mechanical strength, PAN is a
vanced wastewater treatment. Particularly, nanoscale mate- potential material for hydrogel preparation in the water treat-
rials, such as hydrogel films, are typical adsorbents offering ment field (Sebesta et al. 1995). For improved stability and
great utility in dye removal (Wang et al. 2015; Zhang et al. swelling ratio, Fahad S. Al-Mubaddel’s group fabricated a
2011; Zhang et al. 2012b). For hydrogel films, the properties novel hydrogel in two steps for adsorption of rhodamine B
of high flexibility and porosity along with the ability to inter- in aqueous solution (Al-Mubaddel et al. 2015). Firstly, CS was
act with a number of different nanoscale adsorbents are par- interacted with PAN to form CS/PAN blend films. Then, the
ticularly important in the purification field (Zhang et al. 2016). CS in these films was cross-linked with ECH to make the
Compared with synthetic polymers, microorganisms pos- hydrogel films. PAN was found to significantly enhance the
sess many more advantages, among which are maintainable, stability of the fabricated hydrogel film. For instance, with
friendly and unvarying scaffolds with biomacromolecules more than 50% PAN content, the stability reached a good
(Moradi et al. 2016) (Zhou et al. 2016; Zhu et al. 2016). degree, while it sharply decreased with less than 50% PAN
Filamentous fungus, a member of microorganism family, has content. As for the rhodamine B adsorption behavior, the hy-
a large aspect ratio and remarkable chemical characteristics, drogel film’s adsorption ratio rapidly increased during the ini-
for example, high flexibility and ductility. These properties tial time (~ 200 min), but in the equilibrium state, after ~
can make their efficient formation more stable in macroscopic 240 min, the adsorption and desorption of the dyes attained
monoliths (e.g., a porous membrane) (Chai et al. 2015; Wang a balance.
et al. 2015; Zhu et al. 2016). Therefore, fungus hyphae have
been trialed as great reinforcement agents with friendly, low-
cost properties for improved mechanical stability of formed Particles entrapped hydrogel
macroscopic structures by interaction with graphene. Based nanocomposites for adsorption
on interaction between the GO and fungus hyphae at a tem- of contaminants
perature of 130 °C, a porous and flexible hydrogel film was
synthesized successfully and the primary mechanism for in- Proteins are large biomolecules or macromolecules, and they
teraction between the fungus hyphae and GO is based on the are broadly distributed in nature. Proteins can be synthesized
reduction of GO by the biomacromolecules on the cell of the in nature from two main sources, animals and plants. For
microorganism (Zhang et al. 2016). Notably, during this inter- instance, proteins derived from animals are collagen, keratin,
action process, nanoscale building blocks can be effectively and gelatin and proteins derived from plants are soya.
loaded into the film by addition of a nanoparticle. The film- Basically, proteins are chain polymers of high molecular
loading nanoparticles could be assembled in an adsorption weight that are not soluble or only very slightly soluble in
setup to eliminate dyes from aqueous solution, which is useful water. There are two ways to solubilize proteins in water:
for nanoparticles in water-purification applications. In addi- alkaline and enzymatic hydrolysis (Pourjavadi et al. 2006).
tion, the hydrogel film is an excellent reusable and recycled Proteins have the ability to bind thoroughly with heavy-
material that could still maintain a high removal proportion metal because they possess a number of electric arrays of
after ten adsorption-desorption cycles. chemical functionality such as ▬COOH, ▬NH, ▬SH,
Hydrogels based on PAM, polyacrylonitrile (PAN), ▬OH, and imidazole groups. Therefore, it is expected that
methacrylic acid, CS, polyvinylpirrolidone (PVP), and their proteins will enhance the adsorption capacity of hydrogel
derivatives have been shown to form complexes with dyes (Hwang and Damodaran 1997). However, based on our search
(Jeon et al. 2008; Reis et al. 2012). These types of hydrogels data, up to now there has been little research relating to the
usually have been used as adsorbents in water treatment ow- preparation of protein-based hydrogels for removal of heavy-
ing to advantages including high swelling and wettability, metal ions. In 1997, soy protein, which is a sustainable, low
easy loading, creation of chelated complex, and a capacity cost, and abundant plant protein, was applied in preparing a
for semi-continuous operation (Oladipo and Gazi 2015; soy-protein-based hydrogel by crosslinking an ethylenedi-
Wang et al. 2012). With high swelling and wetting, adsorption aminetetraacetic acid dianhydride (EDTAD)-modified soy
of the target molecules or ions of the hydrogel can be en- protein isolate for adsorption of divalent calcium, zinc, mer-
hanced due to the production of more precise surface area cury, and lead ions from aqueous solution (Hwang and
and contact with additional functional groups for adsorption Damodaran 1997). The equilibrium adsorption capacities of
(Wang et al. 2012). In order to develop these approaches, a the hydrogel for these metal ions were 0.70, 0.65, 0.95, and
number of studies have combined natural CS and synthetic 0.70 mmol per gram of dry hydrogel, respectively. In 2017,
PAN. When combined with CS, PAN has a role as an active soy protein was also introduced in new nanocomposite
component of an ion exchanger. Because of its possessing a hydrogels synthesized by the crosslinking method using soy
nitrile group, PAN is able to form hydrogel bonds and com- protein isolate as a matrix and polyethyleneimine (PEI) as a
plexes with other materials of positive charge. Besides, due to functional component to replace EDTAD (Liu et al. 2017).

These nanocomposite hydrogels were effectively demonstrated hydrogel nanocomposite was demonstrated to be suitable for use
for adsorption of Cu2+ ions from aqueous solution, the results as a low-cost, environmentally friendly adsorbent for copper ad-
indicating a Cu2+ adsorption capacity that reached 136.2- sorption and recovery, because the Cu2+ ions adsorbed in the
mg Cu2+/g hydrogel. In addition, the nanocomposite hydrogel hydrogel can be eluted and the hydrogel nanocomposite recov-
showed an excellent selectivity for the removal of Cu2+ ions co- ered by using nitric acid solution. The adsorption capacity of the
existing with competitive heavy-metal ions, including Zn2+, hydrogel, moreover, was maintained at over 90%.
Cd2+, and Pb2+. The two above-noted studies suggest that such Itaconic acid (IA) is a water-soluble monomer having two
a soy protein isolate-based hydrogel is a good candidate for carboxylic acid groups. Due to their double functionality, IA-
selective adsorption and recycling of metal ions in the waste- based polymers are regarded as functional polymers and po-
water treatment industry. Other protein, cottonseed protein, was tential materials for wastewater treatment. Besides, in recent
also used in synthesis process of a cottonseed protein-poly(- years, researches using 2-hydroxyethyl acrylate (HEA) in the
acrylic acid) hydrogel nanocomposite for removal of copper preparation of hydrogels have been reported and, indeed,
and lead ions in aqueous solution. The hydrogels showed high HEA-based hydrogels have been shown to be promising ad-
adsorption capacities that were influenced by various changes sorbents for removal of heavy-metal ions from aqueous solu-
such as the content of cottonseed protein, the initial concentrations (Antić et al. 2015; Li et al. 2013; Wu and Li 2013). By
tion of metal ions, and pH. Moreover, the hydrogel could be combination of IA with 2-hydroxyethyl acrylate, pH-sensitive
easily regenerated in HCl solution and reused while maintain- hydrogels were introduced for use as adsorbents to remove
ing over 90 and 57% of its original adsorption capacity for Cu2+ Pb2+ from aqueous solution (Antić et al. 2016). Because both
and Pb2+ ions, respectively, after four cycles of reuse (Zhang et HEA and IA are materials having a good adsorption capacity,
al. 2012a). Gelatin, another protein derived from collagen, is a HEA/IA hydrogels relative to corresponding homopolymers
natural protein present in the tendons, ligaments, and tissues of also have shown high adsorption capacities for Pb2+ ions. A
mammals. Gelatin has been applied to the preparation of many comparison of the adsorption capacities between the reported
hydrogels for drug delivery through crosslinking reactions with adsorbents indicated that it is the combination between IA and
monomers (Guo et al. 2015). In 2003, a gelatin hydrogel was HEA that significantly enhanced the adsorption capacity of
introduced for removal of Cu2+ and Cr6+ ions from aqueous the HEA/IA hydrogels relative to most of the previously in-
solution (Chauhan et al. 2003). The hydrogels were synthesized vestigated adsorbents. Moreover, the hydrogel nanocomposite
by crosslinking reaction of gelatin with three acrylamides could be easily regenerated, and desorption of the adsorbed
monomers (Acrylamide (AAm), 2-acrylamido-2-methyl-1- Pb2+ ions could be conducted in HNO3, HCl, and CH3COOH
propanesulfonic acid (AAmPSA), and N-iso-propylacrylamide acid solutions. After three cycles, significantly, nearly 90% of
(N-i-PAAm)) in the presence of a crosslinker (N,N-methylene the initial adsorption capacity had been maintained. IA also
bisacrylamide) at different temperatures. The structural aspects has been used in some other studies for synthesis of hydrogels,
of the formed hydrogels depend on the nature of the amine specifically in combination with alginate, a high-molecular-
group and the water uptake capacity. The hydrogels also effec- weight polysaccharide extracted from various species of
tively showed adsorption of metal ions (Fe2+, Cu2+, and Cr6+) brown algae. In 2012, sodium alginate/itaconic (NaAlg/IA)
based on the mechanism of ion exchange. hydrogels were also successfully synthesized by a free-
GO is graphite oxide monolayer having a two-dimensional radical polymerization in which an aqueous solution of 20%
structure. GO is able to be dispersed in polar solvents such as IA was mixed with 10-wt% NaAlg at room temperature
water or organic solvents because of its possession of many (Mahmoud and Mohamed 2012). This hydrogel was effec-
functional hydroxyl, epoxy, and carboxyl groups (Haubner et tively demonstrated for removal of Pb2+ ions to a maximum
al. 2010). Hyperbranched polymers are highly branched three- capacity of 1.23 mmol/L. The same NaAlg/IA-type hydrogel
dimensional polymers. They have a globular and dendritic struc- was synthesized and introduced for removal of dyes, MB
ture, which endows them with many interesting properties, such (Mahmoud et al. 2014). In MB adsorption process, parameters
as abundant groups and numerous end groups, low viscosity, and affecting the MB-adsorption capacity in wastewater including
high solubility. Owing to the end groups in their structure, a concentration of NaAlg and temperature. The presence of
hyperbranched polymers are used to synthesize, by the interac- NaAlg in the hydrogel changed the adsorption efficiency; in
tion of end groups and the hydrogel matrix, polymers or hydrogel particular, when increasing the NaAlg percentage in the hy-
materials with customizable structures (Carlmark et al. 2013). drogel, the adsorption capacity also increased. Especially, for
Through a novel cost-effective and environmentally friendly reuse of the hydrogel after MB adsorption, acid fast red dye
method, a poly(acrylic acid) (PAA) hydrogel nanocomposite (AFR) was used to examine the adsorption capacity for the
was successfully synthesized by using hyperbranched polymers NaAlg/IA hydrogel-loaded MB in a second adsorption from
and GO (Yu et al. 2015b). The PAA hydrogel showed a high aqueous solution. The results showed that after adsorbing MB,
water-adsorption ability and a high, 209 mg g−1 (at pH = 5) ad- the surfaces of the NaAlg/IA hydrogel were covered with a
sorption capacity for Cu2+ ions in water solution. In addition, the layer of canionic dye and that in the second adsorption,

