Carbohydrate Polymers 283 (2022) 119153

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Review

Advances in the application of chitosan-based metal organic frameworks as

adsorbents for environmental remediation
Herbert Musarurwa *, Nikita Tawanda Tavengwa
School of Chemistry, University of Venda, Private Bag X5050, Thohoyandou 0950, Limpopo Province, South Africa

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

Keywords: Chitosan is a bio-adsorbent with many amino and hydroxyl groups. The physicochemical properties of chitosan
Chitosan can be greatly enhanced by the formation of composites with other adsorbents. Thus, some researchers have
Metal organic frameworks incorporated metal-organic frameworks (MOFs) such as MIL (Materials Institute Lavoisier), UiO (University of
Adsorption
Oslo), ZIF (Zeolitic Imidazolate Frameworks) and, HKUST (Hong Kong University of Science and Technology)
Pollutants
series into the chitosan structure resulting in the formation of adsorbents with better adsorptive properties and
Environmental remediation
mechanical stability. The advances in the application of these chitosan/MOF composites during the adsorption of
environmental contaminants are the main aim of this current review. The review showed that composites of
chitosan and MOFs are versatile adsorbents of a variety of environmental pollutants, and most of them can be
easily regenerated and recycled. In addition, the challenges associated with the use of these composites and
future prospects are explored in detail in this review.

1. Introduction et al., 2021; Q. Li et al., 2021; Y. Zhao et al., 2021), functionalised

Anthropogenic activities have resulted in an exponential increase in
pollutants in the environment. Some of the problematic contaminants
discharged into the environment due to human activities include inor­
ganic pollutants such as heavy metals (Pavithra et al., 2021; Sun et al.,
2021; Thanthri et al., 2021) as well as organic pollutants such as dyes
(El-Zawahry et al., 2021; Haroun et al., 2021; Reghioua et al., 2021),
pesticides (Abukhadra et al., 2021; Mohammadi et al., 2021; Singh et al.,
2020) and antibiotics (Jia, Bai, et al., 2021; Liu, Nie, & Yu, 2021; Yaqubi
et al., 2021). These pollutants have adverse effects on the environment
and therefore their effective removal from the ecosystems is imperative.
Adsorptive removal of inorganic and organic pollutants from the
environment has gained popularity over the years (Palacio et al., 2020;
Shafaati et al., 2020; R. Tang, Wang, et al., 2021). This can be attributed
to the fact that it is a less sophisticated technique and is relatively cheap.
The success of the adsorptive removal of pollutants from the environ­
ment hinges on the availability of materials that have good adsorptive
properties. Some of these materials include polydopamine (W. Fan,
Yang, et al., 2021; Feng et al., 2021; Musarurwa & Tawanda Tavengwa,
2021; S. Shi, Xu, et al., 2021; Zhang et al., 2021), activated carbon (El
Kassimi et al., 2021; Guahk et al., 2021; Meez et al., 2021; Spessato
et al., 2021), carbon nanotubes (Abdullah et al., 2021; X. Jiang, Ruan,
conjugate adsorbents (Awual, Yaita, et al., 2020; Kamel et al., 2019),
functionalised composites (Awual & Hasan, 2019; Awual, Hasan, et al.,
2020; El-Sharkaway et al., 2020) and polysaccharide-based adsorbents
(Al-Dhabi et al., 2020; Musarurwa & Tavengwa, 2020; Saad et al., 2021;
Salehi & Hosseinifard, 2021; Zeng et al., 2021; T. Zhang et al., 2021).
The use of polysaccharide-based adsorbents during adsorptive removal
of environmental contaminants is gaining momentum among re­
searchers (Cao et al., 2021; Hu et al., 2020; W. Wang, Ni, et al., 2020).
This can be attributed to the fact that polysaccharides such as chitosan
and cellulose are relatively cheap and readily available. Chitosan is
among the polysaccharide-based adsorbents that have received
increasing attention from researchers in recent years (Elanchezhiyan
et al., 2021; Kaur et al., 2021; Ma et al., 2021; Sun et al., 2021). It has an
edge over most of the conventional adsorbents such as activated carbon
because it is readily available and inexpensive (El-Zawahry et al., 2021;
Haroun et al., 2021). In addition, chitosan has functionalities such as the
amino group (− NH2) and the hydroxyl group (-OH) that act as active
sites during the adsorptive removal of pollutants from the environment
(Kaur et al., 2021; Ma et al., 2021) (Fig. 1A). Chitosan, however, has
relatively low chemical and mechanical stability. The physicochemical
properties of chitosan can be enhanced tremendously through the for­
mation of composites with other adsorbents. Many researchers have

* Corresponding author.
E-mail address: hmusarurwac2@gmail.com (H. Musarurwa).

