Application of Magnetic Chitosan Composites For The Removal of Toxic Metal and Dyes From Aqueous Solutions PDF

Application of magnetic chitosan composites for the removal of toxic
metal and dyes from aqueous solutions

D. Harikishore Kumar Reddy, Seung-Mok Lee
Department of Environmental Engineering, Kwandong University, Gangneung, Gangwondo 210 701, Republic of Korea
a b s t r a c t a r t i c l e i n f o
Available online 11 October 2013
Keywords:
Chitosan
Magnetic chitosan
Chitosan composites
Magnetic composites
Biocomposites
Polysaccharides
Adsorption
Magnetic adsorbents
Magnetic materials
Metals
Dyes
Water pollution
Magnetic chitosan composites (MCCs) are a novel material that exhibits good sorption behavior toward various
toxic pollutants in aqueous solution. These magnetic composites have a fast adsorption rate and high adsorption
efciency, efcient to remove various pollutants and they are easy to recover and reuse. These features highlight
the suitability of MCCs for the treatment of water polluted with metal and organic materials. This reviewoutlines
the preparation of MCCs as well as methods to characterize these materials using FTIR, XRD, TGA and other
microscopy-based techniques. Additionally, an overview of recent developments and applications of MCCs for
metal and organic pollutant removal is discussed in detail. Based on current research and existing materials,
some new and futuristic approaches in this fascinating area are also discussed. The main objective of this review
is to provide up-to-date information about the most important features of MCCs and to showtheir advantages as
adsorbents in the treatment of polluted aqueous solutions.
2013 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
1.1. Objective of this review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
2. Magnetic chitosan composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.1. Chitosan is an ideal candidate for preparing magnetic composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.2. Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.3. Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.4. Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3. Application MCCs for water treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
3.1. Removal of metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
3.1.1. Effect of pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
3.1.2. Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.1.3. Effect of modication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.2. Removal of dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3.2.1. Effect of pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3.2.2. Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3.2.3. Effect of modication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3.3. Desorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4. Adsorption kinetics and equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
4.1. Adsorption kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
4.2. Adsorption equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
5. Mechanism of adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
6. Saturation magnetization and magnetic separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
7. Advantages and disadvantages of MCCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
8. Conclusions and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Advances in Colloid and Interface Science 201202 (2013) 6893
Corresponding author.
E-mail address: leesm@kwandong.ac.kr (S.-M. Lee).
0001-8686/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cis.2013.10.002
Contents lists available at ScienceDirect
Advances in Colloid and Interface Science
j our nal homepage: www. el sevi er . com/ l ocat e/ ci s
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Appendix A. Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Appendix B. Symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
1. Introduction
Currently, water is one of the most vital human resources and has
economic, social, political and environmental importance throughout
the world [1,2]. Water pollution has become a serious environmental
problem and has attracted global concern in recent years, particularly
since various pollutants are entering aquatic systems as a result of
rapid industrialization and urbanization [3]. Pollutants that are of
primary concern include metals, dyes, biodegradable waste, phosphates
and nitrates, heat, sediment, uoride, hazardous and toxic chemicals,
radioactive pollutants, pharmaceuticals and personal care products
[48]. Trace amounts of any of these compounds lead to an enormous
pollution problem and consequently, the treatment of wastewater is
a subject of paramount importance. Researchers in the analytical,
environmental and material sciences have attempted to develop
processes for removing various pollutants and recently, adsorption has
become a widely used technology for the removal of both inorganic and
organic material [911]. A number of materials have been investigated
extensively for this purpose [1220] and activated carbon has un-
doubtedly been the most popular adsorbent used widely throughout
the world for the removal of various pollutants [2124]. However,
activated carbon is relatively expensive, and this has restricted its
application at times. Alternative cost-effective sorbents are required
for the treatment of metal-contaminated waste streams.
The use of adsorbents composed of natural polymers has attracted
signicant interest, and polysaccharides such as chitosan and its de-
rivatives have received particular attention [2531]. This is due to the
fact that chitosan is a low-cost and effective adsorbent compared with
activated carbons and other adsorbents used in treatment organic or
inorganic contaminated water [26,28]. There is an abundance of ci-
tations in the literature describing the performance of chitosan as an
adsorbent for pollutants from water and wastewater including metals,
dyes, phenols, uoride, and phthalates [26,27,32]. Due to the unique
polycationic structure of chitosan, it has proved to have outstanding
removal capacities for anionic dyes such as acid, reactive and direct
dyes [28], and because of its cationic behavior, the protonation of
amine groups in acidic media leads to adsorption of metal anions by ion
exchange. The chelating properties of chitosan and chitosan derivatives
toward metal ions have been studied and discussed by Muzzarelli and
colleagues [25,33,34]. Chelation can be attributed to the presence of a
large number of functional groups (e.g., acetamido, primary amino,
and/or hydroxyl groups) that are capable of coordinating with different
metal ions. The selectivity of chitosan is a highly desirable property,
because alkali metal ions and alkali-earth metal ions (abundant but
not hazardous) are not chelated, while transition and post-
transition metal ions (typically present at trace levels and highly
toxic) are sequestered [35].
There is an increasing number of review articles published on the
use of chitosan and its derivatives as adsorbents for the removal of
contaminants from water/wastewaters [3639]. In 2004, Varma et al.
[40] published a review that outlined the various classes of chitosan
derivatives and compared their ion-binding abilities under varying
conditions, and described analytical methods, the sorption mechanism,
and a structural analysis of the metal complexes using a variety of
methods. Miretzky and Cirelli [41] reviewed Hg(II) removal from
water using chitosan and chitosan derivatives. Wan Ngah et al. [30]
reviewed the adsorption of dyes and heavy-metal ions using chitosan
composites. Muhd Julkapli et al. [42] presented an in-depth review
of the preparation, properties, and applications of chitosan-based
biocomposites/blend materials, including all essential methodological
aspects and applications. Wu et al. [43] reviewed the experimental
verication of chitosan and its derivatives as adsorbents for select
heavy metals. Bhatnagar and Sillanp [26] discussed chitin and chitosan
derivatives for the removal of various pollutants from water and
wastewater.
After adsorption, it can be difcult to separate chitosan-based
adsorbents from the aqueous solution using traditional separation
methods such as ltration and sedimentation, because adsorbents
may block lters or be lost. Furthermore, the adsorbents were discarded
with the process sludge, which generates secondary pollution. To over-
come the problems related to the ease of separation and regeneration of
adsorbents, recent research has been focused on magnetic separation
technology. Separation technologies employing magnetic adsorbents
are an alternative method for treating water/wastewater that has
received considerable attention in recent years [4448]. The main
advantage of this technology is that a large amount of wastewater can
be puried in a very short period of time using less energy and
producing no contaminants [49]. Magnetic separation was rst de-
scribed by William Fullarton in 1792 as a method of separating iron
minerals [50]. During the 1970s and 1980s, scientists were beginning
to realize that materials with magnetic properties were useful for the
separation of metal pollutants that are sensitive to magnetic elds
from a variety of matrices. In 1996, Towler et al. [51] reported the
recovery of radium, lead, and polonium from seawater samples
using a magnetic adsorbent consisting of manganese dioxide coated
magnetite. Since then, other applications of magnetic materials have
been reported [5254].
Magnetism is a unique physical property that can be exploited
in water purication by inuencing the physical properties of the
contaminants in water [55]. In combination with other processes, it
facilitates an efcient purication of water/wastewater. Magnetic com-
posites adsorb contaminants from aqueous efuents and can sub-
sequently be separated from the medium through a simple magnetic
process. Furthermore, by chemically modifying the polymeric shells of
these magnetic composites, the functionality can be tailored for vari-
ous applications in diverse elds such as high-density data storage,
magnetic resonance imaging (MRI), drug delivery, therapy, diagnosis,
bioseparation, and enzyme immobilization [5664].
1.1. Objective of this review
A number of reviews on chitosan and its derivatives that deal with
the elimination of metals and organics using chitosan-based adsorbents
are currently available [3639,43]. Recently, WanNgah et al. [30] briey
discussed the application of chitosan/magnetite composites for the
treatment of heavy metal ions and dyes. However, to date, only one
review article describes the use of magnetic chitosan materials for the
removal of toxic pollutants, and this review was published more than
three years ago [65]. In order to address the complexity of the many
factors that inuence the adsorption process besides its development,
and in light of the continuously increasing number of scientic pub-
lications within this area, the available reviews no longer adequately
cover all of the important aspects of magnetic chitosan materials in
adsorption processes. Hence, this article attempts to summarize recent
studies that address the removal of inorganics and organics using
magnetic chitosan adsorbents. This review describes the development
90
69 D.H.K. Reddy, S.-M. Lee / Advances in Colloid and Interface Science 201202 (2013) 6893
of magnetic composites using chitosan as a base material, and sum-
marizes recent developments in the preparation and properties of
MCCs. Furthermore, we examine various MCCs that are capable of
removing toxic substrates from wastewater and describe their char-
acteristics, advantages, and limitations, as well as discuss the adsorption
mechanisms involved. The goal of this review is to direct attention to
emerging and novel research involving magnetic chitosan materials
that might be relevant to future projects for the treatment of waste-
water, as well as their use in the medical and analytical elds.
2. Magnetic chitosan composites
A magnetic chitosan composite (MCC) consists of a chitosan polymer
matrix and a dispersed phase containing magnetic particles. Chitosan
has been intensively studied as a base material for magnetic carriers
because of its signicant biological and chemical properties. The superior
performance of MCCs has generated global interest in recent years,
prompting extensive research into the synthesis and application of
these materials in various elds of science, which is reected in a
signicant increase in the number of publications on this topic (Fig. 1).
Magnetic chitosan materials are of great interest in various elds for
biomedical (targeting drug carriers, articial muscle, bone regeneration,
anti-cancer embolotherapy, enzyme-based biofuel cells) [6669],
environmental (pollutant removal, toxic pollutant degradation) [7073]
and analytical (biosensor, separation, afnity chromatography,
uorescence probes) applications [7477]. Furthermore, MCCs have
often been used in wastewater treatment [7880]. Compared with
other adsorbents, MCCs possess a high adsorption capacity and a rapid
adsorption rate, even when present in low amounts and at short
equilibrium times. In summary, MCCs are (i) selective for the adsorbate,
(ii) economical, (iii) environmentally friendly, (iv) reusable, and (v)
highly scalable.
2.1. Chitosan is an ideal candidate for preparing magnetic composites
Polymeric materials as base carriers for the preparation of magnetic
composites are particularly attractive because they have a variety of
surface functional groups that can be tailored to specic applications,
excellent mechanical strength for long-term use, and can be produced
rapidly, efciently, and with high yields. By nature, magnetic particles
tend to aggregate, but will not do so in the context of a surrounding
polymeric material [81]. Of all the natural polymers that have been
tested, chitosan is often chosen as a base material for manufacturing
magnetic materials due to its ideal biocompatibility, biodegradability,
cost effectiveness, availability, versatility, lowcytotoxicity and chemical
properties [8185]. Chitosan is a polycationic biopolymer derived from
chitin, the second most abundant biopolymer in nature [86]. Chitin is
inexpensive because it is readily available from the shells of shrimp,
crabs, and lobsters, which are waste products of the seafood processing
industry. Chitosan has one amino and two hydroxyl groups in the
repeating glycosidic residue [87], making it a suitable matrix with
which to synthesize magnetic composites [88]. Since chitosan is soluble
in aqueous acidic solutions it is possible to avoid the use of hazardous
organic solvents while preparing composites.
In general, magnetic nanoparticles are chemically highly active,
and are easily oxidized in air, resulting in a loss of magnetism and
dispersibility [61,89]. When these magnetic particles are coated with
chitosan, they may not only be protected from oxidation, but may also
have reduced toxicity, reduced aggregation and an extended storage life
[9092]. Interestingly, a chitosan coating not only protects and stabilizes
the magnetic particles, but can also be used as a surface for further
functionalization (due to the presence of abundant amino, hydroxyl and
carboxyl groups) with specic components such as catalytically active
species, various drugs, specic binding sites or other chelating functional
groups. The introduction of additional chelating functional groups will
improve the adsorption performance of magnetic chitosan.
One of the biggest advantages of preparing magnetic composites
with chitosan is that it is quite easy to prepare chitosan-conjugated
particles (chitosanmagnetite) using a co-precipitation method because
the functional groups at the surface of iron oxide particles easily react
with those of chitosan or its derivatives [82,93]. Furthermore, chitosan
canact as structure directing agent, and its ability to formmetal chelates
and pH responsiveness are highly useful in the preparation of MCCs.
Chitosan can be easily modied by chemical or physical processes to
prepare chitosan derivatives by attaching newfunctional groups. Several
well-articulatedreviews are available to understandthe physicochemical
characterization of chitosan [9496].
2.2. Synthesis
MCCs are composed of two major components: an inorganic metal
oxide and organic chitosan. In general, chitosan itself does not exhibit
magnetic properties, therefore an additional magnetic component
must be added in order for the particles to function optimally in particle
separation [97]. The magnetic particles that are typically embedded into
chitosan include Fe
3
O
4
, Fe
2
O
3
, NiFe
2
O
4
, CoFe
2
O
4
, CuFe
2
O
4
and ZnFe
2
O
4
[85,98102]. In general the method of preparation leads to the
formation of MCCs with one of two different structures: magnetic
corechitosan shell (Fig. 2a) and/or magnetic multi-cores homo-
geneously dispersed in chitosan (Fig. 2b). Magnetic corechitosan
Fig. 1. A graph showing the number of publications listed by Scopus
on October 31, 2012,

specifying magnetic chitosan as the keyword plotted against the publication year.
Fig. 2. (a) Magnetic corechitosan shell; (b) magnetic multi-cores homogeneously
dispersed in chitosan.
shell materials are of special interest and are widely synthesized and
employed for the treatment of water.
Even though a number of different magnetic cores are described in
the literature, iron oxides, including magnetite (Fe
3
O
4
) or maghemite
(-Fe
2
O
3
),are, by far, the most commonly employed due to their
biocompatibility, strong super-paramagnetic behavior, low toxicity
and ease of synthesis [103105]. Furthermore, the amine groups
(\NH
2
) of chitosan may readily interact with Fe ions in aqueous
solution through ion exchange and complexation reactions [106].