anionic AFR was adsorbed on the hydrogel-loaded MB 2016). For the enhancement of thermal properties, it was demon-
through an electrostatic interaction. The AFR removal ratio strated that the use of bentonite clay can increase the thermal
of the hydrogel-loaded MB could reach 62 to 74%, depending stability of a β-cyclodextrin/bentonite clay nanocomposite hy-
on the amount of MB loaded onto the surface of the hydrogel. drogel (Heydari and Sheibani 2015). It was concluded that the
Clay shows a strong affinity for both cationic and anionic clay plays a role in the prevention of the polymer thermal degra-
dyes, whereas the adsorption capacity for basic dye is much dation. It is the presence of the clay nanolayer inside the polymer
higher than that for acidic dye due to the negative charge on the matrix that led to the improvement and the clays act as barriers to
structure of the clay (Crini 2006). Clay minerals commonly have maximizing the heat insulation and minimizing the permeability
layered structures with a large surface area and high ionic ex- of volatile degradation products to the hydrogels.
change capacity. Besides, its current market price is cheaper than A novel hydrogel nanocomposite was achieved based on
that of active carbon and some other materials (Babel and combining CS, AA, and organically modified nanosilica by 3-
Kurniawan 2003). Numerous clays including kaolinite, laponite, aminopropyl triethoxysilane (APTS) (Fig. 10) (Pourjavadi et al.
montmorillonite, attapulgite, diatomite, vermiculite, alumina, mi- 2015). The applicability of this hydrogel nanocomposite in wa-
ca, potassium humate, sodium humate, glass, smectite, vermicu- ter treatment was demonstrated for adsorption of metal ions
lite, sercite, rectorite, and sodium silicate have been added to the (Co 2+ , Cu 2+ , Pb 2+ , and Zn 2+ ) from aqueous solution.
polymeric matrix to synthesize nanocomposite hydrogel mate- According to the result, the study concluded that the nanosilica
rials (Kabiri et al. 2011; Magalhães et al. 2013). According to played an important role in the properties and adsorption capac-
Zhao group’s review (Zhao et al. 2015), clay mineral-loading ity of this hydrogel. The nanosilica might play the role of a
nanocomposite hydrogels have possessed exceptional composi- physical cross-linker. It is certain, in any case, that the presence
tion and properties. Consequently, it has attracted numerous in- of modified nanosilica significantly contributed to the enhanced
terests in the synthesis of adsorbents over the last decades. Clay- porosity of the hydrogel network. In addition, the nanosilica
mineral can be widely used to add into the hydrogel matrix to functionalized by APTS increased the porosity of the hydrogel
form novel superabsorbent nanocomposite hydrogels with high and created extensive network domains capable of permeating
absorption capacities up to several hundred times for their dried water. The hydrogel showed a high adsorption capacity that
weight. It was investigated that a successful combination between was owed to the presence of amine groups on the nanosilica
montmorillonite clay and cellulose in the design of superabsor- surface as well as the highly porous structure. Also, the effects
bent cellulose/clay nanocomposite hydrogels is illustrated (Peng of different parameters (Pb2+ concentration, adsorbent content,
et al. 2016). In preparation method, these hydrogels were formed pH value, and contact time) on the adsorption capacity of the
by crosslinking method, whose cellulose and CMC will make hydrogel were low. On the other hand, the electrostatic interac-
chemical crosslinking with ECH in the presence of clay nano- tion between the hydrogel’s carboxylate groups and the Co2+,
sheets. The authors revealed that the hydrogels exhibit very high Cu2+, Pb2+, and Zn2+ ions lead to unselectivity for removal of
equilibrium swelling ratio in distilled water and the maximum these metal ions from aqueous solution (Pourjavadi et al. 2015).
ratio can reach 1443 g/g, which indicates their superabsorbent According to Table 2’s comparison, the CS-based hydrogel
properties. Due to the superabsorbent properties, the hydrogels crosslinked with AA exhibited a much higher Cu2+ uptake than
incorporated with intercalated clays exhibited superior MB re- most of the other adsorbents under the same condition.
moval capacity. Furthermore, the characteristic properties of
hydrogels including the mechanical and thermal properties are
able to be largely affected by the content of added clays Adsorption kinetics and mechanisms
(Haraguchi et al. 2003). These properties can be significantly of adsorbates on hydrogel
enhanced when clay minerals are incorporated into the polymer
matrix (Bitinis et al. 2011) because the increasing the clay amount Adsorption kinetics
will lead to an increase in the crosslink density. In some studies of
Haraguchi’s group, for instance, a modified clay was used as the To qualitatively evaluate adsorbents, determination of their
cross-linker to synthesize poly (N-isopropylacrylamide)/clay kinetics is one of the most commonly used methods currently
(Haraguchi et al. 2002) and poly(N,N-dimethylacrylamide)/clay utilized and indeed, adsorption kinetics, are important charac-
nanocomposite hydrogels (Haraguchi et al. 2003) with higher teristics in any evaluation of adsorption efficiency (Zhao and
mechanical properties. They revealed that these hydrogels Mitomo 2008). The purpose of adsorption kinetics is to estab-
showed very high elongation at break, close to or greater than lish a period of time for adsorption of adsorbates on the
1500% and their tensile properties strongly depended on the con- hydrogels and to describe the adsorption process by means
tent of clay. The increase of modulus and strength values is pro- of a theoretical model. Generally, to express the adsorption
portional to the content of clay. In addition, clays can improve the kinetics of hydrogel, most studies have used three models,
higher toughness of hydrogels based on the formation of an in- including the (1) pseudo-first order, (2) pseudo-second order,
tercalated architecture with more cross-linking points (Peng et al. and (3) intra-particle diffusion models (Yagub et al. 2014).

