International Journal of Biological Macromolecules 89 (2016) 507–517

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International Journal of Biological Macromolecules

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

Preparation and characterization of chitosan-clay nanocomposites for

the removal of Cu(II) from aqueous solution
Eid M.S. Azzam a , Gh. Eshaq a , A.M. Rabie a , A.A. Bakr a , Ali A. Abd-Elaal a , A.E. El Metwally b ,
Salah M. Tawfik a,∗
a
Egyptian Petroleum Research Institute (EPRI), Nasr City, 11727, Cairo, Egypt
b
Department of Petrochemicals, Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: In the present study, chitosan assembled on gold and silver nanoparticles were prepared and char-
Received 4 December 2015 acterized by UV–vis, TEM, EDX and DLS techniques. The nanocomposites chitosan (Ch)/clay, chitosan
Received in revised form 27 April 2016 (Ch)/AgNPs/clay and chitosan (Ch)/AuNPs/clay were prepared by solution mixing method and charac-
Accepted 1 May 2016
terized by FTIR, XRD, and SEM techniques. The adsorption of copper(II) ions onto the prepared hybrid
Available online 3 May 2016
composites from an aqueous solution using batch adsorption was examined. The results showed that ben-
efiting from the surface property of clay, the abundant amino and hydroxyl functional groups of chitosan,
Keywords:
the adsorbent provides adequate and versatile adsorption for the Cu(II) ions under investigation. The
Chitosan
Clay
batch adsorption experiments showed that the adsorption of the Cu(II) is considerably dependent on pH of
Nano adsorbent milieu, the amount of adsorbent, and contact time. Batch adsorption studies revealed that the adsorption
Cu(II) ions capacity of Cu(II) increased with increase in initial concentration and contact time with optimum pH in
Adsorption the range around neutral. The maximum uptake of Cu(II) ions by (Ch)/AgNPs/clay composite was found to
be 181.5 mg/g. The adsorption efficiency of Cu(II) ions by prepared (Ch)/AgNPs/clay and (Ch)/AuNPs/clay
is bigger than that the individual chitosan (Ch)/clay composite which clarifies the role of metal nanopar-
ticles in enhancement the adsorption characters. The study suggests that the (Ch)/AgNPs/clay hybrid
composite is a promising nano-adsorbent for the removal of Cu(II) ions from aqueous solution.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Heavy metal contamination of the various water resources is
of great concern given the toxic effect on humans as well as the
biota present in the environment. The major sources of heavy metal
pollutants are several industrial activities including mining, metal
plating, oil refining, electronic device manufacturing, printing, the
production of chemicals, dyes, paints, pulp and paper, textiles,
petrochemicals, leather, fertilizers and pesticides. Clay minerals
application in pollution control has received gross attention over
the past decades. Modification of clay through acid treatment, cal-
cinations, functionalization and pillaring are among several ways
that effort has been made by researchers to enhance its usabil-
ity beyond its application in the natural form [1]. Chitosan is the
most abundant biopolymer next to cellulose. It has been used for
about three decades in water purification processes. Chitosan is the
deacetylated product of chitin, it is a natural polysaccharide present
∗ Corresponding author.
E-mail address: salahtwfk85@yahoo.com (S.M. Tawfik).
in crab, shrimp, lobster, coral jelly fish, butterfly, lady bug etc [2].
Since chitosan has free amino groups can acts as a better chelating
agent than chitin. The special properties of chitosan include bio-
compatibility, biodegradability, and drug absorption enhancement.
Thus, chitosan could be considered as a green polymer applicable in
analytical chemistry, water treatment, agriculture, food ingredients
[3], cosmetics [4], biomedicine [5], pharmaceutical materials [6],
and biotechnology [7]. The noble metal nanoparticles have multi-
pronged use in drinking water purification (removal of organic
compounds, heavy metals and microorganisms). While the chem-
istry of noble metal nanoparticles is unique in the removal of many
contaminants, their high energy surface results in system attempt-
ing to minimize the surface energy through protection or chemical
transformation or agglomeration. Therefore, the nanoparticles are
likely to adsorb a number of other species on the surface. The
same properties of nanomaterials (increased surface area, chem-
ical reactivity, etc.) which confer a unique ability to degrade toxic
species present in the environment may also render them toxic to
humans [8,9]. Reddy et al. studied the application of magnetic chi-
tosan composites for the removal of toxic metal ions and dyes from
aqueous solutions [10]. The removal of lead ions from aqueous solu-

