Journal of Agriculture and Food Research 12 (2023) 100552

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Journal of Agriculture and Food Research

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Adsorption mechanisms of hydrogels for heavy metal and organic dyes

removal: A short review
Honglin Zhu 1, Sunni Chen 1, Yangchao Luo *
Department of Nutritional Sciences, University of Connecticut, Storrs, CT, 06269, United States

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

Keywords: Heavy metal and organic dyes produced in modern industrialization development have polluted the natural
Hydrogel resources human live by due to their adverse effects on all biological organisms. Developing effective,
Adsorption mechanism economical and friendly strategies to tackle environmental pollution has been a hotspot in recent years, among
Pollutant
which adsorption of chemical pollutants from water has been considered of utmost importance. Hydrogel-based
Water treatment
adsorbents with three-dimensional porous structures and versatile functional groups have become the first
choice, whose adsorption involves several mechanisms. In this perspective article, electrostatic interactions,
hydrogen bonding, π-π interactions, ion exchange, surface complexation and coordination/chelation were
introduced in detail to provide an overview for a better understanding of the action mechanisms of various
hydrogels. Combining two or more mechanisms is advantageous to gain great adsorption capacity, which could
be achieved via physical or chemical modification of hydrogels. This short review aims to provide theoretical
guidance to design and prepare hydrogels for applications in water treatment.

1. Introduction adsorption methods are considered effective, economical and friendly.

According to the Web of Science database, Fig. 1 displays the emerging
Water is one of the essential resources on which living organisms trend regarding dyes or metal ions absorption, especially in the past five
depend, and only 2.8% of the total water content on earth could be years, using the search strategy as follows: ((Topic = (dye*) OR Topic =
utilized by humans [1]. However, human activities, such as industry ("metal ion*")) AND Topic = (adsorption).
effluents, daily human wastes, agriculture/urban run-off, etc., discharge Hydrogels have well-defined three-dimensional porous structures
various hazardous chemical compounds (organic and inorganic wastes) and hydrophilicity as well as several functional groups, such as − COOH,
into the water, causing severe pollution. Currently, heavy metals and − NH2, − SO3H and − OH, which allow capturing dyes and metal ions
organic dyes are the main pollutants. Heavy metals are very dangerous from wastewater, attracting more and more attention (Fig. 1, search
to all biological organisms, which damage aquatic systems and human strategy: ((Topic = (dye*) OR Topic = ("metal ion*")) AND (Topic =
organs, including kidneys, lungs, nose, skin, central nervous system, (adsorption) AND Topic = (hydrogel*)) [6]. At present, many review ar­
brain and gastrointestinal tract [2]. As for the organic dyes, less than 1 ticles have been published on the summary of polymer-based hydrogels
ppm of dyes could affect the gas solubility and transparency of water to adsorb dyes and metal ions. However, few review articles have
bodies [3]. To make matters worse, these chemical pollutants cannot be covered the dyes and metal ions removal mechanisms of hydrogels.
degraded in nature due to their complex and stable structure, posing a Therefore, the specific objective of this perspective article is to discuss
long-lasting threat to the environment and human health [4]. some commonly reported mechanisms of different polymer-based
The efforts to remove heavy metal ions and organic dyes from the hydrogels.
water have been broadly made so far. Compared with the traditional
methods (flocculation-precipitation, photocatalysis, reduction-
oxidation, solvent extraction and electrochemical reaction) [5],

* Corresponding author. Nanotechnology and Biodelivery Laboratory, Department of Nutritional Sciences, University of Connecticut, Storrs, CT, 06269-4017,
United States.
E-mail address: [email protected] (Y. Luo).
1
Authors contributed equally to this work.

https://doi.org/10.1016/j.jafr.2023.100552
Received 16 February 2023; Received in revised form 27 February 2023; Accepted 6 March 2023
Available online 7 March 2023
2666-1543/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
H. Zhu et al. Journal of Agriculture and Food Research 12 (2023) 100552

Fig. 1. Number of publications per year relevant to dyes or metal ions ab­
sorption (solid column, left y-axis) using hydrogels (spotted column, right y-
axis) in the Web of Science© database in the previous 15 years (as of February Fig. 3. Schematic illustration of the formation of cellulose/alginate monolithic
15, 2023). hydrogel and the adsorption mechanism for methylene blue [12]. (For inter­
pretation of the references to colour in this figure legend, the reader is referred
to the Web version of this article.)