Therefore, chitosanis able to interact withnegatively chargedmolecules,
such as the hydroxyl (FeOH) groups on the surface of magnetite
particles. Several examples of magnetic chitosan materials that include
iron oxide as the core are shown in Fig. 3 [107109].
In order to be useful, an MCC must be stable, efcient, and
economically viable. Recently, many successful methods of preparing
magnetic chitosan materials have been developed resulting in various
forms including beads, templates, lms, bers, gel beads, microspheres,
nanocomposites, and microcapsules [110114]. The preparation of
MCCs is typically accomplished in two or three steps. The rst step
involves the synthesis of magnetic particles and the second step
involves the grafting, coating, or dispersion of the magnetic particles
with a chitosan solution. Using an in situ synthetic route, this can be
accomplished in a single step [115,116]. Finally, functionalization
of magnetic chitosan through the addition of various chelating ligands
improves the adsorption performance. There are a number of different
approaches for generating magnetic chitosan materials and these
include crosslinking of the chitosantemplate, emulsion-based methods,
and co-precipitation methods. Here we discuss a few of the most
important techniques, and more detailed information can be found in
the published literature [117119].
For the preparation of MCCs, the rst important step is the
preparation of the magnetic particle, which, as stated above, is typically
magnetite (Fe
3
O
4
) or maghemite (-Fe
2
O
3
). Several synthetic methods
for obtaining the appropriate size, distribution, and highly stable
magnetic particles are available and include: co-precipitation, thermal
decomposition and/or reduction, micelle synthesis, hydrothermal
synthesis, sonochemical synthesis and laser pyrolysis [89]. The most
conventional method is co-precipitation of ferric and ferrous ions from
an aqueous basic solution [120].
For the second step in MCC preparation, either crosslinking or
precipitation methods are typically used. One method that has been
used quite often is a water/oil (W/O) emulsion crosslinking technique
in which magnetic particles are dispersed into a chitosan solution and
emulsied as a dispersed phase. More specically, chitosan is dissolved
into an aqueous acetic acid solution, and then iron oxide particles are
added. The W/O emulsion is prepared by a dropwise addition of this
solution into a dispersion medium composed of cyclohexane, n-hexanol
and an emulsier [121,122]. The chitosan chains contained within these
droplets are crosslinked using agents such as glutaraldehyde or glyoxal
[121,123]. The advantage of the W/O emulsion crosslinking technique is
that it improves the porosity and solubility of the resulting MCCs, and it
provides sites for the attachment of other functional groups.
Other crosslinking methods have employed chemicals such as
glutaraldehyde, epichlorohydrin, and ethyleneglycoldiglycidyl ether.
For example, when glutaraldehyde was used as crosslinking agent, the
amine functional groups available on chitosan act as nucleophiles and
react with the carbonyl in glutaraldehyde to form the a polymer on
the surface of Fe
3
O
4
[108]. Fan et al. [124] used this method and
provided a clear illustration of the process (Fig. 4).
A crosslinking step may cause a signicant decrease in the efciency
of metal uptake, especially in the case of chemical reactions involving
amine groups. Inorder to improve the adsorptioncapacity andselectivity
of metal ions, a number of chitosan derivatives have been obtained
by grafting on new functional groups through a crosslinked chitosan
backbone. It is well known that resins containing mercapto and
amino functional groups have good adsorption properties, therefore
chemical reagents like ethylenediamine, thiourea, xanthate, and
diethylenetriamine have been used to modify MCCs [72,125127].
Modications are generally carried out as follows: A suitable cross-
linking agent is reacted with magnetic chitosan, and this mixture
is combined with the chemical reagent and stirred at appropriate
temperatures, and nally the product is ltered, washed with an
appropriate solvent, and dried. In a recent study, Fan et al. [128]
successfully prepared a magnetic thiourea-chitosan using glutaral-
dehyde as crosslinker.
In a recent study, chitosan/magnetite composite beads were prepared
ina simple manner using chemical co-precipitationof Fe
2+
and Fe
3+
ions
with NaOH in the presence of chitosan, followed by hydrothermal
treatment [129]. In another study, Liu et al. [130] synthesized
multifunctional chitosan/TiO
2
/Fe
3
O
4
microspheres with magnetic
properties by using an electrospray technique. Using this technique,
they were able to embed TiO
2
/Fe
3
O
4
nanoparticles within chitosan
(Fig. 5).
To obtain uniform chitosan composite particles of customizable
sizes, Wang et al. [116] employed an electrostatic droplet (ESD)
technique. These authors describe an in situ synthesis strategy through
which they could control the size of the superparamagnetic chitosan
they produced using an ESD method which included co-precipitation
and solidication of ferrogels (Fig. 6).
2.3. Properties
The properties of MCCs that are particularly important for their
application in water treatment include surface area, particle size, pore
Fig. 3. Different forms of chitosan bonded Fe
3
O
4
materials.
Reprinted with permission from refs. [107109]. Ref. [107] Copyright 2012 Elsevier. Ref. [108]
Copyright 2012 Elsevier; Ref. [109] Copyright 2012 Royal Society of Chemistry.
diameter, surface morphology, surface functional groups, and saturation
magnetization. MCCs are typically prepared in the forms of beads or
templates, with most MCCs occurring as particles (micro and nano)
with the surface morphology of micro- or nanospheres [122124,
127,128,131133]. Structural properties such as surface area, particle
size and pore size for select MCCs are included in Table 1. The most
important property of the MCCs is saturation magnetization, which will
be discussed in further detail later in this review.
2.4. Characterization
It is not the purpose of this review to discuss the characterization of
magnetic chitosan materials in-depth; however, it is well known that
the physicochemical properties of a material (size, functional groups,
morphology, and thermal stability) are important in evaluating the
adsorption performance of that material in water treatment. We will
discuss the relevant analytical techniques that are used to characterize
MCCs in order to help the reader choose those that are most ap-
propriate. Because the production of MCCs is a multi-step process, it is
important to observe and assess the products (structural, thermal,
morphological, and chemical properties) at each step therefore it is
essential to use different analytical techniques for this purpose. In
addition, various techniques have been used to measure the binding
interactions between MCCs and either inorganic or organic pollutants.
For example, Fourier transform infrared spectroscopy (FTIR) is one of
the most important and widely used analytical methods for obtaining
information about the availability of certain functional groups in the
structure of the MCCs and for measuring the binding mechanism of
pollutants (inorganic or organic). A typical FTIR spectra of chitosan
includes the following peaks in most cases: 3436 cm
1
for O\H bond
stretching andN\Hbondstretching, 1657cm
1
for C_Oof \NH_C_O
bond stretching, and 1083 cm
1
and 1023 cm
1
for C\OH bond
stretching [134]. Most studies have shown that magnetic chitosan
exhibits the following peaks: ~3430cm
1
due to amine N\Hstretching
vibration and \OH moieties in the chitosan, ~1661cm
1
due to N\H
scissoring from the primary amine because of free amino groups in
the crosslinked chitosan, and ~580 cm
1
for the Fe\O group due to
pure Fe
3
O
4
(Fig. 7) [135]. To evaluate the success of adsorption, it is
necessary to compare spectra before and after adsorption of target
pollutant.
X-ray diffraction (XRD) is an effective method for determining
the crystal structure of MCCs and can provide very useful informa-
tion about the physical and chemical form of the magnetic particles
embedded in chitosan matrix. XRD studies have shown that raw-
chitosan itself is amorphous in nature [136], but MCCs have exhibited
crystallinity due to the presence of iron oxide particles. Furthermore,
diffraction peaks for iron oxide particles were observed at lower
wavelengths after the formation of MCCs. In a recent study, Zhou et al.
[137] synthesized magnetic crosslinked chitosan with ethylenediamine
and observed eight characteristic peaks for Fe
3
O
4
with the following
indices: (1 1 1), (2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1), (4 4 0), and
(6 2 2). In most cases, when peak data was compared with that in the
Joint Committee on Powder Diffraction Standards' (JCPDS) database,
the presence of pure Fe
3
O
4
particles in MCCs was conrmed.
This technique is also useful for determining the particle size of
MCCs by employing the DebyeScherrer equation d = (k / cos ),
where k is the DebyeScherrer constant (0.9 for Cu K radiation), is
the X-ray wavelength (0.15405 nm for Cu K radiation), is the line
Fig. 4. Schematic formation of magnetic chitosan from magnetite and chitosan.
Reprinted with permission from ref. [124], Copyright 2012 Elsevier.
Fig. 5. Schematic diagram of the electrospraying technique for producing CTF-M. Left, the electrospraying equipment. Right, schematic structure of CTF-M.
Reprinted with permission from ref. [130], Copyright 2011, Royal Society of Chemistry.
broadening radian obtained fromthe full width at half maximum, and
is the Bragg angle [138]. Using this method, the particle size of uncoated
Fe
3
O
4
and chitosan-coated Fe
3
O
4
was determined to be 22 nm and
35 nm, respectively [129]. Finally, XRD was used to assess the phase
changes before and after magnetic modication of chitosan as shown
in Fig. 8 [131].
X-ray photoelectron spectroscopy (XPS) can be used to identify
particular elements and to determine the valence state of metals
dispersed with MCCs; however, only a few research groups have used
this method. In one case, the elemental composition of a particular
XMCS, was determined and the peaks were successfully assigned to
the corresponding carbon, nitrogen, oxygen, iron, and sulfur atoms
[139]. Fig. 9 depicts anXPS analysis of XMCS in whichthe dual oxidation
state of iron oxide, as shown by peaks for Fe(II) and Fe(III), was
identied. The identication of these peaks conrms the presence of
Fe
3
O
4
in the composite, further conrming the magnetic property of
XMCS. In a separate study, XPS analysis was used to identify the
presence of C1s, O1s and N1s in magnetic alginatechitosan beads [80].
The morphology of MCCs is important to determinate howwell they
interact withtarget pollutants andtherefore, microscopy techniques are
particularly useful. Scanning electron microscopy (SEM) is often used to
visualize the morphology and surface structures of MCCs and this
technique has been used to observe both micro- and nanoparticles
[72,127,140,141]. SEM images of various MCCs are shown in Fig. 10.
From the overall surface morphological studies, it was found that most
of the MCCs are spherical in shape, which translates into a large surface
area and is a favorable property for maximizing the adsorption of target
pollutants [140,142].
Several researchers have employed transmissionelectronmicroscopy
(TEM) to study the morphology of nanosizedmagnetic chitosanparticles.
Tran et al. [129] used TEM to study chitosan/magnetic nanocomposite
beads and found that the particles were 2530nm and were looser and
less agglomerated than pure Fe
3
O
4
nanoparticles. TEM was also used by
Fan et al. [142] to demonstrate that chitosan immobilization onto the
surface of Fe
3
O
4
particles and the construction was coreshell. Chang
et al. [143] applied TEM to characterize both Fe
3
O
4
nanoparticles
and chitosan-bound Fe
3
O
4
nanoparticles and found that the chitosan
nanoparticles had a mean diameter of 13.5nm.
A common tool to accompany both SEM and TEM is energy
dispersive X-ray analysis, referred to as EDS or EDAX. This technique is
often used to identify elemental composition, relative abundance, and
distribution within a sample. Using EDS, the composition of -KA-
CCMNPs were studied (Fig. 11), and the major elements present in
this MCC were shown to be iron and oxygen [144]. From an atomic
percentage calculation, the ratio of Fe and O was determined to be 2:3,
which led the authors to conclude that it is the presence of -Fe
2
O
3
in
-KA-CCMNPs that confers a magnetic property to the composite.
Thermal methods such as thermogravimetry (TGA), differential
scanning calorimetry (DSC), anddynamical mechanical thermal analysis
(DMTA) have proven to be powerful analytical techniques that mon-
itor the physical and chemical changes that take place during the
heating of MCCs and allow for a determination of chemical structure
Fig. 6. Synthetic strategy for iron oxide nanoparticle-loaded chitosan particles via both co-precipitation and solidication of ferro-gels.
Reprinted with permission from ref. [116] Copyright 2013, Royal Society of Chemistry.
Table 1
Structural properties of some examples of MCCs.
MCC Surface area
m
2
/g
Average pore
size, nm
Particle size Reference
EMCR 68.6 826 80250 m [122]
TMCS 62.3 891 80250 m [123]
MCGO 392.5 2.587 200 nm
a
[124]
MACTS 13.8187 0.25mm
a
[127]
Ag-TCM 7.51 20100 nm [128]
CSTU 64.5 860 130 m
a
[131]
MCCG 402.1 3.178 240 nm
a
[132]
CS/Fe
3
O
4
/Fe(OH)
3
-E 115.8 350 m
a
[133]
a
Average particle size.
Fig. 7. FTIR spectra of Fe
3
O
4
, chitosan and magnetic chitosan nanoparticles.
Reprinted with permission from ref. [135], Copyright 2011, Elsevier.
and composition. Thermal degradation studies have been useful for
estimating the relative amounts of chitosan and iron oxide in MCCs.
For example, TGA was used to follow the decomposition of EMCN and
the results suggested that the average mass of Fe
3
O
4
within this MCC
was about 33.5% at 873 K [145]. Zhou et al. [146] used this technique
to show that the average mass of Fe
3
O
4
in an ion-imprinted magnetic
chitosan resin was 47.6%. In a separate study, the thermal behavior of
chitosan, Fe
3
O
4
,and Fe
3
O
4
-CS nanoparticles were assessed and it was
shown that thermal decomposition temperature of Fe
3
O
4
-CS was
550 C [147]. Chitosan chains surrounding iron oxide nanoparticles
broke down between 200 and 550C and it was estimated that Fe
3
O
4
-
CS nanoparticles contain 50% chitosan (Fig. 12). The decomposition
thermograms for chitosan and magnetic chitosan vary between studies,
suggesting that the introduction of magnetic iron oxide particles into
the complex reduces crystallization.