http://dx.doi.org/10.1016/j.ijbiomac.2016.05.004
0141-8130/© 2016 Elsevier B.V. All rights reserved.
508 E.M.S. Azzam et al. / International Journal of Biological Macromolecules 89 (2016) 507–517
tion onto magnetic hydroxypropyl chitosan/oxidized multiwalled
carbon nanotubes composites was studied by Wang et al. [11].
The study of Li et al. discovered that heavy metal ion adsorption
on Chitosan/Sulfydryl functionalized graphene oxide composites
and it was found that the CS/GO-SH has potential applications in
fields of adsorptive materials due to its superiority of the chemical
characteristic and the specific surface area [12]. Liu et al. [13]. inves-
tigated patulin adsorption onto thiourea modified chitosan resin,
and the result indicated that thiourea modified chitosan resin is
expected to be a new material for removing patulin from aqueous
solution. Mahmoud et al. reported the synthesis and implementa-
tion of nano-chitosan and its acetophenone derivative for enhanced
removal of metals [14]. Lari et al. reported that a simple method
for providing natural hydroxyapatite/chitosan (N HAP/chitosan)
composite was introduced and adsorption suitability of this com-
posite for treating the solutions containing Cu(II) ions [15]. Laus
et al. studied that the adsorption and desorption of Cu(II), Cd(II)
and Pb(II) ions using chitosan crosslinked with epichlorohydrin-
triphosphate as the adsorbent [16]. Haldorai et al. reported that
methodology for the optimization of lanthanum removal from
aqueous solution using a Fe3 O4 /chitosan nanocomposite and ther-
modynamic studies have revealed that the negative values of Gibbs
free energy confirmed the spontaneous and feasible nature of
adsorption [17]. Sheshmani et al. reported that the preparation of
graphene oxide/chitosan/FeOOH nanocomposite for the removal
of Pb(II) from aqueous solution. It found that the GO/Ch/FeOOH
is a promising nano-adsorbent for the removal of Pb(II) ions
from aqueous solution [18]. Most recently the removal of organic
and inorganic pollutants from water is gaining interest. Several
researchers in the field of analytical, environmental and material
sciences are actively designing and developing several material and
methods [19]. In this context activated carbon has been used widely
and is one of the most popular sorbents used for removal of vari-
ous pollutants [20]. The use of activated carbon materials is mainly
limited due to its cost and tedious regeneration methods which
make it less economic. Thus, there is an acute need for develop-
ing alternative sorbents which are cheap, abundant, and efficient
in the removal of metal-contaminated wastewater streams [21]. To
address these natural polymers has attracted significant interest in
both industrial and academia, materials like polysaccharides; chi-
tosan and its derivatives have received particular attention [22].
Chitosan compared with activated carbons and other adsorbents
are cheap and effective adsorbent for the treatment of organic or
inorganic pollutants in water. A wide array of literature describes
the efficacy of chitosan sorbents in the removal of several pollu-
tants such as metals, dyes, phenols, fluoride, and phthalates etc.
The unique cationic behavior of chitosan and chitosan composite
functionalized with amine groups leads to high adsorption of metal
anions [23].Therefore, the present study examined the adsorption
of Cu(II) ions from aqueous solution onto chitosan/metal nanoparti-
cles/clay composite. The adsorbent could be easily synthesized and
applied to remove copper ions from aqueous solution. The effect
of various experimental parameters on adsorption, such as the ini-
tial adsorbent concentration, contact time, and solution pH were
studied in detail.
2. Materials and methods
2.1. Materials
All chemicals with a purity of greater than 99.9% were purchased
as follow: copper nitrate pentahemihydrate (Cu(NO3 )2 ·2.5H2 O),
tetrachloroauric acid (HAuCl4 ), tri-sodium citrate (Na3 C6 H5 O7 ),
silver nitrate (AgNO3 ) was purchased from Sigma–Aldrich Co., chi-
tosan (Low molecular weight) was supplied from Sigma-Aldrich,
USA, clay (sodium montmorillonite) (98%) was supplied by MI
SWCO and glacial acetic acid (HAC, 99%) was supplied from Sigma-
Aldrich. The aqueous solutions used in this work were prepared
with double distilled water.
2.2. Synthesis
2.2.1. Synthesis of gold nanoparticles (AuNPs)
The gold nanoparticles (AuNPs) were prepared by the reduc-
tion of tetrachloroauric acid (HAuCl4 ) using tri-sodium citrate
(Na3 C6 H5 O7 ): 2 ml of tetrachloroauric acid solution (1%) was
heated to boiling temperature then 2.5 ml of tri-sodium citrate
solution (1%) was added slowly and stirring until the color changed
to winy red. All solutions were prepared using pure distilled water
which obtained by passing twice-distilled water through a Milli-Q
system [24].
2.2.2. Synthesis of silver nanoparticles (AgNPs)
The colloidal silver nanoparticles (AgNPs) solution was prepared
by reduction of silver nitrate using tri-sodium citrate. 50 ml of
(1 × 10−3 M) AgNO3 solution was heated to boiling. To this solution,
5 ml of 1% trisodium citrate was added drop by drop. During the pro-
cess solution was mixed vigorously. The solution was heated until
color’s change is evident (pale yellow). Then it was removed from
the heating element and stirred until cooled to room temperature
[25].
2.2.3. Preparation of chitosan assembled onto AuNPs or AgNPs
Preparation of chitosan assembled onto AuNPs or AgNPs was
carried as follow: Chitosan solution (100 ml, 2.0 wt%) were pre-
pared by solubilizing chitosan in 1.0 wt% of HAC sol (pH 3.45) under
constant stirring for 1 h 20 ml of AuNPs or AgNPs solution was
mixed with 5 ml of chitosan solution and stirred for 24 h until the
color of nanoparticles changes to colorless [26].
2.2.4. Fabrication of the clay nanocomposites
The nanocomposites used here were prepared using clay, chi-
tosan, AuNPs and AgNPs as follow: The fabrication of the (Ch)/Clay
nanocomposite was carried according to the previous publication
[27]. A total of 1 g of clay was dispersed in 250 ml of water for
swelling for 48 h, and then separated by centrifugation. The clay
solution transferred into 50 ml solution of Chitosan. The mixture
was stirred for 24 h. The precipitate was separated by centrifuga-
tion, washed with water and dried under vacuum overnight. This
step was carried with Chitosan assembled onto AgNPs and AuNPs
to prepare (Ch)/Clay/AgNPs and (Ch)/Clay/AuNPs Nano composites.
2.3. Characterization of the chitosan with gold/silver
nanoparticles
2.3.1. UV–vis spectroscopy
The UV measurements for the solution of AgNPs and AuNPs with
chitosan were carried out by UV–vis photometer (Shimadzu, UV-
2550, Japan).
2.3.2. Transmission electron microscope (TEM)
A convenient way to produce good TEM samples is to use cop-
per grids. A copper grid pre-covered with a very thin amorphous
carbon film. To investigate the prepared AgNPs and AuNPs using
TEM, small droplets of the liquid were placed on the carbon-coated
grid. A photographic plate of the transmission electron microscopy
employed on the present work to investigate the microstructure of
the prepared samples. Nanoparticle size was determined by using
TEM model “Joel JeM − 2100 (Japan)” (Egyptian Petroleum Research
Institute “EPRI”)
 E.M.S. Azzam et al. / International Journal of Biological Macromolecules 89 (2016) 507–517 509

