Journal of Cleaner Production 315 (2021) 128221

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Journal of Cleaner Production

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

Recent advances in polysaccharide-based adsorbents for

wastewater treatment
Xiaoliang Qi a, 1, Xianqin Tong b, c, 1, Wenhao Pan b, c, Qiankun Zeng b, Shengye You b, c,
Jianliang Shen a, b, d, *
a
State Key Laboratory of Ophthalmology, Optometry and Vision Science, School of Ophthalmology and Optometry, School of Biomedical Engineering, Wenzhou Medical
University, Xueyuan West Road, Lucheng District, Wenzhou, 325027, China
b
Wenzhou Institute, University of Chinese Academy of Sciences, Wenzhou, Zhejiang, 325000, China
c
Department of Orthodontics, School & Hospital of Stomatology, Wenzhou Medical University, Xueyuan West Road, Lucheng District, Wenzhou, 325027, China
d
Oujiang Laboratory, Wenzhou, Zhejiang, 325000, China

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

Handling editor: Mingzhou Jin The existence of toxic water contaminants (heavy metals, dyes, phenols, oils, pharmaceuticals and nutrients)
restricts the sustainable supply of clean water globally. Among various economic and accessible wastewater
Keywords: disposal technologies, adsorption is the most extensively practiced approach due to its economic, feasible and
Polysaccharides sustainable characteristics. In recent years, polysaccharides have been extensively employed for constructing
Adsorption
adsorption materials due to their intrinsic properties including high adsorptive ability, low cost, renewability,
Wastewater treatment
biodegradability, biocompatibility and ease of modification. Here, a systematic review of polysaccharide-based
Adsorbents
Pollutants adsorbents for wastewater treatment is given. This review is aimed at providing: (1) general design principles for
polysaccharide-based adsorbents, (2) some critical factors that may affect the adsorption and (3) future di­
rections for the development of polysaccharide-based wastewater adsorbents. Overall, this review provides
guidelines on the rational fabrication and application of polysaccharide-based adsorbents, which will be bene­
ficial to novice/expert researchers in the field of wastewater remediation. Furthermore, the authors expect that
this review provokes interdisciplinary discussions that would bring a revolution to the application of
polysaccharide-based wastewater adsorbents.

1. Introduction are biodegradation-resistant, remaining in the ecosystem even after

Along with the booming of industrialization and urbanization, water
resources are facing an unprecedented challenge in this century (Liu
et al., 2019b). Untreated wastewater from printing, paper, textiles,
batteries, pharmaceuticals, leather tanning, food processing and rubber
generates many inorganic pollutants (heavy metal ions and nutrients)
and organic pollutants (dyes, pharmaceuticals, phenols and oils). These
contaminations gradually compromise the quality and quantity of
water, warning the world that the water supply will not meet the end of
consumption in the next few decades (Dinu et al., 2017). Meanwhile,
these contaminants could be mutagenic and carcinogenic, causing
damage and dysfunction to multiple systems and organs even at part per
million levels (Cheng et al., 2021). Besides, some hazardous pollutants
numerous chain circulations and long periods of time. Therefore, the
removal of toxic organic and inorganic contaminants from wastewater is
of utmost importance.
Among various techniques for wastewater remediation (Humelnicu
et al., 2020), adsorption (a surface phase transfer process through
chemical and physical interactions) is the most favored and widely
employed strategy because of its low cost, ease of handling and high
efficiency (Raschip et al., 2020). Generally, ideal adsorbent materials
should be featured with economic feasibility, easy accessibility, natural
origin and available modification. Besides, the complex environments of
wastewater (extreme pH, temperature and mixed pollutants) could
impede treatment efficiency and affect the regeneration of adsorbents,
which should also be considered when choosing appropriate adsorbents

* Corresponding author. State Key Laboratory of Ophthalmology, Optometry and Vision Science, School of Ophthalmology and Optometry, School of Biomedical
Engineering, Wenzhou Medical University, Xueyuan West Road, Lucheng District, Wenzhou, 325027, China
E-mail address: shenjl@wiucas.ac.cn (J. Shen).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.jclepro.2021.128221
Received 9 March 2021; Received in revised form 21 June 2021; Accepted 3 July 2021
Available online 4 July 2021
0959-6526/© 2021 Elsevier Ltd. All rights reserved.
X. Qi et al.
for wastewater treatment. Among various materials that can be used to
construct adsorbents, polysaccharides, a broad class of carbohydrate
polymers originating from natural sources, have cut a brilliant figure in
the application of wastewater treatment due to their outstanding prop­
erties adsorptive performance, renewability, biodegradability, biocom­
patibility and ease of modification. However, polysaccharides have
some inherent disadvantages. For example, most polysaccharides are
hydrophilic, and they are not suitable for direct use as adsorbents
because of difficulty in regeneration and reutilization; the mechanical
properties of polysaccharide matrix are generally weak, requiring the
assistance of other matrices (Su et al., 2019).
Scientists are dedicated to developing advanced multifunctional
polysaccharide-based adsorbents to adapt to the extreme environment
and endow them with more desirable properties. Generally, the waste­
water treatment performance of polysaccharide-based adsorbents can be
tuned by adjusting the physicochemical properties of polysaccharides.
For example, the most common way is to introduce functional groups or
chains onto the polysaccharide backbone. Meanwhile, preparing stable
polysaccharide-based adsorbents through cross-linking reactions is a
good choice. Furthermore, combining polysaccharides with some
insoluble matrices like iron oxide, carbon tubes and titanium dioxide,
which can achieve some additional (magnetic, thermal and catalytic)
features, is also an effective strategy. Besides, nanomaterials open a new
area for wastewater treatment, providing more space for researchers to
design polysaccharide-based adsorbents. Integration of polysaccharides
with nanomaterials may significantly improve several adsorption-
related characteristics such as porosity, surface area, density, size dis­
tribution and surface charge. These design strategies provide a steady
stream of polysaccharide-based adsorbents for wastewater treatment.
In the past ten years, many review articles focusing on design ad­
sorbents for wastewater treatment have been published by researchers
from different fields (environmental engineers, materials, chemists,
physics and others), as can be seen in Fig. 1. However, fewer articles are
dedicated to reviewing the recent advances in polysaccharide-based
adsorbents for wastewater treatment, indicating that there are still
research gaps in this field. Therefore, we attempt to pool the experiences
gained so far by researchers in this field.
This review mainly intends to shed more light on the recent advances
in the rational design of polysaccharide-based adsorbents for waste­
water remediation (Fig. 2). Firstly, polysaccharides that are commonly
Fig. 1. The number of published reviews concerning the keywords of “waste­
water treatment + adsorbent + polysaccharide”, “wastewater treatment +
adsorbent” and “wastewater treatment” on indexed journals from 2010 to 2021.
The search results are based on the database of “Web of Science” (*Data
collected in May 2021).
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Journal of Cleaner Production 315 (2021) 128221
utilized to construct adsorbents are presented. Subsequently, different
chemical and physical strategies (radiation, Michael addition, Schiff-
base reaction, click chemistry, enzyme-mediated method, hydrogen
bonding/ionic/hydrophobic interactions, crystallization and colloidal
assembly) used for cross-linking polysaccharides are described. After
that, some crucial principles (kinetics, isotherms, thermodynamics,
mechanisms, regeneration and reusability) for adsorbent design are
introduced. Finally, a brief review of knowledge gaps of polysaccharide-
based adsorbents for wastewater remediation is discussed. The authors
expect that the current review will provide a systematic and solid
foundation for the rational preparation of polysaccharide-based adsor­
bents to realize suitable performance for wastewater remediation, which
may be beneficial to beginners and experts in the field of wastewater
treatment. In addition, the current review is expected to provoke
interdisciplinary discussions that will bring a revolutionary break­
through to the application of polysaccharide-based adsorbents for
treating wastewater.
2. Methodology
This review focused on describing polysaccharide-based adsorbents
for wastewater treatment. To make the current review systematic,
reproducible and explicit, the method used here included three steps: (1)
literature screening, (2) literature selection and (3) literature
categorization.
2.1. Literature screening
The Web of Science database was employed to collect papers pub­
lished from 2000 to 2021. Firstly, 91,330 papers appeared in the
“wastewater treatment” keyword search. Subsequently, the author
added stringent keywords such as “adsorbent”, “adsorption” and
“polysaccharide” to narrow the scope of the search results and obtained
nearly 1000 papers.
2.2. Literature selection
The collected papers were further evaluated after the literature
screening process. Only papers that contained keywords in the main text
(not including references) and closely related to wastewater treatment
were selected. Besides, only high-quality papers contained a complete
list of parameters, a detailed methodology and comprehensive result
discussions were retained for further analysis. Finally, 130 papers
(Table S1, supporting information) had been selected in this review.
2.3. Literature categorization
The remaining papers were divided into three parts: (1) preparation
and design principle of polysaccharide-based adsorbents, (2) charac­
terization of adsorption properties of polysaccharide-based adsorbents
and (3) opportunities and challenges of polysaccharide-based
adsorbents.
3. Classifications of polysaccharides
Polysaccharides represent a broad class of carbohydrate polymers
that are linked by glycosidic bonds. According to the originated sources,
polysaccharides can be divided into animal polysaccharides, plant
polysaccharides and microbial polysaccharides. In this subsection, some
polysaccharides (Fig. 3) that are frequently employed to design low cost
adsorbents for wastewater remediation will be briefly introduced.
3.1. Animal polysaccharides
Animal polysaccharides equipped with numerous advantages have
presented a prosperous future in wastewater treatment. Generally, these
X. Qi et al.
Fig. 2. Schematic illustration for polysaccharide-based adsorbents for wastewater treatment.
polysaccharides fall into two categories: chitin/chitosan and glycos­
aminoglycans (involving heparin, keratan sulfate and hyaluronic acid).
Animal polysaccharides contain a large number of functional groups
such as –OH, –NH2, –COOH and –SO3H groups, which can serve as
actively adsorptive sites for removing toxic substances from wastewater.
However, compared with chitin/chitosan, glycosaminoglycans are
generally more expensive. Thus, the glycosaminoglycan-based adsor­
bent is not a suitable option to design low cost adsorbents for water
remediation. Therefore, in this section, only chitin and chitosan that are
promising for the economical production of adsorbents will be
discussed.
3.1.1. Chitin
Chitin, the richest linear marine polysaccharide composed of β-(1 →
4)-linked 2-acetamido-2-deoxy-β-D-glucose, mainly comes from insects,
crustaceans, fungus and molluscs (Fig. 3). It has an annual global pro­
duction of 6–8 million tons. Chitin possesses many remarkable features
like renewability, high content of hydroxyl/amino groups and biocom­
patibility, which is supposed to be an excellent raw material for
designing adsorbents (Zhou et al., 2004). However, the adsorption ca­
pacity of chitin is limited due to its poor solubility in commonly used
solvents. Therefore, chitin is often employed as a filler material to in­
crease the mechanical properties of adsorbents.
3.1.2. Chitosan
Chitosan, produced by the alkaline deacetylation treatment of chitin,
is a cationic polysaccharide featured with hydroxyl and amino groups on
the backbone (Fig. 3). Chitosan is often employed as a raw material for
fabricating bio-adsorbent due to its outstanding characteristics like
remarkable renewability, high abundance, accessible modification,
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Journal of Cleaner Production 315 (2021) 128221
economic feasibility, superior adsorption capacity and good reusability.
In addition, it is worth mentioning that chitosan is versatile and avail­
able to be fabricated into diverse structures (nanoparticles, fibers,
membranes, films, beads and gels) with various properties (Tong et al.,
2020). These architectures can provide more options when choosing an
appropriate adsorbent for wastewater purification. However, chitosan
presents several disadvantages: poor solubility in many solvents, so­
phisticated extraction procedures and instability in acidic medium
(Dragan and Loghin, 2018). Therefore, multiple modifications for chi­
tosan are proposed, including physical/chemical cross-linking and
immobilization of chitosan on insoluble supports (Shi et al., 2021).
3.2. Plant polysaccharides
Plant polysaccharides are originated from the metabolites of plant
cells, which could be generally divided into two categories according to
their functions in plants. Some of them serve as plant support tissues
such as cellulose, while others promote nutrient supply through enzy­
matic hydrolysis such as starch. There are rich storages of plant poly­
saccharides on the earth, especially cellulose and starch. Under the
background of the energy crisis, plant polysaccharides have inspired
extensive research on wastewater treatment due to their abundantly
available, biodegradable, eco-friendly, biocompatible and appealing
mechanical performance. Here, some representative plant poly­
saccharides are introduced.
3.2.1. Cellulose
Cellulose is prepared by various plants like bamboo, trees, cotton,
hemp, marine algae and crops. The first systematic presentation of the
cellulose unit is reported by Anselme Payen in 1837. The basic cellulose
X. Qi et al. Journal of Cleaner Production 315 (2021) 128221

Fig. 3. Examples of polysaccharides used to construct adsorbents for wastewater treatment.

Fig. 3. (continued).

structure is linear β-1,4-linked D-glucopyranose units with a high den­ is difficult to dissolve in water and other frequently-used solvents due to
sity of hydroxyl groups (Fig. 3). Anhydroglucose units on the backbone crystalline regions in cellulose connected by intramolecular and inter­
of cellulose served as a donor for three reactive hydroxyl groups (posi­ molecular hydrogen bonds. Solvents such as alkali/urea (or alkali/
tions C2, C3 and C6) exhibit low energy conformation. Native cellulose thiourea) aqueous systems, ionic liquids and N-methylmorpholine-N-