value of the amino group on the chitosan is around pH 6.5, and the
carboxylic pKa value is near pH 4.8. Based on this, Wang et al. [9]
fabricated a pH-responsive carboxymethyl cellulose/chitosan hydrogel
to remove anionic and cationic dyes. At pH 11, carboxylic groups
become deprotonated as -COO– and dominated in the composite
hydrogels, which could bind the positively charged methylene blue
(MB), and the adsorption capacity was up to 110 mg/g. Alternatively, at
pH 2, the amino groups on this composite hydrogel existed in their
protonated form (NH+ 4 ), and the adsorption capacity of negatively
charged acid orange II reached 100 mg/g (Fig. 2). Likewise, Tong et al.
[10] prepared sodium alginate/hectorite clay hydrogel beads for copper
ions removal, where the removal percentage was only increased by 3.4%
from pH 2 to 4. Nevertheless, it was then greatly increased by 15.1%
Fig. 2. Schematic diagram and working mechanism of hydrogel adsorption and with a pH from 4 to 5.5. At the optimum pH of 5.2, the removal per­
desorption of methylene blue (up) and acid orange II (down) based on elec­ centage achieved 96.1%. The underlying mechanism mediated via pH is
trostatic interaction [9]. (For interpretation of the references to colour in this
that in lower pH, more H+ ions exist, which compete for the adsorption
figure legend, the reader is referred to the Web version of this article.)
of Cu2+ onto the functional groups; at higher pH, ionization of -OH and
-COOH results in the formation of -O– and -COO–, creating abundant
2. Mechanisms of actions of hydrogels functional sites for the electrostatic interactions between anionic bind­
ing sites and Cu2+ more easily.
Understanding the adsorption mechanism is very important to apply
different hydrogel adsorbents to remove dyes and metal ions. In the
following sections, electrostatic interactions, hydrogen bonding, π-π 2.2. Hydrogen bonding
interactions, ion exchange, surface complexation and coordination/
chelation were respectively introduced in detail. It is worth mentioning Hydrogen bonding is a special kind of intermolecular or intra­
that several mechanisms exist in the adsorption process generally, molecular interaction. Specifically, when an H atom covalently bonded
depending on both the composition of hydrogels (carboxymethyl cel­ to a more electronegative “donor” atom or group (X) is close to an
lulose, chitosan, hectorite clay, graphene, etc.) and the set adsorptive electronegative atom bearing a lone pair of electrons—the hydrogen
condition (pH, temperature, concentration, etc.). bond acceptor (Y), the force is generated between X and Y with
hydrogen as a medium, named as hydrogen bonding (abbreviated to X-
H…Y). N, O and F are the most frequent donor and acceptor atoms. This
2.1. Electrostatic interactions bond is weaker than covalent or ionic bonds but stronger than van der
Waals forces. Hydrogen bonding is one of the major interactions to
The definition of electrostatic interaction is that two oppositely remove dyes in the water together with electrostatic interactions. Sethi
charged molecules/atoms are attracted to each other. Usually, the in­ et al. [11] prepared dialdehyde carboxymethyl cellulose-gelatin
tensity of surface charges and distance between the two interactive hydrogel to remove Rhodamine B (RhB) and Methyl Violet (MV). The
substances profoundly determine the interaction force, where the results showed that the maximum removal percentage of RhB and MV
greater intensity of surface charges and the closer distance, the stronger were 96.5% and 90% at pH 6, respectively, with a combined action of
the attraction [7], suggesting that the solution pH has an indispensable hydrogen bonding (O-H⋯N), van der Waals force and electrostatic in­
effect when applying the adsorbents [8]. In detail, when the solution pH teractions between hydrogels and dyes. The author further explained
differs from the point of zero charges of hydrogels, the surface of that the stronger hydrogen bonding and electrostatic interactions
hydrogels is able to carry either negative or positive charges to remove established via more carboxylic acid groups in RhB over MV contributed
the dyes or metal ions carrying opposite charges. For example, the pKa to a higher removal percentage of RhB than that of MV. Similarly, Yuan

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H. Zhu et al. Journal of Agriculture and Food Research 12 (2023) 100552

Fig. 4. Mechanisms for adsorption of methylene blue and methyl orange onto hydrogels [14]. (For interpretation of the references to colour in this figure legend, the
reader is referred to the Web version of this article.)

-2OH + Mn+ → -O…M…O- + nH+ (4)