Fig. 10 Synthesis route of hydrogel nanocomposite based on chitosan, acrylic acid and modified nanosilica particles (reprinted (adapted) with
permission from Pourjavadi et al. 2015. Copyright (2017) Springer)
Besides, some other models have been applied to describe the Integrating this for the boundary conditions t = 0 to t = t and
mechanism of the kinetics for the adsorption, such as Elovich qt = 0 to qt = qt, the Formula (1) may be rewritten for linear-
model (Bhattacharyya and Ray 2013; Mittal et al. 2015) and ized data plotting as the Formula (2):
Bangham model (Bhattacharyya and Ray 2013).
k1
logðqe −qt Þ ¼ logðqe Þ− t ð2Þ
(1) Pseudo-first-order model: This model describes the pro- 2:303
portion of the adsorbate adsorption with time to the con-
centration of adsorbents (Table 3). where qt and qe are the amounts of pollutants adsorbed
at time t and at equilibrium (mg g−1) and t is the con-
The pseudo-first-order model generally is represented by tact time (min) and k1 is the rate constant of pseudo-
Formula (1) (Lagergren 1898) first-order adsorption (min−1). Values of k1 were calcu-
lated from the plots of ln(qe − qt) versus t for different
dqt concentrations of pollutants and qe being determined
¼ k1 ðqe −qt Þ ð1Þ
dt from the slope and intercept of the plot.
Table 2 Comparison of metal ion

adsorption capacities of different Chitosan-based hydrogels Adsorption capacity (mg g–1) Metal ion Ref.
hydrogels (reprinted (adapted)
with permission from Pourjavadi CS-g-PAAa 161.8 Ni2+ (Zheng et al. 2011)
et al. 2015. Copyright (2017) CS/PAA-MCMb 174.0 Cu2+ (Yan et al. 2012)
Springer) CS-MCMc 108.0 Cu2+ (Yan et al. 2012)
CS/PAA-GLAd 120.0 Cu2+ (Ngah et al. 2002)
CS-cross-linked ECHe 62.47 Cu2+ (Ngah et al. 2002)
CS-AA nanocompositef 795.4 Cu2+ (Pourjavadi et al. 2015)
a
Chitosan grafted onto poly(acrylic acid)
b
Chitosan/poly(acrylic acid) magnetic composite microspheres
c
Chitosan-magnetic composite microsphere
d
Chitosan/poly(acrylic acid)-glutaraldehyde
e
Chitosan-cross-linked epichlorohydrin
f
Chitosan crosslinked acrylic acid

Table 3 Comparison of the

maximum adsorption capacity Adsorbents Adsorbates qmax (mg/g) References
qmax (mg/g) of hydrogels and
other adsorbents I. Dyes
Modified montmorillonite Methylene blue 322.6 (Wibulswas 2004)
Bentonite Methylene blue 175 (Hong et al. 2009)
Clay Methylene blue 58.2 (Gurses et al. 2006)
Kaolin Congo red 1.98 (Vimonses et al. 2009)
Fly ash Methylene blue 7.99 (Weng and Pan 2006)
Active carbon Methylene blue 580 (Qada et al. 2006)
Congo red 300 (Purkait et al. 2007)
Cellulose-clay hydrogel Methylene blue 782.9 (Peng et al. 2016)
CTAB-chitosan hydrogel Congo red 352.5 (Chatterjee et al. 2009)
Lignosulfonate-g-acrylic acid hydrogel Methylene blue 2013 (Yu et al. 2016)
II. Heavy metal ion
Modified montmorillonite Cu2+ 2.76 (Akpomie and Dawodu 2016)
Bentonite Ni2+ 200 (Akpomie and Dawodu 2015)
Active carbon Cu2+ 43.47 (Demiral and Güngor 2016)
Ni2+ 62.5 (Kadirvelu et al. 2001)
Pb2+ 279.72 (Gercel and Gercel 2007)
CM cellulose/ chitosan hyxdrogel Cu2+ 169.4 (Zhao and Mitomo 2008)
CS-AA-APTS hydrogel Cu2+ 795 (Pourjavadi et al. 2015)
Cellulose-graft-acrylic acid hydrogel Cd2+ 562 (Zhou et al. 2012)
(C-g-AA) Pb2+ 825
Ni2+ 380.1
(2) Pseudo-second-order model (Ho and McKay 1999). particle diffusion, and I is the intercept (mg/g). To determine the
rate constants, qt is plotted versus t0.5 to yield a linear relationship,
According to Ho and McKay’s theory, the adsorption ca- and Kid is calculated from the slope of the plot.
pacity of hydrogels depends on the number of active sites (4) Bangham kinetic model:
attached on the hydrogels. The pseudo-second-order model The linear form of this model is given by the following
is expressed as Formula (3): Formula (6) (Bhattacharyya and Ray 2013):
1
dqt lnqt ¼ ln k t þ lnt ð6Þ
¼ k 2 ðqe −qt Þ2 ð3Þ m
dt 1
where m measures the intensity of sorption and kt is the rate
Integrating this for the boundary conditions t = 0 to t = t and constant for sorption. The values of rate constant kt and m can
qt = 0 to qt = qt gives: be obtained by plot versus of lnqt against lnt.
1 1
¼ þ k 2t ð4Þ (5) Elovich kinetic model:
qe −qt qe
where k2 (g/(mg min)) is the second-order rate constant of adsorp- The assumption of various activation energies and hetero-
tion. The constants can be determined by the plot of t/qt versus t. geneous active sites of hydrogels for adsorption of organics
can be represented by Elovich model as the following formula
(2) Intra-particle diffusion model: (Chien and Clayton 1980):
1 1
According to Weber and Morris, the adsorption capacity of an qt ¼ lnðα β Þ þ lnt ð7Þ
adsorbent (qt) will be proportional to t0.5 in adsorption process β β
and can be described as Formula (5) (Weber and Morris 1963): where α and β are the initial rate of adsorption (mg g−1 min−1)
qt ¼ K id t 0:5 þ I ð5Þ and desorption rate constant, respectively. The values of α and
β are determined through plot versus of qt against lnt.
where qt is the adsorption capacity at time t, t0.5 is the half-life As suitable for the adsorption kinetics of an adsorbent,
time in seconds, Kid (mg g−1 min0.5) is the rate constant of intra- most of the literatures have based their models on the liner

regression correlation coefficient (R2). A higher value of R2 The separation factor, RL (also known as the equilibrium
will indicate a better fitness of model. According to the sum- parameter) is a constant that can be calculated as Formula (9):
marized data provided in Table 4, the pseudo-first-order and
1
pseudo-second-order model are the suitable models for de- RL ¼ ð9Þ
scribing the kinetic adsorption data. It is notable that, with 1 þ bC0
intra-particle diffusion, Elovich, and Bangham kinetic models, where C0 is the initial concentration of adsorbates in
only linear regression may carry out since non-linear regres- solution (mg/L).
sion will give the same statistical parameters, while with The value of RL determines the shape and feasibility of
pseudo-first-order and pseudo-second-order models, both lin- isotherms and indicates if the Langmuir process is unfavorable
ear and nonlinear regression can carry out with experimental (RL > 1), linear (RL = 1), favorable (0 < RL < 1) or irreversible
adsorption data (Bhattacharyya and Ray 2013). (RL = 0) (Bhattacharyya and Ray 2013).
(2) Freundlich adsorption isotherm

Adsorption isotherm
Contrary to Langmuir model, the Freundlich isotherm
The feasibility of the adsorption process and interaction be-
model can be applied to assume adsorption isotherm in case
tween the adsorbents and adsorbates at a particular tempera-
of heterogeneous surface as well as multilayer adsorption
ture might be evaluated and described using an adsorption
(Jana et al. 2017). The linear form of this isotherm is given
isotherm. In addition, it is able to predict the distribution of
by the following equation (Freundlich 1906).
adsorbate molecules between the liquid and solid phase at
equilibrium (Mittal et al. 2015). There are several isotherm 1
logqe ¼ logK F þ logC e ð10Þ
models that can be used to describe adsorption isotherm such n
as (i) two parameter isotherm including Langmuir, Freundlich,
where KF is the Freundlich isotherm constants and n is the
Dubinin–Radushkevich, Temkin, Flory–Huggins, and Hill
adsorption intensity.
isotherm models and (ii) three parameter isotherm like
Redlich–Peterson, Sips, Toth, Koble, Khan, and Radke–
Prausnitz isotherm models (Foo and Hameed 2010; Jana et Three parameter isotherm models
al. 2017; Mittal et al. 2015).
(1) Sips isotherm model
Two parameter isotherm models Sips isotherm is a combination of the Langmuir and
Freundlich models deduced for predicting the heterogeneous
Langmuir and Freundlich models are the most two parameter adsorption systems, and it is expressed as (Sips 1948):
isotherms widely used because they have usually shown the
qmax K eq C ne
best fitness to the experimental data than the other isotherms. qe ¼ ð11Þ
1 þ K eq C ne
(1) Langmuir adsorption isotherm model where Keq (L/mg) is the equilibrium constant of the
Sips equation, and qmax (mg/g) is the maximum adsorp-
The Langmuir isotherm model is built based on the as- tion capacity. The heterogeneity factor (n) of the Sips
sumptions of monolayer adsorption. According to the pre- isotherm model represents the nature of the adsorption
sumption of this model, the adsorbent surface is homogeneous process. It is interesting that Sips will reduce to
and has only one type of binding site. The linear form of the Freundlich isotherm at low adsorbate concentrations,
Langmuir isotherm can be represented as formula (8) while it predicts a monolayer adsorption capacity char-
(Langmuir 1916): acteristic of the Langmuir isotherm at high concentra-
Ce 1 Ce tions (Foo and Hameed 2010).
¼ þ ð8Þ
qe qm b q m
(2) Redlich–Peterson isotherm model
where Ce (mg/L) and qe (mg/g) are the adsorbate con-
centration and the amount of adsorbates adsorbed at the The Redlich–Peterson isotherm (Redlich and Peterson
equilibrium, respectively. b is the Langmuir constant (L/ 1959) is a hybrid isotherm featuring both Langmuir and
mg) and qm the maximum adsorption capacity of the Freundlich isotherms. This model assumes that mono-
adsorbent (mg/g) and the values of qm and b can be layer formation and multi-site adsorption can occur
obtained through the plot of Ce/qe vs Ce. simultaneously.