4
X. Qi et al.
Fig. 3. (continued).
oxide have been used to dissolve native cellulose. In addition, cellulose
possesses abundant hydroxyl (–OH) groups, which can act as reactive
sites for specific functional group modifications such as phosphate,
carboxyl and amino groups to achieve more appealing outcomes of
removing pollutants from wastewater. Cellulose can also be processed
into various morphologies such as chains, fibers, nanocrystals, nano­
sheets, fibers, films and sponges. These features make cellulose a
promising raw material for designing adsorbents (Kundu et al., 2019).
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Journal of Cleaner Production 315 (2021) 128221
3.2.2. Pectin
Pectin, an anionic naturally occurring, high-molecular-weight and
biocompatible linear polysaccharide extracted from the cell walls of
higher plants, mainly consists of D-galacturonic acid connected by α-(1
→ 4) glycosidic bonds (Fig. 3). Like most other plant polysaccharides,
the composition of pectin depends on the isolation conditions and
originated sources (Wang et al., 2021a). As an attractive anionic poly­
saccharide, pectin has been applied in biotechnology and pharmacy.
X. Qi et al.
Besides, pectin with many active hydroxyl and carboxyl groups avail­
able for interactions with water pollutants also shows enormous appli­
cation potential for wastewater treatment (Mondal et al., 2021). For
example, Kulal and Badalamoole (2020b) used a chemical cross-linking
approach to fabricate a pectin-based material for wastewater treatment.
The designed pectin-based adsorbent achieved highly efficient removal
of metal ions (Cu2+ and Hg2+) and cationic dye (rhodamine 6G).
3.2.3. Alginate
Alginate is a renewable anionic polysaccharide typically originated
from seaweed. Alginate comprises guluronic acid and mannuronic acid
linked by β-1,4-glycosidic bonds (Fig. 3). The guluronic acid and man­
nuronic acid contents and their sequence and block length are highly
dependent on the derived sources. In addition, the properties of alginate
could be adjusted by varying the guluronic acid/mannuronic acid ratio.
This feature provides good applicability for more advanced fields. For
example, alginate has been widely utilized in various biomedical and
biological applications due to its strong biocompatibility, low toxicity
and biodegradability. Furthermore, alginate has also been extensively
used for the adsorption of inorganic pollutants and organic contami­
nants from wastewater due to its high stability and non-toxic nature (Bo
et al., 2020).
3.2.4. Agarose
Agarose, a neutral polysaccharide mainly extracted from red algae of
seaweeds, comprises 3,6-anhydro-α-L-galactopyranosyl and β-D-gal­
actopyranosyl (Fig. 3). Agarose is a thermo-responsive polymer: agarose
is insoluble in cold water, while it dissolves in hot water and then forms
a hydrogel network as the temperature reduces. During this gelation
process, the polysaccharide structure is changed from a random coil to a
double helix with chain aggregation and entanglement in the junction
area. An agarose hydrogel with tunable mechanical property and pore
size can be obtained by adjusting the molecular weight and concentra­
tion of agarose. Agarose possessing inherent features like low cost,
biodegradability, eco-friendliness and high biocompatibility, is a widely
used thermo-reversible material in various fields, especially in molecu­
lar biology for DNA purification. Notably, the agarose network has
excellent water and ion retention capacity. These characteristics make
agarose a suitable material choice for designing polysaccharide-based
adsorbents in a more environmentally friendly way (Zhang et al., 2017).
3.2.5. Carrageenan
Carrageenan is a natural anionic biopolymer composed of alter­
nating β-(1 → 4)-3,6-anhydro-D-galactose and α-(1 → 3)-D-galactose
units, which can be derived from Rhodophyceae red seaweeds. Ac­
cording to the degree of sulfated content, commercialized carrageenan is
generally divided into three primary forms: kappa (κ, containing one
sulfate group per disaccharide unit), iota (ι, containing two sulfate
groups per disaccharide unit) and lambda (λ, containing three sulfate
groups per disaccharide unit) (Fig. 3). Among these different forms,
κ-carrageenan and ι-carrageenan have the ability to form stable physical
hydrogels; thus, κ-carrageenan and ι-carrageenan are widely used in
industrial, pharmaceutical and biomedical fields. Meanwhile, carra­
geenan owns many carboxyl and hydroxyl groups on polysaccharide
backbone, which can act as coordination and reaction sites for attracting
adsorbates (Kulal and Badalamoole, 2020a). Thus, carrageenan is
considered an excellent macromolecular polymer for preparing a
bio-adsorbent (Yu et al., 2019a).
3.2.6. Guar gum
Guar gum is a hydrophilic, non-ionic and high-molecular-weight
biopolymer composed of 1,4-linked β-D-mannopyranose and 1,6-linked
α-D-galactopyranose units with a molecular weight of almost 200 kDa
(Fig. 3). Guar gum is an excellent candidate that can manufacture ma­
terials for application in various fields like water treatment, biosensors
and drug delivery due to its inherent properties like renewability, low
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Journal of Cleaner Production 315 (2021) 128221
cost, biocompatibility and biodegradability. In addition, compared with
other plant polysaccharides, guar gum has unique properties that can
rapidly swell and produce a viscous solution even in cold water.
Furthermore, guar gum contains numerous –OH groups, providing the
possibility of introducing functional groups such as –COOH, –NH2 and
–SO3H groups through chemical modifications. These modifications will
allow guar gum to remove pollutants from aqueous solutions more
efficiently (Pal et al., 2015).
3.2.7. Konjac glucomannan
Konjac glucomannan is a renewable natural polysaccharide that is
originated from the tubers of konjac. Chemically, it consists of β-(1 → 4)-
linked D-glucose and D-mannose in a molar ratio of 1:1.6 or 1:1.4.
Generally, one acetyl group is located at the C6 position of the polymer
skeleton for every 12 or 18 repeating units (Gan et al., 2015); sidechains
may be present, and the degree of branching is about 8% (Fig. 3). The
molecular weight of konjac glucomannan varies from 500 kDa to 2000
kDa, depending on the processing and plant sources. Konjac gluco­
mannan with good biocompatibility and biodegradability displays
excellent film-forming property and gelation capability, facilitating its
broad application in medical, biological, chemical and food industries
(Zhang et al., 2018). More importantly, people are increasingly inter­
ested in using konjac glucomannan to formulate useful adsorbents
because konjac glucomannan possesses abundant hydroxyl groups that
can act as active sites for removing pollutants from wastewater (Chen
et al., 2017b).
3.2.8. Starch
Starch, a renewable, abundant and low cost polysaccharide with a
source-dependent structure, is commonly found in plants like crop
seeds, roots and stalks. It is composed of a mixture of anhydroglucose
units, namely amylose (a linear biopolymer of α-D-glucopyranosyl units
linked together by 1 → 4 bonds) and amylopectin (a branched
biopolymer of α-D-glucopyranosyl units linked by 1 → 4 bonds at the
main chain and 1 → 6 bonds at the side chain) (Fig. 3). Starch derived
from different plant resources has different contents of amylose and
amylopectin. Generally, most starches contain about 75% amylopectin
and 25% amylose. For example, the amylopectin content of corn and
potato starch is 70–80%, and their amylose content is 20–30%. Starch
swells relatively small in water at ambient temperatures and exists in
granules due to the hydrogen bonds between amylopectin and amylose
units. However, when the water temperature increases, the starch par­
ticles expand and exist in the form of amorphous suspensions because
the crystal arrangement formed by hydrogen bonds between amylo­
pectin and amylose units is destroyed. This transition is irreversible. In
particular, starch, as one of the most available and inexpensive poly­
saccharides with numerous hydroxyl groups, has been widely utilized to
design functional adsorbents for specific environmental usages
(Priyanka and Saravanakumar, 2018).
3.2.9. Cyclodextrins
Cyclodextrins are natural macrocyclic oligosaccharides fabricated by
the enzymatic conversion of starch. These naturally derived cyclic
sugars are composed of repeating D-glucose units linked by α-1,4-
glycosidic bonds. Cyclodextrins possess a truncated cone structure with
a hydrophobic inner cavity and a hydrophilic outer surface. This unique
structure makes cyclodextrins well-known polysaccharide materials to
reversibly bind compounds by forming host-guest inclusion complexes.
Thus, cyclodextrins have long been exploited in the biochemistry field.
The frequently studied cyclodextrins contain six glucopyranoside
monomers (α-cyclodextrin), seven glucopyranoside monomers
(β-cyclodextrin) and eight glucopyranoside monomers (γ-cyclodextrin)
(Fig. 3). In addition, cyclodextrins are widely investigated biopolymers
for environmental governance because their unique adsorption property
can selectively capture water pollutants and efficiently remove con­
taminants from wastewater (Yadav et al., 2020).
X. Qi et al.
3.3. Microbial polysaccharides
Microbial polysaccharides are one of the extracellular polymeric
substances produced by microorganisms under the metabolic process
including xanthan gum, gellan gum, dextran, pullulan, curdlan and
salecan (Li et al., 2017). The microbial polysaccharides typically carry
acyl substituents, either ester-linked acetate or ketal-linked pyruvate,
which may affect the structural conformation and performance of
polysaccharides. Moreover, diverse condensation linkages and varia­
tions of monomer sequences broaden the possibilities of the molecule
architecture and bring multiple physicochemical properties to microbial
polysaccharides. Recently, microbial polysaccharides have attracted
considerable interest in wastewater purification due to their high pro­
duction rates, simple purification/production conditions and
bio-friendly properties (Su et al., 2020). The inherent properties,
modification methods and achieved adsorption outcomes of microbial
polysaccharides will be briefly discussed in this section.
3.3.1. Pullulan
Pullulan, one of the linear unbranched microbial exopoly­
saccharides, is produced by the fungus Aureobasidium pullulans. It com­
prises maltotriose units linked by α-(1 → 6) and α-(1 → 4) glycosidic
bonds (Fig. 3). Each repeated pyranose ring unit of pullulan has nine
hydroxyl groups. According to production conditions, pullulan has
different molecular weights (from 4.5 × 104 Da to 6 × 105 Da). This
exopolysaccharide is highly soluble in water and the maximum tem­
perature bearing capacity of pullulan is around 280 ◦ C. Moreover, pul­
lulan possesses excellent physicochemical properties like high chemical
reactivity, hydrophilicity, flexibility in structural design and enzymatic
degradability (Su et al., 2019). Therefore, it has a wide range of appli­
cations in different fields such as drug delivery, food and tissue engi­
neering. Honestly, the pullulan-associated wastewater disposal research
is limited so far (Pan et al., 2021). However, pullulan holds a prosperous
future as a candidate to achieve further sustainable application for water
pollutant adsorption (Ye et al., 2016). In this review, some typical
pullulan-based materials are briefly shared.
Native pullulan is electrically neutral and thus, numerous re­
searchers try to improve the adsorption ability of pullulan by incorpo­
rating charged groups onto the polysaccharide backbone. Pullulan can
be chemically modified through partial etherification, esterification,
oxidation or sulfonation. For example, functional charged groups like
cationic quaternary ammonium salt could be incorporated onto the
backbone of pullulan to bind anionic pollutants through electrostatic
interactions. Besides, good surface area, remarkable mechanical
strength and swelling capacity also contribute significantly to the
adsorption efficiency of adsorbents, no matter whether the
polysaccharide-based materials are designed by chemical covalent
modification or physical blending. Richa and Roy Choudhury (2020)
designed a wastewater adsorbent by synthesizing a novel nano-gel with
a diameter of 29.5–36.5 nm 2,2-diphenyl-1-picrylhydrazyl was adopted
as a cross-linker to connect gellan gum and pullulan. Methylene blue
was selected as the cationic dye pollutant to study the adsorption
behavior. The obtained pullulan/gellan gum displayed good adsorption
performance, and the isothermal data fitted well with the Freundlich
model.
3.3.2. Dextran
Dextran is a linear non-ionic D-glucose synthesized from sucrose by
some lactic acid bacteria like Lactobacillus, Leuconostoc, Weisella and
Streptococcus (Zhang et al., 2021b). Chemically, it is composed of α-1,
6-linked glucose units with branches of α-1,3 linkages, and the branch is
at positions α-(1 → 3), α-(1 → 2) and/or α-(1 → 4) (Fig. 3). Different
types of dextran with different structures and sizes are produced ac­
cording to the extracellular enzyme produced by the strains. The solu­
bility of dextran depends on the branch link mode: the presence of >43%
α-(1 → 3) linking branches makes dextran water-insoluble, while
7
Journal of Cleaner Production 315 (2021) 128221
dextran containing 95% linear linkages is water-soluble. Dextran is
employed as a plasma substitute in the 1940s, and it is now widely used
in many biomedical applications due to its excellent biodegradability
and biocompatibility. Furthermore, dextran as a building material in
designing advanced adsorbent systems for wastewater remediation is
under extensive investigation (Liu et al., 2019a). In addition, as a
multifunctional polysaccharide, dextran can also be used in cosmetics
and food products.
3.3.3. Salecan
Salecan is a water-soluble β-D-glucan secreted by the agricultural
bacterium sp. ZX09 (Fig. 3). As a newly produced polysaccharide, sale­
can shows outstanding physicochemical and biological characteristics
(Qi et al., 2019b). For example, salecan has superior rheological prop­
erties, capable of forming high-viscosity solutions under low dosage and
low shear forces; the viscosity of the salecan solution remains stable at
various temperatures (5–95 ◦ C) and pH (1–13). Meanwhile, salecan has
fascinating biological properties like biodegradability and biocompati­
bility (Wei et al., 2017). Besides, since salecan contains many active
groups (such as hydroxyl groups) on the salecan backbone, chemical and
biochemical adjustments of salecan can be easily achieved, providing
greater flexibility and convenience for constructing specific materials
with targeted and advanced functions. Thus, in the past ten years,
salecan has become an essential member of the polysaccharide family,
which can be used to design and develop materials for potential appli­
cations in drug delivery, tissue engineering and water purification.
3.3.4. Gellan gum
Gellan gum is an anionic exopolysaccharide extracted from the
fermentation product of the bacterium (Sphingomonas elodea) (Racovita
et al., 2016). It consists of two glucose residues: rhamnose and glucur­
onic acid. Generally, gellan gum with a molecular weight of about 500
kDa exists in two forms: high acyl gellan gum and low acyl gellan gum
(Fig. 3). More interesting, gellan gum undergoes gelation, which is
affected by the polysaccharide concentration, type of cations, temper­
ature, pH and ionic strength. Gellan gum possesses many advantages
such as non-cytotoxicity, biodegradability and tunable physicochemical
properties that have been widely used in drug delivery, tissue engi­
neering and food products. Besides, gellan gum owns many active
groups (such as –OH and –COOH groups) that can act as active
adsorption sites for pollutants, offering a material choice for designing
robust adsorbents for wastewater treatment (Wang et al., 2009).
3.3.5. Xanthan gum
Xanthan gum, one of the branched microbial polysaccharides, is
fermented by Gram-negative bacteria Xanthomonas campestris. The basic
structure of xanthan gum contains a cellulose-like backbone linked with
a side chain via α-1,3 linkage (Fig. 3). Interestingly, xanthan gum has a
five-fold right-hand secondary helical structure and displays a thermo-
induced sol-gel phase transition behavior. Under extreme pH and tem­
perature, xanthan gum still presents extraordinary stability because of
the presence of a dimeric or double-stranded structure. Furthermore,
xanthan gum solution exhibits pseudoplastic and non-Newtonian fluid
properties. Therefore, xanthan gum typically serves as a thickener and
emulsion stabilizer in industrial applications. Additionally, xanthan
gum is non-toxic, non-allergenic and bio-friendly and has been
employed in drug delivery and tissue engineering. Attracted by these
features, xanthan gum can also be used to prepare adsorbents. In this
review, the development of xanthan gum-based materials for waste­
water disposal will be briefly introduced.
4. Synthesis of polysaccharide-based adsorbents
As described in Section 3, polysaccharides with renewable, abun­
dant, stable, modifiable, biocompatible and biodegradable features are
suitable and ideal raw materials for constructing wastewater adsorbents.
X. Qi et al.
However, most polysaccharides are hydrophilic, and the direct use of
them as adsorbents has some deficiencies, such as difficulty in regen­
eration and reuse after adsorption. Researchers propose various
methods to solve these problems, and the methods can generally be