et al. [12] illustrated the formation of cellulose/alginate monolithic
hydrogel and the adsorption mechanism for MB in Fig. 3. The abundant -COOH + M n +
-OH → -COO…M…O- + nH +
(5)
hydroxyl groups in the hydrogels bind to -N(CH3)2 groups in the MB
molecule via hydrogen bonding (O-H⋯N), and the carboxyl groups from Where M is the metal ions and n denotes their ionic charges.
alginate molecule chains bind to = N+(CH)2 groups in the MB molecule However, the metal adsorption capacity and efficiency are highly
via electrostatic interactions. decided by the number of available exchangeable sites of the functional
groups and targeted metal ions size [17,18]. Wu et al. [19] prepared
magnetic sodium alginate/carboxymethyl cellulose composite hydro­
2.3. π -π interactions
gels to remove heavy metal ions from an aqueous solution. According to
the Langmuir model, the maximal adsorption capacity of Mn2+, Pb2+
π-π interactions are a type of noncovalent interactions occurring via
and Cu2+ were 71.83, 89.49 and 105.93 mg/g, respectively. The
π-electron interactions between the acceptor and donor molecules,
different adsorption capacities were attributed to the ionic radius, where
strongly depending on functional groups in hydrogels and organic dyes.
the ionic radius of the Pb2+, Cu2+ and Mn2+ were 1.33 Å, 0.72 Å and
Typically, hydrogels modified with graphene are more likely to adsorb
0.67 Å, respectively. Furthermore, the author explained the interaction
aromatic dyes such as Congo red (CR), MB and methyl orange (MO)
process between this hydrogel and Cu2+ on the basis of the character­
through such interactions because every carbon atom of the honeycomb
ization study done prior and post adsorption experiments. After
lattice framework of graphene exists π-electrons [13]. Mittal et al. [14]
adsorbing Cu2+, symmetric and asymmetric vibration peaks of COO− at
employed graphene oxide as a chemical crosslinker to prepare chito­
1413 cm− 1 and 1622 cm− 1 were shifted to 1399 cm− 1 and 1635 cm− 1,
san/carboxymethyl cellulose hydrogel to treat dyes contaminated
respectively, and at 1023 cm− 1, the stretching vibration peak of C-O was
wastewater. Based on the Langmuir models, the maximum adsorption
almost disappeared in FTIR spectra. Based on the above phenomena, the
capacities were 655.98 mg/g for MB and 404.52 mg/g for MO. The
author speculated that the COO− group in this hydrogel adsorbed the
possible mechanism could be explained by the fact that the composite
Cu2+ ions via the ion exchange reaction. Moreover, the adsorption
hydrogel not only adsorbs cationic and anionic dyes through electro­
isotherm experiment further indicated chemical adsorption accompa­
static interactions and hydrogen bonding because of the existence of CS
nied by ion exchange [20]. Abdel-Halim [21] synthesized starch/poly
and CMC, but also via π-π interactions due to the presence of graphene
(N,N-Diethylaminoethyl methacrylate) hydrogels and applied them to
oxide. The possible detailed interactions between dyes and the adsorp­
remove direct red 81 from water. The dye removal percentage of this
tion sites of this composite hydrogel are shown in Fig. 4. In addition, the
fabricated hydrogel varied at different pH values, where the maximum
strong π–π stacking of graphene sheet and its derivatives could endow
removal percentage was up to 95.96% at pH 1, while it was 0% at pH 10.
excellent mechanical strength into the composite hydrogel, beneficial to
The author explained that the ion exchange mechanism was attributed
the dye adsorption [15].
to the protonation of amino groups, followed by the attachment of the
anionic dye molecule to the protonated amino groups at pH 1. When the
2.4. Ion exchange
pH was 10, more OH– groups meant less protonation to the amino
groups, and accordingly, they were not available as ion exchange sites to
Ion exchange is a reversible chemical reaction where free mobile ions
attract anionic dyes.
of an insoluble solid are exchanged for different ions of like charge
presenting in the solution [16]. Usually, as one of the major mechanisms
of heavy metals removal by hydrogels, ion exchange occurs when 2.5. Surface complexation
hydrogels have protons on oxygen in functional groups such as hydroxyl
and carboxyl groups [7]. Specifically, metal ions are exchanged with H+ Surface complexation (inner- and outer-sphere) is another important
on oxygen, detailed below [8]: mechanism for dyes and metal ions removal. In definition, complexation
is the process where the electron pair donor and electron acceptor
-COOH + Mn+ → -COO…M + nH+ (1) interact to form various complexes. Acceptors usually include organic
-OH + Mn+ → -O…M + nH+ (2) dyes and metal ions, and donors include atoms or ions able to provide
electron pairs regardless of whether they constitute simple substances or
-2COOH + M n+
→ -COO…M…OOC- + nH +
(3) compounds. Hou et al. [22] prepared hydroxyapatite/chitosan com­
posite for the removal of CR from an aqueous solution, where the

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H. Zhu et al. Journal of Agriculture and Food Research 12 (2023) 100552

mechanisms are responsible for the adsorption process, including elec­

trostatic interactions, hydrogen bonding, π-π interactions, ion exchange,
surface complexation and coordination/chelation. As reviewed,
different function groups on the hydrogels physically or chemically
interact with pollutants via one or more mechanisms. Thus, composite
hydrogels are more promising adsorbents compared with simple ones.
Also, the addition of effective functional groups through chemical
conjugation is a promising strategy to further improve adsorption ca­
pacity of hydrogels. However, the safety of applied hydrogels should be
seriously considered to avoid introducing harsh chemical residues when
treating wastewater in the food and agriculture sectors.
On the other hand, although various hydrogels have been well
developed, the applications of most hydrogels are limited to treating
sample solutions in the lab instead of in industries and natural envi­
ronments which are way more complex systems. As a result, extensive
Fig. 5. Illustration summarizing surface complexation of heavy metals on
efforts should be directed to scale up the applications and tested in
hydrogels [23].
practical scenarios.

Data availability

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

Acknowledgement

This work was, in part, supported by research grants from USDA

National Institute of Food and Agriculture, Award No. 2021-67022-
34415, and Hatch Multistate Project Accession No. 1020207.
Fig. 6. Ethylenediamine ligand chelating to a metal with two bonds.
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