https://doi.org/10.1016/j.carbpol.2022.119153
Received 11 October 2021; Received in revised form 15 January 2022; Accepted 16 January 2022
Available online 20 January 2022
0144-8617/© 2022 Elsevier Ltd. All rights reserved.
H. Musarurwa and N.T. Tavengwa
Fig. 1. (A) Structure of chitosan and (B) number of publications involving the
use of chitosan/MOF hybrid materials during the analysis of environmental
pollutants from 2011 to 2020 (Data retrieved from the Web of Science on 2021-
04-27).
formed hybrid adsorbents of environmental pollutants using a combi­
nation of chitosan with materials such as graphene oxide (Jamali &
Akbari, 2021; X. Jiang, Pan, et al., 2021; Shan et al., 2021), carbon
nanotubes (Abdelmonem et al., 2020; Aydin, 2020), polyvinyl alcohol
(Attia et al., 2020; He et al., 2020; Khajavian et al., 2020a; Nguyen &
Bui, 2021) and metal-organic frameworks (MOFs) (Bahmani et al., 2019;
El-Shahat et al., 2020).
Composite adsorbents made from chitosan and MOFs have captured
the interests of many researchers (Khajavian et al., 2021; Samuel et al.,
2020; P. Shi, Hu, & Duan, 2021; J. Tang, Zhao, et al., 2021; Wen et al.,
2020). MOFs are coordination polymers that are highly porous and
crystalline. They consist of metal ions or metal clusters and organic li­
gands (Senosy et al., 2021; X. M. Wang, Kou, et al., 2020). The metals
that are in common use during the synthesis of MOFs include
aluminium, copper, titanium, magnesium, zinc, and zirconium (Dan
et al., 2020; Ghiasi et al., 2020; Moinfar et al., 2020; M. Niu et al., 2020).
The geometric shape (such as trigonal pyramidal, tetrahedral and
octahedral) of the MOFs depends on the coordination number of the
central metal. The organic ligands, on the other hand, that are
commonly used in MOFs include 1,4-benzene dicarboxylic acid; 1,3,5-
benzene tricarboxylic acid; imidicarboxylic acid, and 4,4′ -biphenyldi­
carboxylic acid (Y. Jiang et al., 2020; López et al., 2021; Mohammad­
nejad et al., 2018; Xu et al., 2021). The MOFs, formed by combining
these organic ligands and metal ions, are efficient adsorbents of a variety
of environmental pollutants. Their highly porous nature confers them
with a relatively large surface area for the adsorptive removal of con­
taminants from the environment (Duo et al., 2018; M. Y. Fan, Yu, et al.,
2021; Ghani et al., 2018; Habila et al., 2020; Wenmin et al., 2020; S.
Zhang et al., 2019). Thus, most MOFs have relatively high adsorption
capacities for pollutants in the environment. The hybrid materials
formed from chitosan and MOFs, therefore have excellent adsorptive
properties due to the combination of the good features from the two
adsorbents. These composite materials are stabilised by complexation
between the functionalities in chitosan and the metal centres of the
MOFs as well as interactions such as hydrogen bonds, van der Waals'
forces, and π-π interactions. Consequently, many researchers have
directed their research efforts towards the development of composite
adsorbents using chitosan and MOFs in order to ensure efficient
2
Carbohydrate Polymers 283 (2022) 119153
environmental remediation in recent years (Jamshidifard et al., 2019;
Liang et al., 2018; L. Liu et al., 2019; Reghioua et al., 2021; Samuel et al.,
2020; Zhuo et al., 2017) (Fig. 1B).
There are many recent reviews based on the adsorptive removal of
environmental pollutants using chitosan composite adsorbents (Begum
et al., 2021; da Silva Alves et al., 2021; Karimi-Maleh et al., 2021;
Khademian et al., 2020; Meteku et al., 2020; Nadar et al., 2019; Pal
et al., 2021; Yan et al., 2021). For instance, Begum et al. (2021) wrote a
detailed review on the application of chitosan composites as adsorbents
of heavy metals from the environment. In their paper, they outlined the
preparation of chitosan composites as well as their application during
the sequestration of heavy metals from environmental samples. In
another study, da Silva Alves et al. (2021) reviewed the utilisation of
composites of chitosan with magnetic nanoparticles, graphene oxide,
carbon nanotubes, activated carbon, and silicon during adsorptive
removal of dyes, heavy metals, antibiotics, and other organic pollutants
from environmental samples. In the same vein, Karimi-Maleh et al.
(2021) explored the adsorption of pharmaceuticals from wastewater
using chitosan composite adsorbents. To the best of our knowledge,
none of these reviews well-articulated the utilisation of chitosan/MOF
composite adsorbents during the adsorptive removal of pollutants from
the environment. There are limited comprehensive reviews on adsorp­
tion studies based on these highly porous bio-adsorbents. Thus, the
current review aims at exploring the advances in the application of
chitosan-based composites during the adsorptive removal of pollutants
from food and environmental samples. This study gives complementary
information to other reviews based on chitosan/MOF composites such as
the one by Nadar et al. (2019). In their study, they explored
polysaccharide-based MOFs in general without giving detailed infor­
mation on the application of chitosan/MOFs composite as adsorbents of
environmental pollutants. The major premise of this current study,
therefore, is to provide focussed and detailed elucidation of the role of
chitosan/MOF composites in environmental management. The use of
chitosan/MOFs composites minimizes secondary pollution of the envi­
ronment by the adsorbents since they have relatively high adsorption
capacities and most are recyclable. Thus, this is an informative review
that clearly outlines the positive impact of bio-adsorbents during envi­
ronmental remediation.
2. Application of chitosan/MOF hybrid materials during
environmental remediation
2.1. Chitosan/ZIF hybrid materials
Zeolitic imidazolate frameworks (ZIFs) represent is a special class of
metal-organic frameworks composed of imidazolate linkers and metal
ions, with structures similar to conventional alumino-silicate zeolites
(Chen et al., 2014; Guo et al., 2020) (Fig. 2A). They have intrinsic porous
characteristics and abundant functionalities as well as exceptional
thermal, chemical and mechanical stabilities (Y. Wang et al., 2019; Yang
et al., 2021). These characteristics confer them with good adsorptive
properties. As a result, ZIF MOFs have been used to form composites
with other materials such as chitosan to form adsorbents with excellent
adsorptive properties for environmental pollutants. Their adsorption
mechanisms usually involve the formation of hydrogen bonding, pi-pi
interactions and electrostatic interactions (Table 2). Composites of chi­
tosan with ZIF generally have relatively higher adsorption capacities,
larger surface area and greater mechanical stability as compared to
pristine chitosan. This can be attributed to the highly porous nature of
ZIFs and the presence of additional functionalities in the MOFs that
facilitate the adsorption of pollutants.
Some researchers have used composite materials of chitosan and ZIF
MOFs during the adsorptive removal of pollutants from the environment
(Bahmani et al., 2019; Guo et al., 2020; Khajavian et al., 2020b; Y. Wang
et al., 2019; Yang et al., 2021). For instance, Wang et al. (2019) used ZIF-
8/chitosan nanocomposites (ZIF-8@CS) for the effective removal of
H. Musarurwa and N.T. Tavengwa
Fig. 2. (A) Structures of ZIF-8, ZIF-67 and ZIF-90 (J. Zhang et al., 2020), (B) the
preparation of ZIF-8@CSM (Yang et al., 2021) and (B) the preparation of ZIF-
8@CS nanocomposites (Y. Wang et al., 2019).
Congo red dye from industrial wastewater. The ZIF-8@CS) nano­
composites were fabricated via the in-situ growth method (Fig. 2B). The
stability of the ZIF-8@CS nanocomposite was maintained by chelation
between the metal centres of the ZIF-8 MOF and the functionalities in
chitosan. Structural elucidation of the ZIF-8@CS nanocomposite was
done using SEM, TEM, XPS, FT-IR, and XRD. They systematically
investigated the adsorption behaviour of ZIF-8@CS nanocomposites on
Congo red in an aqueous solution. The data from adsorption isotherm
showed that the adsorption of Congo red by ZIF-8@CS was single-layer
adsorption and this was consistent with the Langmuir isotherm model. A
relatively high maximum adsorption capacity of 922 mg g− 1 was ob­
tained under acidic conditions when ZIF-8@CS composite was used for
the adsorptive removal of Congo red from wastewater. Congo red is an
anionic dye. Under the acidic conditions, protonation of the amino
groups in the nanocomposite occurred making it have a net positive
charge. Thus, electrostatic interactions facilitated the adsorption of
Congo red onto the surface of the ZIF-8@CS nanocomposite. The ki­
netics experiments showed that the adsorption of Congo red fitted the
pseudo-second-order model. Thus, the adsorption rate was mainly