divided into two primary forms: cross-linked polysaccharides (using
polysaccharides to prepare an insoluble matrix that can be understood as
polysaccharide-dominated adsorbents) and immobilized poly­
saccharides (introducing polysaccharides on a pre-existing insoluble
matrix like metal-organic frameworks, clay, activated carbon and zeo­
lites). Generally speaking, the methods for preparing cross-linked
polysaccharides are also suitable for the immobilization of poly­
saccharides on insoluble supports. Therefore, in this section, only the
methods for cross-linking polysaccharide systems will be introduced. A
classical review is recommended for more detailed discussions about the
immobilized polysaccharide systems (Crini, 2005).
Based on the cross-linked methods, polysaccharide networks are
synthesized either chemically or physically. Typically, chemically cross-
linked polysaccharide networks are produced through the reaction be­
tween the water-solubilizing groups in polysaccharide chains (such as
sulfonic acid groups, hydroxyl groups, carboxylic acid groups and amino
groups) with a cross-linking agent and the formed cross-link junctions
are permanent covalent bonds. On the other hand, physically cross-
linked polysaccharide networks are generated without the help of
cross-linking agents and the formed cross-link junctions are dynamic
non-covalent bonds. For example, agarose can form physically cross-
linked three-dimensional hydrogel networks through a heating-cooling
strategy.
Firstly, it should be noted that both physical and chemical cross-
linking methods have their advantages and disadvantages. For
example, chemically cross-linking brings mechanical strength but also
toxicity. In other words, additional pollutants may be brought when
chemical cross-linking is employed to prepare polysaccharide adsor­
bents. Secondly, a balance between physical linkages (influencing the
material’s toughness) and chemical linkages (influencing the material’s
stiffness) should be explored when designing desired cross-linked
polysaccharide adsorbents because it is challenging to meet the perfor­
mance requirements of adsorbents using only one type of cross-linking.
Fig. 4. Typical interactions of physical cross-linkings existed in polysaccharides: hydrogen bonding (A), ionic interactions (B), crystallization (C), hydrophobic
interactions (D) and gelation of colloids (E).
8
Journal of Cleaner Production 315 (2021) 128221
4.1. Physically cross-linked polysaccharides
In physically cross-linked polysaccharides, the polymer chains are
typically connected by non-covalent physical points, including
hydrogen bond interactions, ionic interactions, crystallization, hydro­
phobic interactions and colloidal assembly (Fig. 4). Usually, the stabi­
lization of a physically cross-linked polysaccharide network is more than
just a single type of physical effect but the assistance of multiple physical
interactions.
4.1.1. Hydrogen bonding interactions
Hydrogen bonding interactions that play a vital role in maintaining a
stable structure commonly occur in cross-linked polysaccharides
(Fig. 4A). Many hydrogen donors and recipients in polysaccharides (for
example: –NH2, –COOH, –SO3H and –OH) provide conditions for
hydrogen bonding formation. The hydrogen bonding will undergo a
reversible dynamic change when changing the solution environment,
such as solvent, pH, temperature and ion type/strength. It should be
noted that networks connected by hydrogen bonding alone are generally
unstable. For most cases, the co-existence of different non-covalent and
covalent interactions is a feasible strategy in designing cross-linked
polysaccharide systems for targeted applications. For example, an
ultra-fast and ultra-efficient polysaccharide adsorbent was prepared
when combining hydrogen bonding interactions with covalent bonds
(Qi et al., 2019a).
4.1.2. Ionic interactions
Ionic interactions used for cross-linking polysaccharides require two
oppositely charged molecules to appear simultaneously, which are
mainly divided into two categories (Fig. 4B). (1) Ionic interactions be­
tween polycationic polysaccharides and anions: for instance, a physi­
cally cross-linked structure is formed when chitosan with cationic amino
groups meets some small molecular anionic cross-linkers such as ita­
conic acid and sodium tripolyphosphate (Takeshita et al., 2021); simi­
larly, chitosan with numerous –NH2 groups will form a complex
polyelectrolyte structure with anionic polymers like polyglutamic acid,
gellan gum, xanthan gum, pectin and alginate through –NH+ 3 /–COO
–
interactions. (2) Ionic interactions between polyanionic polysaccharides
X. Qi et al.
and cations: for example, a polysaccharide hydrogel network is pro­
duced when multivalent cations (such as Al3+ and Ca2+) are added into
anionic gellan gum; polyanionic gellan gum forms polyelectrolyte
complexes or hydrogels via electrostatic interactions with polycationic
polymers (such as chitosan, polyethyleneimine, polylysine and
polyarginine).
4.1.3. Crystallization
Crystallization formed in polysaccharides, which is due to ordered
chain aggregation driven by phase separation, is a well-known process
that can be used for constructing polysaccharide networks (Fig. 4C).
Crystalline regions such as crystallites and spherulites can act as junction
knots to connect amorphous regions, forming a network. The heating-
cooling technique is the most common and straightforward method
for preparing a cross-linked polysaccharide structure and many poly­
saccharides (agarose, curdlan, carrageenan, konjac glucomannan, gellan
gum and xanthan gum) can form gels after undergoing a heating-cooling
procedure. Typically, the formation of crystalline regions is influenced
by many factors like the polysaccharide concentration, molecular
weight, pH, temperature and number of cycles. The physicochemical
properties of physically cross-linked gels, such as mechanical perfor­
mance, swelling and pore size, could be nicely controlled by adjusting
these factors. Unlike a two-step crystal formation mechanism (crystal
nucleation and crystal growth) of synthetic polymers like polyvinyl
alcohol and polypropylene, the crystallization process of poly­
saccharides is more complex involving the appearance of a mesomor­
phic phase or spinodal decomposition.
4.1.4. Hydrophobic interactions
Hydrophobic interactions are also an effective method of realizing
polysaccharide cross-linking (Fig. 4D). Most polysaccharides are hy­
drophilic, and thus hydrophobic modification is necessary. Generally,
there are two methods to achieve a physically cross-linked poly­
saccharide matrix by hydrophobic interactions. (1) Introducing hydro­
phobic substances (such as groups and chains) onto polysaccharide
backbone: for instance, a physically cross-linked gel could be obtained
by grafting a hydrophobic unit (dioctylamine) onto a water-soluble
polysaccharide backbone (carboxymethyl cellulose). Using similar
modification methods, other polysaccharides such as curdlan, pullulan,
dextran and chitosan can self-assemble in aqueous solutions to form
physically cross-linked hydrogels. (2) Introducing hydrophobic sub­
stances (such as micelles) into polysaccharide solution: for instance,
Poudel et al. (2018) synthesized a physically cross-linked poly­
saccharide hydrogel material composed of α-cyclodextrin and poly
(ethylene glycol)-block-poly (lactic acid) micelles. The mechanical
strength and gelation can be tuned by varying the α-cyclodextrin
concentration.
4.1.5. Colloidal assembly
Colloidal assembly is a tiny minority of polysaccharide gelation ways
(Fig. 4E). Specific polysaccharides such as nano-cellulose, possess un­
usual self-assembling behavior. Nano-celluloses are colloidal nano­
particles, which can be dispersed in aqueous media homogeneously.
Nano-cellulose nanoparticles have a fluid-like behavior in a diluted
state, while these nanoparticles feature a gel-like character on the
withdrawal of shear. For example, an aggregated gel-like phase was
observed when the cellulose nanocrystals in the solution exceeded 10 wt
% (Ureña-Benavides et al., 2011). However, most cross-linked poly­
saccharide systems formed by colloidal assembly lack physical stability.
Thus, the colloidal assembly used alone commonly cannot meet the
mechanical requirements for wastewater treatment. Combining
colloidal assembly with other physical/chemical cross-linked methods is
a suitable choice to overcome this limitation.
9
Journal of Cleaner Production 315 (2021) 128221
4.2. Chemically cross-linked polysaccharides
Unlike physically cross-linked polysaccharides, chemically cross-
linked polysaccharides tend to be more mechanically stable and per­
manent because of the strong covalent bonds produced between poly­
mer chains, making them attractive candidates for long-term
applications. Almost all covalent cross-linking methods require cross-
linking agents, and some cross-linking reactions also require initiators.
The two most used methods for preparing covalently cross-linked
polysaccharides are radiation cross-linking and chemical reaction
(Michael addition, Schiff-base reaction and click chemistry). What is
more, enzyme-mediated cross-linking is also an exciting approach to
fabricate polysaccharide networks. These gelation methods are dis­
cussed below.
4.2.1. Radiation
Radiation provides a versatile tool for cross-linking polysaccharides.
Depending on the energy used for radiation, there are two main ways:
low energy irradiation (such as ultraviolet light and visible light) and
high energy radiation (including electron beams and gamma rays). Ra­
diation cross-linking involves generating various free radicals, which
induce new chemical bond formation. Converting inert polysaccharide
groups into active groups and initiating unsaturated polysaccharide
bonds are two mechanisms of radiation cross-linking. Fine-tuning re­
action parameters such as polymer concentration, radiation time and
energy is essential for obtaining targeted products. More importantly,
radiation technology is a green method of cross-linking polysaccharides
because cross-linking is generally not required to add other toxic
chemicals like monomers, cross-linkers and initiators. Attracted by this
feature, researchers have prepared many cross-linked polysaccharide
structures through the radiation way. For example, Li et al. (2021) used
ultraviolet light to fabricate a hyaluronic acid-based hydrogel in the
presence of a photo-initiator (lithium phenyl-2,4,
6-trimethylbenzoylphoe-phinate). Hong et al. (2018) used 60Co
gamma radiation at dosages ranging from 20 kGy to 100 kGy to prepare
carboxymethyl cellulose sodium/carboxymethyl chitosan/sodium sty­
rene sulfonate hydrogel adsorbents for removing Zn2+, Fe3+, Cu2+ and
Cr3+ from aqueous solutions.
4.2.2. Michael addition
The functional groups on the polysaccharide backbone, such as –OH,
–NH2, –COOH and –SO3H, can construct cross-linked networks by co­
valent coupling reactions. The commonly encountered chemical reac­
tion strategies are Michael addition, Schiff-base formation and click
reactions. The Michael addition reaction, which is based on the addition
of a nucleophile (Michael donor) to the carbon-carbon multiple bonds of
an activated electrophilic olefin or alkyne (Michael acceptor) to produce
a “Michael adduct”, is commonly used to cross-link polysaccharides
(Fig. 5A). So far, many studies had been conducted to develop electro­
philic groups (such as maleimide, vinyl sulfone and acrylate) and
nucleophilic groups (such as phosphine and thiol) containing poly­
saccharides (Radhakrishnan et al., 2017). For example, different
chemically modified polysaccharides involving tri (2-carboxyethyl)
phosphine-grafted chitosan, acrylic acid-grafted chitosan, methacry­
lated dextran, vinyl sulfone-contained dextran, acrylate-grafted chon­
droitin sulfate and thiol-decorated dextran had been designed for
preparing cross-linked polysaccharide materials through Michael addi­
tion reaction.
4.2.3. Schiff-base reaction
The Schiff-base reaction for polysaccharide cross-linking occurs be­
tween aldehyde and amine groups (Fig. 5B). Using the Schiff-base re­
action, polysaccharides with cross-linked structures could be achieved
without the help of chemical cross-linking agents. Attracted by this
feature, Schiff-base-mediated cross-linking is one of the most widely
utilized strategies for designing injectable hydrogel materials.
X. Qi et al.
Fig. 5. Chemical reactions for cross-linking polysaccharides: Michael addition reaction (A), Schiff-base reaction (B), click reaction (C) and enzyme-mediated cross-
linking (D) (reproduced with permission from Ref (Radhakrishnan et al., 2017).).
Meanwhile, the physical properties and gelation kinetics of hydrogels
can be easily tailored by changing the ratio of aldehyde and amine
groups. A representative example is that the chitosan (containing amine
groups) can be cross-linked using aldehyde-contained molecules like
2,6-pyridinedicarboxaldehyde, glutaraldehyde, oxidized-hyaluronic
acid, oxidized-alginate, polyaldehyde dextran and oxidized-cellulose
(Takeshita et al., 2021). Of note, small-molecule aldehyde-containing
cross-linking agents are generally toxic and should be thoroughly
10
Journal of Cleaner Production 315 (2021) 128221
removed from the fabricated materials before use.
4.2.4. Click chemistry
Click chemistry is also a useful method that can be used for poly­
saccharide coupling under mild conditions (Fig. 5C). In the past two
decades, click reactions have received increasing attention because of
the advantages of high selectivity, high specificity and high yields with
few by-products. Three classical click reactions are furan-maleimide (4
X. Qi et al.
+ 2) Diels-Alder cycloaddition, Cu+-catalyzed thiol-alkene addition and
azide-alkyne (3 + 2) cycloaddition. Among them, the catalyst-free Diels-
Alder reaction, occurring between furan and maleimide without pro­
ducing any by-products and side reactions, has attracted much attention
for preparing environmentally friendly cross-linked polysaccharides in
an additive-free (no additional coupling agents and initiators) manner.
For example, Dou et al. (2019) designed a chitosan-coated carbon
nanotube via Diels-Alder click reaction. The obtained composite with
good adsorption capacity for Cu2+ holds great promise as an adsorbent
for wastewater treatment.
4.2.5. Enzyme-mediated cross-linking
Enzyme-mediated cross-linking is an exciting approach to synthesize
polysaccharide networks. In general, in order to be recognized by en­
zymes and substrates, polysaccharides need to be tailored first, and then
an environmentally friendly polysaccharide-based cross-linked system is
obtained under mild reaction conditions after choosing an appropriate
enzyme and substrate (Fig. 5D). For example, Jin et al. (2011) proposed
a horseradish peroxidase-mediated cross-linking method to design
polysaccharide hydrogel (composed of tyramine conjugated heparin and
tyramine conjugated dextran). Additionally, they reported that the
gelation rate and storage modulus of resulting dextran/heparin hydro­
gels could be tuned by changing the polysaccharide ratio. Similarly,
chitosan hydrogels were rapidly synthesized (within 1 min) by
enzyme-mediated strategy with the help of hydrogen peroxide and
horseradish peroxidase (Jin et al., 2009).
5. Adsorption: working concept
Adsorption is a physicochemical process in which the adsorbed
substance is transferred to the solid adsorption surface in the form of a
liquid or gas. The adsorption phenomenon mainly involves four steps:
bulk diffusion, external mass diffusion or film diffusion, intra-particle
diffusion or pore diffusion, and finally, adsorption through chemical
and/or physical reactions. Generally, the reaction kinetics of adsorption
is governed by the pore diffusion and/or film diffusion since the uniform
distribution of adsorbent and adsorbate makes the bulk diffusion
negligible. Therefore, when designing a suitable polysaccharide-based
adsorbent for wastewater treatment, knowing the critical process like
factors affecting the adsorption capacity, adsorption kinetics, adsorption
isotherms, adsorption thermodynamics and adsorption mechanism is
indispensable to precisely understand the adsorption phenomenon.
5.1. Adsorption capacity
Usually, the adsorption experiments are carried out by a batch
method. Adsorption capacity (qt and qe) and removal efficiency (RE, %)
of polysaccharide-based materials are calculated by Equations (1)–(3)
(Pan et al., 2019):
(C0 − Ct )V
qt = (1)
W ally, the contact time is directly correlated with the active adsorption
(C0 − Ce )V
qe = (2)
W
(C0 − Ce )
RE = × 100 (3)
C0
where C0 (mg/L), Ct (mg/L) and Ce (mg/L) represent the adsorbate
concentration at the initial time, at time t and at equilibrium time,
respectively; W (g) is the mass of dried adsorbent; V (L) is the volume of
the aqueous phase.
5.2. Factors affecting adsorption capacity
Incomplete research on the initial experimental adsorption
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Journal of Cleaner Production 315 (2021) 128221
conditions (including pH, temperature, adsorbent dosage, contact time,
initial pollutant concentration, adsorbent shape and ionic strength) may
lead to insufficient data, thereby affecting the assessment results of re­
action spontaneity, adsorption mechanism and adsorption nature be­
tween the evaluated pollutants and adsorbents. Thus, these factors that
affect the adsorption capacity should be considered.
5.2.1. pH
Solution pH significantly influences the adsorption process because it
directly affects the surface functional groups of adsorbents and the
chemical forms of pollutants. Changes in pH will affect adsorbates and