Fig. 1. (a) The UV–vis absorption spectrum of Ch-AgNPs and Ch-AuNPs (b,c) TEM images of the prepared Ch-AgNPs and Ch-AuNPs.

Fig. 2. DLS of the prepared Ch-AuNPs and Ch-AgNPs respectively (a,b) EDX analysis the Ch-AuNPs and Ch-AgNPs respectively (c,d).

2.3.3. Dynamic light scattering (DLS) by dynamic light scattering (DLS) using a Malvern Zetasizer Nano
The hydrodynamic diameter and zeta potential of the same (Malvern Instruments Ltd., Worcestershire, UK). Each DLS measure-
solution which used in TEM, UV–vis and EDX, was characterized ment was run in triplicate using automated, optimal measurement
510 E.M.S. Azzam et al. / International Journal of Biological Macromolecules 89 (2016) 507–517

Table 1 and 40 mA. The spectra were recorded with a 2␪ step of 0.02◦ at a
Size and zeta potential of colloidal suspensions.
scanning rate of 2 ◦ ␪/min.
Sample Size (r nm) Zeta potential (mv)

Ch-AuNPs 20.0 53.4 2.4.3. Scanning electron microscope (SEM)

Ch-AgNP 44.3
time and laser attenuation settings. The recorded correlation func-
tions and measured particles mobility’s were converted into size
distributions and zeta potentials, respectively, using the Malvern
Dispersion Software (V5.10, http://www.zetasizer.com/).
2.3.4. Energy dispersive X-ray (EDX) spectroscopy
The energy-dispersive X-ray (EDX) spectroscopy was recorded
with an EDX detector (Oxford LINKISIS 300) equipped with a trans-
mission electron microscope (TEM, Hitachi S-520) operated at
10 kV accelerating voltage.
2.4. Characterization of the prepared composites
2.4.1. Fourier transform-infrared spectroscopy (FT-IR)
Fourier transform infrared (FTIR) spectra were recorded for the
synthesized Ch-g-PEG and compared with chitosan on an ATI Matt-
son Infinity Series TM, Bench top 961 controlled by win first TM
V2.01 software (Egyptian Petroleum Research Institute “EPRI”) at
25 ◦ C. About 2 mg of sample with 100 mg of KBr was fully grinded
and ‘mixed. The mixed samples were pressed into pills with a com-
pressor and prepared pellets were used for studies. All spectra were
scanned against a blank KBr pellet back-ground in the range of
4000–400 cm−1 with resolution of 4.0 cm−1 .
2.4.2. X ray diffraction
X-ray diffraction (XRD) patterns of the samples were recorded in
the range 2␪ = 4–80◦ using a Philips powder diffractometer with Cu
K␣ radiation (k = 0.154 nm). The instrument was operated at 40 kV
41.9 Scanning electron microscopy (SEM) images of the gold-coated
catalysts were obtained using a JEOL 5410 system operating at
20 kV.
2.5. Adsorption experiments
The cupper ions, Cu(II), stock solution concentration of 100 mg/L
was prepared by dissolving copper nitrate pentahemihydrate
(Cu(NO3 )2 ·2.5H2 O) in distilled water. The working Cu(II) solution
concentration ranging from 5 to 55 mg/L for all experiments was
freshly prepared from the stock solution. Standard acid (0.01 M
HNO3 ) and alkaline solutions (0.125 M NaOH) were used for pH
adjustments at pH from 3 to 12. The pH of the solution was mea-
sured with a pH meter (Mettler-Toledo AG 8603 Schwerzenbach,
made by Mettler-Toledo Group). The pH meter was calibrated with
buffers of pH 4.0 and 7.0 before any measurement.
The removal of Cu(II) from dilute aqueous solutions, the addi-
tion of adsorbent (Ch)/clay, (Ch)/AgNPs/clay and (Ch)/AuNPs/clay
masses 0.1–0.5 g/L were carried out at constant temperature 25 ◦ C,
using distilled water. After continuous stirring over a magnetic stir-
rer at 160 rpm for a predetermined time interval from 15 to 90 min
to allow the dispersion of adsorbent and metal ions to reach equi-
librium conditions, as found during preliminary experiments. The
solid and solution were separated by centrifugation at 3000 rpm
for 15 min and slightly dried at ambient temperature. Cu(II) con-
centration was determined by Spectrophotometer, LaMotte, model
SMART Spectro, USA and the solid phase was analyzed. The amount
of adsorption qe (mg/g) and the percentage of removal (% removal)
were calculated by the following equations [28]:
qe = (C0 − Ce ) × V/m (1)
%removal = (C0 − Ce )/ C0 × 100% (2)