3
Carbohydrate Polymers 283 (2022) 119153
controlled by the chemisorption mechanism. Congo red has π-electrons
and NH2 functionalities that facilitate the formation of π-π interactions
and hydrogen bonds, respectively. The adsorptive removal of Congo red
from aqueous solutions was, therefore, largely due to electrostatic in­
teractions, hydrogen bonding, π-π conjugation and zinc coordination
effect.
Zhao et al. (2020), on the other hand, used ZIF-8/chitosan beads for
the removal of tetracycline from water samples. The incorporation of
ZIF-8 into the chitosan structure enhanced its adsorption capacity.
Consequently, the ZIF-8/chitosan beads they synthesised had a rela­
tively high adsorption capacity (495.04 mg g− 1) for tetracycline. The
adsorption process of tetracycline by ZIF-8/chitosan beads followed
pseudo-second-order and Langmuir models. Their experimental results
showed that the extraction efficiency of ZIF-8/chitosan beads for
tetracycline was 90% after ten adsorption/desorption cycles. ZIF-8/
chitosan beads are, therefore, reusable and environmentally friendly
adsorbents. Structural characterisation results indicated that the mech­
anism of adsorption of tetracycline by ZIF-8/chitosan beads involved
electrostatic interaction, π-π interactions and hydrogen bond in­
teractions. These interactions can be attributed to the presence of the
hydroxyl and dimethylamine groups in tetracycline that can form
hydrogen bonds with the functionalities in the composite beads. In
addition, the π bonds in the tetracyclic naphthacene carboxamide ring
system and the imidazolate linkers in ZIF-8 facilitate the formation of π-π
interactions, which help to increase the mechanical strength of the
composite beads. Thus, the ZIF-8/chitosan beads are promising green
bio-adsorbents that form strong interactions with pharmaceuticals, and
they can be recovered easily and are reusable.
In another study, Liu et al. (2019) used ZIF-8/chitosan monolithic
composite beads for the adsorption of uranium (VI) from nuclear in­
dustrial wastewater. Monolithic composites, generally, are continuous
adsorbents with tractable morphological and physicochemical charac­
teristics (Acquah et al., 2017). The pore sizes of monolithic adsorbents
can be easily engineered into either macropores, mesopores or micro­
pores resulting in remarkable tailor-made selectivity. In addition,
monolithic adsorbents can be easily fabricated and suitable surface
functionalities may be attached to them resulting in enhanced adsorp­
tion capacities (Gaweł et al., 2010). Thus, the ZIF-8/chitosan monolithic
composite beads had a relatively high adsorption capacity for uranium
of 629 mg g− 1 at pH 3. It was an appealing adsorbent from an envi­
ronmental point of view since it could undergo a series of adsorption/
desorption cycles without significant loss of its adsorption capacity of
uranium (VI). This can be attributed to the relatively high chemical and
mechanical strength of the monolithic composite beads caused by strong
chelation between ZIF-8 metal centres with chitosan as well as the
presence of effective cross-linkages and hydrogen bonds. Structural
elucidation using XPS showed that the adsorption mechanism was
mainly through chelation of uranium (VI) with imidazole, hydroxyl and
amino groups found in the adsorbent.
ZIF functionalised chitosan composite nanofibers have been used by
some researchers during the decontamination of some environmental
samples (Bahmani et al., 2019; Mahmoodi et al., 2020). Generally,
chitosan nanofibers have a larger surface area and higher adsorption
capacity as compared to pristine chitosan. Bahmani et al. (2019), for
instance, synthesised chitosan-g-poly (N-vinylcoprolactum)/ZIF-8 (chi­
tosan-g-PNVCL/ZIF-8) nanofibers and successfully used them for the
adsorption of chromium (VI), arsenic (V) and phenol from water sam­
ples. The chitosan-g-PNVCL nanofibers were synthesised using free
radical polymerization prior to the incorporation of ZIF-8 MOF into their
structures. They characterised the chitosan-g-PNVCL/ZIF-8 adsorbent
using BET, SEM and XRD. Structural elucidation showed that the
incorporation of ZIF-8 into chitosan-g-PNVCL nanofibers caused an
enhancement of their diameter. Thus, the surface area of the nanofibers
increased resulting in an increase in adsorption capacity. Consequently,
their experimental results showed that the adsorption capacities of the
chitosan-g-PNVCL/ZIF-8 nanofibers for chromium (VI), arsenic (V) and
H. Musarurwa and N.T. Tavengwa
phenol were relatively high and they ranged from 395.8 to 495.6 mg g− 1
at pH 3. Acidic conditions promoted the protonation of the NH2 groups
in the composite nanofibers resulting in the formation of positive
charges. Electrostatic interactions between these positive charges and
the negative charges on the arsenate, dichromate and phenoxide ions
facilitated their adsorption. In a similar study, Mahmoodi et al. (2020)
synthesised a pearl necklace-like ZIF-8@chitosan/poly(vinyl alcohol)
(PVA) nanofiber and used it for the adsorption of dye from aqueous
solutions. The ZIF-8@chitosan/PVA nanofiber was synthesised by
coating ZIF-8 on chitosan/PVA electrospun nanofiber. Their experi­
mental results also showed that this adsorbent had a relatively high
adsorption capacity of 1000 mg g− 1 for the dye.
Yang et al. (2021) successfully used nano-ZIF-8@ chitosan micro­
spheres (ZIF-8@CSM) for the adsorptive removal of p-hydroxybenzoic
acid from agro-industrial wastewater. p-Hydroxybenzoic acid is an
emerging pollutant that has multiple sources such as the hydrolysis of
methylparaben, ethylparaben and propylparaben used widely as pre­
servatives in food and drinks. The presence of p-hydroxybenzoic acid in
environmental water poses health problems to living organisms. Thus,
its effective removal from water sources is imperative and ZIF-8@CSM is
a promising adsorbent that can help to achieve this end. Yang et al.
(2021), in their study, fabricated ZIF-8@CSM using a combination of
inverse emulsion method and in-situ growth method (Fig. 2C). The
adsorption kinetic experiments showed that adsorption of p-hydrox­
ybenzoic acid by the ZIF-8@CSM adsorbent rapidly reached equilibrium
in about 30 s. The equilibrium data fitted well into the Langmuir
isothermal model. Experimental results showed that ZIF-8@CSM had a
relatively high maximum adsorption capacity of 128.70 mg g− 1 for p-
hydroxybenzoic acid.
The use of chitosan/MOFs composite adsorbents in aquatic envi­
ronments is usually riddled by biofouling. Thus, there is a need to
develop chitosan/MOFs composite adsorbents with anti-fouling prop­
erties and Guo et al. (2020) performed research to this effect. They
developed a chitosan-graphene oxide/ZIF (GCZ8A) foam adsorbent with
antifouling properties via in situ growth of silver ions doped ZIF-8 on a
chitosan-graphene oxide foam substrate and successfully used it as an
adsorbent of uranium in seawater. The composite adsorbent they syn­
thesised was relatively stable. Its stability can be attributed to strong
interactions between graphene oxide, chitosan and ZIF-8 MOF.
Complexation of the metal centres of ZIF-8 with the carboxyl groups in
graphene oxide and the amino groups in chitosan could have contrib­
uted to the extra stability. In addition, hydrogen bonds and π-π in­
teractions helped to keep the composite intact. Thus, the GCZ8A
composite adsorbent exhibited high mechanical properties with about
352.41 KPa of compression stress and a low degradation rate with 3.26%
of mass loss in seawater. The adsorbent, due to the presence of silver ions
with ant-microbial properties, inhibited the growth of Nitzschia and
their cell death rate was more than 70%. In addition, the GCZ8A com­
posites inhibited cell adhesion on its surface. Thus, the GCZ8A foam
adsorbent had remarkable anti-biofouling properties. On the other hand,
the GCZ8A foam adsorbent had a relatively high maximum adsorption
capacity of 361.01 mg g− 1 for uranium and this was 1.9 times higher
than that of pure ZIF-8 (189.75 mg g − 1) at pH 8.0. Under basic con­
ditions deprotonation of the acidic groups in the composite occurred
resulting in the formation of negative charges, which then electrostati­
cally attracted the positively charged uranium ions. Structural elucida­
tion experiments showed that the GCZ8A foam adsorbent had a
relatively large specific surface area of 200.79 m2 g− 1 as well as nitro­
gen/oxygen functional groups. These are the attributes that can be used
to explain its relatively high adsorption capacity. Another attractive
feature of the GCZ8A adsorbent was that it could undergo a series of
regeneration cycles without significant loss of its adsorption capacity as
a result of its high mechanical stability.
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Carbohydrate Polymers 283 (2022) 119153