adsorbents by protonation or ionization. Charged adsorbents and ad­
sorbates either feel forces of electrostatic attraction or repulsion. For
example, anionic dyes can be effectively adsorbed on the adsorbent at a
lower pH, while anionic dyes cannot be effectively adsorbed on the
adsorbent at a higher pH. Similarly, the increase in solution pH is also
conducive to cationic ions adsorption, and an increase in solution pH is
not beneficial for anionic ions adsorption and vice-versa. Therefore,
optimization of solution pH is indispensable for adsorbing environ­
mental pollutants from wastewater.
5.2.2. Temperature
The reaction temperature is also a critical parameter that may
positively or negatively affect the adsorption process. If adsorption in­
creases with enhancing temperature, this phenomenon indicates that the
adsorption reaction is exothermic, and this phenomenon happens
because the adsorption force becomes stronger between the adsorbed
molecules and the reacted sites of adsorbents. Additionally, as the
temperature enhances, the random movement of the adsorbate mole­
cules enhances, so the possibility of adsorbate molecules interacting
with the active sites of adsorbents also increases. However, if the in­
crease in temperature hinders the adsorption process, this phenomenon
is called endothermic adsorption. The reason for endothermic adsorp­
tion is that the adsorption force between the critical parts of the
adsorbent surface and the adsorbate molecules is weakened as the
temperature rises. For example, He et al. (2014) designed chitosan mi­
crospheres to remove Pb2+, Cd2+ and Cu2+ from aqueous solutions, and
the adsorption capacity for these three metal ions decreased with the
increase of temperature. The reason was that the mobility of Pb2+, Cd2+
and Cu2+ ions increased as the temperature rose, thus favoring the
dechelation/desorption of adsorbates.
5.2.3. Contact time
Contact time is an integral part of accurately determining the
adsorption process since both chemical and physical reactions are
influenced by the contact time provided for adsorbent and adsorbate
interaction. Generally speaking, the contact time is longer, and
adsorption occurs more efficiently. However, an inappropriate adsorp­
tion procedure could be produced if the adsorption equilibrium takes
more time. Thus, the adsorption equilibrium with less time-consuming is
better from the perspective of costs and reaction efficiency. Addition­
sites. At the beginning of adsorption, the adsorbates are quickly attached
to the active adsorption sites of adsorbents. Later, the active parts of
adsorbents will gradually be occupied by the adsorbed molecules and
adsorption gradually reaches equilibrium; in this case, adsorption will
take more time.
5.2.4. Initial pollutant concentration
The initial pollutant concentration affects the adsorption capacity of
the adsorbents. At the beginning of the adsorptive process, the adsorbate
concentration and adsorbent binding sites have a linear relationship due
to a large number of vacancies on the surface of the adsorbent. As initial
adsorbate concentration increases, the mass transfer resistance between
adsorbent and adsorbate solution becomes smaller because of the
increased driving force, resulting in increased adsorption capacity.
X. Qi et al.
However, these vacant sites are gradually reduced and entirely occupied
by the pollutants, leading to a sharp downfall in adsorption. Therefore,
optimization research for initial pollutant concentration is indispensable
when selecting a suitable material for the adsorption of environmental
pollutants.
5.2.5. Ionic strength
Ionic strength is a complex factor that may positively or negatively
affect the adsorption capacity of polysaccharide materials. The bridging
interaction of ions and electron donor-acceptor interactions are the
dominant mechanisms. For example, the effective adsorption sites of
adsorbents may be occupied by metal ions in the solution, forming a
hydration shell of metal cations. This shell can shield or intrude the
hydrophobic sites and compete with the surface active sites of adsor­
bents, thereby inhibiting remediation. On the contrary, metal ions can
improve the adsorption efficiency of adsorbents through the salt effect
induced by bridging interactions; meanwhile, the anionic ions in the
solution can also act by the electron donor-acceptor effect (Li et al.,
2020). For example, Flores-Chaparro et al. (2018) found that the
adsorption capacity of designed chitosan/macroalgae adsorbents
decreased when the ionic strength was greater than 0.6 M, and the
reason was due to pore occlusion and competitive effect.
5.2.6. Adsorbent dosage and shape
The optimal dosage of the adsorbent should be evaluated to maxi­
mize the interaction between pollutants and adsorbents. Increasing the
adsorbent dosage is beneficial for the quick achievement of adsorption
equilibrium until reaching saturation point. However, adsorption effi­
ciency decreases accordingly because of excessive adsorption sites.
Consequently, it is necessary to find a balance between the increased
adsorbent dosage and decreased adsorption efficiency. Besides, the
adsorbent shape also significantly influences the adsorption behavior.
Generally, the choice of powdered adsorbents is preferable compared to
the granular adsorbents because powdered adsorbents require relatively
more minor surface adsorption time, while granular adsorbents require
longer time attributing to slow superficial adsorption and diffusion. In
addition, adsorbents with three-dimensional structures have a higher
surface area and exhibit higher adsorption ability than one-dimensional
or two-dimensional adsorbents.
5.3. Adsorption kinetics
Adsorption kinetics is an essential parameter for designing and
evaluating adsorbents, which can be used to find the time required for
adsorption saturation and investigate adsorption control mechanisms
(Demirbilek and Dinç, 2016). The kinetics of adsorption usually involves
three basic steps. The first step is the massive transfer of contaminants
from the bulk solution to the external surface of the adsorbent. The
second step is the diffusion of contaminants from the surface through the
pores to the active sites of the adsorbent. Thirdly, the interaction be­
tween the contaminants and the active adsorbent sites occurs.
Commonly, the adsorption kinetics of pollutant removal from waste­
water could be modeled by the pseudo-first-order (PFO) kinetic model
(Equation (4)), pseudo-second-order (PSO) kinetic model (Equation
(5)), Weber and Morris kinetic model (Equation (6)) and Elovich kinetic
model (Equation (7)) (Dragan et al., 2019). The most suitable value of
the linear regression correlation coefficient provided by the adsorption
model or the diffusion model is determined by varying the parameters
like temperature, initial pollutant concentration, pH and adsorbent
dosage in batch experiments. A brief discussion of these models is
summarized below:
( )
qt = qe 1 − e− k1 t (4)
k2 q2e t
qt = (5)
(1 + k2 qe t)
12
Journal of Cleaner Production 315 (2021) 128221
qt = ki t0.5 + C (6)
qt = ln(αβ) / β + ln(t) / β (7)
where qt (mg/g) and qe (mg/g) are the adsorption capacity at time t
(min) and at equilibrium time (min), respectively; k1 (1/min), k2 (g/mg
min) and ki (mg/g min1/2) are the rate constants of PFO, PSO and intra-
particle diffusion models, respectively; C (mg/g) denotes the intercept
influenced by the thickness of the boundary layer; α (mg/g min) and β
(g/mg) represent the rate constant of chemisorption and the constant of
the coverage, respectively (Mu et al., 2020).
5.4. Adsorption isotherms
Adsorption isotherms are a convenient parameter for comparing
various polysaccharide adsorbents. Isotherm studies help predict the
interactions between the adsorbent and adsorbate that can provide in­
formation about the maximum adsorption. Adsorption isotherms
depend on certain physical properties of the solution like ionic strength,
temperature and pH. Many adsorption isotherm models are available,
among which Langmuir (Equation (8)), Freundlich (Equation (9)), Sips
(Equation (10)), Tempkin (Equation (11)), Dubinin-Radushkevich
(Equation (12)) and Redlich-Peterson (Equation (13)) are most
commonly used (Saez et al., 2020). It is worth noting that mechanistic
conclusions based solely on a good fit of such models should be avoided
for the particular system under consideration since the good fit of these
models does not necessarily mean that all stated assumptions are valid.
A brief explanation of these adsorption isotherm models is mentioned as
follows:
qm KL Ce
qe = (8)
(1 + qm KL Ce )
qe = KF Ce1/n (9)
ks CeβS
qe = ( ) (10)
1 + αS Ce S
β
RT
qe = lnAT Ce (11)
bT
{ [ ( )]}
1
qe = qDR exp − β RT ln 1 + (12)
Ce
qe = (
Kr− p Ce
) (13)
1 + αr− p Ceg
where qe (mg/g) is the equilibrium adsorption capacity; qm (mg/g) is the
maximum sorption capacity; Ce (mg/L) is the equilibrium aqueous
concentration; KL (L/mg), KF (L/mg), ks (L/g), bT (J/mol) and β (mol2/
kJ2) are the Langmuir, Freundlich, Sips, Temkin and Dubinin-
Radushkevich constants, respectively; βS is Sips isotherm model expo­
nent; aS (L/mg) is Sips isotherm model constant; AT (L/g) is the Temkin
isotherm equilibrium binding constant; R (8.314 J/mol K) is the uni­
versal gas constant; T (K) is temperature; qDR (mg/g) is the maximum
adsorption capacity; Kr–p and αr–p are the characteristics of the Redlich-
Peterson isotherm; g represents exponent that lies between 0 and 1.
5.5. Adsorption thermodynamics
Adsorption capacity is greatly affected by temperature, whether the
adsorption process is exothermic/endothermic or non-spontaneous/
spontaneous. Based on a thermodynamic study, it is possible to better
understand the mechanisms of external mass transfer, reaction on ad­
sorbent’s external surface or internal active sites and intraparticle
diffusion. Therefore, a thermodynamic study is essential for proper
X. Qi et al.
analysis of the adsorption phenomenon from a practical viewpoint. The
thermodynamic parameters of adsorption such as Gibb’s free energy
(ΔG◦ ), entropy (ΔS◦ ) and enthalpy (ΔH◦ ) are prevalently determined
according to the following equations:
ΔG◦ = − RT lnkc (14)
ΔS◦ ΔH ◦
lnkc = − (15)
R RT
ΔG◦ = ΔH ◦ − TΔS◦ (16)
where R (J/mol K) is the universal gas constant; T (K) is the absolute
temperature; kc denotes the equilibrium reaction constant. The ther­
modynamic parameters obtained from Equations (14)–(16) can judge
whether the adsorption is feasible. Specifically, negative or positive ΔH◦
values suggest the endothermic or exothermic adsorption phenomenon.
A positive value of ΔS◦ shows a high affinity between sorbate and sor­
bent; while ΔS◦ with a negative value is more common in adsorption
because the degree of freedom of the solute decreases after adsorption at
the solid-liquid interface. A negative value of ΔG◦ indicates that the
adsorption process is spontaneous and thermodynamically favorable,
whereas a positive value of ΔG◦ reflects that the adsorption process is
not favorable from the second law of thermodynamics.
5.6. Adsorption mechanism
Understanding the adsorption mechanism of polysaccharide-based
materials is essential, which can directly imply improvements in the
feasibility of adsorption by advancing adsorption/desorption conditions
and adsorbent design. Improved adsorption feasibility promotes the
further improvement of the adsorption process in the reaction envi­
ronment, economic sustainability, renewability, recyclability and prac­
ticality. However, determining the adsorption mechanism of
polysaccharide-based adsorbents is a very complicated and tedious
work due to the complexity and particularity of polysaccharides (such as
complex functional groups and changeable chemical structures).
Therefore, several possible mechanisms responsible for the adsorptive
removal of pollutants from wastewater using polysaccharide-based
materials are presented.
5.6.1. Physisorption
Physisorption, also called physical adsorption, is the most widely
studied mechanism involving reversible weak physical interactions be­
tween molecules such as hydrogen bonding, van der Waals interactions
and hydrophobic interactions. Physisorption refers to surface adsorption
without destroying the electronic orbitals of the adsorbate and adsor­
bent, showing non-selective behavior and requiring little energy (Baig
et al., 2021). However, determining the interaction of superficial func­
tional groups of adsorbent and adsorbate during physical adsorption is
challenging. The use of electron spin resonance, X-ray diffraction anal­
ysis, thermogravimetric analysis, X-ray photoelectron spectroscopy,
scanning electron microscope and energy-dispersive X-ray spectroscopy
is highly recommended for exploring the role of the surface functional
groups in the process of physisorption, and combining different char­
acterization methods can better explore the physical adsorption mech­
anism. The experimental parameters and surface functional groups can
be adjusted according to the information provided by these techniques.
5.6.2. Chemisorption
Chemisorption (also called chemical adsorption) refers to that the
pollutant molecules are chemically combined with the adsorbent, which
is irreversible. Compared with physisorption (20–40 kJ/mol), chemi­
sorption requires more energy (80–240 kJ/mol) since the generated
bonds on the surface of the adsorbent are chemical rather than physical
(Baig et al., 2021). Generally, the chemical adsorption process may
involve proton displacement, chelation, complex formation, redox
13
Journal of Cleaner Production 315 (2021) 128221
reactions and covalent bonding. Due to chemical bonds forming,
changes in the adsorbent electronic state could be characterized by
different analytical techniques like X-ray diffraction analysis, X-ray
photoelectron spectroscopy, Fourier transform infrared spectroscopy
and Raman spectroscopy. In addition, the chemisorption rate negatively
depends on the activation energy of reactants since the adsorption
process is chemical. For example, a lower adsorption rate is observed for
the adsorption process loaded with higher activation energy since more
time is required to achieve adsorption equilibrium. Therefore, the effi­
cient interactions between the adsorbates and active sites of adsorbents
are significant for chemisorption from energy-saving perspectives.
Moreover, chemisorption is temperature-dependent, and thus adsorp­
tion process governed by chemisorption could be tuned by adjusting the
environmental temperature.
5.6.3. Ion-exchange
Ion-exchange is an adsorptive phenomenon, which is electrostatic,
stoichiometric and reversible. In an ion-exchange process such as water
demineralization, the ions on the adsorbent surface are replaced by the
ions of adsorbate, where anions (cations) are replaced by OH− (H+).
There are two types of ion-exchange systems: anion exchangers with
negative charge ions can replace anions, and cation exchangers with
positive charge ions can replace cations. The electronic balance is
maintained throughout the process since the adsorbent releases equiv­
alent electron-charged species adsorbed by the surrounding charged
ions. Besides, the co-ions that present in the exchange matrix signifi­
cantly affect transport efficiency. Therefore, understanding the inter­
action mechanism between adsorbate and adsorbent is crucial for
improving the selection of targeted adsorbate, process conditions, co-
ions and particle diffusion.
6. Regeneration and reusability
In addition to the adsorption properties, the regenerative charac­
teristics of the sorbent are also essential to reduce the cost of adsorption,
avoid the generation of secondary waste from the spent adsorbent, and
open up the possibility of recovering contaminants from wastewater.
The recovery of the adsorbent is usually a fast two-step process, which
involves desorbing the adsorbed pollutants from the adsorbent and then
activating the adsorbent for the next adsorption cycle. An ideal adsor­
bent is one that possesses both good adsorption and regeneration func­
tions. Unfortunately, most of the developed adsorbents described in the
published literatures only focus on adsorption, while the regeneration
aspects are rarely investigated. In the few exceptions on regeneration
studies, the adsorption-desorption cycle generally does not exceed five
times. Regeneration is also as crucial as adsorption. Some critical pa­
rameters for regeneration, such as selecting an appropriate regeneration
approach, optimum regeneration time, stability of adsorbent during the
regeneration process and reproducibility performance of regenerated
adsorbent, should be considered when designing a suitable adsorbent.
6.1. Desorption
During the adsorption process, contaminants continue to accumulate
on the polysaccharide-based adsorbents until adsorption equilibrium. If
the exhausted polysaccharide-based adsorbents are discarded in a
landfill, it will cause new environmental problems. An alternate option
that is economically attractive and environmentally safe is to regenerate
the saturated adsorbents. Regeneration of adsorbent is usually a fast
two-step process involving desorption of adsorbate and activation of
adsorbent. Many methods including thermal, biological and chemical
processes are proposed for this purpose (Ahmed et al., 2020). Compared
with other technologies, the advantages of the chemical method are that
the regeneration is relatively fast, no adsorbent loss and less energy
requirement. Besides, chemical regeneration can realize the recovery of
adsorbents and adsorbates simultaneously. The most common chemical
X. Qi et al. Journal of Cleaner Production 315 (2021) 128221