100
100
90 Chitosan
80
80
60 Ch-Clay.-Cu
70
100 Clay 40
80
60 100
40 80
100
Ch/C 60
% T

80 Ch-Clay.-AuNPs-Cu
T%

60 40
40
20 20
0
100
Ch-Au/C
100
80

60

40
80
20

100
0
60
80 Ch-Ag/C
40 Ch-Clay.-AgNPs-Cu
60
40
20 20
0
4000 3500 3000 2500 -1 2000 1500 1000 500
cm 4000 3500 3000 2500 2000 1500 1000 500
-1
cm
Fig. 3. FTIR of Chitosan and the prepared nanocomposites Ch/Clay, Ch/Clay/AuNPs and Ch/Clay/AgNPs before adsorption of Cu(II) and Ch/Clay, Ch/Clay/AuNPs and
Ch/Clay/AgNPs after adsorption of Cu.
 E.M.S. Azzam et al. / International Journal of Biological Macromolecules 89 (2016) 507–517 511

500
400
Ch/clay
300
200
100
0
500

Intensity (a.u)
400
Ch/Clay/AuNPs
300
200
100
0
250
200
Ch/clay/AgNPs
150
100
50
0
0 20 40 60 80
2 Theta (degree)
Fig. 4. XRD of the prepared nanocomposites Ch/Clay, Ch/Clay/AuNPs and Ch/Clay/AgNPs.