The most important analytical tool for characterizing MCCs is the
vibrating sample magnetometer (VSM), which is often used for
measuring the magnetic properties of samples [89]. This technique
has been widely used to characterize MCCs based on the saturation
magnetization value (M
s
), which represents the susceptibility of a
sample to an external magnetic eld. Typical magnetization curves for
naked Fe
3
O
4
and CG-MCS nanoadsorbent are shown in Fig. 13 [148].
Lower magnetization value 21.6 emu/g was observed for CG-MCS
compared to naked iron oxide nanoparticles 39.7 emu/g. The decrease
in saturation magnetization of MCCs was observed in several studies
and this may be due to the presence of non-magnetic chitosan on the
surface of magnetic particles [130].
3. Application MCCs for water treatment
3.1. Removal of metals
As discussed previously in Section 1, the presence of toxic metal ions
in aqueous solutions has become a pervasive problem throughout the
world. Because of their strong binding ability, MCCs have increasingly
attracted attention for their potential to remove metal ions. The
summaries of various MCCs that have been used to treat metal-
contaminated water along with their adsorption capacity of each are
presented in Table 2. It was observed that metal ion sorption was
inuenced by pH, temperature and various functional groups present
on MCCs. Here we have outlined the above mentioned factors that
inuenced the metal ions removal.
3.1.1. Effect of pH
In adsorption process, solution's pH is one of the vital parameters
that affect the solubility of metal ion, degree of ionization, and the
surface characteristics of MCC's. Thus most of the studies involved in
metal ions adsorption onto MCCs are extensively investigated the pH
effect. Table 2 summarizes the ndings of optimum pH values for
various metal ion removal by MCCs. It can be seen that the optimum
pH values are dependent on types of MCCs and target metal ion. The
optimum pH value for the removal of majority of cationic metal ions
by MCCs was observed as pH5.0 and pH5.5. In case of cationic metal
ions it was observed that with increase in pH metal removal was
increasedat higher pHvalues removal was either decreasedor increased.
Most of the MCCs contain various functional groups such as \NH
2
, \NH,
\COOH, \OH and C_S [142,144,158] with the change in the solution
pH the behavior of these functional groups will also changes. At low
pH, most of these functional groups present in MCCs are protonated
and presented in positively charged form. In addition the presence of
large number of H
+
and H
3
O
+
in the aqueous solution may compete
with the metal ions for adsorption sites available on MCCs. Thus
electrostatic repulsion will occur between metal ions and positively
charged MCCs surface thus a lower adsorption was observed at low pH
in most of the studies.
Similar trends were observed in several studies with divalent metal
cations withvarious MCCs. Ina study Cu(II), Ni(II) andHg(II) adsorption
on TMCS was studied in the pH range from 2 to 8 [123]. They reported
that removal percentage increased with increasing pH values for all
the studied metal ions. Similar trend was observed in another study;
adsorption of Hg(II), Cd(II) and Zn(II) ions onto CSTU resin in the pH
range from 1 to 5. Increasing pH from 1 to 5 removal percentage was
increased and they found optimum for all studied metal ions at pH 5
[131].
However it was observed that even a lower pH values good
adsorption was observed in several reports, due to the formation
metal anion (MCl
3
). The presence of HCl in the aqueous medium
results the formation of anion complex such as MCl
3
, this anion was
able to exchange through the Cl
, which is electrostatically attached

to the MCC according to the fallowing reactions [122,142]:
RNH
2
HClRNH
3
Cl
RNH
3
Cl
MCl
3
RNH
3
MCl
3
Cl
:
At higher pH range, H
+
ions decrease and the surface of MCCs
becomes negatively charged this favors the metal ion removal due to
electrostatic interaction. In addition with increase in pH deprotonation
Fig. 8. XRD patterns of: (a) pure Fe
3
O
4
, (b) cross-linked chitosan-phenylthiourea, and
(c) cross-linked magnetic chitosan-phenylthiourea.
Reprinted with permission from ref. [131]. Copyright 2012 Elsevier.
Fig. 9. XPS spectrum of XMCS.
of functional groups is possible this results the free lone pair of electrons
suitable for coordination with metal ions to give the corresponding
MCC-M complex. At very high pH values adsorption of metal cation is
attributed to the formation of metal hydroxide species such as soluble
M(OH)
+
and/or insoluble precipitate of M(OH)
2
.
Further various researchers have studied the effect of pH on anion
adsorptionby MCCs andit was observedthat adsorptionwas dependent
on the type of anion and type of MCC. In a study Cr(VI) adsorption by
using EMCMCR was studied in the pHrange 18 by using three different
metal ion concentrations (Fig. 14) [153]. They reported that adsorption
capacity decreased with increasing pH from 2 to 8 and reported the
optimum pH2 for Cr(VI) removal. Under acidic conditions, the amino
groups (\NH
2
) on would be in a protonated cationic form (\NH
3+
)
and would therefore have a stronger attraction for negatively charged
ions, such as HCrO
4
. In another study Cr(VI) removal by magnetic

chitosan nanoparticles reported that, the adsorption capacity was
highly pH dependent and the maximum adsorption was occurred at
pH 3 [164]. However in an interesting investigation using R2 resin for
Cr(VI) removal it was reported that at higher adsorption of Cr(VI) at
alkaline medium [155]. In this study two resins R1 and R2 were
employed to evaluate the effect of pH on Cr(VI) adsorption, resin R2
exhibited a higher afnity towards Cr(VI) in an alkaline medium,
adsorbing 2.8 mmol/g at pH 8. The plausible reason for the higher
adsorption efciency of R2 at neutral and basic conditions was due to
the presence of trimethylammonium chloride in resin R2 which acts
as an anion exchanger. Similar trend was reported for Mo(VI) using
and glycidyltrimethylammonium (R2) and found that R2 removed
Mo(VI) as molybdate from acidic, neutral, and basic media [154].
(b)
(c) (d)
(a)
Fig. 10. SEMimage of various magnetic chitosan composites: (a) magnetic chitosan bead; (b) magnetic chitosan modied with diethylenetriamine; (c) magnetic chitosan nanoparticles;
(d) thiourea-modied magnetic ion-imprinted chitosan/TiO
2
.
Panel a is reproduced withpermissionfromref. [141], Copyright 2012Elsevier. Panel b is reproducedwithpermission[127]. Copyright 2009Elsevier. Panel c is reproducedwithpermission
from ref. [140], Copyright 2012 Elsevier. Panel d is reproduced with permission from ref. [72], Copyright 2012 Elsevier.
Fig. 11. EDS analysis of -KA-CCMNPs.
Reprinted with permission from ref.
[144], Copyright 2009 Elsevier.
Fig. 12. TGA thermograms of (a) Fe
3
O
4
, (b) Fe
3
O
4
-CS nanoparticles, and (c) pure CS
powder.
Reprinted with permission from ref. [147], Copyright 2010 Wiley-VCH.
To assess the ideal pH for metal adsorption, many researchers have
used the point of zero charge (PZC) of MCC's to study the inuence of
pH on metal ion removal process [137]. For example in one interesting
study EMCN having a PZC 4.8 remove the both anionic Pt(IV) and
cationic Pd(II) metal ions below PZC. At pH values below the PZC the
surface of EMCN is positively charged, whereas the metal ions were
taken in the form of K
2
PtCl
6
and PdCl
2
, therefore chloro-anionic species
formed will be adsorbed on to the positively charged EMCN [137].
3.1.2. Effect of temperature
Temperature of the solution is an important parameter for the
sorption of metal ions onto MCCs; an increase or decrease in tem-
perature will change the equilibrium capacity of MCCs during the
process of adsorption. From Table 2 it was observed that most of the
adsorption reactions of metal ions onto MCCs are exothermic; the
adsorption capacity decreases with the increasing of temperature. This
is due to the fact that as temperature increases the mobility of metal
ions increases, causing desorption or dechelation from the MCCs
[80,128]. Therefore, the amount metal that can be adsorbed on MCCs
will decrease with increase in temperature.
Adsorption of Co(II) onto the magnetic chitosan nanoadsorbent was
studied with increasing temperature from20 to 45C [149]. They found
that adsorption was decreased with increase in temperature and they
explained this exothermic nature as, at higher temperatures the
electrostatic interaction between chitosan and Co(II) ions was lower.
Similar trend was observed in case of adsorption of Cu(II), Co(II) and
Ni(II) by CSIS adsorbent [121]. Adsorption capacity for all studied
metal ion was decreased with increasing temperature from 15 to
35 C, which is explained by weaker interactions between the metal
ions and active groups of CSIS at high temperature. In another study
temperature dependence of U(VI) onto IMCR was explored in the
range from298 to 318Kand observed that withincrease in temperature
adsorption was decreased [146]. Cu(II) and Cr(III) adsorption on
magnetic CS microcapsules was studied in the temperature range
from 20 to 40 C [110]. Authors reported that adsorption capacity
increased from 20 to 30C, then decreased upto 40C, the process was
denoted as exothermic.
Apart from the exothermic adsorption process, several studies
reported on adsorption process are of endothermic in nature. For
example adsorption of Cr(VI) on CAGS showed that uptake of Cr(VI)
increased with increase in temperature from 15 to 45 C. The authors
explained this as increase of temperature provides number of active
sites along with lower resistance for diffusion of metal ions toward the
active sites [78]. Similar trend was observed in case of Cr(VI) adsorption
on, with increase in temperature from 30 to 50 C. Authors found
that adsorption capacity increased with increase in temperature
(144.9mg/g to 169.5mg/g), favorable adsorption at higher temperature
[170]. Adsorption of Cu(II) onto magnetic chitosan nanoparticles was
reported as an endothermic process [135]. In this study adsorption
capacity was increase from 29.6 mg/g to 35.5 mg/g with increase in
temperature from 288.15K to 308.15K.
3.1.3. Effect of modication
Most of the MCCs used for metal ion removal were modied with
chelating ligands to improve their adsorption performance. The most
promising of these is an amino-functionalized MCC, for which anionic
metal species are bound via electrostatic interaction, ion exchange, or
hydrogen bonding, while cationic metal species can interact with the
amino groups. Ethylenediamine is one of the most widely used
chelating agents for this purpose [171173].
Because of the high afnity of amine groups for metal ions, several
researchers have modied magnetic chitosan with cheap, industrial-
grade ethylenediamine. In one study, MCC nanoparticles were modied
with ethylenediamine (resulting in a resin called EMCN) by using
ephichlorihydrine as a crosslinking agent. When tested for the ability
to bind Pt(IV) or Pd(II), this composite exhibited a greater adsorption
capacity and a marked preference for Pt(IV) [137]. The same group
found that because of the increased number of amine-active sites on
EMCR as compared to unmodied chitosan, EMCR had an exceptionally
high binding afnity for Hg(II) andselectively separated this metal from
Cd(II), Pb(II), Zn(II), Cu(II), Ca(II), and Mg(II) [122]. A similar compo-
site, ethylenediamine-modied crosslinked magnetic chitosan resin
(EMCMCR), which was prepared in three steps, effectively removed
Cr(VI) from aqueous solutions, but only when the solution was at low
pH [153]. Under acidic conditions, the amino groups (\NH
2
) on
EMCMCR would be in a protonated cationic form (\NH
3+
) and
would therefore have a stronger attraction for negatively charged ions,
such as HCrO
4
. Effect of initial solution pH on Cr(VI) removal was

shown in Fig. 14. In a similar study, ethylenediamine-modied mag-
netic chitosan (EMMC) proved effective at binding uranyl ions when
the solution was at pH27 [125].
Monier and colleagues have contributed extensively to the de-
velopment and application of magnetic chitosan composites for
treating metal contaminated wastewater. This group has synthesized
novel MCCs containing numerous ligands with amine groups (2-
aminopyridine glyoxal, isatin, diacetylmonoxime), and the resulting
magnetic chitosan Schiff's base resins, CSIS, CSAP, and CSMO, have
proved useful for the removal of Cu(II), Cd(II), Co(II) and Ni(II) ions
[121,151,152]. The authors thoroughly characterized all these materials
using FTIR, XRD, SEM, TGA, VSM and
1
H NMR techniques. In the case of
CSAP the metal ion binding was due to the presence high percentage
of nitrogen as unsubstituted amines, azomethines (C_N), and
heterocyclic nitrogens. Further authors suggest that the specicity of
CSAP for Cu(II) over Cd(II) and Ni(II) may be attributed to the Jahn
Teller effect, which is common for copper complexes. Since Cu(II) has
nine d electrons (3d
9
), it generally occurs as a JahnTeller distorted
complex. Further Cu(II) forms stable complexes with nitrogen and
oxygen-donor ligands due to JahnTeller distortion. As a result Cu(II)
exhibits higher sorption afnity than Cd(II) and Ni(II) ions. Chitosan
derivatives containing nitrogen as the heteroatom and showing a
preference for copper is consistent with previous reports. The relative
adsorption capacities of the three resins described in this works are as
follows: CSAP N CSIS N CSMO. In a similar study, Abou El-Reash et al.
[78] synthesized CAGS resin and tested the ability to bind Cr(VI) and
As(V). Magnetic chitosan nanocomposites have also been modied
using amines and the resulting materials have a strong afnity for
metals with a binding preference as follows: Pb
2+
N Cd
2+
N Cu
2+
[174]. By comparing the adsorption efciency of modied chitosan on
the surface of magnetic nanoparticles with amine-functionalized mag-
netite nanoparticles and carbonyl-magnetite nanoparticles for Pb
2+
,
Fig. 13. Magnetization curves of (a) Fe
3
O
4
nanoparticle and (b) GC-MCS nano-absorbent.
Table 2
Adsorption capacities and experimental conditions of MCCs for the removal of metals from aqueous solutions.