2.2. Chitosan/MIL hybrid materials
MIL (Materials of Institute Lavoisier) MOFs are coordination poly­
mers composed of trivalent metal nodes (such as chromium (III), va­
nadium(III) and iron(III)) complexed with porous carboxylate ligands
(Elrasheedy et al., 2019; Ghiasi et al., 2020) (Fig. 3A). They possess
significantly large channels/cages with topologies similar to zeolites.
These MIL MOFs have an open-framework structure, and their pore sizes
and shapes depend on the strength of the host-guest interactions. They
have relatively high chemical and mechanical stabilities (Moinfar et al.,
2020; Senosy et al., 2021). The physicochemical properties of adsor­
bents such as chitosan can be improved by incorporating MIL MOFs into
their structures. This results in the formation of highly porous adsor­
bents with multi-functionalities and improved mechanical strength.
These features make MIL composites to be suitable for use as adsorbents
of pollutants in food and environmental samples. Thus, hybrid materials
made from chitosan and MIL MOFs are slowly gaining popularity among
researchers during the adsorptive removal of pollutants from the envi­
ronment (El-Shahat et al., 2020; L. Liu et al., 2016; Y. Wang, Wang,
et al., 2020; Xiong et al., 2020) (Table 1). Chitosan/MIL-based adsor­
bents form many types of interactions such as hydrogen bonding, elec­
trostatic interactions, pi-pi interactions and cation-pi interactions with
environmental pollutants during adsorption (Table 2).
One of the MIL MOFs used by researchers is MIL-101 (Y. Wang,
Wang, et al., 2020; Xiong et al., 2020). It is a mesoporous MOF that is
composed of chromium or iron has a metal centre and terephthalate as
the organic linker. MIL-101 has a large surface area and pore volume as
well as having fairly good resistance to common solvents and thermal
stability (Darvishnejad et al., 2020; Ghiasi et al., 2020). Its framework
consists of terephthalate linkers and M3O-carboxylate trimers (M = Cr or
Fe) with octahedrally coordinated metal ions binding terminal water
molecules. The water ligands can be removed from the MIL-101 MOF by
thermal treatment and this creates active unsaturated coordinate sites,
which can be used during complexation with other adsorbents such as
chitosan to form composites (Maksimchuk et al., 2012). The incorpo­
ration of MIL-101 into the chitosan structure enhances its chemical and
thermal stability as well as the introduction of additional functionalities
that aid the adsorption process of pollutants from the environment.
Chitosan sponge adsorbents are highly porous and present a large
surface area during the adsorptive removal of pollutants from the
environment. The porosity of chitosan sponges can be further enhanced
by the formation of composites with MOFs such as MIL-101. In addition,
chitosan/MIL-101 sponge adsorbents have relatively high mechanical
stabilities and high adsorption capacities as well as being multifunc­
tional. These properties make chitosan/MIL-101 sponges good adsor­
bents of environmental pollutants. Wang, Kou, et al. (2020), for
instance, successfully used a nano-MIL-101(Fe)@chitosan hybrid
sponge to remove anionic dyes from aqueous solutions. Chelation be­
tween the unsaturated coordinate sites in MIL-101(Fe) and the NH2
groups in chitosan helped to stabilise the composite as well as hydrogen
bonds. The hybrid sponge composite had a porous structure and high
elasticity as well as good mechanical stability. These characteristics
conferred it with good adsorption capacity and re-usability. The hybrid
polymeric sponge adsorbent was prepared using a freeze-drying method
and then characterised using SEM, TEM and FT-IR. The characterisation
results showed that the rhombic MIL-101(Fe) particles were embedded
into the hybrid sponge uniformly. The adsorption efficiency of the
hybrid sponge for the anionic dyes was relatively high as compared with
the pristine chitosan sponge. This can be attributed to the presence of
additional functionalities as well as the improved surface area from the
porous MIL-101(Fe) MOF. Thus, the hybrid sponge adsorbent had rela­
tively high adsorption capacities for the anionic dyes. For instance, the
maximum adsorption capacity of MIL-101(Fe) @chitosan sponge for
acid red 94 was 4518 mg g− 1. The adsorption mechanisms mainly
involved electrostatic interactions and hydrogen bonding.
In the same vein, Liu et al. (2016) prepared a magnetic composite
H. Musarurwa and N.T. Tavengwa
Fig. 3. (A) Structures of MIL-100(Fe), MIL-101 (Cr) and MIL-127(Fe) (Chanut et al., 2016; C. Wang et al., 2018), (B) SEM image of chitosan and (C) SEM image of
MIL-125-NH2@cross-linked chitosan (El-Shahat et al., 2020) (Copyright permission granted).
bio-adsorbent using chitosan, iron oxide nanoparticles and MIL-101(Cr)
MOF (m-CS/Fe3O4/MIL-101). The composite was also stabilised by
complexation between the functionalities in chitosan and the unsatu­
rated sites in the MIL-101(Cr) structure. The m-CS/Fe3O4/MIL-101
composite was characterised using XRD, BET and vibrating sample
magnetometer prior to its application during the adsorptive removal of
methyl orange dye from aqueous solutions. The characterisation results
showed that the composite adsorbent had a large surface area for the
adsorption of methyl orange dye and enough magnetism to enable it to
be retrieved from the bulk solution using an external magnet. Electro­
static interactions and hydrogen bonds were involved during the
adsorptive removal of methyl orange from water. The bio-adsorbent had
a relatively high maximum adsorption capacity of 117.6 mg g− 1 for
methyl orange. This can be attributed to the presence of the MIL-101
MOF, which has a highly porous structure and a large surface area.
The enhanced adsorption capacity was indicative of the high extraction
efficiency of the m-CS/Fe3O4/MIL-101 composite for methyl orange. In
addition, the composite bio-adsorbent was reusable several times
without significant loss of its adsorption capacity due to increased me­
chanical strength from the MIL-101(Fe) MOF and it could be recovered
easily from the bulk solution using an external magnetic field. These
attributes made m-CS/Fe3O4/MIL-101 bio-adsorbent to be more
appealing to environmentally conscious researchers.
In a similar study, Zhuo et al. (2017) successfully used composite
beads (MIL-101(Cr)/CS) made from chitosan and MIL-101(Cr) MOF for
the adsorption of pharmaceuticals and personal care products (PPCPs)
from water. The stability of the composite beads was maintained by
complexation between the functionalities of the PPCPs and the metal
centres of MIL-101 as well as electrostatic interactions and hydrogen
5
Carbohydrate Polymers 283 (2022) 119153
bonds. They studied the adsorptive removal of three PPCPs, namely
benzoic acid, ibuprofen and ketoprofen, from water using the MIL-101
(Cr)/CS composite beads. The composite beads exhibited relatively
high adsorption capacity for the PPCPs as compared to pristine chitosan.
The adsorptive properties of the composite were enhanced by the
incorporation of the highly porous MIL-101 MOF into the chitosan
structure. Structural elucidation using X-ray photoelectron spectroscopy
showed that the extraction of the PPCPs from wastewater occurred
through electrostatic interactions between the protonated amino groups
of chitosan and the Cr centres of the MIL-101(Cr) MOF. Adsorption
isotherms and π-energy analysis showed that π − π interaction of the
aromatic groups between adsorbents and contaminants was another
possible mechanism during the adsorptive removal of PPCPs from
wastewater. They also observed that the MIL-101(Cr)/CS composite
beads could undergo a series of adsorption/desorption cycles without a
significant decrease in adsorption capacity. Thus, the MIL-101(Cr)/CS
composite beads are reusable, as a result of enhanced mechanical
strength, and environmentally friendly adsorbents.
Some researchers used MIL-125 MOF to fabricate chitosan and suc­
cessfully used the composites during the adsorptive removal of pollut­
ants from environmental samples. MIL-125 was first reported by Dan-
Hardi et al. (2009) and was synthesised using titanium(IV) isopropoxide
as the metal cluster and 1,4-benzene dicarboxylic acid as the organic
linker. It is thermally stable up to 290 ◦ C, highly porous and has a large
surface area. These attractive features make it have good adsorptive
properties for environmental pollutants. Thus, the fabrication of other
adsorbents such as chitosan with MIL-125 results in the enhancement of
their physicochemical properties. Liang et al. (2018), for instance, used
composite beads composed of MIL-125 MOF and chitosan (MIL-125/CS)
H. Musarurwa and N.T. Tavengwa Carbohydrate Polymers 283 (2022) 119153