where C0 and Ce are the initial Cu(II) concentration and the con-
centration at equilibrium in mg/L, m is the mass of the adsorbent
and V is the volume of solution.
2.6. Effect of initial solution pH
The effect of pH on the removal of cupper ions was evaluated
by making a series of 55 mg/L Cu(II) solutions at an adsorbent
dosage of 0.3 g/l, the starting solution pH was adjusted to the
designed values (3–12). The resulting (Ch)/clay, (Ch)/AgNPs/clay
and (Ch)/AuNPs/clay suspensions were filtered and then the resid-
ual Cu(II) concentrations were analyzed.
2.7. Effect of adsorbent mass
Different amounts of chitosan (Ch)/clay, (Ch)/AgNPs/clay and
(Ch)/AuNPs/clay (0.1–0.5 mg/L) were added to a series of 100 ml of
copper solutions with initial concentration of 55 mg/L at pH 7.0,
and shaken rate 160 rpm for different contact time (15–90 min) to
reach the equilibrium. Then the aqueous samples were filtered, and
then the residual Cu(II) concentrations were analyzed.
3. Results and discussion
3.1. Characterization of (Ch)/AgNPs and (Ch)/AuNPs
3.1.1. UV–vis spectroscopy
The stability of silver and gold nanoparticles after addition of
chitosan was established using UV–vis photometer. UV–vis absorp-
tion spectrum of (Ch)/AgNPs and (Ch)/AuNPs were represented in
Fig. 1a.The UV–vis absorption of the colloidal suspension showed
a sharp peak at 529 nm in the case of (Ch)/AuNPs which related to
the Surface Plasmon Resonance (SPR) of gold nanoparticles. On the
other hand in case of (Ch)/AgNPs characteristic peak at 435 nm is
related to SPR of silver nanoparticles. It was observed that there
is a quite shifting in SPR peaks value probably due to change in
dielectric constant around the nanoparticles [25].
3.1.2. Transmission electron microscope (TEM)
The morphology of the prepared (Ch)/AgNPs and (Ch)/AuNPs
were investigated by transmission electron microscope (TEM). It
was seen from TEM images Fig. 1b,c that the (Ch)/AgNPs and
(Ch)/AuNPs were predominantly spherical in shape and poly-
dispersed. TEM images showed good stabilization of gold and silver
nanoparticles due to interaction with the free amino group of chi-
tosan molecules [29].
3.1.3. Dynamic light scattering (DLS)
Dynamic light scattering technique was performed to under-
stand the size distribution and the stability of prepared (Ch)/AgNPs
and (Ch)/AuNPs with chitosan using zeta potential values. Accord-
ing to DLS results, the diameter range of (Ch)/AgNPs and
(Ch)/AuNPs are 44 and 20 nm respectively as shown in Fig. 2a and
b. Zeta potential is the net surface charge of the nanoparticles when
they are inside a solution. The fact is that particles push each other
and their agglomeration behavior depends on the large negative or
positive zeta potential. The zeta potential playing an important role
limits in the stability of solutions is +30 mV or −30 mV. To regard
the particles as stable, zeta potential should be either higher than
+30 mV or lower than–30 mV [30]. By inspection data in Table 1,
it was found that the zeta potential values of prepared (Ch)/AgNPs
and (Ch)/AuNPs are greater than +30 mV, which is indicating high
stability of (Ch)/AgNPs and (Ch)/AuNPs against agglomeration [31].
3.1.4. Energy dispersive X-ray (EDX) spectroscopy
EDX spectroscopy results confirmed the significant presence of
pure silver with no other contaminants. The optical absorption peak
at 3 keV is typical for the absorption of metallic silver nanoparti-
cles due to surface plasmon resonance. Fig. 2c and d shows the
EDX analysis of the AgNPs, AuNPs stabilized by chitosan. The EDX
spectrum showed a strong and typical optical absorption peaks at
approximately 3 keV and 2.1 keV, which were attributed to the SPR
512 E.M.S. Azzam et al. / International Journal of Biological Macromolecules 89 (2016) 507–517
Fig. 5. SEM of the prepared nanocomposites Ch/Clay (a), Ch/Clay/AuNPs (b) and Ch/Clay/AgNPs (c) before adsorption of Cu ions and Ch/Clay (d), Ch/Clay/AuNPs (e) and
Ch/Clay/AgNPs (f) after adsorption of Cu ions.
of the metallic Ag and Au Nano crystals respectively [32]. There are
other bands for C O peaks which appeared due to the scattering
caused by chitosan molecules that are bound to the surface of silver
and gold which indicating that the chitosan act as a good stabilized
agents for silver and gold nanoparticles
3.2. Characterization of the prepared nanocomposites before and
after adsorption of copper
3.2.1. Fourier transform-infrared spectroscopy (FT-IR)
The prepared nanocomposites (Ch)/clay, (Ch)/AuNPs/Clay and
(Ch)/AgNPs/Clay were charactered using FTIR as shown in Fig. 3.
The FTIR results show an idea about the interaction between
Chitosan with clay and nanoparticles in the prepared nanocom-
posites as follow. The FTIR spectrum of clay in the figure shows the
vibration bands at 3619 cm−1 for O H ␯s, 3425 cm−1 due to inter-
layered O H ␯s (H- bonding), 1637 and 1502 cm−1 for H O H
bending, 1033 and 994 cm−1 for Si O stretching, 594 cm−1 for
Al OH, 896 cm−1 due to (Al, Mg) −OH vibration modes and 537 and
464 cm−1 for Si O bending. The FTIR spectra of Ch/C and Ch Ag/C
show the combination of the characteristic absorption bands due to
clay, AgNPs and amine groups of Chitosan. The FTIR spectra of the
(Ch)/Clay, (Ch)/AuNPs/Clay and (Ch)/AgNPs/Clay in Fig. 3 show the
combination between the absorption bands related to the presence
of clay, nanoparticles and amine groups of chitosan. There is more
broadening in the peak at 3425–3292 cm−1 of O H and NH over-
lapping in pure chitosan. In addition, the −NH2 peaks are shifted
to 1637 and 1563 cm−1 in the (Ch)/Clay and (Ch)/NPs/Clay. This
shift is corresponding to the deformation vibration of the amine
group of Chitosan [33]. It is noticed from Fig. 3 that the C O stretch-
ing at 1073 cm−1 of pure chitosan is approximately disappearing.
The FTIR results after adsorption of Cu(II) are represented in Fig. 3.
It is noticed that the Cu(II) loaded adsorbent showed either shift
or reduction in adsorption peaks suggesting the vital role played
by the functional groups. There are some shifts in the absorbance
peaks after adsorption of Cu(II) such as the peak at 3425–3292 cm−1
become less board and the −NH2 peak shifted to ∼1645, C O
stretching of pure chitosan clearly appears at ∼1036 cm−1 . These
shifts in the wavelength showed that there was a metal binding
process taking place at the surface of the adsorbents. The appear-
ance of the peaks located at ∼446–534 cm−1 and shift of the peaks
at ∼689–790 cm−1 after adsorption of Cu(II) was due to the loading
effect of metal.
3.2.2. X ray diffraction (XRD)
The XRD in Fig. 4 shows that the crystalline peak of chitosan
appeared at 2␪ = 20◦ was weakened due to the interaction of Chi-
tosan with MMT structure of clay, AuNPs and AgNPs in the prepared
 E.M.S. Azzam et al. / International Journal of Biological Macromolecules 89 (2016) 507–517 513

400
100

350

80 300

Adsorpon capacity (mg/g)

Cu(II) removal % 250
60

200

40 150

Cu(II) removal % using chit.-Ag-clay

100
Cu(II) removal % using chit.-Au-clay
20 Cu(II) removal % using chit.-clay
Adsorpon capacity of chit.-Ag-clay 50
Adsorpon capacity of chit.-Au-clay
Adsorpon capacity of chit.-clay
0 0
0 20 40 60 80 100
Time (min)

Fig. 6. Effect of contact time on Cu(II) removal% and adsorption capacity using chit.-clay, chit.-Au-clay and chit.-Ag-clay. Conditions: Cu(II) initial concentration (55 mg L−1 ),
adsorbent mass (0.3 g L−1 ), stirring rate (160 rpm), 298 K, pH 7.