Adsorbent Characterization Metal
ion
Optimum
pH
Optimum
temperature
(K)
Nature of
adsorption
Adsorption
capacity
(mg/g)
Kinetic model Isotherm Reference
CAGS FTIR, WAXRD and TGA As(V) 2 298 Exothermic 62.42 PSO Langmuir [78]
Cr(VI) 2 298 Endothermic 58.48 PSO Langmuir
Magnetic-alginate chitosan beads XRD, FTIR, XPS La(III) 2.8 298 Exothermic 97.1 PSO Langmuir [80]
CS-MCM SEM, FTIR, TG and VSM Cu(II) 5.5 303 108.0 PSO Langmuir [71]
CS/PAA-MCM SEM, FTIR, TG and VSM Cu(II) 5.5 303 174.0 PSO Langmuir [71]
MICT FTIR, SEM-EDX Cd(II) 7.0 298 256.41 PSO Langmuir [72]
Ag-TCM SEM, BET, VSM, FT-IR Ag(I) 5 303 Exothermic 531.80 PSO Langmuir [128]
Chitosan/magnetite nanocomposite beads XRD, FTIR, FE-SEM and TEM, VSM,
SEM/EDS
Pb(II) 6 Room temperature 63.33 Langmuir [129]
Ni(II) 6 Room temperature 52.55 Langmuir
CSTU FTIR,
1
H NMR, SEM XRD, VSM
and TGA
Hg(II) 5.0 303 Exothermic 135 3 PSO Langmuir [131]
Cd(II) 5.0 303 Exothermic 120 1 PSO Langmuir
Zn(II) 5.0 303 Exothermic 52 1 PSO Langmuir
EMCR Optical microscopy, FTIR,
BET, TGA, VSM
Hg(II) 5 298 Exothermic 539.59 PSO Langmuir [122]
MACTS FTIR, SEM and BET Cu(II) 6.0 293 [127]
Zn(II) 6.0 293 Endothermic PSO Generalized and
Freundlich
Cr(VI) 3.0 293
TMCS XRD, Elemental analysis, VSM, FTIR,
TGA, BET,
Hg(II) 5.0 301 Exothermic 625.2 PSO Langmuir [123]
Cu(II) 5.0 301 Exothermic 66.7 PSO Langmuir
Ni(II) 5.0 301 Exothermic 15.3 PSO Langmuir
Magnetic chitosan nano-adsorbent FTIR, magnetometer Co(II) 5.5 298 Exothermic 27.5 Langmuir [149]
Magnetic chitosan nanoparticles XRD, TEM, FTIR, VSM, EDS Cu(II) 5.0 308.15 Endothermic 35.5 Langmuir [135]
FeCc SEM, EDX, FTIR, VSM UO
2
2+
4.0 298.15 Endothermic 666.67 Langmuir [150]
Th
4+
5.5 298.15 Endothermic 312.50 Langmuir
CSIS FTIR,
1
H NMR, WAXRD, TGA Cu(II) 5.0 301 Exothermic 103.16 PSO Langmuir [121]
Co(II) 5.0 301 Exothermic 53.51 PSO Langmuir
Ni(II) 5.0 301 Exothermic 40.15 PSO Langmuir
CSMO SEM, FTIR,
1
H NMR, WAXRD
and TGA
Cu(II) 5.0 301 Exothermic 95 4 PSO Langmuir [151]
Co(II) 5.0 301 Exothermic 60 1
Ni(II) 5.0 301 Exothermic 47 1
CSAP FTIR, TGA, XRD, VSM Cu(II) 5.0 303 Exothermic 124 1 PSO Langmuir [152]
Cd(II) 5.0 303 Exothermic 84 2 PSO Langmuir
Ni(II) 5.0 303 Exothermic 67 2 PSO Langmuir
IMCR TGA, FT-IR, XRD, optical microscop,
VSM, surface area and pore size
U(VI) 5.0 298 Exothermic 187.26 PSO Langmuir [146]
NIMCR U(VI) 5.0, 298 160.77 PSO Langmuir
-KA-CCMNPs TEM, XRD, VSM, FTIR, EDS Cu(II) 6.0 295 2 96.15 Langmuir [144]
CMC FTIR, SEM, EDS Cr(VI) 4.0 69.4 First-order rate
equation
Langmuir [134]
EMCN TEM, XRD, FTIR, TGA Pt(IV) 2.0 298 171 Langmuir [137]
XMCS FTIR, XPS, XRD Co(II) 5.0 303 18.5 PSO Langmuir [139]
(continued on next page)
7
7
D
.
H
.
K
.
R
e
d
d
y
,
S
.
-
M
.
L
e
e
/
A
d
v
a
n
c
e
s
i
n
C
o
l
l
o
i
d
a
n
d
I
n
t
e
r
f
a
c
e
S
c
i
e
n
c
e
2
0
1
2
0
2
(
2
0
1
3
)
6
8
9
3
Table 2 (continued)
Adsorbent Characterization Metal
ion
Optimum
pH
Optimum
temperature
(K)
Nature of
adsorption
Adsorption
capacity
(mg/g)
MCS Co(II) 5.0 303 2.98 PSO Langmuir
Magnetic chitosan beads SEM, XRD, EDS Sr
2+
8.2 303 11.58 Intra particle
diffusion
Langmuir [141]
EMMC SEM, FTIR and XRD UO
2
2+
3.0 303 Exothermic 82.83 PSO Sips [125]
CMMC SEM, TEM, FTIR Zn
2+
5.0 298 Exothermic 32.16 Langmuir [142]
EMCMCR SEM Cr(VI) 2.0 293 Exothermic 51.81 PSO Langmuir and Temkin [153]
Chemically modied chitosan magnetic resins R1 FTIR Mo(VI) 5.1 333 Endothermic 541.11 PSO Langmuir [154]
Chemically modied chitosan magnetic resins R2 FTIR Mo(VI) 5.1 333 Endothermic 872.10 PSO Langmuir
Chemically modied chitosan magnetic resin R1 FTIR Cr(VI) 8.0. [155]
Chemically modied chitosan magnetic resins R2 FTIR Cr(VI) 8.0. 328 Endothermic 181.99 PSO Langmuir
CS-co-MMB-co-PAA Pb(II) 5.5 298 163.90 (linear),
151.82 (non-linear)
Freundlich [156]
Cd(II) 5.5 298 135.51 (linear)
132.76 (non-linear)
Langmuir
Cu(II) 5.5 298 152.42 (linear)
163.03 (non-linear)
Langmuir
Chemically modied chitosan resin with
magnetic properties
FTIR Au(III) 303 Exothermic 675.60 PSO Langmuir [157]
FTIR Ag(I) 303 Exothermic 239.47
a
PSO Langmuir
Modied magnetic chitosan resin FTIR Hg(II) 5 303 Exothermic 613.81 PSO Langmuir [158]
CSTG SEM, FTIR,
1
H NMR, TGA, XRD, VSM Hg
2+
5.0 303 Exothermic 98 2 PSO Langmuir [159]
Cu
2+
5.0 303 Exothermic 76 1 PSO
Zn
2+
5.0 303 Exothermic 52 1 PSO
XMCS FTIR, EDS, XPS Pb(II) 5.0 298 76.9 Langmuir [126]
Cu(II) 5.0 298 34.5 Langmuir
Zn(II) 5.0 298 20.8 Langmuir
Chitosan-bound Fe
3
O
4
nanoparticles SEM, TEM, XRD Cu(II) 5 300 Exothermic 21.5 Langmuir [143]
Chitosan coated magnetic nano-adsorbent Au(III) 2 298 59.52 PSO Langmuir [160]
Magnetic chitosan microspheres XRD, SEM and VSM Cu(II) 5.0 298 19.4 PSO [161]
SICCM TEM, XRD and FTIR Cu(II) 4.5 301 144.9 Langmuir [162]
Magnetite-loaded chitosan microspheres SEM, conductometric tritration Cu(II) 5 298 182 PSO Langmuir [163]
CMC FTIR, SEM Cu(II) 6.0 Room temperature 78.13 First-order
Langergren
Langmuir [111]
Magnetic chitosan nanoparticles XRD, SEM, TEM and VSM Cr(VI) 3 298 55.80 PSO Langmuir [164]
CS/Fe
3
O
4
/Fe(OH)
3
-E SEM, TEM, XPS, XRD As(III) 8.47 PSO Langmuir & Freundlich [133]
CS/Fe
3
O
4
/Fe(OH)3-C As(III) 4.72 PSO Langmuir & Freundlich [133]
Magnetic CS microcapsule FT-IR, VSM, TEM Cu(II) 7.0 303 Exothermic 104 PSO Langmuir [110]
Cr(III) 7.0 303 Exothermic 159 PSO Langmuir [110]
Magnetic chitosan composite bead Cu(II) 5.0 308.15 Exothermic 121.9 Intra-particle
diffusion
Freundlich [165]
EYMC FTIR, SEM Pb(II) 5.5 303 Endothermic 127.37 PSO Langmuir [166]
Super paramagnetic chitosan microparticles FTIR, SEM, XRD, SQUID Cu(II) 6 298 30.3 Langmuir [116]
MCNCs XRD, TEM, Raman spectra, SQUID Cr(VI) 5 300 Exothermic 35.2 PSO Freundlich [167]
Fe
3
O
4
-TETA-CMCS Elemental analysis, IR, solid state
13
C NMR, XRD, TEM, BET, TGA
Pb(II) 6 298 Exothermic 370.63 PSO Langmuir [168]
CG-MCS nano-adsorbent FT-IR, TEM, XRD, VSM, elemental
analysis
Hg(II) 303.15 285 PSO Langmuir [148]
Porous-magnetic chitosan beads SEM Cd(II) 6.5 298 518 [169]
7
8
D
.
H
.
K
.
R
e
d
d
y
,
S
.
-
M
.
L
e
e
/
A
d
v
a
n
c
e
s
i
n
C
o
l
l
o
i
d
a
n
d
I
n
t
e
r
f
a
c
e
S
c
i
e
n
c
e
2
0
1
2
0
2
(
2
0
1
3
)
6
8
9
3
the authors concluded that the large number of NH
2
groups on the
chitosan composite conferred a higher adsorption capacity. A schematic
of the magnetic chitosannanocomposites andtheir use inPb
2+
removal
is shown in Fig. 15.
In a separate study, a chitosan-based hydrogel that was graft-
copolymerized with methylenebisacrylamide and poly(acrylic acid)
(CS-co-MMB-co-PAA) was shown to adsorb Pb(II), Cd(II), and Cu(II)
ions [156]. The hydrogels were prepared with and without magnetic
properties, and from adsorption isotherm modeling, the authors con-
clude that adsorption of Pb(II) ions ts the Freundlich isotherm model
and the adsorption of Cd(II) and Cu(II) ions ts the Langmuir
isotherm model. Several other amino functionalized MCCs were
also prepared using various ligands such as tetraethylenepentamine
and glycidyltrimethylammonium [154] for treating Mo(V); tetra-
ethylenepentamine, glycidyltrimethylammonium chloride [155] use
to remove Cr(VI); diethylenetriamine [127] to remove Cu(II) N
Zn(II) NCr(VI) and triethylenetetramine [168] for treating Pb(II) from
aqueous solutions.
Grafting of organosulfur-based compounds (e.g. thiourea or
xanthate), which provide a high stability and specicity for metal ions,
onto chitosan has been a successful approach taken by many groups.
Thiolated chitosans are typically derivatized at the primary amine
groups and the sulfur group has been shown to form a stable complex
with highly polarizable, soft heavy metals such as Hg, Ag, Au, and, to a
lesser extent, Cd and Zn [14]. Donia et al. [157] synthesized a magnetic
chitosan resin using thiourea/glutaraldehyde in the presence of
magnetite and the resulting resin was used for the removal of Au(III)
and Ag(I). The observed preference for Au(III) over Ag(I) was attributed
to two different interactions between the resin and these ions (ion pairs
and chelation, respectively). Using a similar method, Donia et al. [158]
prepared a thiourea modied MCC and used it for the removal of
Hg(II), demonstrating that ~90% of the maximum Hg(II) uptake was
achieved within 70 min and that Hg(II) could be selectively separated
from Cu(II), Pb(II), Cd(II), Zn(II), Ca(II), and Mg(II). The recovery of
Hg(II) was similar to that observed for a commercial resin, Dowex-
D3303. Zhou et al. [123] synthesized TMCS using thiourea and found it
useful for the removal of Hg
2+
, Cu
2+
, and Ni
2+
ions. The authors
conclude that a high percentage of nitrogen and sulfur was responsible
for the metal ion binding via chelation and the presence of sulfur led
to a higher adsorption capacity for Hg(II).
Monier [159] prepared a novel chitosanthioglyceraldehyde Schiff's
base crosslinked magnetic resin (CSTG) and used this resin for the
removal of Hg(II), Cu(II), and Zn(II) ions. The authors concluded that
the high adsorption afnity for Hg
2+
was due to the presence of a sulfur
group and the preference for Cu
2+
over Zn
2+
is attributed to the Jahn
Teller effect. The high adsorption of Hg
2+
depends on the principle of
hard and soft acids and bases. Mercury (soft Lewis acid) prefers
formation of strong covalent bond with sulfur (soft base). Further due
Fig. 14. The effect of initial solution pH on Cr (VI) removal by EMCMCR at various initial
concentrations (10, 60 and 100 mg/L).
Fig. 15. A schematic of the synthesis route of magnetic chitosan nanocomposites and their use as a facile tool for Pb
2+
removal with the help of an external magnetic eld.
Reprinted with permission from ref. [174], Copyright 2009 American Chemical Society.
to its electronic conguration (3d
9
) copper occurs as a JahnTeller
distorted complex, thus Cu
2+
preferentially adsorb onto CSTG than
Zn
2+
. To follow up, Monier and Abdel-Latif [131] then synthesized
crosslinked magnetic chitosan-phenylthiourea (CSTU) resin by
introducing a thioamide bond between the amino group in chitosan
and the active isothiocyanate group of phenylisothiocyanate. CSTU
had a higher adsorption capacity than other resins and the data obtain-
ed from the Langmuir isotherm showed the following preference:
Hg
2+
N Cd
2+
N Zn
2+
. In order to achieve better selectivity and afnity
for target metal ions, some authors have prepared ion imprinted MCCs.
Fan et al. [128] synthesized (Ag-TCM) using Ag(I) as an imprinted
ion and were able to show that this resin is strongly selective for the
adsorption of Ag
+
over Cd(II), Zn(II), Pb(II), and Cu(II). Preparation
of Ag-TCM and its application for selective adsorption of Ag
+
was
shown in Fig. 16. In a similar study, a novel type of adsorbent, MICT,
was prepared for the removal of Cd(II) [72].