Table 4 Summary of hydrogel adsorption kinetics and mechanisms of pollutants for various pollutants
24586
Hydrogel Pollutant Adsorption te pH Initial Isotherm model Kinetic model Adsorption mechanism References
capacity pollutant
(qmax) concentration
1. Hydrogel beads
Carboxylmethyl cellulose Pb2+, 5.15 mmol/g – 7.0 15 mmol/L Langmuir isotherm – Coordination bonds of (Yang et al. 2010)
Ni2+ 4.06 mmol/g metal ions with oxygen
Cu2+ 6.49 mmol/g atoms in carboxyl groups.
CM cellulose/CS Cu2+ 169.4 mg g−1 2 h 5.0 100 ppm Langmuir isotherm Intra-particle diffusion Electrostatic interaction, (Zhao and Mitomo 2008)
model chelation
PVA-CS Pb2+ 2 mg g−1 1h 2.0–7.6 30 mg/L – – Ion exchange, electrostatic (Jin and Bai 2002)
interaction
Glutamic-chitosan (GCS) Ni2+ 103.4 mg g−1 5 h 5.0 200 mg/L Langmuir isotherm; Pseudo-second order electrostatic interaction (Abdelwahab et al. 2016)
Cu2+ 83.33 mg g−1 Freundlich isotherm
CS/PAM Cd2+, 86 mg g−1 170 min 6.0 400 mg/L Langmuir isotherm; Pseudo-second order Ion-exchange interaction (Ma et al. 2017)
Cu2+, 99.4 mg g−1 5.0 400 mg/L
Pb2+ 138.4 mg g−1 5.0 200 mg/L
PAAM Cr+6 – 5h 10.3 – Langmuir isotherm; Pseudo-first-order Hydrogen bonding (Pal and Banat 2015)
Freundlich model
isotherm
PDopa-PAH PEC Pb2+ 1625 mg g−1 30 min 6.0 20 mM Langmuir isotherm; Pseudo-second-order; Metal ions chelated by (Yu et al. 2015a).
Cd2+ 657 mg g−1 30 min Pseudo-first-order catechol group and
Cu2+ 388 mg g−1 90 min carboxyl and/or amino
groups
Pectin hydrogel Cu2+ 120 mg g−1 8h 5.5 – – – Electrostatic interaction (Guilherme et al. 2010)
Pb2+ 130 mg g−1
ATP/FA/PAA Pb2+ 38 mg g−1 24 h 5.0 100 mg/L Langmuir isotherms Pseudo-second-order - Chelating interaction of (Jiang and Liu 2014)
Intra-particle Pb2+ ions and carboxyl
diffusion; group;
- Electrostatic interaction
PAA-AAM/amylose Crystal 28.60 mg g−1 3 days 7.4–8 50 mg/L Langmuir isotherms Pseudo-second-order; Combination of electrostatic (Li 2010)
Violet and hydrophobic interaction
GO/PEI hydrogels MB 334.4 mg g−1 200 min – 10 mg/L – Pseudo-second-order Electrostatic interactions; (Guo et al. 2015)
RhB 131.9 mg g−1 4 mg/L hydrogen bonding
HNTs/CS MB 75.37 mg g−1 40 min – 160 mg/L Langmuir isotherm; Pseudo-second-order External diffusion and (Peng et al. 2015)
MG 276.9 mg g−1 7 days 750 mg/L Freundlich isotherms Intra-particle diffusion pore diffusion
CTAB-CS Congo red 352.5 mg g−1 3.5 h 4.0–9.0 500 mg/L Langmuir and Sips Pseudo-second-order; Electrostatic interaction (Chatterjee et al. 2009)
isotherm Intra-particle diffusion
LS-g-AA MB 2013 mg g−1 200 min 3.0–8.0 2400 mg/L Freundlich isotherm; Pseudo-second-order; Electrostatic interaction (Yu et al. 2016)

Amphoteric hydrogels AR9 866 mg g−1 800 min < 3 2000 mg/L Langmuir isotherm; Pseudo-second-order; Electrostatic interaction (Kono 2015)
AR13 911 mg g−1
AB92 816 mg g−1
NaAlg/PVP blend RR 116.8 mg g−1 600 min 1.2–5.0 300 mg/L Langmuir isotherm; Pseudo-second-order; Electrostatic interaction (Inal and
CBR 73.3 mg g−1 250 mg/L Erduran 2015).
RBB 55.3 mg g−1 250 mg/L
60
PVA-P (AA-co-AM) Co 184 mg g−1 3h 4.0–6.0 250 mg/L Freundlich Pseudo-second-order Multi-molecular layer (Wang et al. 2016)
Environ Sci Pollut Res (2018) 25:24569–24599
332 mg g−1 400 mg/L isotherms chemisorption

Table 4 (continued)
Hydrogel Pollutant Adsorption te pH Initial Isotherm model Kinetic model Adsorption mechanism References
capacity pollutant
(qmax) concentration
137
KNiHCF Cs 64 mg g−1 60 min 1–12 50 mg/L Langmuir isotherms; Pseudo-second-order Ion exchange (Dwivedi et al. 2015)
Freundlich isotherm
137
KZnHCF Cs – 2h 3–10 5–20 mg/L – – Ion exchange (Pathak et al. 2016)
Fixing of Cs ion into porous
framework of hydrogel.
2. Hydrogel film
CS-MUA-SO3Na-CD Ca2+ 150 mg g−1 – – 5 × 10−4 M – – Ion exchange (Baruah et al. 2016)
Mg2+ 218 mg g−1
Environ Sci Pollut Res (2018) 25:24569–24599
Agr/CD Cr6+, Cu2+, – 12 h – 10 mg/L – – Chitosan in hydrogel films (Gogoi et al. 2015)
Fe3+, Pb2+, forms chelates with
Mn2+ heavy metals
CS-Fe3O4-Glyoxal Cr6+ 27.5 mg g−1 110 min 4.0 30 mg/L Langmuir isotherm Pseudo-first-order Ion exchange and (Mirabedini
Pseudo-second-order electrostatic interactions et al. 2017)
Cellulose-C-g-AA Cd2+, 562 mg g−1 6 h 5.0 2000 mg/L Langmuir isotherm Pseudo-second-order Ion exchange and chelation (Zhou et al. 2012),
Pb2+ 825 mg g−1
Ni2+ 380.1 mg g−1
GO/cellulose Cu2+ 94.34 mg g−1 150 min 1.0–7.5 200 mg/L Langmuir isotherm Pseudo-second-order; Ion exchange between (Chen et al. 2016)
COO_ group and Cu2+
ion
St-g-PAA/SH Cu2+ 2.83 mmol/g 60 min 2.7–5.0 0.02 mol/L Langmuir isotherm Pseudo-second-order; Ion-exchange and chelation (Zheng et al. 2010)
between Cu2+ ion and
COO− group of hydrogel
GO/fungus hyphae Orange G 387 mg g−1 – 2.0 500 mg/L – – Chelation and, electrostatic (Zhang et al. 2016)
interaction
CS/PAN RB 21.90 mg g−1 240 min 7.0 100 mg/L Langmuir isotherm Pseudo-second-order; Hydrogen bonding (Al-Mubaddel
et al. 2015)
Soy protein/ EDTAD Zn2+ 0.65 mmol/g 48 h 4.0–6.0 0.3 mM – – Electrostatic interactions (Hwang and
Pb2+ 0.70 mmol/g 0.2 mM Damodaran 1997)
Hg2+ 0.95 mmol/g 0.2 mM
3. Hydrogel nanocomposites
Soy protein/PEI Cu2+ 136.2 mg g−1 24 h 4.0–5.5 250 ppm Langmuir isotherm; Pseudo-second-order Ion exchange and (Liu et al. 2017)
Freundlich model Pseudo-first order electrostatic interactions
kinetic
Cottonseed Cu2+ 1.45 mmol/g 180 min 4.0–5.5 2.0 mmol/L Langmuir isotherm Pseudo-second-order; Electrostatic interactions (Zhang et al. 2012a)
protein-PAA Pb2+ 1.44 mmol/g Freundlich model