method practiced in adsorbent regeneration is solution (acids and bases) extraction.

leaching. Desorption of adsorbates is achieved by choosing a suitable
agent such as sodium hydroxide, ammonium hydroxide, hydrochloric 7. A brief review of polysaccharide-based adsorbents for
acid, sulfuric acid and nitric acid. wastewater treatment

6.2. Recovery Heavy metals produced by agricultural and industrial wastewater

Desorption and adsorption are opposite phenomena. When using the
chemical desorption approach, choosing appropriate chemical eluents is
vital for achieving high desorption efficiency. Generally, several pa­
rameters like pH, temperature, time and metal concentration should be
taken into account. Recently, the recovery of noble metals (a tight but
relatively essential resource) in wastewater like gold and platinum has
attracted broad concerns. Immense efforts have been committed to
recovering these precious sources under various conditions, especially
refining wastewater. However, conventional extraction methods appear
less cost-effective, energy-consuming and toxic. Therefore, it is crucial to
develop a more sustainable and environment-friendly method for
precious metal recovery. Some researchers try to use polysaccharide-
based adsorbents to achieve metal recovery since polysaccharides
possess abundant reactive groups, which could offer multiple design
options for adsorption and recovery.
For example, Wang et al. (2012) synthesized a chitosan derivative by
chemical modifications (carboxymethylation and sulfonation). The
modified chitosan possessed a high adsorption capacity for Au3+.
Meanwhile, the desorption of Au3+ from the chitosan adsorbent was
easily achieved using thiourea/hydrochloric acid as the washing sol­
vent. Besides, the adsorption ability of regenerated chitosan adsorbent
remained unchanged even after four cycles. Swantomo et al. (2020) used
gamma irradiation to create chitosan graft copolymers to promote gold
cyanide adsorption. Adsorption could be reversed in the alkaline solu­
tion of CN− via electrostatic interactions and ion exchange. At the same
time, the authors found that the designed polyacrylamide-grafted chi­
tosan possessed good desorption performance and 18.7% of the gold can
be recovered from the adsorbent. The desorption process was related to
the concentrations and species of the desorption agent. However, cya­
nidation is an environmentally destructive method. Therefore, a sus­
tainable gold recovery technology should be developed. Hence, Chen
et al. (2020a) developed a thiosulfate leaching method using
three-dimensional molybdenum disulfide/chitosan (MoS2/chitosan)
aerogel for in situ Au reduction. MoS2 was selected as a reduction agent
for Au + ions, which worked through double mechanisms (combining
chemical reduction and photo-reduction simultaneously). Chitosan
served as a three-dimensional porous matrix, and Au+ was reduced to
gold particles on the aerogel surface. This work demonstrated that the
MoS2/chitosan aerogel could be a novel and promising material for gold
discharge are toxic, carcinogenic and non-biodegradable, and their
excessive intake through polluted water can have harmful effects on
human health (Dragan et al., 2017). In this section, representative ani­
mal, plant and microbial polysaccharides used to fabricate adsorbents
for adsorption of heavy metals are discussed and some adsorption results
are listed in Table 1.
7.1. Adsorption of heavy metals
7.1.1. Adsorption of heavy metals using animal polysaccharide-based
adsorbents
Chitosan is the most extensively used animal polysaccharide for
designing adsorbents. Chitosan has amino (position C3) and hydroxyl
groups, which are the main active sites for metal adsorption. The
adsorption mechanism of chitosan includes chelation, ion-exchange,
electrostatic interaction and van der Waals forces (Dinu et al., 2018).
However, the native chitosan has poor solubility, hindering its further
applications in the highly complicated wastewater environment. The
chemical modifications of chitosan can solve this issue. Generally, the
modified chitosan-based materials can promote the adsorptive capaci­
ty/selectivity/stability and other physicochemical features like me­
chanical performance and structural stability. For example, Zhang et al.
(2020c) prepared a recyclable chitosan-based adsorbent for wastewater
treatment (Fig. 6). To enhance the acid-resistance ability, glutaralde­
hyde was adopted as a cross-linker to connect the iron oxide (Fe3O4)
nanoparticles and chitosan. Subsequently, poly (acryloyloxyethyl­
trimethyl ammonium chloride) (PDAC) was grafted onto the backbone
of chitosan to provide reactive quaternary ammonium sites for adsorp­
tion of adsorbates. The obtained adsorption system (denoted as
Fe3O4-CS/PDAC) was employed for removing Cr6+ and organic dye
(sunset yellow). The developed Fe3O4-CS/PDAC exhibited good
adsorption performance (maximum adsorption capacity of 769.2 mg/g
and 163.9 mg/g for sunset yellow and Cr6+, respectively) and excellent
reusability (>90% removal efficiency after five cycles of regeneration).
Ahmad et al. (2019) developed a novel diphenyl carbazide (DPC)
cross-linked chitosan-based adsorbent for Cu2+ ions removal from
water. Diphenylcarbazide (DPC) was chosen as a cross-linker to increase
the mechanical strength of the adsorbent. The maximum adsorption
ability of DPC/chitosan for Cu2+ was 185.5 mg/g, which was achieved
at solution pH 6.0.

Table 1
Adsorption of heavy metals using polysaccharide-based adsorbents.
Polysaccharides used in preparing Heavy Best kinetic Best isothermal Maximum sorption capacity (mg/ References
adsorbents metals models models g)

Chitin Cr6+ PSO Langmuir 387.7 Liang et al. (2018)

Chitosan Mg2+ PSO Freundlich 177.9 Yan et al. (2016)
Cellulose Pb2+ PSO Langmuir 558.7 Wang et al. (2017a)
Pectin Pb2+ PSO Langmuir 390.9 Wang et al. (2021a)
Alginate Pb2+ Elovich Redlich-Peterson 234.8 Facchi et al. (2018)
Agarose Co2+ PSO Langmuir 105.1 Zhang et al. (2017)
κ-Carrageenan Hg2+ PSO Freundlich 229.9 Kulal and Badalamoole
(2020a)
Guar gum Cr6+ PSO Langmuir 101.0 Dinari et al. (2020)
Konjac glucomannan Pb2+ PSO Langmuir 95.2 Chen et al. (2017b)
Starch Ni2+ PSO and Elovich Langmuir and Sips 83.3 Dragan and Loghin (2018)
β-Cyclodextrin Cd2+ PSO Langmuir 24.7 Kundu et al. (2019)
Pullulan Cu2+ PSO Freundlich 100.9 Zeng et al. (2020)
Dextran Cd2+ PSO Langmuir 269.0 Liu et al. (2019a)
Salecan Cd2+ PSO Langmuir 412.5 Hu et al. (2021)
Gellan gum Cr3+ PSO Freundlich 42.4 Wang et al. (2009)
Xanthan gum Pb2+ PSO Langmuir 1012.2 Ghorai et al. (2014)

14
X. Qi et al.
Fig. 6. Schematic illustration for the fabrication and adsorption of Fe3O4-CS/PDAC (reproduced with permission from Ref (Zhang et al., 2020c).).
Additionally, mixing chitosan with other systems is also a good
choice (Lazar et al., 2019). Various inorganic and organic materials like
silica, zeolites, graphene oxide, polyvinyl alcohol (PVA) and polyvinyl
chloride can be combined with chitosan. Recently, a substantial number
of chitosan blending materials are developed for wastewater disposal.
For example, Facchi et al. (2018) fabricated a chitosan/alginate/­
Fe3O4@SiO2 hydrogel composite to eliminate Pb2+ from wastewater.
The authors first designed stable magnetic particles (Fe3O4@SiO2) by
coating SiO2 onto the surface of Fe3O4. Then, Fe3O4@SiO2 particles were
incorporated into a polysaccharide matrix, which was composed of
chitosan and alginate. As anticipated, magnetic separation of Pb2+ was
achieved and the optimized adsorption performance of the designed
composite hydrogel reached 220 mg/g. Clinoptilolite (CPL), one of the
naturally available zeolites, is also a good choice for constructing cheap
chitosan-based blending adsorbents. Dinu and Dragan (2010) embedded
CPL particles into the chitosan matrix to obtain beads with a diameter of
800 μm. The authors systematically investigated the adsorption perfor­
mance of the CPL/chitosan system for different heavy metals (Ni2+,
Co2+ and Cu2+). Results showed that the removal ability of chito­
san/CPL was related to pH, contact time and initial concentration of
metal ions. The proposed chitosan/CPL adsorbents displayed good
adsorption and desorption performance.
Besides, changing the structural morphology of adsorbents appears
to be another possible breakthrough for designing robust chitosan-based
wastewater treatment materials. As mentioned above, low surface
effectiveness, limited life span and unstable desorption process severely
restrict the practical application of chitosan-based adsorbents. Nano­
technology that shows great potential to address the inherent limitations
of polysaccharide-based adsorbents has been gradually entered the field
of adsorption. Typically, adsorbents possessing a high surface area could
increase the chemical activity, promote the surface binding energy and
diminish internal diffusion resistance. Thus, it is a good choice to pre­
pare a chitosan-consisted nano-matrix. For example, Francis et al.
(2015) synthesized amphiphilic graft copolymers by incorporating
three-arm polystyrene onto the backbone of chitosan to obtain a
self-assemble “core-corona” nano-structure. The authors found that the
metal ions were prone to be chelated on the surface of the micellar ag­
gregates and turned to metal nanoparticles through a reduction
15
Journal of Cleaner Production 315 (2021) 128221
mechanism. These copolymers performed well in the adsorption process
and could be reused after the desorption process. Meanwhile, integra­
tion of chitosan with a pre-existing nano-matrix by physical blending or
chemical cross-linking is also an effective approach. Organic and inor­
ganic nanomaterials like carbon-based materials, titanium dioxide
(TiO2), and Fe3O4 can be employed to fabricate multifunctional chitosan
nano-adsorbents. These attempts may accelerate the large-scale indus­
trial application of chitosan-based adsorbents.
7.1.2. Adsorption of heavy metals using plant polysaccharide-based
adsorbents
Polysaccharides are promising candidates to prepare adsorbents for
removing heavy metals from contaminated water. However, cellulose,
the most abundant natural plant polysaccharide, has not fully reached
its potential application in treating wastewater because of its limited
solubility in water. Destroying the crystalline domains of cellulose,
which are formed due to the hydrogen bond interactions between
polysaccharide chains, can significantly increase the solubility of cel­
lulose. One of the vital keys to breaking the strong hydrogen interactions
is to utilize an alkaline solution containing thiourea or urea. Like chi­
tosan derivatives, introducing some hydrophilic groups onto the back­
bone of cellulose could enhance the solubility of cellulose. Some
functional groups such as carboxyl, sulfo and amino groups connected
onto the backbone of cellulose by interacting with hydroxyl groups of
cellulose have received extensive attention. Cellulose can achieve high
solubility and remarkable adsorption capacity simultaneously after a
suitable modification using these active groups. For example, Song et al.
(2019) fabricated a hydrogel composed of carboxymethyl cellulose
(CMC) and polyethyleneimine (PEI) for Cr6+ removal. PEI provided
many imine groups that can enhance the hydrogel adsorption capacity.
Additionally, the authors observed that Cr6+ was reduced to Cr3+ and
then fixed on the surface of CMC/PEI. These results suggested that
CMC/PEI had the potential for wastewater disposal. Apart from the
covalent modification, the physical blending can also offer some reac­
tive groups to form stable complexes. Zhou et al. (2004) obtained a
stable cellulose/chitin structure by this way, and the designed cellulo­
se/chitin beads displayed good adsorption capacity for adsorbing cat­
ions (Pb2+, Cd2+ and Cu2+). Wang et al. (2013) created
X. Qi et al.
collagen/cellulose hydrogel beads to adsorb Cu2+ from water. The
amino groups of collagen can provide adequate binding sites for Cu2+.
As expected, the designed collagen/cellulose adsorbent exhibited su­
perior recycling stability and still presented high adsorption efficiency
(>95%) even after four cycles.
Nano-cellulose possesses a large surface area and holds many nega­
tively charged groups on its surface, thus displaying excellent adsorption
performance. For example, Bahadoran Baghbadorani et al. (2019) pre­
pared a super-adsorbent composed of starch-g-poly (acrylic acid) and
cellulose nanofibers (CNFs) to remove Cu2+ ions from aqueous solu­
tions. The authors found out that carboxylate groups were prone to be
protonated in a low degree of pH level (= 2), thus hindering the in­
teractions between adsorbent surface and Cu2+ ions, while the opti­
mized pH of the solution for uptaking Cu2+ ions was 5.
CNFs-incorporated hydrogel displayed better adsorption performance
than untreated hydrogel. The results indicated that this hydrogel
exhibited an excellent capacity for Cu2+ ions removal and recovery.
Similar to CNFs, cellulose nanocrystals have also been widely studied for
metal adsorption. Besides, some other nanomaterials like Fe3O4, clay
and metal-organic frameworks (MOFs) are widely used for preparing
cellulose-based nano-adsorbents. Among them, MOFs, which are porous
crystalline materials with network structures by integrating inorganic
metal ions or clusters and organic ligands, possess good adsorption
characteristics like high surface area, stability and affinity. These fea­
tures make MOFs desirable adsorbents for removing metal ions. For
example, Wang et al. (2017a) developed a new cellulose-contained
adsorbent composed of MOFs and cellulose nanocrystals, which dis­
played the excellent capacity to remove Pb2+ from water. The maximum
adsorption ability of cellulose-contained adsorbent was 558.7 mg/g.
More interestingly, some novel cellulose-based materials are adopted
as sensitive detectors to trace heavy ions quantitatively and selectively.
Yu et al. (2019b) fabricated a carbon dots/cellulose system. Carbon dots
served as desirable photoluminescence providers, while
millimeter-sized carboxylic acid cellulose spheres acted as matrices. The
authors found that the designed sensor exhibited a highly sensitive
detection feature for Hg2+ (detection limit of 26 nM) and Cu2+ (the
visual and fluorescence limits were 3 μM and 0.11 μM, respectively).
This phenomenon was because numerous metal/amine complexes
Fig. 7. Synthesis of the BEPE-cross-linked pullulan/polydopamine hydrogel for removing heavy metals (reproduced with permission from Ref (Zeng et al., 2020).).
16
Journal of Cleaner Production 315 (2021) 128221
formed, aggregated and then concentrated on the spheres, resulting in
the change of color.
7.1.3. Adsorption of heavy metals using microbial polysaccharide-based
adsorbents
As is well known, abundant groups (hydroxyl and carboxylic groups)
on the microbial polysaccharide backbone can serve as reactive sites for
the adsorption of heavy metals. For example, Zeng et al. (2020) prepared
a pullulan/polydopamine hydrogel that was cross-liked by 1,2-bis(2,
3-epoxypropoxy)-ethane (BEPE) for Cu2+, Co2+ and Ni2+ adsorption
using a facile one-pot method (Fig. 7). As a result, the maximum
adsorption of Cu2+ reached 100.9 mg/g and the adsorption process
obeyed PSO kinetic and Freundlich isotherm models. Interestingly,
combining microbial polysaccharides with inorganic matrices (such as
multi-walled carbon nanotubes and clay) can overcome the defect of the
structural instability of polysaccharides. For example, the feasibility of
the polyacrylamide grafted xanthan gum/SiO2 hybrid nanocomposite
for Pb2+ adsorption was systematically evaluated by Ghorai et al.
(2014). The results of batch adsorption experiments demonstrated that
the developed nanocomposite possessed superior adsorption ability
(maximum adsorption capacity = 1012.1 mg/g) and rapid pollutant
removal ability (adsorption efficiency = 99.5% within 25 min). The
authors speculated that the chelating and other synergistic effects of
nanocomposite with Pb2+ through electrostatic interactions were the
main mechanisms that governed the adsorption process. More impor­
tantly, the biopolymer-based nanocomposite was easily regenerated by
ethylenediaminetetraacetic acid/hydrochloric acid and displayed
excellent recovery (>87.2%) after the fourth adsorption-desorption
cycle. Lai et al. (2020) used an eco-friendly and simple ice-templating
technique to prepare a polysaccharide-based three-dimensional com­
posite (GXT) for adsorptive removal of Pb2+ in wastewater. GXT was
composed of xanthan gum, graphene oxide and TiO2. It possessed a
porous sponge-like structure that displayed high temperature stability.
Excellent maximum adsorption ability (199.2 mg/g) was accomplished
for Pb2+ due to hydrophilic character, high surface area and functional
moieties of GXT. Moreover, the as-prepared GXT also exhibited promi­
nent regenerability property, and its adsorption capacity was still kept at
84.8% even after five operation cycles.
X. Qi et al. Journal of Cleaner Production 315 (2021) 128221