Other types of sulfur ligands have also been used to functionalize
chitosan composites. Xanthates, which contain \CS
2
groups, are
particularly reactive towards metal ions. Zhu et al. [126] prepared a
novel xanthate-modied magnetic chitosan (XMCS) and applied
it to the competitive adsorption of Pb(II), Cu(II), and Zn(II) in single
and ternary metal systems. In single and ternary system, the
metal adsorption showed the following order of preference:
Pb(II) N Cu(II) N Zn(II). Chen and Wang [139] used XMCS to remove
Co(II) and showed that this modied resin bound better than the
unmodied form, suggesting that the sulfur group played an important
role.
In recent years there has been a growing interest in using magnetic
chitosan nanoparticles for the removal of metals from contaminated
water. Nanoparticles can easily be manipulated by anexternal magnetic
eld, and thus should be suitable as a support for adsorbents [149].
Several researchers have investigated the use of chitosan magnetic
nanocomposites for binding metal ions and some of the pioneering
work on this topic was performed by Chang and Chen [143,149,160].
These authors prepared a magnetic nanoadsorbent and applied it to
the removal of Cu(II) [143]. This material had an extraordinary
adsorption rate (N1 min), which was due to the absence of internal
diffusion resistance. The same research group subsequently extended
these studies and measured the recovery of Au(III) using this magnetic
nanoadsorbent [160]. A high adsorption capacity (59.52 mg/g) was
measured based on the Langmuir equation was found, and it was
observed that adsorption was increased with decreasing pH due to
protonation of the amino groups in chitosan. A signicantly shorter
equilibrium time, as a result of the larger available surface area, was
measured. In a similar study, the same authors used the magnetic
chitosan nanoadsorbent for the removal of Co(II) [149].
Chitosanmagnetite nanoparticles were also used for the adsorption
of Cu(II) in a batch system and the binding was supported by the
Langmuir isothermand pseudo-second-order equation with an adsorp-
tion capacity of 19 mg/g [161]. In another study, nanoparticles of 8
40 nm were prepared using a simple one-step in situ co-precipitation
method and both the Langmuir and DubininRadushkovich models t
the adsorption data reasonably well, with a maximum adsorption
capacity of 35.5 mg/g for Cu(II) [135]. Peng et al. [162] took a different
approach and immobilized Saccharomyces cerevisiae on the surface of
chitosan-coated magnetic nanoparticles and found that these particles
had a particularly high adsorption capacity (144.9 mg/g) for Cu(II)
removal. When chitosan-coated magnetic nanoparticles were modied
with -ketoglutaric acid (-KA), the maximum adsorption capacity for
Cu(II) removal was 96.15 mg/g [144]. Nanoparticles for which
epichlorohydrin was used as a crosslinking agent to block hydroxyl
groups and make amino groups available for adsorption were shown
good adsorption efciency for Cr(VI) [164]. However, in this case, the
adsorption process was relatively slow (100 min), with adsorption
kinetics following a pseudo-second-order model.
A number of groups have developed and tested variations on the
traditional MCCs that were described above and a description of these
is included in this section. Magnetic chitosan composite particles
(FeCc) exhibited very high adsorption capacity for both UO
2
2+
(666.67 mg/g) and Th
4+
(312.50 mg/g) and the authors conclude
that the OH and \NH
2
groups were involved in this process [150]. An
ion-imprinted magnetic chitosan resin (IMCR) that was prepared
using U(VI) as a template and glutaraldehyde as a crosslinker, was
and applied for the removal of U(VI) [146]. These uranium-imprinted
resins showed a higher adsorption capacity and selectivity than non-
imprinted magnetic chitosan resins (NIMCR), and selectively bound
Fig. 16. Synthesis route of Ag-TCM and their application for removal of Ag
+
with the help of an external magnetic eld.
U(VI) from a mixture containing Th
4+
, Fe
3+
, Zn
2+
, Ni
2+
, Co
2+
, and
Cu
2+
.
In another study, stable magnetic alginatechitosan gel beads were
prepared by loading iron oxide nanoparticles onto a combined alginate
and chitosan absorbent for the removal of lanthanum ions from
aqueous solution [80]. This bead design is useful for the selective
separation of Ln(II) from co-existing metal ions such as Pb(II), Cd(II),
Co(II), Ni(II), and Cu(II). In a recent study, the adsorption behavior of
Pb(II) and Ni(II) ions on chitosan/magnetite composite beads was
studied [129]. The beads exhibited a good adsorption efciency and
the adsorption parameters demonstrated good compatibility with the
Langmuir model. Vu et al. [133] prepared chitosan(CS)/magnetic(Fe
3-
O
4
)/ferric hydroxide (Fe(OH)
3
) microspheres by both electrospraying
and conventional methods. The microspheres prepared by
electrospraying exhibited a higher adsorption capacity towards As(III)
than the microspheres obtained using conventional methods. Due to a
high surface area (115.8 m
2
/g) in the case of CS/Fe
3
O
4
/Fe(OH)
3
E, the
sorption was relatively quick and followed the pseudo-second-order
model. More recently, Zhang et al. [110] studied the application of
magnetic chitosan microcapsules for the removal of Cu(II) and Cr(III)
from aqueous solutions. The microcapsule had saturation capacities of
104mg/g and 159mg/g for Cu(II) and Cr(III) ions, respectively. Further
adsorption of these metal ions in a binary metal solution was studied,
and the adsorption capacity for Cr(III) is higher than Cu(II). Novel
chitosan/Fe
3
O
4
composite beads were prepared and employed for the
removal of Cu(II) fromaqueous solution[165]. The equilibriumsorption
capacity for removal of Cu(II) was found to be 121.9mg/g. Intraparticle
diffusion played an important role in the sorption mechanismof Cu(II).
In a recent investigation, Wang et al., [116] employed supermagnetic
chitosan microparticles for the adsorption of Cu(II) from aqueous
solution. These particles exhibited a good adsorption capacity towards
copper with a maximum capacity of 30.3mg/g.
3.2. Removal of dyes
Dyes are natural or synthetic organic compounds that have
been used for coloring many different types of materials for thousands
of years. Synthetic dyes have been used extensively recently
due to their low cost, bright colors, resistance to fading, and ease
of use. This extensive use along with a high level of industrial
production (e.g., textile, paper and pulp, dye and dye intermediates,
pharmaceutical, tannery, and Kraft bleaching, etc.) has led to pollution
of natural water resources and wastewater treatment systems [176].
Furthermore, in dye production, approximately 15% of the material is
lost to wastewater during synthesis and processing [177]. One of the
biggest sources of this type of pollution worldwide is wastewater from
the textile industry. Release of the colored waste into the environment
is undesirable because it affects the esthetics, the water transparency,
and the gas solubility of bodies of water. Moreover, most of these dyes
cause allergic reactions, dermatitis, skin irritation and also lead to
mutations and cancer in humans [99,100]. Due to the worldwide
concern about water pollution, global regulations have become more
stringent [178], and the efuent from dye manufacturing must be
treated carefully before it is discharged. This has resultedinanincreased
demand for eco-friendly and economic technologies for removing dyes
from aqueous efuent and various technologies have been developed
for this purpose [98]. Adsorption-based magnetic separation is an
attractive and effective option. Several research groups have developed
MCCs that are being used to remove dyes from aqueous solutions, and
Table 3 summarizes this work.
3.2.1. Effect of pH
The effect of solution pHis an important factor affecting not only the
surface charge of MCCs, but also the degree of ionization of the material,
the dissociation of the functional groups on the active sites of MCCs and
solubility of some dyes. Further the pH effect on the dye adsorption by
MCCs is dependent on the type of dye and the type of MCCs. In general,
at low pH the adsorption of cationic dyes by MCCs tends to decrease,
while for anionic dyes adsorption increase. The optimum pH values
obtained for various dye removal by MCCs were summarized in
Table 2. In case of cationic dyes at low pH solution decrease in
adsorption was observed whereas at high pH solution increase in
cationic dye adsorption was observed by MCCs. In general at high pH
solution number of positively charged active sites decreases and the
MCC surface appears negatively charged, and results in higher cationic
dye adsorption.
For example, adsorption of MB and CV GMby OC-BzMnanoparticles
increased with increasing pHfrom3.0 to 7.0 [179]. The authors reported
that the increased adsorption was due to the electrostatic interactions
between active groups present on the surface of OC-BzM nanoparticles
and cationic dyes. In another study the effect of solution pH on the
adsorption of three cationic dyes, MB, CV and 7GL by CS-MCMs and
CS-Glu-MCM was studied in the pH range from 2.0 to 10.0 [188]. The
adsorption capacities for all three dyes increased with increasing pH
(within the range of pH 210) for both adsorbents (Fig. 19). They
found that pH dependence of dye adsorption might be associated with
the carboxyl and amino groups on CS-Glu-MCM whereas the presence
of only amino groups on CS-MCMs. At lower pH the surface charge of
both composites was positively charged which results lower adsorption
whereas with increase in pH due to deprotanization of amino and
carboxyl groups negative charge on surface of adsorbents increases
resulting a higher adsorption.
Whereas at a lower pH solution the number of positively charged
active sites increased due to the protonation of functional groups of
MCCs; this increase the electrostatic attraction between the negatively
charged anions and positively charged surface of MCCs, result in an
increase in anionic dye adsorption. Due to this majority of anionic dye
adsorption studies onto MCCs showed the optimum pH is in the range
of pH25 (Table 3).
By considering the importance of pH Travlou et al. [175] studied the
effect of pHon adsorptiondesorption of reactive dye by GO-Chm. They
reported that reactive dye adsorption decreased from 81% to 35% with
the increase of pH from 3 to 12. Adsorption was optimum under acidic
conditions (pH 3) and desorption occurred under alkaline conditions
(pH12). In another study adsorption of AR dye by MIMC was studied
in the pH range 28 [182]. The dye uptake was decreased from
39.5mg/g to 17.6mg/g with increase in pH from 2 to 8. A lower uptake
belowpH3 was observed authors explained this as availability of lower
concentration of anionic dyes species due to the decrease in AR
dissociation. Similar trend was observed in case of AO7 and AO10
adsorption onto EMCN, under highly acidic conditions (bpH3) uptake
was very low [145]. Adsorption of methyl orange (MO) onto m-CS/-
Fe
2
O
3
/MWCNT was studied in the pH range 1.74 to 11.60 with effect
of contact time [136]. With increase in pH from 1.74 to 4.29 the
adsorption capacity increased from 24.92mg/g to 32.78mg/g and then
decreased from 32.78 mg/g to 13.50 mg/g with change in pH from
4.29 to 11.60.
3.2.2. Effect of temperature
Temperature is considered as an important factor that can inuence
dye adsorptionat liquidsolid interfaces, as most of the textile andother
dye efuents are discharged at relatively high temperatures. In addition
temperature affects the mobility of dyes and the solubility of dyes.
Hence various researchers investigated the effect of temperature on
dye adsorption process by MCCs.
The RY145adsorptiononto Fe
3
O
4
-CS was reportedas anendothermic
process [147]. Adsorption capacity increased from 47.62 mg/g to
76.92 mg/g with increase in temperature from 25 C to 35 C. Similar
trend was observed in case of CR adsorption by CCIO composite, the
adsorption capacity increased from 42.62 1.14 to 56.66 2.79 with
increase in temperature from295K to 315K and the adsorption process
was also observed as endothermic [185]. Zhu et al. [114] studied the
Table 3
Adsorption capacities and experimental conditions of MCCs for dye removal from aqueous solution.
Adsorbent Characterization Dyes pH Temperature
(K)
Nature of adsorption Adsorption
capacity (mg/g)
Magnetic chitosan-Fe(III) hydrogel SEM, EXAFS, XPS AR 73 12 293 294.5 PSO LangmuirFreundlich [70]
Modied chitosan resin R1 FTIR, surface area, zeta
potential
RB5 3 298 Endothermic 0.63
a
PSO Langmuir [79]
Modied chitosan Resin R2 FTIR, surface area, zeta
potential
RB5 3 298 Endothermic 0.78
a
PSO Langmuir [79]
MCGO FT-IR, XRD and SEM Methyl blue 5.3 303 Exothermic 95.31 PSO Langmuir [124]
OC-BzM TEM, FTIR, Mssbauer
spectroscopy, VSM and TGA
MB 7.0 333.15 Endothermic 223.58 PSO LangmuirFreundlich [179]
CV 7.0 333.15 Endothermic 248.42 PSO
MG 7.0 333.15 Endothermic 144.79 PSO
M-Fe
2
O
3
/CSCs XRD, FT-IR, TGA, DSC, SEM
and VSM
MO 6.6 300 - PSO [180]
EMCN TEM, VSM, TGA, FTIR AO7 4.0 298 Exothermic 1215 Langmuir [145]
TEM, VSM, TGA, FTIR AO10 3.0 298 Exothermic 1017 Langmuir
m-CS/PVA HBs XRD, VSM and TGA CR 5.0 298 Endothermic 470.1 PSO Langmuir [114]
m-CS/-Fe
2
O
3
/MWCNT XRD, FTIR, TGA and DTG MO 3.146.5 297 Exothermic 66.09 PSO Langmuir [136]
L-Cht/-Fe
2
O
3
FTIR, TEM, VSM and TGA Remazol Red 198 298 Endothermic 267 PSO LangmuirFreundlich [181]
CDCM FTIR, SEM and XRD Methyl blue 5 303 Exothermic 2.78 g/g PSO Langmuir [140]
Chitosan coated magnetite nanoparticles TEM, XRD, TGA, EPR Reactive yellow 145 3.0 318 Endothermic. 70.10 Langmuir [147]
MIMC SEM, FT-IR, XRD Alizarin red 3 303 Exothermic 43.08 PSO Langmuir [182]
Carboxymethylated chitosan-conjugated
magnetic nano-adsorbent
TEM, XRD AO12 3 298 Endothermic 1883 PSO Langmuir [183]
AG25 3 298 Endothermic 1471 PSO Langmuir
-Fe
2
O
3
/SiO
2
/chitosan composite XRD, SEM MO 5.0 310 Exothermic 34.29 PSO Langmuir [184]
-Fe
2
O
3
/chitosan composite lms XRD, FTIR, TGA, DSC MO 2.91 330 Exothermic 29.41 PSO Langmuir [113]
Magnetic composite (chitosan
coated magnetic Fe
3
O
4
particle)
CR 2.0 315 Endothermic 56.66 Langmuir [185]
MCCG FTIR, SEM, TEM and XRD MB Endothermic 84.32 PSO Langmuir [132]
GO-Chm SEM/EDAX, FTIR, XRD, XPS,
DTA, DTG
RB5 3 338 Endothermic 425 PSO [175]
Glutaraldehyde cross-linked
magnetic chitosan beads
Direct red 23 4.0 Room temperature 1250 Langmuir [186]
Fe
3
O
4
/ZrO
2
/chitosan FTIR, SEM, TEM, BET Amaranth 2 99.6 PSO Freundlich [187]
Tartrazine 2 47.3 PSO Freundlich
CS-MCMs FTIR, TG, SEM, VSM MB 7.0 293 33.6 PSO Langmuir [188]
CV 7.0 293 86.6 PSO Langmuir
7GL 7.0 293 26.3 PSO Langmuir
CS-Glu-MCMs FTIR, TG, SEM, VSM MB 7.0 293 182.5 PSO Langmuir [188]
CV 7.0 293 403.2 PSO Langmuir
7GL 7.0 293 236.4 PSO Langmuir
MagCH bead XRD, TEM MO 4 293 779 PSO Langmuir [189]
CS-m-GMCNTs XRD, VSM, SEM-EDS andBET CR 6 298 Exothermic 263.3 PSO Langmuir [190]
a
mmol/g.