PAA/GO Cu2+ 209 mg g−1 24 h 5.0 100 mg/L – – Electrostatic interaction; ion (Yu et al. 2015b)
exchange; forming of
complexation interaction
P(HEA/2IA) Pb2+ 392.2 mg g−1 48 h 3.0–6.0 520 mg/L Langmuir; Pseudo-second-order; Electrostatic interaction (Antić et al. 2016)
P(HEA/10IA) 409.8 mg g−1 Freundlich;
Redlich–Peterson.
NaAlg/IA Pb2+ 6.9 mmol/g 24 h 5.0 1.2 mmol/L Freundlich model
24587
Mahmoud et al. 2014)

The non-linear and linear forms of the Redlich–Peterson
(Pourjavadi et al. 2015)

isotherm are described as Formulas (12) and (13), respectively
Mohamed 2012;
(Peng et al. 2016)

(Paulino et al. 2011).
(Mahmoud and
References
AC e
qe ¼ ð12Þ
1 þ BC ge

Ce
electrostatic intercation ln A −1 ¼ g lnC e þ lnB ð13Þ
qe
reacted with functional
Pseudo-second-order Hydrophobic interaction;
Pseudo-second-order Electrostatic interactions

Pseudo-second-order; Ion exchange: Pb2+ ions
Adsorption mechanism
groups of hydrogel;
where A, g, and B are the Redlich–Peterson constants, Ce (mg/

L) is the adsorbate concentration remaining in the solution,
and qe (mg/g) is the adsorption capacity of the hydrogels at
equilibrium.
This model can be applied both homogeneous or heteroge-
neous systems due to its versatility. In the limitation, it only
Intra-particle diffusion
Pseudo-first-order;
approaches Freundlich isotherm model at high concentration

and Langmuir isotherm model at low concentration (Foo and
Kinetic model
Hameed 2010).
The applicability of isotherm models to the removal of
contaminants by hydrogels was evaluated in terms of regres-
sion coefficient (R2) and non-linear x2. In the good fitness, R2
will be close to unity; x2 will be very low (Bhattacharyya and
Langmuir isotherm
Langmuir isotherm
Ray 2013).
Isotherm model
Adsorption mechanism
One of the biggest challenges to the development of new ad-

concentration
sorbents for adsorption of pollutants in wastewater is to clearly

200 mg/L
120 min 3.5–5.5 400 ppm

80 mg/L
pollutant
define and identify the adsorption mechanism. Especially, it is

Initial
really important to represent the interaction between adsorbates

and adsorbents at the interface. To determine the adsorption
mechanism, most studies have used two isotherm models,
1–11
8.0
pH
namely the Langmuir and Freundlich models, which are

expressed the above section (Jiang and Liu 2014). Moreover,
in order to better understand the mechanism of pollutant sorp-
782.9 mg g−1 40 h
5h
tion on hydrogels, a number of studies have used FTIR, XPS

te
scans, and X-ray diffraction to examine the functional groups

9.16 mg g−1
795 mg g−1
Adsorption
and structure of the adsorbent before and after adsorption of

capacity
pollutants. XPS is a commonly used technique to realize the

(qmax)
mechanism of heavy-metal adsorption on hydrogels, as it can

indicate the change of the distribution of the electrons around
the corresponding atoms caused by the interaction between
Pollutant
metal ion and functional groups (Deng et al. 2003).

Cu2+
MB
MB
According to Table 4’s summarized data, electrostatic in-

teractions have been regarded the main mechanisms in the
adsorption of pollutants by hydrogels. The functional groups
in unique particles or monomers of hydrogels, such as the
Table 4 (continued)
▬COOH group in AA (Jiang and Liu 2014; Li 2010;

CS-AA-APTS
Cellulose-clay
Pourjavadi et al. 2015; Yu et al. 2015b), GO (Guo et al.

2015), IA (Antić et al. 2016), cellulose (Peng et al. 2016)
Hydrogel
and cellulose ampholytes (Kono 2015), the amine group in

CS (Jin and Bai 2002, Mirabedini et al. 2017), the imine group

in poly(m-phenylenediamine) (Zhang et al. 2016), the tertiary can be achieved by a cation-exchange Reaction (1)
amine group in PVP (Inal and Erduran 2015), and PEI (Guo et (Vrtoch et al. 2011).
al. 2015), will interact with pollutants because of their charge
oppositeness. In the adsorption mechanism by electrostatic K2−X NiIIX=2 NiII FeII ðCNÞ6
interaction, the functional groups on the surface of hydrogels
þ Csþ ↔K1−X CsNiIIX=2 NiII FeII ðCNÞ6 þ Kþ ð1Þ
will protonate to form anions attracting cationic pollutants
(metal ions, cationic dyes) or deprotonate to form cations Baruah’s group specifically explained, as in Fig. 12, the ion
interacting with anionic pollutants. For cationic pollutants, exchange mechanism in the adsorption process of Ca2+ and
such as metal ions and cationic dyes, most studies in the liter- Mg2+ from solution on CS-MUA-SO3Na-CDs hydrogel film
ature have used the ▬COOH group as a functional group for (Baruah et al. 2016). The scheme indicates that the electrostat-
adsorption of pollutants through electrostatic interactions. The ic interaction between the positively charged amine groups of
▬COOH group deprotonate as negatively charged ▬COO− CS and the negatively charged sulphonate groups on the sur-
groups under the optimum condition of pH and the negatively face of the CDs is maintained under acidic condition. In the
charged functional groups attract the positively charged ions. left-hand scheme, when hydrogel films are dipped in sodium
In order to increase the adsorption efficiency and prevent the hydroxide solution, the sulphonate groups of the CDs interact
hydrolysis of cationic pollutants, the selection of the optimum with Na+ ions to form ion-pairs (Na+ SO3−) and thereby, the
pH, where hydrogels will reach the highest adsorption capac- Na+ ions adhere to the CDs embedded in the hydrogel film. In
ity, is very important (Jiang and Liu 2014). Generally, the pH the right-hand scheme, because of the presence of M2+ (Ca2+/
value commonly selected for adsorption of metal ions and Mg2+) metal ions in the aqueous solution, the M2+ ions are
cationic dyes will be higher than the pKa of unique particles able to replace Na+ ions in the hydrogel film through ion
or monomers containing ▬COOH groups (Chatterjee et al. exchange interactions. In this way, Na+ ions from the hydrogel
2009, Li 2010) and that value commonly is neutral or basic. film are released into the solution and M2+ ions in the solution
On the other hand, in the case of anionic pollutants, such as are adsorbed into the hydrogel film.
anionic dyes (Congo red (CR), AR9, AR13, and AB92), ad- Other studies have demonstrated that the adsorption of pollut-
sorption usually occurs under the acidic condition. For exam- ants by hydrogels also can take place by several other mecha-
ple, the tertiary amine groups of PVP molecules in the hydro- nisms: hydrogen bonding (Al-Mubaddel et al. 2015; Pal and
gel protonates and possesses a positive charge in acidic pH, to Banat 2015), coordination bonds (Yang et al. 2010), chelating
which charge dye anions of negative charge are attracted (Inal interaction (Gogoi et al. 2015; Yu et al. 2015a), or a combination
and Erduran 2015). Especially, in acidic solution, a metal cat- of interactions, such as ion exchange/electrostatic interaction (Jin
ion, Cr+6, also can be adsorbed on the surface of hydrogel, and Bai 2002; Liu et al. 2017; Mirabedini et al. 2017; Yu et al.
because it exists as HCrO4− with a pH < 4. The electrostatic 2015b), chelating/electrostatic interaction (Zhang et al. 2016),
interactions in the adsorption of HCrO4− by Fe3O4 NPs/CS/ ion-exchange/chelating interaction (Zheng et al. 2010; Zhou et
glyoxal hydrogel film are illustrated in Fig. 11. Under acidic al. 2012), electrostatic interaction/chelation (Jiang and Liu 2014;
condition, the amino groups (▬NH2) of CS protonated to Zhang et al. 2016; Zhao and Mitomo 2008), or electrostatic/
form the ▬NH3+ group and the surface of the hydrogel were hydrophobic interaction (Li 2010; Peng et al. 2016).
loaded with a positive charge. The adsorption of Cr+6 ion was
accomplished through the electrostatic interaction between Adsorption capacity and affecting factors
HCrO4− ions (negative charge) and the ▬NH3+ group (posi-
tive charge) (Mirabedini et al. 2017). Adsorption capacity
Beside electrostatic interaction, ion exchange is also an
important mechanism in the adsorption of pollutants from The adsorption process of hydrogels can be divided into two
aqueous solution. Several studies have indicated that some stages: first stage (or rapid stage) at initial time of adsorption
metal ions can be effectively removed from solution by the and second stage (or slow stage) at later time of adsorption
ion exchange mechanism. Charu Dwivedi et al. (2015) and (Kasgoz et al. 2003; Tu et al. 2017). During the first stage,
Pathak et al. (2016) used potassium nickel hexacyanoferrate adsorption process will be so fast due to the high concentra-
(KNiHCF) and potassium zinc hexacyanoferrate (KZnHCF) tion of ions and also the high number of free adsorptive sites,
loaded onto hydrogel beads to remove cesium ions accord- while at second stage, adsorption process will slow down and
ing to the principle of ion exchange. The adsorption of then reach an equilibrium state because of a concentration
cesium ions onto KNiHCF or KZnHCF particles takes reduction and exhaustion of the free adsorptive sites (Pour
place by the exchange between a potassium ion of and Ghaemy 2015). Adsorption capacity of a hydrogel may
KNiHCF or KZnHCF and a cesium ion (Dwivedi et al. be determined as an equilibrium adsorption capacity through
2015; Pathak et al. 2016). According to the hypothesis of mentioned adsorption isotherm models. It will be determined
L. Vrtoch and co-workers, this ion exchange mechanism when the contact time between adsorbents and adsorbates is