400
100

350

80 Cu(II) removal % using chit.-Ag-clay 300

Adsorpon capacity (mg/g)

Cu(II) removal % using chit.-Au-clay
250
Cu(II) removal %

Cu(II) removal % using chit.-clay

60
Adsorpon capacity of chit.-Ag-clay
200
Adsorpon capacity of chit.-Au-clay

40 Adsorpon capacity of chit.-clay 150

100
20

50

0 0
0 10 20 30 40 50 60
Inial Cu(II) concentraon (mg L-1)

Fig. 7. Effect of initial Cu(II) concentration on Cu(II) removal% and adsorption capacity using chit.-clay, chit.-Au-clay and chit.-Ag-clay. Conditions: adsorbent mass (0.3 g L−1 ),
stirring rate (160 rpm), 298 K, pH 7, 60 min.

composites. The shift to lower 2␪ values of the (001) and (002)
reflections corresponding to Na+ -montmorillonite in clay structure
is related to the swelling in inter lamellar space of the clay mineral.
The XRD pattern of (Ch)/Clay/AuNPs in Fig. 4 shows that four peaks,
the mean peak at 2␪ = 27.4◦ corresponds to (110) and the other
three slightly weak peaks at 2␪ = 42.6◦ , 63.8◦ , and 68.5◦ corresponds
to the (200), (220) and (311) planes of the cubic Au crystal, respec-
tively. The results of the XRD for (Ch)/Clay/AgNPs in Fig. 4 shows
that the sample has a high-intensity sharp peak at 2␪ = 26.6◦ cor-
responding to the (111) plane. The other three slightly weak peaks
are shown at 2␪ = 42.4◦ , 68.04◦ , and 79.5◦ corresponds to the (200),
(220) and (311) crystallographic planes of face-centered cubic (fcc)
silver crystals, respectively [34].
514 E.M.S. Azzam et al. / International Journal of Biological Macromolecules 89 (2016) 507–517

400
100

350

Cu(II) removal % using

80 chit.-Ag-clay
300
Cu(II) removal % using

Adsorpon capacity (mg/g)

chit.-Au-clay
Cu(II) removal % using
250
Cu(II) removal %
chit.-clay
60 Adsorpon capacity of
chit.-Ag-clay
Adsorpon capacity of 200
chit.-Au-clay
Adsorpon capacity of
40 chit.-clay 150

100
20

50

0 0
0 0.1 0.2 0.3 0.4 0.5 0.6
Adsorbent mass (g L-1)

Fig. 8. Effect of adsorbent masses on Cu(II) removal% and adsorption capacity. Conditions: Cu(II) initial concentration (55 mg L−1 ), stirring rate (160 rpm), 298 K, pH 7, 60 min.

400
100 Cu(II) removal %
using chit.-Ag-clay
Cu(II) removal % 350
using chit.-Au-clay
80 Cu(II) removal %
300
using chit.-clay

Adsorpon capacity (mg/g)

Adsorpon capacity
of chit.-Ag-clay
250
Cu(II) removal %

Adsorpon capacity
60
of chit.-Au-clay
Adsorpon capacity 200
of chit.-clay

40 150

100
20

50

0 0
0 2 4 6 8 10 12 14
pH

Fig. 9. Effect of initial solution pH on Cu(II) removal% and adsorption capacity using chit.-clay, chit.-Au-clay and chit.-Ag-clay. Conditions: Cu(II) initial concentration
(55 mg L1 ), adsorbent mass (0.3 g L−1 ), stirring rate (160 rpm), 298 K, 60 min.

3.2.3. Scanning electron microscope (SEM)
We used the SEM technique for further investigation of the sur-
face morphologies of the prepared nanocomposites as shown in
Fig. 5. The surface morphology of (Ch)/Clay composite in Fig. 5.
shows a massive layered structure with some large flakes and some
inter layer spaces. While, the SEM images of the (Ch)/AuNPs/Clay
and (Ch)/AgNPs/Clay nanocomposites show approximately differ-
ent morphologies. It is noticed, that the inter layer spaces of clay
are decreased (see Fig. 5b and c), which indicate the impregnation
of the chitosan assembled on nanoparticles between the clay lay-
ers. This is related to the interaction of −NH2 groups in chitosan
and the nanoparticles with clay layers. The SEM images (Fig. 5d–f)
also show the good difference in the surface morphology after the
adsorption of Cu(II) with the appearance of small particles on the
surface of the prepared nanocomposites. The small particle size and
the porous structure provide a good adsorption capacity for Cu(II).
It is observed that after the adsorption of Cu(II) most of the pores
in the adsorbents were covered.
 E.M.S. Azzam et al. / International Journal of Biological Macromolecules 89 (2016) 507–517 515

250

200 318 K
308 K
298 K

Adsorpon capacity (mg/g) 150

100

50

0
0 10 20 30 40 50 60
Inial Cu(II) concentraon (mg L -1)

Fig. 10. Effect of initial Cu(II) concentration at different temperatures on Cu(II) adsorption capacity using chit.-Ag-clay. Conditions: adsorbent mass (0.3 g L−1 ), stirring rate
(160 rpm), pH 7, 60 min.