8
2
D
.
H
.
K
.
R
e
d
d
y
,
S
.
-
M
.
L
e
e
/
A
d
v
a
n
c
e
s
i
n
C
o
l
l
o
i
d
a
n
d
I
n
t
e
r
f
a
c
e
S
c
i
e
n
c
e
2
0
1
2
0
2
(
2
0
1
3
)
6
8
9
3
effect of temperature on CR adsorption by m-CS/PVA HBs and found
that adsorption process is endothermic.
However exothermic nature of the adsorption process was also
reported for several dyes by MCCs. Effect of temperature on adsorption
of MB onto CDCMwas studied in a batch systemin the range of 303K to
323K [140]. The authors reported that adsorption was favored at lower
temperature and the adsorption process was exothermic in nature. Few
other examples of exothermic process are AO7 and AO10 adsorption
onto EMCN [145], MO adsorption onto m-CS/-Fe
2
O
3
/MWCNT [136],
adsorption of MB onto MCGO [124].
3.2.3. Effect of modication
Ingeneral, amine groups are the primary sites where dyes containing
D\SO
3
groups adsorb via ionic interactions. In light of this observation,

Zhou et al. [145] prepared ethylenediamine-modied magnetic chitosan
nanoparticles (EMCN) for the removal of Acid Orange 7 and Acid Orange
10 dyes. The authors successfully enhanced the concentration of amine
groups (3.8 mmol/g) on these nanoparticles and achieved good
adsorption capacities of 1215 mg/g and 1017 mg/g for C.I. Acid Orange
7 and C.I. Acid Orange 10, respectively. In a similar study, Elwakeel
[79] synthesized chitosan resins using tetraethylenepentamine and
glycidyltrimethylammonium chloride. Both of the two resins exhibited
a very high uptake of reactive black 5 with adsorption efciencies of
0.63 and 0.78mmol/g, respectively.
Using a molecular imprinting technique, Fan et al. [182] prepared an
adsorbent (MIMC) by coating a magnetite surface with chitosan using
Alizarin red (AR) as the template. MIMC had a very good adsorption
capacity (40.12 mg/g), and at pH 3, it was selective for AR in mixed
dye solutions. The same group also synthesized -cyclodextrin
chitosan (CDC) modied Fe
3
O
4
nanoparticles (CDCM) for the removal
of methyl blue [140]. The adsorption mechanism in this case was
hypothesized to be hostguest interactions of -CD molecules, which
have hydroxyl, carboxyl and amino functional groups.
Fan et al. [124,191] combined the large surface area and mechanical
strength of graphene oxide with the favorable adsorption properties of
chitosan to develop a novel magnetic chitosan and graphene oxide
(MCGO) adsorbent for the purpose of removing methyl blue (MB) and
found it to be very effective (95.16 mg/g). In another study, taking
advantage of the various features of graphene oxide (surface property),
-cyclodextrin (hydrophobicity) and chitosan (abundant hydroxyl and
amino groups) Fan et al. [132] prepared a high surface area (402.1m
2
/g)
magnetic -cyclodextrinchitosan/graphene oxide nanoadsorbant for
the removal of methyl blue and measured a good adsorption capacity of
84.32mg/g. In a separate study [175], graphite oxide was functionalized
with magnetic chitosan to prepare a nanocomposite material (GO
Chm) that was useful for the removal of Reactive Black 5 and exhibited
a fast adsorption phenomenon and higher adsorption capacity
(425 mg/g). Authors reported that ~75% adsorption capacity was
improved due to the functionalization of GO with Chm.
Fig. 17. Picture showing the variationof colors (a) control (b) Chitosan-Fe(III) hydrogel (c)
adsorption of dye onto chitosan-Fe(III) hydrogel.
Fig. 18. Response surface for adsorption of MG, by OC-BzM nanoparticles (q
e
mg/g) in
function of temperature (C) and initial dye concentration (C
in
mg/L).
Fig. 19. Effects of initial solution pH on various dyes uptakes onto the magnetic
microspheres, MB (/ onto CS-MCM/CS-Glu-MCM), CV (/ onto CS-MCM/CS-Glu-
MCM) and 7GL (/onto CS-MCM/CS-Glu-MCM). The inset is the photographs of various
dye solutions before and after adsorption using CS-Glu-MCM at pH 7.0 including the
effects of actual magnetic separation.
Amagnetic chitosan-Fe(III) hydrogel was prepared by using chitosan
andiron salts that rapidly (b10min) and efciently removed the anionic
dye Acid Red 73 across a wide range of pHvalues, witha highadsorption
capacity (294.5 mg/g) at pH 12 [70]. This material displayed a N90%
removal rate for a variety of different anionic dyes. The authors are
credited for their extensive discussion of adsorption mechanisms, the
visual changes in the dye color after adsorption with chitosan-Fe(III)
hydrogel was shown in Fig. 17. To utilize the various advantageous
properties of silica (SiO
2
), Zhu et al. [184] prepared a -Fe
2
O
3
/SiO
2
/
chitosan composite and undertook a comprehensive study to examine
the adsorption performance of this composite towards methyl or-
ange azo dyes. They measured the effect of adsorbent dosage, initial
dye concentration, solution pH, and competing inorganic anions on
adsorption performance and reported a higher adsorption capacity
(34.29mg/g) than that of other low-cost adsorbents.
Considering the superior adsorption performance of multi-walled
carbon nanotubes than other traditional adsorbents for dyes removal,
m-CS/-Fe
2
O
3
/MWCNT was developed for the purpose of removal of
MO and achieved a good adsorption capacity [136]. In another study
the same group have prepared CS-m-GMCNTs using suspension cross-
linking technique. This material exhibited a good adsorption capacity
262.9mg/g for Congo Red [190].
Debrassi and co-workers [179] prepared OC-BzM nanoparticles and
applied for the removal of three cationic dyes: methylene blue, crystal
violet, and malachite green. This was a very thorough study employing
a variety of analytical techniques, including FTIR, TGA, TEM, Mossbauer
and VSM, to fully understand the properties of the adsorbent. It was
concluded that the composite particles had the following charac-
teristics: an inorganic content of 34.74%, a mean size of 14 nm,
a saturation magnetization of 18.4 emu/g, and superparamagnetic
behavior. Using Mossbauer spectroscopy to identify the phase of the
magnetic particles contained in the adsorbent, authors reported that
ironoxide is present inthe formof maghemite. The maximumefciency
of pollutant removal from aqueous solutions will only be possible if
the optimum operating parameters are determined. However, most
adsorption studies have tested only one independent variable and
have kept other parameters constant. With this in mind, a study was
carried out using RSM to optimize the experimental variables. The
authors calculated a response surface plot to reect the inuence
of the initial MG concentration and temperature on the adsorption
response (q
e
mg/g) (Fig. 18) [179]. It was found that adsorption
increased with an increase in the initial dye concentration as well
as with temperature. When the Langmuir and LangmuirFreundlich
isothermmodels were applied to study the adsorption isothermdata,
it was shown that the LangmuirFreundlich isotherm was a better
model. The same group used magnetic N-lauryl chitosan particles to
remove Remazol Red 198 and observed a good adsorption capacity
(267 mg/g) with data that t well to the LangmuirFreundlich
equation [181].
By applying a microemulsion process, Zhu et al. [180] prepared
magnetic -Fe
2
O
3
/crosslinked chitosan composites (M-Fe
2
O
3
/CSC)
that were very efcient at removing methyl orange (MO) and were
separated from the reaction solution in 10 s. Kalkan et al. [147] used
chitosan-coated magnetite nanoparticles for the removal of Reactive
Yellow 145 and, using the Langmuir model, calculated a maximum
adsorption capacity of 47.62mg/g. Jiang et al. [113] prepared magnetic
chitosan nanocomposite lms for the removal of methyl orange and
measured an adsorption capacity of 29.41mg/g.
Sanlier et al. [186] prepared glutaraldehyde-crosslinked magnetic
chitosan beads and reported a very high maximum adsorption capacity
(1250 mg/g) at pH 4.0 for the removal of Direct Red 23. For this
composite, the magnetic properties were conferred by barium ferrite.
In another report Fe
3
O
4
/ZrO
2
/chitosan composite was synthesized and
employed for the removal of Amaranth and Tartrazine dyes removal
[187]. A good adsorption capacities 99.6 and 47.3 mg/g for Amaranth
and Tartrazine dyes were observed. In another investigation Yan et al.
[188] prepared CS-MCMs and CS-Glu-MCM and tested adsorption to
three cationic dyes, methylene blue, crystal violet and Cationic Light
Yellow 7GL. Authors reported that CS-Glu-MCM showed a higher dye
uptake compared with CS-MCMs, this higher uptake was due to the
presence of carboxyl groups on glutamic acid of CS-Glu-MCM.
Obeid et al. [189] prepared a magsorbent using chitosan and
maghemite, this material was effective for the removal of MO with
higher adsorption capacity of 779 mg/g. In addition authors examined
the efciency of cross-linking step by dispersing MagCH beads in nitric
acid. Authors observed loss of iron under acidic medium below pH2.5.
3.3. Desorption
Desorption of sorbate from the adsorbent is of utmost importance
which will provide the benecial features including (i) reusability of
adsorbent, (ii) recovery of pollutants, (iii) reduces the process cost,
(iv) reduces the generation of secondary wastes and (v) identifying
the adsorption mechanism. To achieve successful desorption process
selection of appropriate eluent is an important aspect, and a successful
eluant must be non-reactive to the adsorbent, effective, economic and
environmental friendly. A number of eluents have been used for the
desorption process such as acids, bases and chelating agents. However,
acids such as HCl, HNO
3
, bases like NaCl, NaOH and chelating agents
thiourea, ethylendiaminetetraacetic acid(EDTA) were widely employed
in desorption process of MCCs. In case of metal ions EDTA has proved as
a successful eluant which was widely employed for desorption of vast
number of metal ions (Table 4). Further it was reported HCl could not
be advisable as an eluent solution that it has a much higher rate of
dissolution of Fe
3
O
4
, the magnetic component of MCCs [135,137].
Of these, the work of Monier et al. [152] examined EDTA and HCl to
desorb Cu(II), Co(II) and Ni(II) from metal loaded CSAP and it was
concluded that EDTA is the more efcient desorption solution than the
HCl solution. In another study over 90% desorption of Hg(II) was
achieved by using 0.02 M of thiourea concentration. These eluent was
used for 5 cycles and it was found that the adsorption capacity of the
EMCR could still be maintained at 90%. In another study a wide variety
of eluents including HNO
3
,NH
4
OH and thiourea alone and combination
of these eluents were employed for the desorption of Pt(IV) and Pd(II)
[137]. The high percentage of desorption was observed with 0.4 M
HNO
3
1.0 M thiourea. In another study three eluents EDTA, HCl, and
NaOH were employed to desorb Cr(VI) from EMCMCR. It was observed
that 87.96% of the loaded Cr (VI) stripped with 0.1NNaOH. The authors
explained that at alkaline medium the electrostatic interactions
between EMCMCR and Cr(VI) will be weaken and this promotes the
desorption of Cr(VI) ions [153]. In another study by using 0.2 M NaOH
was used to desorb As(V) and Cr(VI) from CAGS resin and over 92 and
93% desorption was achieved [78]. In a recent study EDTA and HCl
solutions were used for desorption of Hg
2+
, Cu
2+
and Zn
2+
from
metal loaded CSTG [159]. It was found that the metal ions adsorbed
on CSTG were easily desorbed by using EDTA solution with desorption
efciency about 98%, whereas lower desorption efciency was observed
with the HCl solution about 89%. The authors explained the plausible
reason that desorption of metal ions by EDTA was due to the formation
of stable complexes with the metal ions whereas desorption took place
with HCl solution was due to the ion exchange. Similar ndings were
observed in case of CSTU adsorbent with Hg
2+
, Cd
2+
and Zn
2+
ions
by using EDTA and HCl solution [131]. From the overall studies of
metal ion desorption from MCCs it was found that EDTA has proven as
effective eluent for various metal ions with high desorption efciency.
This is due to the fact that EDTA is well known as strong chelating
agent which forms stable complex with many metal ions. Therefore
EDTA could be utilized as eluant for desorption of metal ion loaded
MCCs.