7.2. Adsorption of dyes
Water contamination caused by dyes poses serious ecological issues.
Dye removal remains a challenge because of the inert properties and low
concentration of dyes in wastewater. Polysaccharide-based materials
might be as practical and eco-friendly as industrialized decolorizing
agents (such as activated carbon), which could be attractive candidates
for eliminating dyes. Generally, to find the optimal polysaccharide-
based adsorbents, the main factors involving the initial concentration
of dye, adsorbent dosage, pH and temperature that may influence the
adsorption capacity should be considered. Here, some animal, plant and
microbial polysaccharides used to prepare adsorbents for removing dyes
from wastewater are introduced (Table 2).
7.2.1. Adsorption of dyes using animal polysaccharide-based adsorbents
Physical cross-linking is an effective method for designing adsor­
bents derived from animal polysaccharides. For example, a functional­
ized clay/chitin composite microsphere with hierarchical architecture
was put forward to realize the highly efficient removal of methylene
blue from water (Xu et al., 2018). As a result, the maximum removal
capacity of methylene blue on clay/chitin adsorbent was 156.7 mg/g.
Compared with physical cross-linked chitosan-derived materials,
chemically cross-linked chitosan systems gain wide approval for dye
effluent disposal based on their high efficiency and facile fabrication.
For example, Jabli et al. (2014) designed some chemically cross-linked
chitosan-based microspheres, denoted as 2-hydroxypropyl-β-cyclode
xtrin-chitosan (HP-β-CD-chitosan), PVA-polyvinylpyrroldone-chitosan
(PVA-PVP-CS), PVA-chitosan, polyvinylpyrrolidone-chitosan (PVP-chi­
tosan) and plain chitosan. The authors compared the dye adsorption
properties of these materials. HP-β-CD-chitosan possessed the best per­
formance for adsorption of dyes due to the formation of inclusion
complex between the pollutants and the adsorbents through host-guest
interactions. Melo et al. (2018) fabricated a chitosan-g-poly (acrylic
acid) hydrogel employing N,N′ -Methylenebisacrylamide as a
cross-linker in the presence of cellulose nanowhiskers. The obtained
composite hydrogel displayed robust (1968 mg/g) and rapid (60 min)
adsorption ability for methylene blue (Fig. 8). Ekici et al. (2011) pre­
pared chitosan/polyacrylamide hydrogel adsorbents using glutaralde­
hyde and N,N′ -Methylenebisacrylamide as covalent cross-linkers. The
dye removal mechanism of chitosan/polyacrylamide hydrogel was
electrostatic interactions between anionic dye molecules (–SO–3 groups)
and protonated hydrogel (–NH+ 3 groups). Meanwhile, the authors
observed that the chitosan/polyacrylamide hydrogel adsorbent
possessed better performance than the form of powder, film and bead
adsorbents. In addition, some scholars have studied the removal of
multiple dyes in complicated systems. Kang et al. (2020) fabricated a
composite gel composed of montmorillonite and chitosan for removing
methyl orange and methylene blue simultaneously. The maximum
adsorption capacity of the designed composite gel for methyl orange was
1060 mg/g in the presence of methylene blue.
7.2.2. Adsorption of dyes using plant polysaccharide-based adsorbents
Synthetic dyes are widely used in numerous manufacturing in­
dustries, like leather, textile, plastics, paper, cosmetics and food (Qi
et al., 2019a). Dye-polluted wastewater directly drained into the natural
environment can induce harmful effects on human health (Gholami
et al., 2016). As mentioned in Section 3 , plant polysaccharides pos­
sessing abundant functional groups can serve as actives for dyes (Perju
et al., 2012). Liu et al. (2015) reported a new three-dimensional acryl­
amide and acrylic acid modified cellulose adsorbent to eliminate the dye
pollutants from an aqueous solution. This adsorbent can efficiently
remove acid blue 93 (anionic dye) and methylene blue (cationic dye)
from single or binary dye water solutions. The adsorbent also displayed
good recyclability. Cellulose-based adsorbent modified with glycidyl
methacrylate and sulfosalicylic acid was also investigated (Zhou et al.,
2014). The results indicated that the maximum adsorption capacity for
crystal violet was 218.8 mg/g when the temperature went up to 50 ◦ C
and adsorption efficiency increased 70.8% compared to that of un­
modified one, in which electrostatic attraction between –COOH/–SO3H
groups of adsorbents and crystal violet molecules played a significant
role.
Unlike the adsorption and recovery of heavy metals, it is usually
difficult to recover the adsorbed dyes from polysaccharide-based ad­
sorbents because dyes are inert. Besides, polysaccharide-based adsor­
bents work low-efficiently when the dye concentration in wastewater is
low. To acquire better dye removal efficiency, composite and hybrid
polysaccharide-based materials have been extensively developed by
introducing some functional materials to the polysaccharide matrix. For
example, Sethi et al. (2019) synthesized a carboxymethyl cellulose/ge­
latin hydrogel, which carried silver nanoparticles as the catalyst to
realize the efficient removal of rhodamine B and congo red dyes from
wastewater. The composite hydrogel achieved better mechanical/­
thermal properties and higher adsorption capacity (80 g/g at pH = 10).
Chen et al. (2017a) synthesized a novel dye adsorbent composed of
hydroxypropyl cellulose (as a hydrogel matrix) and MoS2 (as a photo­
catalyst) to remove methylene blue from wastewater. The addition of

Table 2
Adsorption of dyes using polysaccharide-based adsorbents.
Polysaccharides used in preparing Dyes Best kinetic Best isothermal Maximum sorption capacity References
adsorbents model model (mg/g)

Chitin Methylene blue PSO Langmuir 156.7 Xu et al. (2018)

Chitosan Methyl orange PSO Langmuir 1060.0 Kang et al. (2020)
Cellulose Acid blue 93 and PSO Freundlich 1372.0 Liu et al. (2015)
methylene blue
Pectin Rhodamine 6G PFO Langmuir and 43.5 Kulal and Badalamoole
Freundlich (2020b)
Alginate Methylene blue PSO Langmuir and Sips 452.3 Dinu et al. (2017)
Agarose Methylene blue PSO Langmuir 242.3 Duman et al. (2020)
κ-Carrageenan Crystal violet PSO Langmuir 28.2 Gholami et al. (2016)
Guar gum Reactive blue 4 PSO Langmuir 579.0 Pal et al. (2015)
Konjac glucomannan Methyl orange PSO Freundlich 51.6 Gan et al. (2015)
Starch Congo red PSO Langmuir 1428.6 Priyanka and Saravanakumar
(2018)
β-Cyclodextrin Brilliant green PSO Langmuir and 2.3 Yadav et al. (2020)
Temkin
Pullulan Methylene blue PSO Langmuir 25.8 Su et al. (2020)
Dextran Methyl orange PSO Langmuir 84.0 Das et al. (2020)
Salecan Methyl violet PSO Freundlich 178.9 Qi et al. (2019a)
Gellan gum Methylene blue PFO Freundlich 192.1 Cai et al. (2021)
Xanthan gum Crystal violet PSO Langmuir 1567.0 Mittal et al. (2021)

17
X. Qi et al.
Fig. 8. Schematic illustration of the fabrication of chitosan-g-poly (acrylic acid)/cellulose nanowhiskers adsorbent for removing methylene blue (reproduced with
permission from Ref (Melo et al., 2018).). (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)
MoS2 increased the dye removal ability and the cycling property of
cellulose-based hydrogel. Wang et al. (2017b) designed a composite
cellulose hydrogel composed of cellulose and La2MnNiO6. In this
wastewater purification system, cellulose carbon xerogel provided the
adsorption sites for dyes, while La2MnNiO6 served as a catalyst. The dye
removal efficiency of this system was significantly enhanced under mi­
crowave irradiation. Micro-fibrillated carboxymethyl cellulose was also
possibly regarded as the carrier of Zn–Cu–Mg mixed metal hydrox­
ide/g-C3N4, which presented synergistic degradation activity through
photocatalysis and sonocatalysis (Gholami et al., 2020). Interestingly,
yeast-incorporated composite PVA/CMC materials were exploited by
Zhang et al. (2020b). The adsorption could be achieved chemically and
physically. The synergistic effect that existed in adsorbent (the valence
forces of hydroxyl groups, the interactions of carboxylate groups and the
larger surface area induced by the foaming phase of yeast) effectively
enhanced the methylene blue adsorption ability of the designed
yeast-incorporated PVA/CMC composite. Thanks to the existence of
yeast, the adsorbed dye can be biodegraded in the metabolism process.
The dye removal efficiency was nearly doubled, bringing a bio-friendly
strategy for wastewater treatment.
7.2.3. Adsorption of dyes using microbial polysaccharide-based adsorbents
Microbial polysaccharides are generally soluble in water, making
them difficult to use directly. Multiple attempts, such as forming a co­
valent bond and binding these polysaccharides with organic/inorganic
matrices, have been proposed to improve adsorption performance for
wastewater management. The features of incorporated groups, chains or
matrices with different dimensions could bring unique features to native
polysaccharides (Cai et al., 2021). For example, Das et al. (2020)
designed a dextran hydrogel using a simple one-pot synthesis to remove
methylene blue and methyl orange. The dextran hydrogel adsorbent was
obtained by cross-linking dextran with hexamethylene diisocyanate.
Chaudhary et al. (2018) synthesized a xanthan gum-psyllium-graft-poly
(acrylic acid-co-itaconic acid) adsorbent based on a free radical
18
Journal of Cleaner Production 315 (2021) 128221
polymerization technique. This grafted copolymer can remove toxic
effluents of textile. Abu Elella et al. (2019) used a facile and eco-friendly
approach to prepare a bifunctional hydrogel that possessed both dye
removal property (crystal violet) and antibacterial ability (Escherichia
coli). N,N,N-trimethyl chitosan and xanthan gum were adopted to create
an interpenetrating network hydrogel through electrostatic and
hydrogen bonding interactions. The adsorption process behaved in a
Langmuir isotherm model and the designed hydrogel adsorbent had
good regeneration ability. Mittal et al. (2021) successfully introduced
graphene oxide nanosheets into the hydrogel matrix composed of xan­
than gum and poly (acrylic acid-co 2-acrylamido-2-methyl-1-propane­
sulfonic acid). A maximum adsorption capacity of 1567.0 mg/g was
attained for crystal violet. This can be ascribed to the synergistic effect of
graphene oxide nanosheets and polysaccharide-containing hydrogel
matrix. Furthermore, the adsorption process was endothermic that fol­
lowed PSO kinetic model. Meanwhile, the adsorbent could be regener­
ated through acetone or ethanol, and the regenerated adsorbent still
possessed outstanding adsorption capacity even after twenty running
cycles.
7.3. Adsorption of other contaminants
In addition to dyes and heavy metals, other toxic water pollutants
like phenols, oils, pharmaceuticals, nutrients, arsenic and fluoride
restrict the sustainable clean water supply worldwide. In this section,
polysaccharide-based adsorbents for removing these pollutants are
briefly introduced (Table 3).
7.3.1. Adsorption of phenols
Phenolic pollutants such as p-chloro-m-xylenol, bisphenol A, keto­
profen and triclosan presented in wastewater are generally produced by
chemical, paper, pulp, gas, coke manufacture, pesticides, resin, paint
and dyeing industries. The existence of phenols in water worsens the
aquatic environment. These pollutants are toxic even at low
X. Qi et al. Journal of Cleaner Production 315 (2021) 128221

Table 3
Adsorption of other potential pollutants using polysaccharide-based adsorbents.
Polysaccharides used in preparing Adsorbates Best kinetic Best isothermal Maximum sorption capacity References
adsorbents model model (mg/g)

Chitin Cephalexin PFO Langmuir 245.2 Khanday et al. (2019)

Chitosan Ciprofloxacin PSO Langmuir 82.0 Afzal et al. (2018)
Cellulose Tetracycline PSO Freundlich 44.9 Sun et al. (2021)
Pectin AsO3−
4 PSO Langmuir 180.5 Mondal et al. (2021)
Alginate Phosphate PSO Langmuir 16.4 Wang et al. (2020)
Agarose Ofloxacin PFO Langmuir 581.4 Wang et al. (2021b)
κ-Carrageenan Ciprofloxacin PSO Sips 229.0 Yu et al. (2019a)
Guar gum 2-Chlorophenol PSO Langmuir 75.6 Sharma et al. (2017)
Konjac glucomannan Phosphate PSO Langmuir 16.1 Zhang et al. (2018)
Starch Gear oil PSO Langmuir 670.0 Priyanka and Saravanakumar
(2018)
β-Cyclodextrin Bisphenol A PSO Langmuir 25.5 Chen et al. (2020b)
Pullulan Fluorid PSO Langmuir 12.9 Ye et al. (2016)
Dextran Murexide PSO Langmuir 206.5 Demirbilek and Dinç (2016)
Gellan gum Cefuroxime PFO Langmuir 62.2 Racovita et al. (2016)
sodium
Xanthan gum Bisphenol A PSO Freundlich 458.0 Chen et al. (2019)

concentrations. For example, phenolic pollutants may cause human
diseases like jaundice and cancer, and phenolic pollutants (herbicide) in
drinking water cannot exceed 100 ng/L (Ahmed et al., 2020).
To remove phenolic pollutants from wastewater, various
polysaccharide-based adsorbents have been manufactured. Bahmani
et al. (2019) designed a chitosan-grafted-poly (N-vinylcaprolactam)
system in the presence of MOFs by the electrospinning method for
adsorption of phenol from water. The maximum experimental adsorp­
tion of the prepared nanofibers for phenol adsorption was 152.3 mg/g.
The adsorption mechanism was due to the synergistic effect of pore
filling and surface adsorption, π-π stacking and ion exchange. Mean­
while, regeneration of composite nanofibers could be achieved using
nitric acid. Chen et al. (2020b) synthesized a β-cyclodextrin-modified
graphene oxide membrane for removing bisphenol A. The designed
membrane had the characteristics of high efficiency in removing
bisphenol A from wastewater since bisphenol A molecules could form
stable complexes with β-cyclodextrin molecules via host-guest recogni­
tion. In addition, the as-fabricated membrane was easily regenerated by
washing with ethanol and the regenerated membrane still displayed
excellent removal ability (nearly 100%) after four repeated running
cycles. Sharma et al. (2017) synthesized a nanocomposite hydrogel
adsorbent consisted of pectin, guar gum, Fe3O4 and methyl­
enebisacrylamide for adsorption of o-chlorophenol and m-cresol. The
as-prepared adsorbent achieved maximum adsorption capacities of 75.6

Fig. 9. Fabrication and rapid absorption of oils by the alginate-based sponge (reproduced with permission from Ref (Ramakrishnan et al., 2021).).