Table 1
Application of chitosan-based MOF adsorbents during removal of environmental pollutants.
Matrix Analyte Chitosan-based MOF adsorbent Metal Adsorption capacity (mg g− 1) Reference
centre

Radioactive Uranium cCS/PVA/UiO-66-NH2 membrane Zirconium 316.50 Wang et al., 2021

wastewater
Industrial Methylene blue HKUST-1/cellulose/chitosan aerogel Copper 526.30 Q. Liu, Yu, et al.,
wastewater 2021
Water Anionic dyes MIL-101(Fe)@chitosan hybrid sponge Iron 4518.00 Y. Wang, Wang,
et al., 2020
Water Dyes chitosan/poly(vinyl alcohol)]ZIF-8 Zinc/cobalt – Khajavian et al.,
2020a
Aqueous solutions p-Hydroxybenzoic acid ZIF-8@chitosan microspheres Zinc/cobalt 128.70 Yang et al., 2021
Aqueous solutions Antimony (Sb (III) MIL-100(Fe)/Fe2O4/chitosan composite Iron – Xiong et al., 2020
Environmental water Iodide ions MIL-125-NH2@Chitosan Titanium 399.68 El-Shahat et al.,
2020
Seawater Uranium Chitosan - graphene oxide/ZIF-8 foam Zinc/cobalt 361.01 Guo et al., 2020
adsorbent
Pharmaceutical Tetracycline MOF (ZIF-8, ZIF-67, HKUST-1, and Fe-BTC)/ Copper/ 495.04 Zhao et al., 2020
wastewater chitosan composites iron
Industrial Dyes ZIF-8 crystal was coated on chitosan/ Zinc/cobalt 1000.00 Mahmoodi et al.,
wastewater polyvinyl alcohol electrospun nanofiber 2020
Industrial Methylene blue Cu-3(btc)(2)/chitosan /graphene oxide Copper 357.15 Samuel et al., 2020
wastewater composite
Environmental water Chromium (VI), arsenic (V) Chitosan-grafted-poly(N-vinylcaprolactam)/ Zinc/cobalt 269.2 (Cr(VI)), 258.5 (As (V) and Bahmani et al.,
and phenol ZIF-8 composite 152.3 (Phenol) 2019
Industrial Congo red ZIF-8 dotted chitosan nanocomposites Zinc/cobalt 922.00 Wang et al., 2019
wastewater
Environmental water Uranium Chitosan/ZIF-8 composite monolithic beads Zinc/cobalt 629.00 Liu et al., 2019
Environmental water Lead(II), cadmium (II) and PAN/chitosan/UiO-66-NH2 nanofibrous Zirconium 372.60 (chromium), 415.60 Jamshidifard et al.,
chromium (VI) ions adsorbent (cadmium) and 441.20 (lead) 2019
Aqueous solutions Congo red Chitosan/UiO-66 monolith Zirconium 246.21 Wen et al., 2020
Beverages and water Bisphenols MIL-53(Al)/CS foam Aluminium Li et al., 2020
Water Herbicides UiO-66 on ionic liquid modified chitosan Zirconium – Huang, Feng, et al.,
2020
Sewage wastewater Sulfanilamide Hierarchical porous starch-chitosan-UiO-66- Zirconium – Jia, Zhang, et al.,
COOH composite 2021
Water Methyl orange Cs/UiO-66 composite Zirconium 370.37 Ediati et al., 2021

NOTE: - not given; cCS- crosslinked chitosan; PVA- polyvinyl alcohol; UiO – University of Oslo; BTC - benzene-1,3,5-tricarboxylic acid; ZIF - zeolitic imidazole
framework; PAN- polyacrylonitrile; MIL - Materials of Institute Lavoisier; HKUST - Hong Kong University of Science and Technology.

as an adsorbent of lead (II) ions from wastewater. The MIL-125/CS
composite beads were synthesised by combining MIL-125 and chitosan
using a template-free solvothermal method under ambient conditions.
The use of ambient conditions during its synthesis, made the MIL-125/
CS adsorbent appealing from an environmental point of view. Struc­
tural characterisation of the beads was done using FT-IR, XPS, SEM and
TGA. The characterisation results showed that the MIF-125 fillers were
successfully embedded into the chitosan matrix. In addition, they
showed that MIL-125/CS had relatively high thermal stability. This can
be attributed to the presence of the thermally stable MIL-125 MOF in its
structure. The maximum adsorption capacity of the composite beads for
lead (II) ions was relatively high (407.50 mg g− 1) at ambient tempera­
ture. This can be explained in terms of the highly porous nature and
large surface area of the adsorbent due to the presence of the MIL-125
particles embedded into the composite. The adsorption of the Pb2+ by
the MIL-125/CS was favoured by alkaline conditions. Under basic con­
ditions, deprotonation of the acidic groups in the composite would occur
resulting in the formation of negative charges. Electrostatic interactions
between the negative groups in the composite and the positively charged
lead (II) facilitated the adsorption process. They performed a series of
adsorption/desorption cycles for lead (II) ions using MIL-125/CS com­
posite beads as adsorbents and there was no significant decrease in
adsorption capacity. The enhanced mechanical stability of the MIL-125/
CS composite made it remain relatively intact during each adsorption/
desorption cycle. The MIL-125/CS composite beads are, therefore,
reusable and very appealing from an environmentally point of view.
In the same vein, El-Shahat et al. (2020) successfully used a mem­
brane synthesised from MIL-125-NH2 and cross-linked chitosan for the
adsorptive removal of iodide ions from radioactive wastewater. The
incorporation of MIL-125-NH2 and cross-linkages greatly enhanced the
chemical and thermal stability of the chitosan membrane. The chitosan
films were synthesised using solvent casting technique while the chito­
san/MIL-125-NH2 composite films were prepared by post-synthetic
modification of the chitosan membrane. The composite was stabilised
by strong hydrogen bonds between the functionalities in chitosan and
MIL-125-NH2 MOF as well as complexation between the T4+ metal
centres and the OH/NH2 groups in the polysaccharide. The synthesised
chitosan/MIL-125-NH2 membrane was characterised using SEM, FT-IR,
BET, XRD and TGA. The SEM image of crosslinked chitosan revealed that
it had hexagonal porous surfaces (Fig. 3B). The presence of MIL-125-
NH2 in the structure of crosslinked chitosan resulted in the enhancement
of its pore sizes (Fig. 3C) as well as its specific surface area. The
adsorption of iodide ions by this membrane adsorbent occurred through
electrostatic interactions after the protonation of the –NH2 group under
acidic conditions as well as chemosorption via host-guest interactions. A
relatively high adsorption capacity of 399.68 mg g− 1was obtained when
the chitosan/MIL-125-NH2 membrane was used for the adsorptive
removal of iodide ions from wastewater. The enriched chitosan/MIL-
125-NH2 membrane was immersed in 0.5 M NaCl solution during
desorption and stirred overnight at room temperature. After filtering off
the NaCl solution, the membrane was washed several times with
deionised water until no iodine could be detected using UV–vis spec­
trophotometer. The membrane was reusable for several times without
significant loss of its adsorption capacity.
MIL-100(Fe) is another MOF that has excellent adsorptive properties.
It can be synthesised easily using the microwave-assisted hydrothermal
method, which involves the spontaneous coordination between iron(III)
cations and 1,3,5-benzene tricarboxylate linkers resulting in the gener­
ation of a porous architecture (Cutrone et al., 2019). The MIL-100(Fe)
structure is accessible through the 5.6 and 8.6 Å mesoporous windows