Various acidic, basic solutions and solvents have been employed to
desorb dyes fromMCCs however fromthe publishedliterature however,
it was observed that NaOH was effective for successful desorption of
dyes from MCCs. For example, Shen et al. [70] used NaAc, NaOH,
NaHCO
3
, Na
2
CO
3
, Na
2
HPO
3
, NH
4
OH, methanol, ethanol, acetone and
EDTA with different concentration to desorb C.I. Acid Red 73 from
chitosan-Fe(III) hydrogel. They reported that 1 mol/L NaOH had
efciently desorbed 94.4% of C.I. Acid Red 73. In another study to desorb
MB from MCGO three eluents, HCl, NaOH and H
2
O were used and a
maximum desorption efciency of 95.01 with 0.5 mol/L NaOH was
observed [124]. The authors explained that deportation of amino
group in basic medium results in weaker interactions between MCGO
and dye thus a high desorption was observed with NaOH. In a separate
study to desorb MB from CDCM the authors used 0.1 M NaOH
concentration in ethanol [140]. In a few studies mixture of solutions
was also used for example, AO7 and AO10 dyes from EMCN were
desorbed by using NH
4
OH/NH
4
Cl [145].
A schematic illustration of the removal of toxic pollutants from
aqueous solution using MCCs and further regeneration of the composite
was presented in Fig. 20.
4. Adsorption kinetics and equilibrium
4.1. Adsorption kinetics
For a practical application of MCCs in pollutant removal, knowledge
of the kinetics of this process is required. Kinetic models have been
developed to analyze experimental data to determine the adsorption
mechanism and the potential rate-limiting steps, which may include
mass transport and chemical reaction processes [192]. The rates at
which adsorbate is transferred from bulk solution to the adsorbent
surface and accumulate determine the kinetics of adsorption, and
hence, the efciency of the adsorption process [193]. In practice, most
kinetic studies are carried out in batch reactions using more than one
parameter, and then linear and/or non-linear regression equations are
used to determine the best-tting kinetic rate equation. A number of
kinetic models have been established to understand the adsorption
kinetics and rate-limiting step, excellent reviews are available on the
Table 4
Some desorption studies examples of metal and dyes loaded MCCs.
MCC Eluent Optimum
concentration
Pollutant Desorption % Reference
CSIS EDTA 0.01M Cu(II), Co(II) and Ni(II) 85.8 (Cu
2+
), 87.2 (Co
2+
) and 82.5 (Ni
2+
) [121]
CSMO EDTA 0.01M Cu(II), Co(II) and Ni(II) 87.4 (Cu
2+
), 89.8 (Co
2+
) and 84.3 (Ni
2+
) [151]
EMCR Thiourea 0.02M Hg(II) 90.6 [122]
EMCN HNO
3
thiourea 0.4 M HNO
3
1.0M thiourea
Pt(II), Pd(II) 97.3 (Pd), 90.5 (Pt) [137]
EMCMCR NaOH 0.1 N Cr(VI) 87.96 [153]
CAGS NaOH 0.2 M As(V) and Cr(VI) 92.5 (As(V)) and 93.8 (Cr(VI)) [77]
TMCS EDTA 0.01M Hg(II), Cu(II) and Ni(II) 89.6 (Hg
2+
), 90.8 (Cu
2+
) and 88.2 (Ni
2+
) [123]
Magnetic chitosan nanoparticles EDTA 0.020.1 M Cu(II) N90% [135]
Magnetic chitosan composite particles HNO
3
0.1 M Th(VI) and U(VI) 87.38 (Th
4+
) and 88.75 (UO
2
2+
) [150]
MIMC NaOH 0.1 mol/L Alizarin red 93.5 [182]
MCGO NaOH 0.5 mol/L Methyl blue 95.01 [124]
Chitosan Fe(III) hydrogel NaOH 0.1 mol/L C.I. Acid Red 73 94.4 [70]
Fig. 20. A schematic diagram of the magnetic separation process of polluted water based on using magnetic chitosan composites (MCC).
application of various sorption kinetic models [192,193]. Nevertheless,
three most popular kinetic models have been widely used to study
the adsorption of metal and dyes using magnetic chitosan materials:
(i) the pseudo-rst-order kinetic model [194,195]; (ii) the pseudo-
second-order kinetic model [195197]; and (iii) the intra-particle
diffusion model [198]. These kinetic models provide the valuable
information about adsorbent surface, chemical reaction, and/or dif-
fusion mechanisms, which controls the adsorption process [28]. The
summaries of best t of kinetic model for removal of metal and dyes
using various MCCs were shown in Tables 2 and 3.
As mentioned earlier most of the studies used the pseudo-rst-order
and pseudo-second-order kinetic models to study the adsorption of
metal or dye pollutants onto MCCs. For instance Chen et al., [72] applied
bothpseudo-rst and pseudo-second-order models to the experimental
kinetic data for cadmium removal by using MICT at three different ini-
tial concentrations (50, 100, and 200 mg/L). The results showed that
the removal process had well followed pseudo-second-order model.
Monier et al. [131] reported a similar results in the study of Hg(II),
Cd(II) and Zn(II) sorption kinetics by CSTU resin. Pseudo-second-order
model well tted to the kinetic data for all the studied metal ions rather
than pseudo-rst-order. Further the theoretical q
e
values obtained from
pseudo-second-order model are closely similar to the experimental
values. In another study, Zhou et al. [123] study the removal of Hg
2+
,
Cu
2+
, and Ni
2+
ions using TMCS adsorbent and they demonstrate that
the adsorption process followed pseudo-second order kinetic model.
This is an indication that the rate-limiting step in the adsorption of
target pollutants onto magnetic chitosan materials involves chem-
isorption due to valence forces through the sharing or exchange of
electrons between sorbent and sorbate, complexation, coordination,
and/or chelation [199]. However some MCMs have deviated from this
kinetic mechanism, for example chromium(VI) adsorption onto CMC
beads the kinetic data was well tted with the rst-order Langergren
rate equation [134]. In case of copper adsorption onto cross-linked
magnetic chitosan beads the equilibrium time reached about 60 min
andthe kinetic data followed rst-order Langergrenrate equation[111].
Further most studies related dye adsorption onto MCCs also followed
pseudo-second-order model indicating chemisorption process (Table 3).
The possible reason for the chemisorption is that most of the MCCs
contain chelating functional groups including hydroxyl, amine, amino,
carboxyl, etc. For instance Jiang et al. [113] studied the removal of
MO using -Fe
2
O
3
/chitosan composite lms and they reported that
adsorption process was better explained by PSO that represent chem-
isorption. However various MCCs were combined withcarbonmaterials
including nanotubes, graphite and graphene to utilize their high surface
area thus in few studies it was observed that both chemisorption
and physisorption were involved, this complex mechanism was best
described using intraparticle diffusion model [124].
In addition to surface adsorption, pore diffusion or intraparticle
diffusion plays a signicant role, and therefore the rate-limiting step
may be affected by lm and/or pore diffusion. To determine if the rate
limiting step is intraparticle diffusion or not few researchers applied
the WeberMorris model and Fickian diffusion law, etc. For example
in a recent study along with pseudo-rst-order and pseudo-second-
order models, intraparticle diffusion model was employed to obtain
the adsorption mechanism of RB5 adsorption onto two MCC resins
[79]. They observe limited effect of boundary layer on the rate of
adsorption. In another study intraparticle diffusion model was applied
to determine the rate of adsorption of MO onto -Fe
2
O
3
/silica/
chitosan composite and demonstrated intraparticle diffusion related
to adsorption but not as sole rate-controlling step [184]. As another
example, Zhuet al. [114] applied this model and found that intraparticle
diffusion is not only the rate limiting step. The adsorption of Sr(II) onto
magnetic chitosanbeads has been studied by Chenand Wang [141]. The
kinetic data was well represented by an intra-particle diffusion model;
both external mass transfer and intra-particle diffusion were the rate-
controlling factors. Most of the studies summarized in Tables 2 and 3
indicate that the adsorption of MCCs typically follows the pseudo-
second order model, which suggests that this model is the most
appropriate representation adsorption process.
4.2. Adsorption equilibrium
Adsorption equilibrium is one of the vital pieces of information
needed for the proper analysis and design of adsorption system. Several
reviews are available on adsorption isotherm modeling [192,200].
A number of empirical models have been employed to analyze
experimental data and describe the equilibrium of adsorption, the
most popular and widely used of these are the Langmuir [201] and
Freundlich [202] isotherms. In addition to the popular Langmuir and
Freundlich isotherm models, BrunauerEmmettTeller (BET) [203],
Sips [204], DubininRadushkevich [205], Temkin [206] and Redlich
Paterson [207] isotherm models have also been used to examine the
adsorption equilibriumdata of various pollutant adsorption onto MCCs.
There have beenseveral studies inwhichthe Langmuir or Freundlich
isothermmodels have been used to describe the equilibriumadsorption
of toxic pollutants. As evidenced by the data shown in Tables 2 and 3,
the Langmuir model ts the adsorption data of metal ions and dyes
onto MCCs in most cases. This suggests that the adsorbed material
forms a monolayer on a surface with a nite number of identical sites
that are homogeneously distributed across the adsorbent surface. It is
notable that most of the studies used linear regression modeling
for isotherm studies. Linearization using such data transformations
implicitly alters the error structure. In order to evaluate the t of the
isotherm equation to the experimental equilibrium data, an error
function is required for the optimization procedure [208]. Also, most
of the MCCs were chemically modied withvarious chelating functional
groups, and most of these materials are predominantly chelating the
adsorbates. Application of the DubininRadushkevich isotherm reveals
information regarding the physical and/or chemical sorption mech-
anisms that govern the equilibrium, but only a fewstudies have applied
the DubininRadushkevich isotherm to model the sorption equilibrium
between target adsorbates (metal ions and dyes) and MCCs.
5. Mechanism of adsorption
A major challenge in the eld of adsorption is to identify the
mechanism by which target pollutants are taken up by the adsorbent
and thereby evaluate the efciency of the adsorbent material. Despite
the large number of papers describing the performance of MCCs, only
few determine the mechanism by which adsorption process occurs. It
could be that the adsorption mechanism for MCCs is more complex
than that for other materials. In general, most of the inorganic and
organic pollutants adsorb to the surface of MCCs through different
kind of interactions including ion-exchange, physical adsorption,
chemical bonding (complexation and/or chelation), vander Wall forces,
etc. In addition adsorption mechanism was signicantly inuenced by
wide range of factors such as structure of the composite, solution pH
and functional groups present on the composite.
Avariety of analytical techniques suchas FTIR, SEM-EDXand XPS are
useful for analyzing this interaction. Hritcu et al. [150] employed
energy dispersive X-ray spectroscopy (EDX) to dene the chemical
composition of magnetic chitosan particles before and after adsorption
and describe the distribution of metal ions on the material using EDX
maps (Fig. 21). In another study based on FTIR spectral analysis, Chen
and Wang [141] reported that the mechanism for the adsorption of
Sr
2+
onto magnetic chitosan beads was likely via the amine groups.
Similarly, Yuwei and Jianlong [135] used FTIR to show that copper
ions bind to the NH
2
and OH in chitosan. XPS spectra is one the most
effective tools used to dene adsorption mechanisms, and Zhu et al.
[126] used this method to conclude that Pb(II), Cu(II), and Zn(II)
coordinate with the nitrogen and sulfur atoms in XMCS.
In general, metal ions bind to MCCs via the available functional
groups (hydroxyl, carboxyl, thiol and amine groups) on the composite.
These functional groups can react with the different metallic species
through chelation and/or ion-exchange [209]. Liu et al. [174] presents
a schematic illustration of the mechanism of Pb
2+
adsorption and
desorption processes and describes the coordination of Pb
2+
by two
\OH groups and one \NH
2
group from chitosan. The target metal
ions were not only bound by hydroxyl and amine groups on chitosan
but also by other functional groups (thiol, amino, and carboxyl groups)
that are added during the modication of chitosan. Along with this
(chelation of target metal ions by chemical functional groups) surface
adsorption also plays an important role in the removal of metal ions.
For instance, adsorption of Cr(VI) onto EMCMCR is physicochemical
process though ionic and electrostatic interactions between these two
components [153]. The overall ndings suggest that MCCs have a
complex adsorption mechanism; however, it can be concluded that
the predominant mechanism is chemisorption via hydroxyl and/or
amine groups of chitosan as well as the additional chemical functional
groups (thiol, amino, carboxyl, etc.). An ion exchange mechanism also
plays an important role. Zhou et al. [122] propose that Hg(II) forms a
complex withEMCRvia a four-ring (ve-membered) structure between
the metal and the amine and hydroxyl groups of EMCR. The authors
state that the amine groups on EMCR are the primary reactive groups
that bind to Hg(II) (Fig. 22). Recently, crosslinked magnetic modied
chitosan (CMMC) was prepared and studied as an adsorbent for the
removal of Zn(II) from aqueous solution [142]. The presence of free
lone pairs of electrons on nitrogen atoms in CMMC facilitated the
coordination of the metal ion to form the corresponding resinmetal
complex.
In general, the adsorption mechanisms by which dyes bind to MCCs
include different kinds of interactions including; chemical bonding, ion
exchange, hydrogen bonds, and physical adsorption. Several groups
have investigated these complex reactions further. Shen et al. [70]
proposes a chelation mechanism between the dye molecule and
chitosan-Fe(III) hydrogel. In another study [183], acid dye adsorption
onto chitosan-conjugated Fe
3
O
4
nanoparticles was explained by ionic
interactions between the dye molecule and the amino groups of
chitosan (Fig. 22). A similar adsorption mechanism for the binding of
acid dyes to EMCN was described by Zhou et al., [145]. Majority of
studies related to the removal of anionic dyes by MCCs revealed that
the predominant adsorption mechanism is electrostatic interactions
between the anionic groups of dye and the cationic groups of MCCs
under acidic conditions as follows:
MNH
2
H
Protonation
MNH
3
DSO
3
Na
dissociation
DSO
3
Na
MNH
3
DSO
3
Electrostatic interaction
MNH
3
O
3
SD:
Fig. 22. Proposed modes of complexation of (a) Hg(II) with EMCR. (b) Mechanismof acid dyes adsorption onto the carboxymethylated chitosan (CMCH)-conjugated Fe
3
O
4
nanoparticles.
Panel a is reprinted with permission from ref. [122]. Copyright 2010 Elsevier publishers. Panel b is reprinted with permission from ref. [183]. Copyright 2005 Wiley-VCH.
Fig. 21. EDX map showing uniform distribution of the thorium (a) and uranyl (b) ions onto the composite particle surface.