Scheme 1. Adsorption mechanism of Cu(II) using chitosan-clay nano composites.

Table 2
Comparison of performance of the proposed adsorbent with some other adsorbents for the removal of copper ions from aqueous solution.

Adsorbent Qmax (mg g−1 ) Reference

Amino-modified Fe3 O4 12.43 [42]

m-PAA-Na-coated MNPs 30.0 [43]
Sawdust 8.07 [44]
Rice husk 31.85 [45]
Chitosan–zeolite composites 14.75–51.32 [46]
Semi-IPN hydrogel based on chitosan and gelatin 153.9 [47]
Xanthate-modified magnetic chitosan 34.5 [48]
Chitosan nanofibrils 168.6 [49]
Chitosan (Ch)/clay, chitosan (Ch)/AgNPs/clay and chitosan (Ch)/AuNPs/clay 181.5 This study
516 E.M.S. Azzam et al. / International Journal of Biological Macromolecules 89 (2016) 507–517
3.3. Adsorption studies
3.3.1. Effect of contact time
The effect of the contact time on the percentages of
Cu(II) removal and adsorption capacities (mg/g) for (Ch)/clay,
(Ch)/AuNPs/clay and (Ch)/AgNPs/clay is shown in Fig. 6. The contact
time varied in the range from 0 to 90 min. and the initial metal con-
centration was fixed at 55 mg/L. It can be seen that the adsorption
rate was considerably fast within the first 45 min (96.4, 132.3 and
156.9 mg of Cu(II) adsorbed per gram of (Ch)/clay, (Ch)/AuNPs-clay
and (Ch)/AgNPs/clay respectively), then gradually slowed down
and thereafter, the adsorption equilibrium was reached at 60 min
(134.5, 174.1 and 181.5 mg of Cu(II) adsorbed per gram of (Ch)/clay,
(Ch)/AuNPs/clay and (Ch)/AgNPs/clay, respectively). The fast rate of
Cu(II) removal at the beginning may be attributed to the rapid diffu-
sion of Cu(II) from the solution to the external surfaces of (Ch)/clay,
(Ch)/AuNPs/clay and (Ch)/AgNPs/clay. On the other hand, the slow
adsorption process is attributed to the longer diffusion range of
Cu(II) into the inner-sphere of (Ch)/clay or the ion-exchange in the
inner surface of (Ch)/AuNPs/clay and (Ch)/AgNPs/clay. Such slow
diffusion will lead to a slow increase in the adsorption curve at later
stages [35]. Moreover, the initial rapid adsorption may be because
of an increased number of available sites at the initial stage.
3.3.2. Effect of initial Cu(II) concentration
The effect of different Cu(II) concentrations was determined
after experimental studies for a range of metal concentrations. A
definite mass of (Ch)/clay, (Ch)/AuNPs/clay and (Ch)/AgNPs/clay
adsorbents (0.3 g/L) was added to a series of 100 ml of copper solu-
tions with the different initial concentrations from 5 to 55 mg/L
at pH 7.0, and were shaken at 160 rpm for contact time 60 min
to reach the equilibrium. Effect of initial Cu(II) concentrations
on the percentages of Cu(II) removal and adsorption capacities
(mg/g) for (Ch)/clay, (Ch)/AuNPs/clay and (Ch)/AgNPs/clay is rep-
resented in Fig. 7. The adsorption capacity increased to 134.5, 174.1
and 181.5 mg/g for (Ch)/clay, (Ch)/AuNPs/clay and (Ch)/AgNPs/clay,
respectively, and saturated beyond a certain concentration. Satu-
ration resulted when no more metal ions could be adsorbed on the
surface of (Ch)/clay, (Ch)/AuNPs/clay and (Ch)/AgNPs/clay where
the adsorption occurred. The experimental studies also showed
that the high capacity for Cu(II) removal could be obtained over a
relatively short period of time up to 60 min. The removal with ini-
tial Cu(II) concentrations means that the removal amounts were
linearly proportional to the initial metal concentrations. How-
ever, the complete removal of copper ions was observed from 5
to 45 mg/L from the initial concentrations (55 mg/L) for (Ch)/clay,
(Ch)/AuNPs/clay and (Ch)/AgNPs/clay, respectively.
3.3.3. Effect of adsorbent dose
The effect of varying the adsorbent amount from 0.1 to 0.5 g/L,
while keeping other parameters such a pH and contact time
constant. Fig. 8 reveals that the adsorption of metal ions gradu-
ally increased by increasing its dosage. The adsorption capacity
increases rapidly with increasing the adsorbent dose till 0.3 g/L
of (Ch)/AgNPs/clay, (Ch)/AuNPs/clay and (Ch)/clay, respectively.
This may be attributed to the large surface area in turn num-
ber of adsorption sites. [36]. The maximum removal of Cu(II) ion
was 100%. Further addition of prepared composites didn’t show
any significant removal of the metal ion. Thus, the maximum
adsorption capacity had taken place at the optimum dose 0.3 g/L
of (Ch)/AgNPs/clay, (Ch)/AuNPs/clay and (Ch)/clay, respectively,
hence, the metal ion in the solution remains constant.
3.3.4. Effect of pH
The pH of the metal ion solution plays an important role in the