6
H. Musarurwa and N.T. Tavengwa Carbohydrate Polymers 283 (2022) 119153

Table 2
Synthesis of chitosan/MOF adsorbents for specific applications and their advantages and limitations.
Chitosan/MOF Synthesis Adsorption Advantages Limitations Interactions Application Reference
adsorbent technique capacity (mg
g− 1)

UiO-66/ In situ growth 490.72 and High adsorption Expensive Hydrogen bonding, Adsorption of Eltaweil et al.,
GOCOOH@SA 343.49 capacity and reusable electrostatic methylene blue and 2021
interactions and copper (II) ions
cation-pi
interactions
Cs/UiO-66 Impregnation 370.37 Improved surface area Environmental risk Pi-pi interactions, Adsorption of Ediati et al.,
techniques for adsorption hydrogen bonding methyl orange 2021
compared to pristine and electrostatic
chitosan, higher interactions
adsorption capacity
Cs/PEO@MOF-5 Electrospinning – Has highly ordered, May have crack Size exclusion Adsorption of Pan et al., 2021
nanofiber uniform, and crystals defects PM2.5
membrane and is reusable
Fe3O4/ZIF- In situ growth 119.05 Reusable, large Risk of Electrostatic Adsorptive removal Omer et al.,
67@AmCs adsorptive surface environmental interactions and pi- of chromium (VI) 2021
composite area and high pollution by organic pi interactions ions from water
beads adsorption capacity solvents
Cu-BTC/Cs/PVA Layer-by-layer – Large surface area and May have crack Van der Waals CO2 capture Jiamjirangkul
nanofibrous assembly are reusable defects resulting in interactions et al., 2020
membrane gas leakages
MIL-125/Cs Template-free 407.50 Synthesised under May cause pollution Electrostatic Adsorptive removal Liang et al.,
composite solvothermal ambient conditions, of the environment interactions and of lead (II) ions 2018
beads approach reusable and high by organic solvents cation-pi from wastewater
adsorption capacity interactions
UiO-66/tannic In situ growth – High chemical May have crack Electrostatic Adsorption of Shi, Hu, &
acid/Cs/PES stability and can be defects interactions and chromium (VI), acid Duan, 2021
membrane recycled hydrogen bonding brilliant scarlet dye
and methylene blue
dye
Citric acid In situ growth 225± 4 High mechanical and Environmental risk Hydrogen bonding, Adsorption of Niu et al., 2021
crosslinked (chromium(VI)) chemical stability, electrostatic chromium (VI) ions
ZnBDC/Cs and 202±3 high adsorption interactions and pi- and methyl orange
(methyl orange) capacity and reusable pi interactions dye
Cs/MOF-SH In situ co- – High affinity for lead Environmental risk Electrostatic Solid-phase Huang, Huang,
precipitation (II) and cadmium (II) interactions and extraction of lead et al., 2020
ions high chemical cationic (II) and cadmium
stability and can be interactions (II) from food
reused samples

Note: - not given; MOF – metal-organic frameworks; UiO – University of Oslo; GOCOOH- carboxylated graphene oxide; SA – sodium alginate; CS – chitosan; ZIF-8 -
zeolitic imidazole framework; AmCs - aminated chitosan; PVA – poly(viny alcohol); BTC - benzene-1,3,5-tricarboxylic acid; ZnBDC - zinc 1,4-benzenedicarboxylate;
PM2.5 – particulate matter with a diameter of 2.5 μm or less; PEO - polyethylene oxide; MOF-SH -thiol modified metal-organic framewor.

and it forms 24 and 29 Å internal cages. These mesoporous windows and
internal cages increase the surface area of MIL-100(Fe). In addition, it
forms a significant amount of accessible Lewis acid metal sites upon
dehydration (Hei et al., 2014). These unoccupied sites are available
during chemical modification and formation of composites with other
adsorbents such as chitosan. Thus, some researchers have taken
advantage of these unique properties of MIL-100(Fe) and used it to form
versatile composite adsorbents with multi-functionalities and enhanced
mechanical strength. Xiong et al. (2020), for instance, used nano-MIL-
100(Fe) modified chitosan for the adsorption of antimony (III) from
aqueous solutions. The MIL-100(Fe)/chitosan adsorbent was prepared
by grafting iron oxide nanoparticles and MIL-100(Fe) onto chitosan
prior to characterisation using FT-IR and XRD. Optimum conditions for
the removal of antimony (III) from aqueous solutions were evaluated
using batch experiments. Their results indicated that the adsorption
efficiency for antimony (III) increased with an increase in the concen­
tration of the MIL-100(Fe)/chitosan adsorbent as well as an increase in
pH. They obtained a maximum adsorption efficiency of 96.8% using a
10 mg L− 1solution of antimony (III) and an adsorbent with a concen­
tration of 15 g L− 1 at a pH of 11. Thus, their findings showed that MIL-
100(Fe)/chitosan adsorbent could be used for the effective adsorptive
removal of antimony (III) from aqueous solutions. In addition, the MIL-
modified chitosan adsorbent could be easily recovered and reused
several times without significant loss of its adsorption capacity.
2.3. Chitosan/UiO hybrid materials
UiO (University of Olso) are co-ordination polymers that belong to
the zirconium–carboxylate-based MOF family. UiO-66, UiO-67 and UiO-
68 are among the common zirconium-based MOFs that are used for the
adsorptive removal of pollutants from the environment (Duo et al.,
2018; Mao et al., 2019; Mehta et al., 2019) (Fig. 4A). They possess
substantial chemical stability and exceptional thermal stability
(Elrasheedy et al., 2019). In addition, they are highly porous and have
good mechanical stability. UiO-66, however, has been widely used by
researchers as an adsorbent for environmental pollutants since it has
outstanding stability as compared to the other UiO MOFs (Cao et al.,
2021; Jamshidifard et al., 2019; Wen et al., 2020) (Table 1). This
remarkable stability may be attributed to the compact structure of UiO-
66 as well as the strong Zr–O bonds (Ru et al., 2021). These properties
make UiO-66 suitable for use during the formation of composite ad­
sorbents with materials such as chitosan. Its unique pore sizes confer
composite adsorbents with some selectivity during the adsorptive
removal of environmental pollutants.
Hybrid materials composed of chitosan and UiO-66 MOFs have been
applied during the adsorptive removal of some pollutants from envi­
ronmental samples (Jamshidifard et al., 2019; Y. Wang et al., 2021; Wen
et al., 2020). For instance, Wen et al. (2020) successfully used chitosan/
UiO-66 MOF composite monolith as an adsorbent for the removal of
Congo red dye from wastewater. The composite monolith was prepared