Fig. 11 Adsorption of Cr6+ ion on

Fe3O4 NPs/CS/glyoxal hydrogel
film by electrostatic interactions
under optimum condition (pH 4)
sufficient, and the adsorption rates and the desorption rates are presents a comparison of the maximum adsorption capacity q-
equal (Foo and Hameed 2010). There are many factors affect- max (mg/g) between hydrogel materials and other adsorbents for
ing adsorption capacity, such as contact time, pH of medium, dyes and metal ion from aqueous solution (Table 3). Among the
initial adsorbate concentration, mechanical properties, and adsorbents, hydrogels loaded unique particles show a highest
competition, and some of the factors are discussed in the next qmax value for both dyes and metal ions. Especially, in case of
section. Optimization of such conditions will define the max- lignosulfonate-g-acrylic acid hydrogels and cellulose-graft-
imum adsorption capacity of hydrogels. acrylic acid hydrogels (C-g-AA), these hydrogels have a three-
Compared with other conventional adsorbents, it is notable fold greater qmax value to active carbon, a popular material for
that hydrogels possess a remarkable adsorption capacity. It pollutant adsorption in water and wastewater. This
Fig. 12 Scheme illustration of adsorption mechanism of Ca2+, Mg2+ on Ch-SO3Na-CD hydrogel nanocomposite based on principle of ion exchange
(reprinted (adapted) with permission from Baruah et al. 2016. Copyright (2017) Royal Society of Chemistry)

demonstrates that hydrogels are one of the most potential ma- pH values (Peng et al. 2016). Besides electrostatic interaction,
terial for water/wastewater treatment in the present and future. an electro-osmotic expanding network-like ultrastructure in
the hydrogels can be produced by electrostatic repulsive
pH of solution forces among adjacent ionized groups in the hydrogel matrix,
which forces are generated by the increased levels of ionized
The pH of the adsorption media is one of the most important groups at high pH values, which further results in greater
external parameters that can affect the adsorption capacity of uptake of MB (Yu et al. 2016). By contrast, for adsorption
hydrogel (Kono 2015). Generally, the pH of a solution can of anionic dyes (congo red, AR9) into hydrogels, the process
cause the protonation or deprotonation of functional groups, is inversely proportional to the change of the solution pH:
such as carboxylic (Yang et al. 2010) or amine (Abdelwahab when the pH of the adsorption solution is increased, the ad-
et al. 2016; Zhao and Mitomo 2008) groups and the precipita- sorption capacity of hydrogels usually decreases. This mech-
tion of metal ions in hydrogels. In most of kinetic studies in anism is indicated by the change in the electrostatic interaction
adsorption of heavy metals, the adsorption capacity of between the dye anions and the hydrogel cations under differ-
hydrogels for metal ions will increase towards the basic pH ent conditions of pH (Chatterjee et al. 2009; Inal and Erduran
of the solution; in fact, there is a range of optimal pH values 2015; Kono 2015).
wherein the highest adsorption capacity can be reached. Some
of the literature has explained this phenomenon in terms of the Initial concentration of pollutant and adsorbent dosage
fact that at low pH (acidic solution), the concentration of H+ is
high and the functional groups in hydrogels are easily proton- The initial concentration of pollutants and the adsorbent dos-
ated to form an electrostatic repulsion of cationic metal ions; age are parameters that play important roles in the adsorption
therefore, there is a completion between H+ and cationic metal efficiency of hydrogels. The effects of the initial adsorbate
ions, which causes a decrease of adsorption capacity. When concentration and the adsorbent weight mainly depend on
increasing the pH of solution, the H+ concentration declines, the direct relation between the concentration of adsorbates
and consequently, deprotonation of functional groups occurs and the available sites on an adsorbent surface (Peng et al.
and electrostatic repulsion decreases. As a result, the adsorption 2015). Several studies have indicated that the increase of ad-
capacity of metal ions increases (Abdelwahab et al. 2016; Jiang sorbate concentration leads to enhancement in the adsorption
and Liu 2014; Yang et al. 2010; Zhao and Mitomo 2008). capacity represented by the value of qe (adsorption amount per
However, a further increase in pH leads to the precipitation of unit adsorbent weight), but decreases the adsorbate removal
metal hydroxide, thereby inhibiting the adsorption process. At efficiency (Abdelwahab et al. 2016; Pourjavadi et al. 2015;
pH > 7.0, precipitation will occur, and then a pH of 5.0–6.0 Yang et al. 2010; Zhou et al. 2012). However, the increase of
usually is chosen as the optimal value for the adsorption pro- adsorbent weight showed opposite results which gradually
cess of metal ions (Chen et al. 2016; Liu et al. 2017; Yu et al. increase the removal ratio of pollutants and decrease the ad-
2015b; Zhao and Mitomo 2008; Zheng et al. 2010; Zhou et al. sorption capacity (Antić et al. 2016; Chatterjee et al. 2009;
2012). For Cr6+ ions, because they exist predominantly as an- Chen et al. 2016; Dwivedi et al. 2015; Kono 2015;
ions (HCrO4−) in solution, so the maximum capacity of Cr6+ Mirabedini et al. 2017; Peng et al. 2015). These phenomena
adsorption is attained at the pH of 4.0 (Mirabedini et al. 2017). are explained in the following way: at low adsorbate concen-
In the case of the adsorption of cesium, Pathak et al. and Charu trations, the ratio of the initial number of moles of adsorbate
Dwivedi et al. introduced the types of hydrogel that can be ions to the available surface area of hydrogel is large, whereas
effectively adsorb cesium with a wide range of pH (3–10) be- at higher concentrations, the available sites of adsorption be-
cause transition metal hexacyanoferrates are able to effectively come fewer, and the percentage removal of pollutants de-
bind cesium under both acidic- and alkaline-pH conditions creases in turn (Abdelwahab et al. 2016). In the case of an
(Dwivedi et al. 2015; Pathak et al. 2016). increasing amount of hydrogel, there are two explanations of
In the dye-adsorption process, the adsorption efficiency those phenomena. First, the higher adsorbent dosage offers a
also is strongly pH-dependent, because pH can change the larger number of active sites and a larger surface area for
chemical structure of dye molecules and functional groups adsorption (Dwivedi et al. 2015); second, a decrease in the
on the surface of hydrogels (Inal and Erduran 2015). In the total surface area of the adsorbent and the correspondingly
case of cationic dyes MB or CV, the adsorption capacity will high adsorbent concentration results in particle interactions,
increase with increasing pH, which is the same phenomenon such as aggregation (Chen et al. 2016).
as is operative in the adsorption process of metal ions (Li
2010; Peng et al. 2016). Peng and co-workers explained this Existence of other ions and the selectivity of hydrogel
phenomenon based on the electrostatic interaction of positive-
ly charged MB with negatively charged hydrogels, which in- The existence of multiple ionic species in aqueous solution
teraction is increased at high pH values and decreased at low can influence the adsorption efficiency of hydrogel for each