whole adsorption process and particularly on the adsorption capac-
ity by the modification of the level of ionization of Ch. (Fig. 9). Effect
of initial solution pH on: (a) the percentages of Cu(II) removal and
(b) adsorption capacities (mg/g) for (Ch)/clay, (Ch)/AuNPs/clay and
(Ch)/AgNPs/clay. It can be seen from Fig. 9 that the amount of Cu2+
adsorbed by (Ch)/clay, (Ch)/AuNPs/clay and (Ch)/AgNPs/clay com-
posites slowly increased when pH of Cu2+ solution increased from
2 to 7, the optimum adsorption pH being located at 7. At low pH,
most of the amino groups of Ch in the composite were ionized and
presented in the form of −NH3+ , electrostatic repulsion between
Cu2+ and −NH3+ ions may prevent the adsorption of Cu2+ ions onto
the composite. At pH > 7 the Cu2+ retention decreased because a
small amount of Cu2+ started to deposit as Cu (OH)2 . This also sup-
ports the chelation of Cu2+ on the prepared chitosan composites
[37]. Considering the formation of Cu (OH)2 when the pH value of
Cu2+ solution exceeds 7. The pH of 7 was selected as the initial pH
value of Cu2+ solution for the adsorption experiments.
3.3.5. Effect of initial Cu(II) concentration on Cu(II) adsorption
capacity at different temperatures
The effect of initial Cu(II) concentration on Cu(II) adsorption
capacity was studied at different temperatures using Ch/Ag/clay
as displayed in Fig. 10. The results revealed that the adsorbent
removed reasonable amounts of copper ions at different temper-
atures. It is clear that the removal efficiency increases until it
reaches a point at which there is no more ions could be further
adsorbed on the surface of the adsorbent. The results also reveal
that the adsorption capacities increase with increasing the opera-
tional temperature. A maximum adsorption capacity of 239 mg g−1
was obtained using adsorbent mass of 0.3 g L−1 , pH 7 and stirring
rate of 160 rpm at 318 K for only 60 min.
3.3.6. Adsorption mechanism
The adsorption mechanism of metal ions using chitosan as a
sole adsorbent has been widely studied in the lasts decades. Schol-
ars have reported that a metal ion complex was formed as a result
of the interaction between the metal ion and chitosan functional
groups [38,39]. A metal chelate might form through the coordina-
tion of the hydrated metal cation and the chitosan’s amino and
hydroxyl groups [40]. The hydroxyl group’s oxygen and amino
group’s nitrogen possess a pair of electrons, which can be shared
with cation. Nevertheless, amino group’s nitrogen has more ten-
dencies to donate its electron than the hydroxyl group’s oxygen
[41]. In our case, chitosan-clay nanocomposites provide additional
active sites for metal ion adsorption including cation exchange sites
and additional surface area. In particular, when the nanocomposites
were dispersed in the copper ions solution, there exists a synergy
between chitosan and clay in the adsorption of copper ions from
aqueous solution. The chitosan’s functional groups tend to coordi-
nate with copper ions where the metal ions act as a Lewis acid that
can accept electron pairs from the amino and hydroxyl groups of
chitosan (Lewis base). Meanwhile, some other copper ions replace
the interlayer cations of clay as shown in Scheme 1. This syner-
gistic effect greatly enhances the adsorption performance, which
suggests the chitosan-clay nanocomposite as a promising adsor-
bent for the removal of copper ion from aqueous solution. As seen
in Table 2, the maximum uptake of Cu(II) ions by our proposed
adsorbent was found to be 181.5 mg/g is better than that of other
adsorbents reported in the literature [42–49].
4. Conclusions
This work examined the adsorption of Cu(II) ions from aqueous
solution onto chitosan-clay nanocomposites materials. The adsorp-
tion using chitosan hybrid composites is becoming a promising
alternative to replace conventional adsorbents in removing heavy
metal ions. The copper ion removal is independent on contact time,
 E.M.S. Azzam et al. / International Journal of Biological Macromolecules 89 (2016) 507–517
initial concentration of Cu(II) ions, adsorbent dose and pH of the
solution. In this study, the composite (Ch)/AgNPs/clay revealed high
efficiency for the adsorption of copper ion than the individual chi-
tosan/clay composite and suitable as an adsorbent for the removal
of copper ion from aqueous solution.
Acknowledgment
Financial support by Egyptian Petroleum Research Institute is
gratefully acknowledged.
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