7
H. Musarurwa and N.T. Tavengwa
Fig. 4. (A) Structures of UiO-66, UiO-67 and UiO-68, (B) schematic of the
synthesis of nanofibers/MOFs and its application for the removal of metal ions,
(C) SEM image of PAN/chitosan nanofiber and (D) SEM image of PAN/chitosan
nanofiber 10 wt% UiO- 66-NH2 MOF (Jamshidifard et al., 2019) (Copyright
permission granted).
using the ice-templating method. Chelation between the metal centres of
the UiO-66 MOF and the functionalities in chitosan helped to keep the
composite monolith stable. The stability of the monolith in aqueous
solutions was also enhanced by cross-linking UiO-66 MOF with glutar­
aldehyde prior to its formation. After synthesis, the monolith was
characterised using SEM, N2 adsorption, and XRD. These structural
characterisation techniques revealed that the composite monolith
possessed hierarchical pores with UiO-66 particles embedded on the
surface of the chitosan matrix. The presence of hierarchical pores
conferred the composite monolith with a large surface area for the
adsorption of the Congo red dye. The monolith managed to adsorb about
90% of the Congo red dye from aqueous solutions in 60 min. Thus, the
adsorption efficiency of the monolith was very high with a maximum
adsorption capacity of 246.21 mg g− 1.
Jamshidifard et al. (2019) incorporated amino-functionalised UiO-
66-NH2 MOF into polyacrylonitrile (PAN)/chitosan nanofibers and used
the resultant composite for the adsorption and membrane filtration of
lead (II), cadmium (II) and chromium (VI) ions from aqueous solutions.
The amino-functionalised UiO-66 was synthesised by microwave
8
Carbohydrate Polymers 283 (2022) 119153
heating method using zirconium chloride, N,N-dimethylformamide, 2-
aminoterephthalic acid and hydrochloric acid followed by drying at
room temperature for 24 h (Fig. 4B). The UiO-66-NH2 MOF formed was
then incorporated into a mixture of solutions of PAN and chitosan
resulting in the formation of UiO-66-NH2/PAN/chitosan nanofibers. The
stability of the nanofibrous membrane was maintained by complexation,
electrostatic interactions and hydrogen bonds. Structural characterisa­
tion of the nanofibers was done using XRD, BET, FT-IR and SEM. The
SEM images of PAN/chitosan nanofibers revealed that the adsorbent had
a smooth morphology with an average diameter of the nanofibers being
235 nm (Fig. 4C). The incorporation of UiO-66-NH2 into PAN/chitosan
nanofibers caused them to have a well-defined morphology and there
was also an enhancement of diameter to about 345 nm (Fig. 4D). Sub­
sequently, the nanofibers were used for the adsorption of lead (II),
cadmium (II) and chromium (VI) ions from aqueous solutions. The in­
clusion of UiO-66-NH2 greatly enhanced the adsorption capacities of
PAN/chitosan nanofibrous adsorbent due to its highly porous nature and
large surface area. The lead (II), cadmium (II) and chromium (VI)
adsorption capacities were increased from 87.5, 83 and 78 mg.g− 1 to
115, 107.6 and 99.5 mg.g− 1, respectively by loading 10 wt% UiO-66-
NH2 MOF into the PAN/chitosan nanofibrous adsorbent. The long syn­
thetic procedure for the adsorbent, however, is a cause of concern from
an environmental point of view since it increases the risk of secondary
pollution of the environment.
Wang et al. (2021) successfully used porous membrane synthesised
from crosslinked chitosan, polyvinyl alcohol and UiO-66-NH2 (cCS/
PVA/UiO-66-NH2) membrane adsorbent during the adsorptive removal
of uranium (VI) ions from radioactive wastewater. The presence of the
UiO-66 MOF and cross-linkages greatly enhanced the mechanical sta­
bility of the chitosan membrane adsorbent. Experimental results
revealed that the cCS/PVA/UiO-66-NH2 membrane adsorbent had a
relatively high adsorption capacity of 316.50 mg g− 1 under optimum
conditions. The relatively high adsorption capacity can be explained in
terms of the presence of the highly porous UiO-66 MOF with a large BET
surface area in the membrane structure. They also observed that the
membrane adsorbent exhibited high selectivity for the uranium ions in
wastewater. The high selectivity can be attributed to the unique pore
sizes conferred to the membrane due to the presence of UiO-66 MOF in
chitosan. The adsorptive removal of uranium (VI) ions from wastewater
occurs mainly through surface complexation and cation-exchange
mechanisms. The cCS/PVA/UiO-66-NH2 membrane adsorbent was
relatively stable and consequently, it could undergo a series of
adsorption-desorption cycles without significant loss in its adsorption
capacity. The membrane is, therefore, reusable and this made it to be
more appealing from an environmental point of view.
2.4. Chitosan/HKUST hybrid materials
HKUST-1 or copper-1,3,5-benzenetricarboxylate (Cu-BTC) is an MOF
composed of copper (II) ion nodes and benzene tricarboxylate (BTC)
linkers (Domán et al., 2021; Vepsäläinen et al., 2021) (Fig. 5A). It was
first synthesised by Chui et al. (1999) using a solvothermal method.
From that time other synthetic techniques such as the mechanochemical
method (Klimakow et al., 2010) and continuous flow (Dunne et al.,
2016) have been successfully used by researchers during the production
of HKUST-1. It has a relatively high surface area of 600–1600 m2 g− 1, a
large pore volume of approximately 0.7 cm3 g− 1 and good thermal
stability (up to 350 ◦ C) (Bouson et al., 2017). These attractive properties
of HKUST-1 make it suitable for use as an adsorbent of environmental
pollutants. Its use as an adsorbent, however, is hampered by the fact that
it has lower water stability and poor mechanical strength. The chemical
and mechanical stability of HKUST can be improved by cross-linking and
the formation of composites with other adsorbents such as graphene
oxide and cellulose.
Composites of chitosan and HKUST MOFs have been used by some
researchers as adsorbents during adsorption since they form strong
H. Musarurwa and N.T. Tavengwa
Fig. 5. (A) Structure of HKUST-1 (Isaeva et al., 2018) and (B) preparation of HKUST/cellulose/chitosan composite aerogel (Q. Liu, Yu, et al., 2021) (Copyright
permission granted).
interactions with environmental pollutants. (Q. Liu, Yu, et al., 2021;
Samuel et al., 2020; Zhao et al., 2020) (Table 1). The interactions be­
tween chitosan/HKUST adsorbent and environmental pollutants usually
involve the formation of electrostatic interactions, hydrogen bonding
and π − π interactions (Table 2). Chitosan/HKUST composites result in
the formation of multi-functional adsorbents with relatively high
adsorption capacities. The mechanical strengths of chitosan/HKUST-1
composites, however, are relatively low. Thus, there is a need to
incorporate into the composites other adsorbents such as cellulose with
high mechanical stabilities. For instance, Liu, Yu, et al. (2021) used
HKUST-1/cellulose/chitosan composite aerogel for the adsorptive
removal of methylene blue from industrial wastewater. Chitosan aero­
gels have large specific surface area (149–739 m2g− 1) (Lovskaya et al.,
2020). The incorporation of HKUST MOF into the chitosan aerogels
caused an improvement of their specific surface area. This can be
attributed to the highly porous nature of the HKUST MOF. The me­
chanical stability of the composite aerogel was enhanced by the incor­
poration of cellulose into its structure as well as by cross-linking. The
aerogel was prepared using in-situ growth that involved the combina­
tion of covalent cross-linking, vacuum freeze-drying and solvothermal
methods (Fig. 5B). The incorporation of cellulose did not only confer the
aerogel with good stability but it also enabled the composite to maintain
fine morphology and structure under acidic conditions. The BET surface
9
Carbohydrate Polymers 283 (2022) 119153
area of the HKUST/cellulose/chitosan aerogel (457.75 m2 g− 1) was
larger than that of the cellulose/chitosan aerogel (9.74 m2 g− 1). Thus, as
already alluded to, the inclusion of the HKUST MOF extensively
enhanced the surface area of the aerogel. Consequently, the adsorptive
removal of methylene blue from wastewater was characterised by a
relatively high adsorption capacity of 526.3 mg g− 1. In addition,
HKUST/cellulose/chitosan aerogel had good recycling capability due to
enhanced mechanical stability and this made it to be more appealing
from an environmental point of view.
Some researchers have incorporated graphene oxide into chito­
san@HKUST composites during the adsorptive removal of environ­