ion species (Antić et al. 2016). Some of the pollutants in the with EDA, was not significantly selective to any metal ion,
effluent might decrease the adsorption of others through com- while the other Mannich product prepared with DETA (M10)
petition or enhance the adsorption together through cosorption possesses a distinct selective towards Cu2+ ions. This differ-
(Zheng et al. 2010). Moreover, there are always several co- ence is mainly due to the presence of the secondary amine
existing ions in wastewater in real applications (Liu et al. groups in the hydrogel matrix. Compared to M10, however,
2017); thus, it is necessary to examine the adsorption selectiv- M11 hydrogels prepared with TETA have the lower selectivity
ity performance of hydrogel under typical multi-component towards Cu2+, although TETA has higher amount of second-
conditions. According to Ma and co-workers, the presence of ary amine groups than that of DETA. This is because of the
interference ions (K+, Na+, Mg2+, and Ca2+) in solution can result of lower amine value and a decrease in swelling degree
cause competition around the same active sites of the adsor- due to crosslinking during the Mannich reaction. Contrary to
bent between these ions and the target ions (Cd2+, Cu2+, and amine group, the presence of carboxylate group in hydrogel
Pb2+), which decreases the removal efficiency of heavy-metal matrix (S2) showed a very distinct selectivity towards Pb2+.
ions. In addition, the inhibitory effect of these co-ions on the
removal of Cd2+, Cu2+, and Pb2+ ions follow the order: Ca2+ > The swelling degree of hydrogel
Mg2+ > Na+ > K+ (Ma et al. 2017). The reason for the adsorp-
tion decrease through competition in the vicinity of chelation Swelling behavior is one of the most important characteristics
sites on hydrogels or the sharing of the same binding sites was of the hydrogel as well as adsorbents and the formation of
also explained (Antić et al. 2016; Hwang and Damodaran porous structure may lead to the high swelling ratio of hydro-
1997; Zheng et al. 2010). gel. According to Flory’s theory, swelling degree of a gel
Besides, the functional groups of unique particles depends on the ionic osmotic pressure, crosslinking density
entrapped in hydrogel, such as carboxyl and amine groups and affinity of the gel for water (Flory 1953). Many studies
have shown adsorption selectivity to specific ions based on indicated that the pH value in solution has a significant impact
ion properties including radius, electronegativity, and ioniza- on the swelling degree of the hydrogel in term of increase in
tion potential. For instance, the carboxyl group in ATP/FA/ swelling ratio along with increasing the pH of medium
PAA nanocomposite hydrogel beads has a higher adsorption (Mahmoud et al. 2014; Souda and Sreejith 2014; Zhou et al.
selectivity to Pb2+ ions than to Cu2+, Cd2+, Ni2+, or Zn2+ ions, 2011). At pH < pKa of functional groups (carboxylic and
owing to their different properties (Jiang and Liu 2014). If ions amine groups), these functional groups are protonated
have a larger ionic radius, they will possess a higher affinity (▬COOH), which result in a decrease of swelling ratios due
with hydrogels than with other ions. In other words, the larger to the reduction of the electrostatic repulsion between the mo-
the ionic radius, the better the binding capacity (Antić et al. lecular chains of the hydrogel (Mahmoud et al. 2014). At
2016; Hwang and Damodaran 1997; Zhou et al. 2012). pH > pK a , these functional groups are deprotonated
Therefore, the selectivity of hydrogels for these ions also is (▬COO−) and this increases amount of ionized group, which
better than for other ions. Besides ionic radius, the selectivity causes electrostatic repulsion forces among the adjacent ion-
of hydrogels for ions can be affected by ion hydration radius ized groups of polymer matrix. This produces an expansion
as well. Dwivedi’s group demonstrated that the removal per- network-like ultrastructure of the hydrogels, which will im-
centage and adsorption capacity of KNiHCF-gel hydrogel prove the swelling ratio (Zhou et al. 2011). In the relation
beads for cesium ions had no significant change in the pres- between the swelling ratio and the adsorption capacity of
ence of interfering cations (Na+, Ca2+, and Ba2+), because the hydrogels, it is found that the higher swelling capacities means
cesium ion has a smaller hydration radius than that of the other the higher number of ionic groups in hydrogels (Flory 1953),
interfering ions (Dwivedi et al. 2015). which will enhance the adsorption capacity of hydrogels.
The selectivity of an adsorbent for a target adsorbate can be Therefore, the adsorption capacity of hydrogels will be pro-
altered by changing the types and structures of the polymeric portional to the swelling degree. It was found that because the
matrix. However, it is found that the functional groups play a high swelling capacity of the hydrogel networks is likely to
more critical role in changing the selectivity because the func- give high specific surface area and more functional groups
tional groups are where the adsorbates are adsorbed (Fritz exposed are readily approachable for adsorption, the high
2005). It was demonstrated that the metal ion adsorption se- swelling ratio can facilitate the adsorption of metal ions
lectivity of a series of PAM hydrogels prepared by Mannich (Trakulsujaritchok et al. 2011).
reaction using different amine compounds, such as Also, the swelling ability can largely depend on the content
ethylenediamine (EDA), diethylenetriamine (DETA), of nanoparticle entrapped on the hydrogels. It was found that
triethylenetetramine (TETA), and sulfomethylation reaction, when amount of added clays can be uniformly dispersed into
largely depends on the functional groups (Kasgoz et al. hydrogel networks, the hydrogel’s swelling ratio will be en-
2003). These hydrogel’s selectivity is displayed in (Fig. 13). hanced due to their surface containing negative charges (Peng
The M8 hydrogel, a Mannich product which was prepared et al. 2016). However, the swelling ratio will decrease as the

Fig. 13 The metal ion selectivity

properties of various hydrogels at
pH = 4.5. M8—hydrogel which
was prepared by Mannich
reaction with EDA. M10—
hydrogel which was prepared
Mannich reaction with DETA.
M11—hydrogel which was
prepared Mannich reaction with
TETA. S2—hydrogel which was
prepared by sulfomethylation
reaction (reprinted (adapted) with
permission from Kasgoz et al.
2003. Copyright (2018) Elsevier)
clay contents is so high. This phenomenon can be explained desorption agent instead of HCl, as a consequence of which,
that a stable structure will be formed to inhibit traversing of the high adsorption capacities for removal of organic pollut-
water molecules based on hydrogen bonds formed between ants (rhodamine B and ρ-nitrophenol) were not significantly
polymers and the crosslinking agent when increasing the con- decreased.
tent of crosslinking agents (Tu et al. 2017). In another study, a chelator-mimetic multi-functionalized
hydrogel possessing a high adsorption capacity for metal ions
(Cd, Pb, and As) and excellent reusability was introduced
Recycling and recovery of used hydrogel (Mohammadi et al. 2017). By using a low concentration of
HCl acid, the hydrogel can be regenerated in its functionality,
To economically and usefully evaluate the effect of an adsor- and also, the ions adsorbed by the hydrogel can be eluted. This
bent, one of the most important factors is the recyclable and particular hydrogel could maintain a better-than 60% removal
recoverable ability. This means that effective hydrogels must ratio after five consecutive sorption-wash-reuse cycles.
be easily reused for more than a few cycles without incurring Employing a similar method, Pourjavadi and co-workers per-
any significant change in its adsorption capacity. The regen- formed recycling experiments for a novel hybrid hydrogel
eration and reuse ability is also an essential factor for broad, based on CS, AA, and amine-functionalized nanosilica
practical assessment of the applicability of a material. A novel (Pourjavadi et al. 2015). HCl (1 M) solution was used as a
hydrogel based on polydopamine (PDA)-functionalized solvent to recover the Pb2+-loaded CS-g-acrylic hydrogel.
graphene (PDA-GH) was successfully synthesized, and this Then, the adsorbent was regenerated by filtering and washing
hydrogel effectively demonstrated its adsorption capacity for with distilled water and reused in the next cycle of the adsorp-
different contaminants, such as heavy-metal ions (Pb2+ and tion process. Significantly, the desired capacity of the regen-
Cd2+) and organic pollutants (rhodamine B and ρ-nitrophenol) erated adsorbent remained at 685–715 (mg g−1) after three
(Gao et al. 2013). Notably, the hydrogel could be easily re- cycles. Thus, due to its good recycling efficiency, the hydrogel
generated by a simple process using low-cost reagents, and it nanocomposite was judged to be suitable for practical
maintained a high adsorption capacity even after multiple applications.
adsorption-desorption cycles. According to the authors, to re- Vivek and Prasad described the regeneration and reusabil-
cover the ions (Pb2+, Cd2+) from the adsorbents of PDA-GH, ity process of a self-healing hydrogel prepared by a novel
they used HCl solution (0.1 M) as the desorption agent. The method using in situ polymerization of AA and acrylamide
reduced stability of the PDA covering in a strong acid possibly (Vivek and Prasad 2015). The hydrogel performed with re-
can cause the decline of the adsorption capacity of PDA-GH. markable efficiency (90–98%) in adsorbing organic dyes (MB
Nevertheless, the regenerated PDA-GH still maintained a high and methyl orange) and metal ions (Cd2+, Pb2+, and Hg2+).
adsorption capacity (more than 80%) after ten adsorption and The hydrogel was recovered by using methyl orange as the
desorption cycles. Hence, PDA-GH has been highly regarded adsorbent. The methyl orange adsorbed from the hydrogel
as a potential adsorbent, owing especially to its easy recycla- was extracted by ethanol solution, and the hydrogel was sep-
bility and reusability in the process of heavy-metal ion remov- arated when reaching the equilibrium condition. According to
al. However, to regenerate the hydrogel in the case of the the result of that study, it took approximately 20 min to con-
adsorption of organic pollutants, they used ethanol as a duct the desorption process, and the dye-recovery efficiency