19
X. Qi et al.
mg/g for o-chlorophenol and 176.1 mg/g for m-cresol. Experimental
results demonstrated that the Langmuir isotherm model could well
describe the phenol adsorption process of this nanocomposite hydrogel.
7.3.2. Adsorption of oils
Oil leakage incidences frequently occur in recent decades. The
discharge of oil pollutants jeopardizes environmental sustainability,
causing life-threatening effects and irrecoverable long-term damage to
natural ecosystems. To overcome these petroleum contamination chal­
lenges, substantial studies have been committed to fabricating
polysaccharide-based adsorbents (Tian et al., 2020). For example,
Ramakrishnan et al. (2021) designed a lightweight conjugate sponge
composed of sodium alginate and gum kondagogu (Fig. 9). This porous
sponge can effectively uptake crude oil (maximum adsorption capacity
= 28.5 g/g) from water. At the same time, the developed sodium algi­
nate/gum kondagogu bio-based adsorbent was proven to have good
mechanical integrity, robust structural stability and excellent reusability
that could retain 90% adsorption efficiency for diesel even after ten
recurring adsorption-regeneration cycles. Besides, the designed sponge
from renewable resources was biodegradable (92% degradation rate
after 28 days), which can eliminate the possibility of secondary pollu­
tion caused by the disposal of the sponge after reaching the expected
function, offering a green option for clearing oil spills from water. Gong
et al. (2019) reported a mechanically compressible and robust aerogel
composed of cellulose nanocrystals, PVA and silicone coating for
oil-water separation. The as-prepared adsorbent with hydrophobic
(water contact angle > 144.5◦ ), porous (porosity > 97.7%) and ultra­
light (density = 22.5–36.1 mg/cm3) features displayed high adsorption
ability (21.2–32.7 times its original weight of oils) and outstanding
regeneration capacity that behaved efficiently without a noticeable
Fig. 10. Preparation of alginate/κ-carrageenan gel beads for adsorption of ciprofloxacin hydrochloride (reproduced with permission from Ref (Li et al., 2019).).
20
Journal of Cleaner Production 315 (2021) 128221
decrease in oil adsorption capacity after ten consecutive regeneration
cycles.
Considering the complex contaminated aqueous phase, ions in the
solution usually impede oil adsorption efficiency. Thus, it is necessary to
eliminate ion interference in an oil-water complex phase. For this pur­
pose, Xiong et al. (2018) designed a cellulose-based adsorptive agent
(CH-TBM) composed of layered titanate nanofibers, δ-Bi2O3 and cellu­
lose. In this system, the layered titanate nanofibers were used to ex­
change metal cations, the oxygen vacancy provided by δ-Bi2O3 was
employed to capture anions, and the layer-by-layer assembled
nano-cellulose membrane was adopted to repel oil droplet. The devel­
oped multifunctional CH-TBM was demonstrated to be able to simulta­
neously remove oils (vegetable oil, crude oil and diesel), anions (Br− , I− ,
SeO2− 2− 2+
4 and SeO3 ) and cations (Cs , Cu , Sr
+ 2+
and Pb2+).
7.3.3. Adsorption of pharmaceuticals
Due to the continuous release by medicine factories and hospitals,
and extensive consumption by humans and animals, pharmaceuticals
like analgesics, antibiotics, painkillers and anti-inflammatories have
received more and more attention as emerging micro-pollutants (Singh
et al., 2019). The most widely used pharmaceutical compounds are
ciprofloxacin, tetracycline, ibuprofen, paracetamol, citalopram, diclo­
fenac, carbamazepine, acetylsalicylic acid and naproxen (Wang et al.,
2021b). These compounds are commonly resistant to biodegradation
and contain radioactive elements harmful to health through excessive
intake of contaminated water.
To remove pharmaceuticals from wastewater, different
polysaccharide-based adsorbents were fabricated. For example, Li et al.
(2019) prepared polysaccharide gel beads composed of alginate and
κ-carrageenan for the removal of ciprofloxacin hydrochloride (Fig. 10).
X. Qi et al.
The maximum adsorption of the alginate/κ-carrageenan gel system
reached 291.6 mg/g due to multiple interactions such as electrostatic
interactions and hydrogen bonding between the adsorbent and cipro­
floxacin hydrochloride. Sun et al. (2021) designed a cellulose adsorbent
to remove antibiotics from water. To increase the operational flexibility
of adsorption, cellulose extracted from Pennisetum sinese Roxb was
magnetized. Experimental results indicated that neutral pH and high
temperature could favor tetracycline adsorption, whereas ions and
humic acid inhibited tetracycline adsorption. Moreover, this magnetic
cellulose adsorbent exhibited high efficiency (80%) for removing
tetracycline from water. The possible adsorption mechanism was
attributed to the synergistic effect of pore adsorption and surface
adsorption. Afzal et al. (2018) prepared a sustainable and economical
chitosan/biochar hydrogel bead for removing ciprofloxacin from
aqueous solutions. The optimum pH for ciprofloxacin removal was 3 and
the maximum uptake ability of the chitosan/biochar adsorbent was
about 36.7 mg/g. The adsorption process obeyed Langmuir isotherm
and PSO kinetic models. Besides, this chitosan/biochar hydrogel
adsorbent presented good recyclability even after six repeating
adsorption-desorption cycles.
7.3.4. Adsorption of nutrients
The release of nutrients (phosphates, nitrates and ammonium salts)
into the natural ecosystem (Nie et al., 2020) enhances the level of
growth-limiting nutrients in the aquatic environment and promote the
growth of photosynthetic organisms like aquatic plants and organism,
Fig. 11. Possible mechanisms for phosphate removal using alginate-based composite (TAL) beads (reproduced with permission from Ref (Wang et al., 2020).).
21
Journal of Cleaner Production 315 (2021) 128221
which can decrease the oxygen content of water, causing eutrophication
of the aquatic ecosystem. The polysaccharide-based adsorbent is an
effective strategy to remove these tricky pollutants from water. For
example, Zhang et al. (2020a) prepared a composite (PAA/CTS/BC)
consisted of poly (acrylic acid)-grafted chitosan and biochar for
adsorptive removal of ammonium. The PAA/CTS/BC realized fast
(>90% within 20 min) and efficient (149.25 mg/g at 25 ◦ C) adsorption
of ammonium from water. Meanwhile, desorption of ammonium from
PAA/CTS/BC can also be achieved. These features make the designed
PAA/CTS/BC adsorbent a potential soil conditioner for sustainable
nitrogen-fertilizer use in agriculture. Wang et al. (2020) synthesized low
cost alginate beads in the presence of clay and lanthanum (La3+) ions for
phosphate adsorption. Several factors, including the adsorbent dosage,
solution pH, La3+ concentration, clay content and co-existing ions
(SO2−
4 , NO3 and Cl ) that may influence the adsorption efficiency, were
− −
investigated in batch experiments. The maximum adsorption capacity of
alginate beads for PO3− 4 was 50.3 mg/g, which was achieved at pH 4.
The PO3− 4 adsorption process of alginate beads fitted well to the Lang­
muir isotherm model and followed PSO kinetic model, suggesting
forming a monolayer of phosphate on the alginate beads. Multiple in­
teractions (Fig. 11) involving complexation (Lewis acid-base interac­
tion), ligand exchange and electrostatic interactions participated in the
removal process.
7.3.5. Adsorption of arsenic and fluoride
Arsenic and fluoride are two kinds of common contaminants in
X. Qi et al.
wastewater. Their safe concentration in drinking water is suggested no
more than 0.01 and 1.0 mg/L by the World Health Organization.
Considering this situation, Meng et al. (2013) fabricated a cellulose
hydrogel modified by poly (N, N-dimethyl aminoethyl methacrylate) for
removal of AsO3− 4 , AsO2 and F from aqueous solutions. Outstanding
− −
adsorption capacities (88.99, 3.47 and 3.80 mg/g for AsO3− 4 , AsO2 and
F− ions, respectively) were achieved. This functionalized cellulose
hydrogel adsorbent also demonstrated rapid adsorption (within 20 min),
and the adsorption process followed the intraparticle diffusion and PSO
kinetic model. These features make the as-fabricated cellulose hydrogel
a prominent adsorbent to tackle harmful anions from wastewater. Pin­
cus et al. (2021) developed various chitosan-based adsorbents
cross-linked by polyvalent metal ions (Fe3+, Al3+, Cu2+, Ni2+ and Zn2+).
Among these adsorbents, chitosan/Fe3+ showed the best performance
for selective adsorption of AsO3−
4 and AsO2 in the presence of interfer­
−
ence (phosphate). The maximum removal capacities of the chi­
tosan/Fe3+ complexes were 25.40 mg/g for AsO3− 4 and 6.00 mg/g for
AsO−2 . This work provided a facile and convenient method to develop
chitosan-based adsorbents for removing arsenic and other oxyanion
contaminants (selenium and hexavalent chromium) under the existence
of competitors (bicarbonate and silicate). Scalable synthesis of a stable
bio-adsorbent (HCOM3) was achieved by the entrapment of solid par­
ticulate waste collagenic fibers within a network of apple pomace
pectin-grafted-pentapolymer (Mondal et al., 2021). A maximum uptake
(180.47 mg/g for AsO3− 4 ) could be realized. Meanwhile, the HCOM3
system still maintained high adsorption efficiency (>92%) even after
five adsorption-desorption cycles.
7.4. Integration of adsorption with other wastewater treatment
technologies
Under certain circumstances, such as the co-existence of complex
multi-component pollutants (organic dyes, heavy metals, organic sol­
vents and oils), it is challenging to achieve wastewater purification and
pollutant recovery simultaneously by the adsorption approach. Gener­
ally, the integration of adsorption with other wastewater treatment
technologies (filtration, oxidation, membrane separation, ion exchange,
irradiation and biological degradation) is necessary. To seek more in­
sights on the roles of polysaccharide-based adsorbents in wastewater
disposal, some promising synergistic wastewater treatment strategies
will be discussed.
7.4.1. Integration of adsorption with microbial degradation
Adsorption and microbial degradation are often combined to treat
low concentrations of organic pollutants such as dyes because it is
challenging to remove low concentrations of pollutants from wastewater
by a single adsorption method. Microbial degradation of pollutants is a
biocompatible and sustainable approach. Various micro-organisms or
genetically engineered organisms (yeast, fungi, algae and bacteria) can
be used for wastewater treatment. For example, Saccharomyces cerevisiae
immobilized onto the polysaccharide beads could alleviate the harmful
effects of synthetic dyes. Lentinus polychrous Lév., a kind of fungi capable
of degrading dyes, was coated with chitosan, which could adsorb
anionic reactive dyes and promote decolorization efficiency (Wangpra­
dit and Chitprasert, 2014). Flores-Chaparro et al. (2018) prepared a
macroalgae composite to serve as a potential adsorbent. Chitosan and
pectin were selected as precursors to enhance the stability and appli­
cability of macroalgae biomass towards removing contaminants.
Attracted by these advantages, more polysaccharide-based bio-­
adsorbents that combine adsorption and microbial degradation will be
produced for wastewater treatment in the near future.
7.4.2. Integration of adsorption with enzyme degradation
Compared to microbial degradation, isolated enzymes loosen the
restriction of external conditions because microbial growth is vital to
degrade pollutants. Enzymatic decolorization is deemed as one eco-
22
Journal of Cleaner Production 315 (2021) 128221
friendly and specific method to cope with the issues of dye pollution.
Typically, the enzymes can be loaded into the polysaccharide-based
matrix by physical adsorption, chemical attachment and entrapment
that could be protected from extreme stimuli after immobilizing in the
polysaccharide-based matrix, benefiting the degradation of dyes. Under
appropriate conditions, high removal efficiency could be achieved by
these enzyme-loaded polysaccharide systems. For example, Veismoradi
et al. (2019) reported a polyacrylonitrile/chitosan composite membrane
system immobilized with tyrosinase to decolorize two common azo dyes
(acid blue 113 and direct black 22). Sun et al. (2015) entrapped laccase
into a chitosan-based sponge-like hydrogel to decolorize acid orange 7
and malachite green. The adsorption of chitosan hydrogel and enzy­
matic degradation endowed the designed platform with outstanding dye
removal performance. These results suggest that the integration of
adsorption with enzyme degradation is an effective method for treating
wastewater. However, the cost-effectiveness of production, the stability
of catalyst and catalyst generation hinder the development of enzymatic
decolorization.
7.4.3. Integration of adsorption with oxidation
Advanced oxidation processes (AOPs) are highly efficient in handling
organic pollutants (Rueda-Marquez et al., 2020). Photocatalysts produce
electron-hole in the conduction and valence bands by irradiating light,
creating superoxide radicals and hydroxyl radicals, thus decolorizing the
organic pollutants from the wastewater through redox reactions. Inte­
gration of adsorption with oxidation may be an effective strategy for
treating multicomponent wastewater systems. For example, the organic
pollutants can be degraded first and then other pollutants such as
inorganic contaminants were adsorbed to achieve highly efficient
wastewater purification.
Zhou et al. (2017) prepared a nano-TiO2/chitosan/poly (N-isopropyl
acrylamide) composite hydrogel to remove ionic dyes under ultraviolet
irradiation. Chitosan served as a biocompatible adsorbent, and nano-­
TiO2 worked as a photocatalyst to further realize more stable and effi­
cient dye degradation. Zhao et al. (2020) fabricated a novel
adsorption/photocatalyst system consisted of Fe-chitosan and mont­
morillonite nanosheets (MMTNS). Chitosan acted as a chelating agent
for the adsorption of Fe3+ ions. After introducing MMTNS into
Fe-chitosan solution, a self-assembled gel formed due to the interactions
between the MMTNS and Fe-CS, such as hydrogen bonding and elec­
trostatic force. Subsequently, the authors found that the designed
MMTNS/Fe-CS gel possessed superior removal efficiency for methylene
blue due to the synergistic effects of Fenton and adsorption. Besides,
heterogeneous semiconductor photocatalysis also brings rapid oxidation
and remarkable removal efficiency. For example, Pathania et al. (2016)
created a nano-sized composite consisting of ZnS nanoparticles and
chitosan-g-polyacrylamide to treat dye pollutants from water (congo red
and methyl orange) in the presence of solar irradiation. In this system,
chitosan was served as an excellent biomatrix for the adsorption of dyes,
while ZnS nanoparticles were acted as photocatalytic agents to degrade
dyes. Alimard (2019) developed an intriguing Nd–Ce doped Fe3O4-chi­
tosan nanocomposite that possessed a core-shell structure. Fe3O4 was
chosen as a catalyst to degrade dye (direct red 81) using hydroxyl rad­
icals. Nd3+ and Ce3+ can enhance magnetic responsiveness and catalytic
activity, while chitosan was responsible for adsorption. The experi­
mental outcomes indicated that the dye degradation efficiency was 28%
under optimum conditions. Moreover, the designed nanocomposite
could be recollected and reused. Pan et al. (2021) designed a Fenton-like
catalyst composed of polydopamine-coated Fe3O4 nanoparticles and a
pullulan matrix. In this work, polydopamine was acted as a bridge that
can simultaneously improve the stability of the pullulan network and the
catalytic degradation performance of magnetic nanoparticles. The
designed Fenton-like catalyst possessed superior degradation efficiency