mental pollutants. This can be attributed to the fact that graphene oxide
has relatively high chemical and mechanical stability. Thus, its inclusion
into chitosan@HKUST composites greatly improved the physicochem­
ical properties of the adsorbents (Papageorgiou et al., 2017). In addition,
graphene oxide has oxygen functionalities that enabled it to be dispersed
easily in different chemical environments (Dideikin & Vul”, 2019).
Consequently, it can be combined easily with other materials such as
chitosan to form adsorbents with enhanced mechanical stabilities and
relatively high adsorption capacities. For instance, Samuel et al. (2020)
used HKUST MOF immobilized on graphene oxide-chitosan hybrid
composite for the adsorption of methylene blue from aqueous solutions.
They characterised the adsorbent using XRD, FTIR, SEM, TEM and BET.
H. Musarurwa and N.T. Tavengwa
The structural characterisation of the adsorbent showed that chitosan
and HKUST were embedded into the structure of graphene oxide. The
adsorption of methylene blue by the graphene oxide-chitosan@HKUST
composite was modelled using Langmuir isotherm and pseudo-second-
order kinetic model. The adsorbent had a relatively large BET surface
area and rough morphology. The large surface area can be attributed to
the highly porous nature of HKUST-1. Consequently, its adsorption ca­
pacity for methylene blue (357.15 mg g− 1) was relatively high. The
combination of HKUST-1, chitosan and graphene oxide resulted in the
formation of a multi-functional adsorbent, which could form strong
electrostatic and π − π interactions with methylene blue.
In another study, Jiamjirangkul et al. (2020) used HKUST-integrated
chitosan/polyvinyl alcohol (PVA) nanofibrous membrane for the selec­
tive capture and filtration of CO2 from the environment. The HKUST-
integrated chitosan/PVA nanofibrous membrane was synthesised by
layer-by-layer deposition of Cu2+ as metal cluster and BTC as the organic
precursor to form HKUST MOF on the surface of the chitosan/PVA
nanofiber. The hybrid nanofibrous membrane formed had a relatively
high surface area due to the presence of many functional groups in its
structure. Consequently, the adsorption capacity of the membrane for
CO2 was relatively high. Their experimental results showed that the
specific surface area and the pore size distribution of the hybrid mem­
brane could be controlled by changing the order the precursors were
mixed. The specific surface area of the membrane was greatly enhanced
by immersing the chitosan/PVA nanofibrous membranes into the metal
solution prior to the organic solution. The resultant HKUST/chitosan/
PVA nanofibrous membrane exhibited great potential for the selective
capture and filtration of CO2 in the environment.
3. Challenges and future prospects
Chitosan/MOF composite adsorbents have excellent physicochem­
ical properties essential for the adsorptive removal of environmental
contaminants (P. Shi, Hu, & Duan, 2021; J. Tang, Zhao, et al., 2021).
They are highly porous adsorbents with multi-functional groups that act
as active sites for the adsorption of pollutants from environmental
samples (El-Shahat et al., 2020; Mahmoodi et al., 2020). Thus, chitosan/
MOF adsorbents generally have relatively high adsorption capacities for
both organic and inorganic pollutants. In addition, chitosan can form
stable complexes with metal ions in MOFs and this facilitates the inte­
gration of the two (Nadar et al., 2019). Despite these attractive features,
the use of chitosan/MOF adsorbents have some challenges.
Chitosan has very low solubility in water and this has a negative
impact during the formation of composites with MOFs. This is due to the
fact that the conversion of chitosan to a water-soluble form is imperative
during composite formation. Neufeld et al. (2017), for instance, had to
react chitosan with acetic acid in order to convert it to a water-soluble
form prior to composing it with MOF. This has the effect of increasing
the production cost of the chitosan/MOF composites. On the other hand,
the stability of some MOFs is a cause of concern during the synthesis of
chitosan/MOF composites. For instance, HKUST MOF has generally low
mechanical strength. Thus, materials such as graphene oxide should be
incorporated into the chitosan/HKUST composites in order to make
them mechanically stable. The incorporation of graphene oxide into the
composite makes it to be expensive.
The chitosan/MOF composite adsorbents are prone to fouling
(organic fouling, colloidal fouling, and biofouling) during the adsorptive
removal of pollutants in aquatic environments (Das et al., 2013). Fouling
reduces the pore sizes and surface roughness of the chitosan/MOF ad­
sorbents as well as blockage of surface functional groups (Das et al.,
2013; Guo et al., 2020). This has negative effects on the extraction ef­
ficiencies of the composite adsorbents. Thus, concerted research efforts
should be directed towards the development of smart adsorbents with
anti-fouling properties. Biofouling is among the most problematic forms
of fouling when chitosan/MOF composite adsorbents are used for the
adsorptive removal of pollutants in aquatic environments. This
10
Carbohydrate Polymers 283 (2022) 119153
predicament can be minimised by the fabrication of nanoparticles with
anti-microbial activities into the structures of chitosan/MOF composites
(Guo et al., 2020).
Selectivity of the chitosan/MOF composite adsorbents is a cause of
concern when used during adsorptive removal of environmental pol­
lutants. Any pollutant with complimentary functionalities as those
found on the chitosan/MOF adsorbent can be adsorbed by the com­
posite. Selectivity can be greatly enhanced if the composite is formed
using molecularly printed chitosan and MOFs. This enables the forma­
tion of tailor-made cavities in the adsorbents that can selectively adsorb
specific pollutants from contaminated environments. In addition,
incorporation of other multi-functional polymeric adsorbents such as
polydopamine (T. Zhang et al., 2021) and conjugated materials (Awual
et al., 2019; Kamel et al., 2019) into the chitosan/MOF composites may
result in the enhancement of the adsorption capacities of the adsorbents.
Chitosan/MOF composites are promising adsorbents for environ­
mental pollutants. Their use on a large scale, however, is hampered by
the fact that the synthetic routes for most of these composites are very
long and this makes the process uneconomical. To pave way for indus­
trial application, more research efforts should be directed towards
establishing alternative synthetic routes for these composites that are
short and less expensive. In addition, there is a need to scale-up research
efforts towards the development of more chitosan/MOF composites that
can be easily recovered and recycled. Thus, the lack of high-throughput
synthesis and cheap regeneration methods for the chitosan/MOF ad­
sorbents are among the major drawbacks for their large-scale
applications.
4. Conclusion
Chitosan/MOF hybrid materials are efficient adsorbents for both
organic and inorganic pollutants in environmental samples. The incor­
poration of MOFs into chitosan enhances tremendously its adsorption
capacity of a myriad of environmental pollutants. This can be attributed
to the highly porous nature of the MOFs that increases the adsorptive
surface area of the hybrid adsorbent. The inclusion of the MOFs also
improves the mechanical properties of the composite adsorbents and
this confers them with low degradation rates. Thus, most chitosan/MOF
adsorbents can undergo many adsorption/desorption cycles without
significant loss of adsorption capacity. Desorption of the pollutants from
the enriched adsorbents is usually done using organic solvents and there
is a risk of secondary pollution of the environment. Thus, there is a need
to develop more physical methods, such as thermal and magnetic
retrieval, for the recovery of pollutants from the enriched adsorbents. In
addition, many chitosan/MOF adsorbents, generally, have high thermal
and chemical stabilities. The adsorptive removal of environmental pol­
lutants usually occurs via the following mechanisms: hydrogen bonding,
electrostatic interactions, and π-π interactions.
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.
Acknowledgement
The authors are grateful to the Research Centre, University of Venda,
for financial support.
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