was rather high, about 97%. Besides, the authors indicated the prepared hydrogel is much larger than TiO2 NPs, separa-
that with five cycles of regeneration process, the hydrogel still tion is very convenient. The recyclability of this hydrogel was
performed at an excellent adsorption capacity, maintaining an evaluated using MB and some other dyes. The results indicat-
adsorption rate of 90–98%. ed that the degradation of MB can be maintained until the fifth
Magnetic hydrogels represent one of the most effective cycle with high photodegradation efficiency, and that it grad-
techniques widely used for removal of metal ions from ually decreases beginning with the sixth cycle. In addition, the
flowing streams (Yavuz et al. 2009). Recently, a novel mag- recyclability of the hydrogel for various dyes was demonstrat-
netic hydrogel possessing advantages in fast Cr(IV) removal ed using acidic dyes (MB, MO) and an alkaline dye (RhB).
and a high adsorption capacity of about 200 mg g−1 was de- There were two different trends that were noted with respect to
veloped (Tang et al. 2010). Another advantage of this hydro- the photocatalytic efficiency. The photodegradation ability
gel is that it shows an easy recoverability by regeneration in with the MB and MO dyes increased until the second cycle
sodium chloride solution (Tang et al. 2014). The application and then decreased slightly in the third cycle, whereas that
utility of any magnetic hydrogel in wastewater depends on with RhB decreased progressively after the third cycle. The
two factors: a reduced amount of recovery solution and an reason for the difference was that various dye parameters,
increased metal-ion concentration in that solution. Tang’s such as pH and molecular structure, effected different diffu-
group’s method, schematized in Fig. 14, satisfies these re- sion mechanisms and adsorption behaviors. More importantly,
quirements. Briefly, treated wastewater is collected in a mag- with this type of hydrogel, pure TiO2 NPs can be recovered by
netic separation unit that separates the hydrogel; sodium chlo- the simple process shown in Fig. 15. In this process, after
ride at various concentrations is added for the regeneration recycling, the hydrogel is re-melted at high temperature into
process; the recovery solution is collected by separating the a diluted TiO2/agarose aqueous solution (Fig. 15a, b). Then,
magnetic hydrogel. Tang et al. conducted a set of regeneration centrifugation is conducted to separate TiO2 NPs, the result
tests with stepwise additions of NaCl solution. They collected being that higher-purity TiO2 NPs can be obtained (Fig. 15c,
the recovery solution, followed by another addition of NaCl d). For further-increased purity, the purification process is re-
solution. Their results suggested that the Cr(VI) removal and peated several times.
recovery performance of the magnetic hydrogel were likely to Reusability is one of the most essential properties for most
be maintained for 20 cycles for a 97–98% Cr(VI)-removal applications for hydrogels; however, it is a huge challenge for
efficiency. According to their data, the Cr concentration in conventional hydrogels because they are commonly poor
the recovery solution reached 500–600 mg/L with the step- strength and unrecyclable due to the lost mechanical tough-
wise adsorption and regeneration process, representing a 40:1 ness after swelling in water (Kamata et al. 2014). Therefore,
wastewater- to-recovery-volume ratio. enhancing the strength mechanical plays a key role in main-
Easy separation and recycling without additional costs are taining the adsorption capacity of pollutant-adsorbed
important factors impacting on the practical applicability of hydrogels. If hydrogels possess strength mechanical proper-
hydrogel-based photocatalysts. In 2017, a hydrogel-based ties, their reusability in practical applications is available to be
smart photocatalyst, TiO2/agarose hydrogel, which has an ex- greatly enhanced (Gong et al. 2016). Hydrogels with desirable
cellent recyclability was introduced (Mai et al. 2017). Because mechanical properties is available to maintain their service life
Fig. 14 Schematic illustration of

wastewater treatment prototype
with magnetic separation unit
(reprinted (adapted) with
permission from Tang et al. 2014.
Copyright (2017) American
Chemical Society)

Fig. 15 Recovery of pure TiO2

NPs from a TiO2/agarose. a
Melting, b dilution, c
centrifugation, and d separation
(reprinted (adapted) with
permission from Mai et al. 2017.
Copyright (2017) Royal Society
of Chemistry)
due to their self-healing ability when they suffer the swollen and advantages. According to the hydrogel-synthesis method
state. Cui’s group also supported these when they introduced a and the contaminant type, particles are chosen for improved
graphene oxide (GO)/hydrophobically associated PAM nano- adsorption efficiency and enhancement of hydrogel properties
composite hydrogels (GHA gels) as a reusable adsorbent for including mechanical strength, swelling ratio, pH sensitivity,
the removal of dye pollutants by incorporating GO with recyclability, and regeneration. Many hydrogels have already
hydrophobically associated PAM (Cui et al. 2015). This hy- been effectively synthesized and successfully applied for re-
drogel has superior mechanical strength and high toughness moval of pollutants from water, with more, no doubt, to come
due to strong hydrogen bonds between GO sheets and poly- in the near future.
mer chains. They also indicated that incorporation of GO
highly increases the wall thickness of GHA gels and the Funding information This research was supported by a grant from R&D
Program of the Korea Railroad Research Institute (KRRI) and by the
higher GO concentration lead to thicker pore walls.
Basic Science Research Program through the National Research
Therefore, GHA gels can go through the swollen state in water Foundation of Korea funded by the Ministry of Education (NRF-
over a long period of time without breakdown. It is the pres- 2017R1D1A1A09000642) and by the Korean Ministry of
ervation of desired mechanical properties of GHA gels after Environment’s GAIA project (2015000550006).
swelling that significantly enhances their reusability and
makes it promising to use them as recyclable adsorbents in
pollutant removal. Also, Gong’s group has the same point of
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Environmental Science and Pollution Research (2018) 25:24569–24599

Hydrogel applications for adsorption of contaminants in water

Keywords Hydrogel . Heavy metal . Dye . Radioactive . Adsorption . Water/wastewater treatment

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Table 1 The physiochemical properties of three types of hydrogel

Physiochemical Morphology Swelling Mechanical properties Thermal Reference

Fig. 1 Preparation of CMC

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Fig. 6 a OM image and b SEM

Fig. 7 Illustration of procedure

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Table 2 Comparison of metal ion

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Table 3 Comparison of the

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(2) Freundlich adsorption isotherm

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332 mg g−1 400 mg/L isotherms chemisorption

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Mahmoud et al. 2014)

(Pourjavadi et al. 2015)

(Peng et al. 2016)

Pseudo-second-order Hydrophobic interaction;

Pseudo-second-order Electrostatic interactions

where A, g, and B are the Redlich–Peterson constants, Ce (mg/

approaches Freundlich isotherm model at high concentration

One of the biggest challenges to the development of new ad-

sorbents for adsorption of pollutants in wastewater is to clearly

120 min 3.5–5.5 400 ppm

define and identify the adsorption mechanism. Especially, it is

really important to represent the interaction between adsorbates

namely the Langmuir and Freundlich models, which are

tion on hydrogels, a number of studies have used FTIR, XPS

scans, and X-ray diffraction to examine the functional groups

and structure of the adsorbent before and after adsorption of

pollutants. XPS is a commonly used technique to realize the

mechanism of heavy-metal adsorption on hydrogels, as it can

metal ion and functional groups (Deng et al. 2003).

According to Table 4’s summarized data, electrostatic in-

▬COOH group in AA (Jiang and Liu 2014; Li 2010;

Pourjavadi et al. 2015; Yu et al. 2015b), GO (Guo et al.

and cellulose ampholytes (Kono 2015), the amine group in

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Fig. 11 Adsorption of Cr6+ ion on

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Fig. 13 The metal ion selectivity

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Fig. 14 Schematic illustration of