for tetracycline (86.3% within 60 min) and outstanding regeneration
ability (almost 100% degradation efficiency after five cycles), offering a
facile and convenient approach for removing antibiotics from
X. Qi et al.
biomedical wastewater.
Electrochemical AOP is a novel and eco-friendly chemical decolor­
ization technique that can produce free radicals to degrade organic
pollutants. For example, Li et al. (2018) reported a poly­
saccharide/electrochemical system for organic pollutant removal using
the AOP strategy. The authors chose Pt sheets as the anodic and cathodic
electrodes, while chitosan/Fe3O4 magnetic nanoparticles served as
dispersed electrodes to facilitate the electrolytic efficiency. Chito­
san/Fe3O4 magnetic nanoparticles were regarded as three-dimensional
electrode reactors because of their role as electron suppliers, which
possessed good adsorption and specific surface areas. Using the Pt/chi­
tosan/Fe3O4 system, satisfying results (the max color removal efficiency
= 87.2%) were obtained under voltage 15 V in the presence of H2O2 and
NaBF4. Similarly, Cai et al. (2020) prepared a carbon composite derived
from Fe3O4@SiO2/starch, which can effectively degrade safranin T from
wastewater under the optimal conditions (99.1% within 20 min).
Microwave radiation is also a commonly employed method for
wastewater treatment, which can increase the temperature within ma­
terials. The microwave radiation-AOP is achieved under two possible
mechanisms, including heterogeneous and homogeneous processes. On
the one hand, the hotspot could indirectly promote reactive oxygen
species (ROS) production under microwave exposure. On the other
hand, the microwave could directly drive the activation of oxidants, thus
obtaining ROS and accelerating the chemical reactions. Water contam­
inants might be eliminated by AOP or thermal decomposition if they are
heating responsive. Generally, microwave-mediated AOPs are combined
with others methods like Fenton reactions, photocatalysis, ultraviolet/
H2O2 to degrade water pollutants. Another alternative ultrasonic wave
in an aqueous medium could lead to the production of microbubbles,
cavitation effect and various ROS. Additionally, relevant research in­
dicates that sonication poses a marked impact on the adsorption kinetics
of polysaccharide composite adsorbents. It would be reasonably antici­
pated that the other multiple and versatile polysaccharide-based systems
could be exploited by integrating AOPs and adsorption (physically or
chemically), enhancing the final removal efficiency of toxic pollutants.
8. Knowledge gaps in the future development
Polysaccharides as exciting raw materials to construct adsorbents for
wastewater treatment have received extensive attention from re­
searchers due to their excellent adsorption performance, low cost,
environmental friendliness, biocompatibility, biological activity and
biodegradability. However, there are still many investigation un­
certainties and gaps. More relevant research is needed to bridge these
knowledge gaps in the future.
8.1. Rational design and selection of material
What kinds of functional groups, chains and matrices combined with
polysaccharides depend on the intended adsorption goal. Categories,
amounts and locations of the introduced materials certainly play
different functional roles. Specifically, (1) incorporating functional
groups onto the polysaccharide backbone makes the preparation of
polysaccharide adsorbents with strong adsorption properties possible.
The most representative examples are cellulose and chitosan. Their
solubility and adsorption abilities could be improved through appro­
priate chemical modifications such as sulfonation, phosphorylation,
carboxylation and quaternization. (2) The introduction of some specific
ligands enables selective adsorption of polysaccharides possible. For
example, benzo-18-crown-6 possesses excellent recognition ability to
form a complex with Cs+ selectively through host-guest interactions (Yu
et al., 2017). Thus, introducing benzo-18-crown-6 to polysaccharides
will endow the designed adsorbents with high selectivity for removing
Cs+ from wastewater. (3) Choosing different cross-linking strategies can
adjust the mechanical, swelling and adsorptive properties of poly­
saccharides. For example, the interpenetrating polymer network
23
Journal of Cleaner Production 315 (2021) 128221
technique offers a convenient and effective route to enhance the
swelling response and mechanical performance of polysaccharide-based
adsorbents; cryogelation is also an appealing method to prepare porous
polysaccharide-based adsorbents with excellent mechanical property,
rapid adsorption rate and high adsorption capacity. (4) Constructing
polysaccharide materials with different architectures such as nano­
materials, beads, fibers, films, membranes, sponges and gels can achieve
different stability and adsorption performance. (5) Additional features
like magnetic, thermal and catalytic activities could be realized by
combining polysaccharides with specific matrices such as Fe3O4, carbon
tubes and TiO2. Therefore, reasonable material selection and design are
essential to achieve the resulted polysaccharide-based adsorbents with
desired adsorption performance.
8.2. In-depth understanding of adsorption mechanism
Exploration of primary adsorption mechanisms and influencing
factors help to select more proper adsorption materials under the com­
plex environment. The interactions between the polysaccharide adsor­
bents and adsorbates encourage scientists to seek balances among
variables under aqueous conditions. Firstly, as described in the review
before, the reactive sites on polysaccharides exert adsorbing ability for
pollutants due to various interactions like electrostatic interactions,
hydrogen bonding and chelation. Secondly, the solution pH, tempera­
ture, contacting time, pollutant concentration, adsorbent dosage and
adsorbent shape would undoubtedly affect the adsorption capacity and
behavior. Thirdly, the adsorption is interfered with by various factors
due to the complexity of water components and the natural environment
in real assessments such as multiple pollutants and salts. Only when the
mechanisms under different conditions are identified can the adsorbents
possibly work maximum efficiency.
8.3. Focusing on regeneration performance
The regeneration of the adsorbent is vital to reduce the operating
cost, avoid secondary waste generation and open up the possibility of
pollutant recovery. However, most researchers only focus on achieving
high adsorption performance, and adsorbent regeneration is rarely
mentioned. Among the few exceptions in regeneration research, the
adsorption-desorption cycle is generally not more than five times. Apart
from adsorption ability, an excellent adsorbent must possess a regen­
eration function from the perspective of industrial applications, which
can recover contaminations from wastewater, avoiding the generation
of secondary pollution. To achieve this goal, some key regeneration
parameters should be studied in detail like suitable regeneration
methods, optimal regeneration time, stability of polysaccharide-based
materials during the regeneration process and repeatability perfor­
mance of regenerated adsorbents.
8.4. Emerging contaminants
The continuous discharge of new chemicals into the environment
leads to new pollutants, which will seriously threaten the ecosystem and
human health. Water pollution caused by emerging contaminants
(personal care products, pharmaceuticals, toxins, hormones, endocrine
disrupters, disinfection by-products and volatile organic compounds)
makes wastewater treatment much more complicated and poses more
challenges to polysaccharide-based adsorbents. For example, metfor­
min, the most commonly used prescription drug for treating type 2
diabetes, is considered an emerging micropollutant since it is not
metabolized by humans, and the unmodified excretion of metformin can
lead to potential ecotoxicology (Zhang et al., 2021a). Thus, further de­
velopments on the polysaccharide-based adsorbents with appropriate
performance for removing emerging contaminants from wastewater
should be investigated.
X. Qi et al.
8.5. Other potential fabrication strategies and adsorbents
In addition to the preparation approaches proposed in the review,
there are other possible methods suitable for manufacturing
polysaccharide-based adsorbents. Developing new polysaccharide-
based adsorbents is essential since conventional techniques and adsor­
bents carry irremediable disadvantages. Generally, newly rising tech­
niques and adsorbents will provoke controversies. The key to
eliminating these controversies is how to attain a convincing adsorption
outcome. More interesting, it is still possible to prepare new poly­
saccharide adsorbents without the help of new preparation strategies.
The large-scale production of low cost and even customized new mi­
crobial polysaccharides is possible due to the continuous development of
fermentation and identification technology. These new polysaccharides
will provide a steady stream of materials for designing new adsorbents.
For example, salecan, a newly water-soluble extracellular β-D-glucan, is
produced by microbial fermentation. In the past ten years, salecan has
become a vital member of the polysaccharide family to construct ad­
sorbents for wastewater treatment (Qi et al., 2019b).
8.6. Upscaling and technology integration
The current adsorption technology using polysaccharide-based ad­
sorbents needs to be upgraded or integrated because it is difficult to use
the single adsorption technology to solve various complex situations in
real assessments. Multiple toxic water contaminants severely limit the
application area of adsorption technology. It is a good choice to upgrade
the adsorption technology or integrate the adsorption technology with
other water purification technologies like filtration, oxidation, mem­
brane separation, ion-exchange and irradiation. For example, thorough
adsorption performance assessment of polysaccharide-based adsorbents
could be predicted by machine learning and data mining strategies,
which promise a higher success rate of adsorption technology upscaling;
the integration of adsorption with an advanced oxidation process could
help improve water purification efficiency; combining polysaccharides
with some cutting-edge water generation approaches like solar energy
water evaporation is also an effective strategy for wastewater treatment.
These attempts may accelerate the large-scale industrial application of
polysaccharide-based adsorbents.
8.7. Future practical application of polysaccharide-based adsorbents
Laboratory research usually focuses on applying polysaccharide-
based adsorbents in simulated wastewater treatment. However, the
actual wastewater treatment often significantly differs from the labo­
ratory simulated wastewater treatment. For example, actual wastewater
usually comprises various pollutants (metals, dyes, phenols, pharma­
ceuticals and oils). Therefore, future adsorption research on
polysaccharide-based adsorbents should be extended to multi-pollutant
evaluation, rather than just focusing on the investigation of a single
pollutant. Furthermore, the selective removal of these multiple pollut­
ants is of great significance. The adsorbed pollutants can be recycled for
resource reuse, while the adsorbents can be regenerated and reutilized
in the next adsorption-desorption cycle. Secondly, the laboratory envi­
ronment is often very different from the natural environment, especially
involving continuous fluctuations in temperature and pH, which will
significantly affect the adsorbent performance. Fitting characteristics of
realistic pollutant removal environment and laboratory adsorption data
into machine learning models is a facile method that could predict the
optimal conditions and the practicality of polysaccharide-based adsor­
bents under the practical wastewater treatment environment. Thirdly,
the current fabrication strategies for polysaccharide-based adsorbents
still need to be improved because many synthesis methods are limited to
laboratories and are challenging to industrialize. A rapid, facile, inex­
pensive and efficient approach for constructing polysaccharide-based
wastewater adsorbents is necessary.
24
Journal of Cleaner Production 315 (2021) 128221
Overall, for the future practical applications of polysaccharide-based
adsorbents on an industrial scale, some critical aspects like
manufacturing/operation cost, large-scale production, pollutant
resource recycling, reusability, adaptability to complex environments
and spent adsorbent management should be considered.
9. Conclusions
The water pollution problems have become a significant concern for
everyone. Treating wastewater before discharge is a top priority. How­
ever, it is still challenging to provide a universal strategy for removing
all contaminants from wastewater. Adsorption is a well-established and
sustainable method to handle effluents in the industry since it has ach­
ieved satisfactory results in eliminating different water pollutants. The
adsorption process principally occurs by chemisorption, physisorption
and ion-exchange mechanisms, which can be predicted by different ki­
netic, isotherm and thermodynamic models. The adsorption process is
affected by various factors like adsorbents, the nature of contaminants
and the operation process variables.
Polysaccharides are promising candidates to construct adsorbents for
wastewater treatment due to their excellent properties like high
adsorptive performance, low cost, renewability, biodegradability,
environmental friendliness, ease of modification and functionalization.
However, native polysaccharides also possess some intrinsic drawbacks,
such as low surface area and poor mechanical strength. Therefore, the
practical design of polysaccharide-based adsorbents is vital because of
wastewater purification requirements. Meanwhile, more versatile and
intelligent polysaccharide adsorptive systems should be put forward to
develop current remediation strategies. Besides, sustainable re-
utilization and recycling would be necessary for further exploration,
whether the adsorbent or the adsorbate. These changes require an in-
depth understanding of the design and wastewater treatment applica­
tion of polysaccharide-based materials. That is precisely the purpose of
this review.
The present review highlights insights on the recent advances of
polysaccharide-based materials and systems in wastewater treatment.
Firstly, different types of polysaccharides that are often used to prepare
adsorbents are introduced. Secondly, different physical or chemical
cross-linking methods used to cross-link polysaccharides are discussed.
Thirdly, some of the design principles that should be considered in
adsorbent fabrication are summarized. Finally, a brief review of
knowledge gaps of polysaccharide-based adsorbents for cleaning pol­
lutants from wastewater is outlined. The authors hope that the current
review will provide a systematic and solid foundation for the rational
fabrication and development of polysaccharide-based adsorbents to
achieve suitable performance, bringing a revolution to polysaccharide-
based adsorbents for wastewater remediation. People may be lucky
enough to witness the large-scale transformation of polysaccharide-
based wastewater adsorbents from laboratory to industrialization.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This project was supported by the Wenzhou Medical University
(KYYW201906 and KYYW201901).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jclepro.2021.128221.
X. Qi et al. Journal of Cleaner Production 315 (2021) 128221

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