Reprinted with permission from ref. [150]. Copyright 2012 Elsevier publishers.
6. Saturation magnetization and magnetic separation
As discussed in Section 1, removal of the adsorbent itself from the
solution is an important factor in the wastewater treatment processes.
Magnetic separation technology is a promising solution because it is
efcient, economical, and fast. This technology has advantages over
other conventional techniques [210]. In that a large mass of wastewater
can be treated in a very short period of time and secondary waste is not
generated [211]. Importantly, treatment can be conducted in either
batch or continuous ow systems. The magnetic adsorbent is added to
aqueous solution containing the target adsorbate, which is then bound
to adsorbent, and this nal product is removed from aqueous solution
using an appropriate magnetic separator. This process is depicted in
Fig. 23 where a column is used to collect the magnetic particles [55].
Saturation magnetization (M
S
) is used to measure the maximum
magnetic strength of adsorbent, a key factor for successful magnetic
separation [212]. Materials with a high saturation magnetization
promise rapid separation of metal-loaded materials from wastewater
[213]. The saturation magnetization is a measure of the maximum
magnetic eld that can be generated by a material, beyond which no
further increase in magnetization occurs. This is particularly important
for ferromagnetic materials, such as iron, nickel, cobalt, and their alloys.
Saturation magnetization is an intrinsic property not dependent on
particle size, but it is dependent on temperature. In addition it depends
on the characteristic of the atomic constitutions; the strength of the
dipole moments and packing density of the atoms that present in the
material. Saturation magnetization values for various MCCs are given
in Table 5. A conventional magnet was used in most of the studies to
separate the MCCs from the aqueous solution. The magnetic saturation
values of magnetite composites are experimentally determined to be in
the range of 1.4462 emu/g. However, lower saturation magnetization
values were obtained for MCCs when compared with Fe
3
O
4
particles
(63 emu/g) [97,214]. Lower saturation magnetization values for MCCs
were due to the presence of non-magnetic chitosan [130,144]. The
most important parameter to consider for the practical application of
magnetic materials is that the time it takes to separate the magnetite
from the solution must be short [213,215217]. Zhu et al., [136]
separated the methyl orange-loaded CS/-Fe
2
O
3
/MWCNT within 10 s
by applying a permanent magnet, and the saturation magnetization of
the material was 4.81 emu/g. They then applied the M-Fe
2
O
3
/CSCs
adsorbent for the treatment of azo dye and separated the dye-loaded
adsorbent in 10s by applying the magnetic eld.
7. Advantages and disadvantages of MCCs
Magnetic chitosan materials are a signicant improvement over
conventional materials that have been used to treat polluted water.
Chitosan, the basic material comprising MCCs, is biocompatible and
economic. Chitosan can also be modied with various chelating ligands
for selective and efcient binding to particular pollutants. Traditional
adsorbents, which include activated carbon, ion exchange resins, and
biosorbents, require complex separation techniques. The advantages
of MCCs include: (i) low-cost natural polymer as the base; (ii) fast
adsorption rate; (iii) high efciency, even in very dilute solutions; (iv)
versatile structure (insoluble beads, gels, sponges, nanomaterials,
lms, membranes); (v) high selectivity and sensitivity for specic
target pollutants when functionalized; (vi) selective recovery using
magnetic separation; (vii) environmentally friendly; and (viii) eas-
ily regenerated. The disadvantages of MCCs include: (i) tedious
preparation procedures; (ii) functionalization is expensive; and
(iii) adsorption is pH dependent.
8. Conclusions and future perspectives
Magnetic chitosan composites are emerging materials that have
attracted considerable attention from academics and researchers in
multiple industries due to their exemplary biocompatibility, super-
magnetism, and chelation properties. The use of these materials in
water treatment results in markedly improved performance features
over conventional adsorbents. In this review, we focused on recent
developments related to the removal of metal ions and dyes from
water using MCCs. A survey of the literature on the synthesis of MCCs
reveals a wide variety of materials chelating ligands, nanomaterials,
inorganic oxides and biomaterials have been used to enhance the
adsorption performance. These materials offer a wide range of features
including no secondary pollution, easy separation and recovery, and
strong chelating capabilities. An analysis of adsorption mechanisms
reveals that the amine and hydroxyl groups of chitosan are
predominantly responsible for binding inorganic andorganic pollutants.
Fig. 23. A typical high-gradient magnetic separation facility.
Reprinted with permission from ref. [55] Copyright 2012
Elsevier publishers.
Table 5
Saturation magnetization values for various magnetic chitosan composites.
Magnetic chitosan adsorbent Saturation
magnetization
(emu/g)
Reference
CS-MCM 14.2 [71]
CS/PAA-MCM 13.0 [71]
Ag-TCM 10.16 [128]
Chitosan/magnetite nanocomposite beads 55 [129]
EMCR 15.4 [122]
Chitosan/TiO
2
/Fe
3
O
4
microspheres 19 [130]
CSTU 30.5 [131]
TMCS 17.6 [123]
Magnetic chitosan nano-adsorbent 62 [149]
Magnetic chitosan nanoparticles 36 [135]
Magnetic chitosan composite particles 24 [150]
CSIS 20.2 [121]
CSMO 22.3 [151]
IMCR 29.7 [146]
-KA-CCMNPs 33.5 [144]
OC-BzM 18.4 [179]
-Fe
2
O
3
/crosslinked chitosan composites
(M-Fe
2
O
3
/CSCs) (1:10 M-Fe
2
O
3
/CSCs)
1.44 [180]
EMCN 25.6 [145]
m-CS/PVAHBs 21.96 [114]
m-CS/c-Fe
2
O
3
/MWCNTs 4.81 [136]
L-Cht/-Fe
2
O
3
9 [181]
ARMCM 23.2 [218]
MCCG 55.13 [132]
CS/Fe
3
O
4
/Fe(OH)
3
23.7 [133]
GO-Chm 9 [175]
Magnetic CS microcapsules 8.89 [110]
Superparamagnetic chitosan microparticles 35.3 [116]
MCCs modied with various inorganic oxides (i.e. TiO
2
and ZrO
2
)
exhibit multifunctional properties. In this article, various synthesis
strategies and characterization techniques for MCCs have been
reviewed comprehensively. Unfortunately, these materials have not
been scaled up from the laboratory into industry because several
technical, scientic, and economical issues still need to be resolved.
Further it is important to estimate the cost of any adsorption system
but MCCs have not been used at a commercial level to any extent,
there is no data available to estimate the cost of production and
application. However it was hypothesized that MCCs can be obtained
at low-cost as the major component of MCCs are chitosan and iron
oxide. In general iron oxide materials have been described as low-cost
adsorbent materials used previously in water treatment [219] and
iron oxide magnetic particles, which are widely used, can be
produced through simple, inexpensive synthetic routes [220]. In
addition chitosan is a biopolymer available at low-cost, however it
is recommended to study the cost of the adsorption system using
MCCs. The adsorption of toxic pollutants by MCCs is attractive
over conventional adsorbents as long as the following points are
considered:
1. The mechanism of adsorption should be explained using a variety of
analytical tools.
2. Statistical analysis should be performed to evaluate the quality of the
applied mathematical models.
3. The synthesis procedures for the modication of chitosan should be
simplied. The preparation of MCCs in a single step should be
encouraged. In addition, multi-component reactions using the
microwave methods are advised to carry in future studies to reduce
energy costs.
4. An evaluation of the cost of these materials should be performed to
compare with other adsorbents, including activated carbon and
agricultural biosorbents.
5. The performance of MCCs should be optimized such that
maximum uptake is achieved. The application of response sur-
face methodology to optimize the adsorption performance is
encouraged.
6. These studies should not be limited to lab-scale batch studies, but
should be scaled up to pilot plants to evaluate their feasibility on a
commercial scale. These adsorbents must be tested with industrial
efuent wastewater.
7. Multi-purpose, economically feasible magnetic chitosan composites
should be developed to remove a variety of pollutants.
Acknowledgments
This work was supported by the National Research Foundation
of Korea (NRF) grant funded by the Korean government (MEST)
(No. 2012R1A2A4A01001539).
Appendix A. Abbreviations
AFM Atomic force microscopy
Ag-TCM Thiourea-chitosancoating onthe surface of magnetite (Fe
3
O
4
)
AG25 Acid green 25
AO7 Acid Orange 7
AO10 Acid Orange 10
AO12 Crocein orange
AR Alizarin red
ARMCM Amino-reserved magnetic chitosan microsphere
BET BrunauerEmmettTeller
CAGS Cross-linkedmagnetic chitosananthranilic acidglutaraldehyde
Schiff's base
CCIO chitosan coated magneticFe
3
O
4
particle
CDCM -cyclodextrinchitosan modied Fe
3
O
4
nanoparticles
chit-PTU chitosan-phenylthiourea
CMC Cross-linked magnetic chitosan
CMCH Carboxymethylated chitosan
CMCN -cyclodextrin modied magnetic chitosan nanoparticles
CMMC Cross-linked magnetic modied chitosan
CR Congo Red
CSAP Cross-linked magnetic chitosan-2-aminopyridine glyoxal
Schiff's base resin
CS-Glu-MCMs glutamic acid modied chitosan magnetic composite
microspheres
CSIS Cross-linked magnetic chitosan-isatin Schiff's base resin
CSMO Chitosandiacetylmonoxime Schiff's base resin
CS-MCM Chitosan magnetic composite microspheres
CS-m-GMCNTs Chitosan-modied magnetic graphitized multi-walled
carbon nanotubes
CS/PAA-MCM Chitosan/poly(acrylic acid) magnetic composite microspheres
CSTG Chitosanthioglyceraldehyde Schiff's base cross-linked
magnetic resin
CSTU Cross-linked magnetic chitosan-phenylthiourea
CTS/-Fe
2
O
3
/FACs Chitosan/y-ash-cenospheres/-Fe
2
O
3
CS-co-MMB-co-PAA Chitosan-based hydrogel, graft-copolymerized
with methylenebisacrylamide and poly(acrylic acid)
CV Crystal violet
DSC Differential scanning calorimetry
DMTA Dynamical mechanical thermal analysis
EDX Energy dispersive X-ray spectroscopy
EDAX Energy-dispersive X-ray spectroscopy
EDTA Ethylenediaminetetraacetic acid
EMCR Ethylenediamine-modied magnetic cross-linking chitosan
microspheres
EMCN Ethylenediamine-modied magnetic chitosan nanoparticles
EMCMC Ethylenediamine-modied cross-linked magnetic chitosan
resin
EMMC Ethylenediamine-modied magnetic chitosan
EYMC ethylenediamine-modied yeast biomass coated with
magnetic chitosan microparticles
FeCc Magnetic chitosan composite particles
FTIR Fourier transform infrared
GO-Chm Graphite OxideMagnetic Chitosan Composite
HSAB Hard and soft acids and bases
HCl Hydrochloric acid
ICT ion-imprinted chitosan
IMCR Ion-imprinted magnetic chitosan resins
L-Cht/-Fe
2
O
3
Magnetic N-lauryl chitosan particles
MACTS Magnetic amination chitosan beads
MB Methylene blue
MCC Magnetic chitosan composite
MCCG -cyclodextrinchitosan/graphene oxide materials
MCGO Magnetic chitosan and graphene oxide and multi-walled
carbon nanotubes
MCM Magnetic composite microspheres
MICT Thiourea-modied magnetic ion-imprinted chitosan/TiO
2
MIMC Chitosan coating on the surface of magnetite (Fe
3
O
4
)
MO Methyl orange
M-Fe
2
O
3
/CSCs Magnetic -Fe
2
O
3
/crosslinked chitosan composite
m-CS/PVA HBs Magnetic chitosan/poly(vinyl alcohol) hydrogel beads
m-CS/c-Fe
2
O
3
/MWCNTs Chitosan wrapping magnetic nanosized
c-Fe
2
O
3
NIMCR Non-imprinted magnetic chitosan resins
NaCl Sodium chloride
NaOH Sodium hydroxide
MICT Thiourea-modied magnetic ion-imprinted chitosan/TiO
2
MCT Modied but non-imprinted chitosan
MO methyl orange
OC-BzM N-benzyl-O-carboxymethylchitosan magnetic nanoparticles
PFO Pseudo-rst order model
PSO Pseudo-second order model
RB5 Reactive Black 5
RSM Response surface methodology
SEM-TEM SEM coupled with transmission electron microscopy
SICCM Immobilized Saccharomyces cerevisiae on the surface of
chitosan-coated magnetic nanoparticles
TMCS Thiourea-modied magnetic chitosan microspheres
VSM Vibrating sample magnetometry
W/O water/oil
TEM Transmission electron microscopy
TiO
2
Titanium dioxide
TMCS Thiourea-modied magnetic chitosan microspheres
XRD X-ray diffraction
XMCS Xanthate-modied magnetic chitosan
XPS X-ray photoelectron spectroscopy
-KA -ketoglutaric acid
-KA-CCMNPs Chitosan-coated magnetic nanoparticles modied with
-ketoglutaric acid
7GL Cationic light yellow 7GL
1
H NMR Nuclear Magnetic Resonance Imaging
Appendix B. Symbols
C intercept from WeberMorris equation, mg/g
C
0
initial concentration of adsorbate in aqueous solution, mg/L
C
e
concentrationof adsorbate inaqueous solutionat equilibrium,
mg/L
C
t
concentration of adsorbate at time t
K
i
WeberMorris kinetic constant, mg/gmin
0.5
K
1
pseudo-rst-order kinetic constant (min
1
)
K
2
pseudo-second-order kinetic constant (g/mg/min)
q
m
Maximum adsorption capacity
M
S
saturation magnetization
q
e
adsorption capacity
q
exp
experimental mass of adsorbate adsorbed, mg/g
q
max
maximum adsorption capacity, mg/g
R
2
correlation coefcient
T temperature
t time
V volume of the solution.
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Application of magnetic chitosan composites for the removal of toxic

metal and dyes from aqueous solutions

on October 31, 2012,

, which is electrostatically attached

. In another study Cr(VI) removal by magnetic

. Effect of initial solution pH on Cr(VI) removal was

groups adsorb via ionic interactions. In light of this observation,

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