International Journal of Biological Macromolecules 116 (2018) 255–263

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International Journal of Biological Macromolecules

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

Equilibrium, kinetic and mechanism studies of Cu(II) and Cd(II) ions

adsorption by modified chitosan beads
Zetty Azalea Sutirman a, Mohd Marsin Sanagi a,b,⁎, Khairil Juhanni Abd Karim a,
Wan Aini Wan Ibrahim a,b, Binta Hadi Jume a,c
a
Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia
b
Centre for Sustainable Nanomaterials, Ibnu Sina Institute for Scientific and Industrial Research, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia
c
Chemistry Department, Aljouf University, Sakaka 72388, Saudi Arabia

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

Article history: In this study, the Cu(II) and Cd(II) ions removal behavior of crosslinked chitosan beads grafted poly
Received 15 January 2018 (methacrylamide) (abbreviated as crosslinked chitosan-g-PMAm) from single metal ion solutions was investi-
Received in revised form 2 April 2018 gated. The modified chitosan beads presented a remarkable improvement in acid resistance. The batch experi-
Accepted 6 May 2018
ments demonstrated that pH of solution played a significant role in adsorption. It was found that the
Available online 7 May 2018
adsorption of Cu(II) and Cd(II) were optimum at pH 4 and pH 5, respectively. The maximum adsorption capaci-
Keywords:
ties for Cu(II) and Cd(II) based on Langmuir equation were 140.9 mg g−1 and 178.6 mg g−1, respectively. Pseudo-
Modified chitosan second order gave a better fit for adsorption data with respect to linearity coefficients than pseudo-first order
Adsorption suggesting that chemisorption or electron transfer is the dominant mechanism of the metal ions onto crosslinked
Kinetic chitosan-g-PMAm. In addition, X-ray photoelectron spectroscopy (XPS) investigations revealed that adsorption
Mechanism of both metal ions took place on the surfaces of crosslinked chitosan-g-PMAm by chelation through C\\NH2,
C\\O and C_O groups. Overall, the modified chitosan has proved a promising adsorbent for removal of metal
ions.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction water decontamination applications and analytical separation purposes.

Wastewaters containing heavy metals are mainly originated from
industries such as metal plating, mining operations, fertilizer industries,
tanneries, batteries, paper industries and pesticides [1]. Their discharge,
either directly or indirectly, into water bodies without prior proper
management process pose potential hazard to the aquatic environment.
These pollutants can contaminate surface waters such as rivers, lakes,
ponds, reservoirs and underground water by leaking from soil after
rain events. Unlike organic wastes, heavy metals are of considerable
concern because they are non-biodegradable and toxic even at low con-
centration. Exposure to elevated levels of heavy metals can adversely af-
fect water resources and endangering the ecosystems as well as human
health.
Several methods have been developed for removing pollutants from
contaminated water including chemical precipitation, solvent extrac-
tion, ion exchange, evaporation, reverse osmosis, electrolysis and ad-
sorption. Adsorption is established as the most effective method for
⁎ Corresponding author at: Department of Chemistry, Faculty of Science, Universiti
Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia.
E-mail address: marsin@kimia.fs.utm.my (M.M. Sanagi).
It offers advantages over the other options such as simplicity in terms of
design and operation, uses less chemicals, requires low initial costs and
able to remove different types of pollutants [2,3]. The most important
factors that determine adsorption, especially for large scale treatment
applications are efficiency and treatment cost. In recent years, the devel-
opment of adsorbent containing biopolymer origin has been considered
as one of the most favorable options for the removal heavy metals from
aqueous solutions. Biopolymers such as cellulose, starch, alginate, chitin
and chitosan have been intensively studied as they are inexpensive,
abundant, renewable and non-toxic, and have favorable physio-
chemical properties and highly selective towards contaminations [4,5].
Chitosan is an amino polysaccharide produced from chitin and can
be found naturally in some fungi. It is a versatile biopolymer for a
broad range of applications because of its biocompatibility, biodegrad-
ability and antibacterial property. Furthermore, this material is regarded
as an ideal adsorbent. The presence of\\NH2 and \\OH groups on the
polymeric backbone can serve as chelating and reaction sites towards
pollutants [6]. Despite its fascinating properties, chitosan has severe
drawbacks that restrict its application in water treatment and purifica-
tion. Chitosan is commonly available in powder or flake form as end
product during the production process. It has crystallized structure

https://doi.org/10.1016/j.ijbiomac.2018.05.031
0141-8130/© 2018 Elsevier B.V. All rights reserved.
256 Z.A. Sutirman et al. / International Journal of Biological Macromolecules 116 (2018) 255–263

Fig. 1. Proposed chemical structure of crosslinked chitosan-g-PMAm.

and presents poor acid resistance and low porosity. In view of these lim-
itations, raw or unmodified chitosan is not suitable to be used in adsorp-
tion process without appropriate prior chemical modification [7].
Modification of chitosan has two main goals. The first is to increase
the chemical stability of the polymer in aqueous media over a wide
pH-range. The second is to improve the sorption performance such as
sorption capacity and selectivity towards different pollutants [8]. Mod-
ification of chitosan can be carried out by either physical or chemical
techniques, or both.
Previously, we have successfully modified chitosan through
crosslinking using glutaraldehyde and thereafter, grafting with
methacrylamide in the presence of ammonium persulfate [9]. The mod-
ified chitosan beads showed good adsorption capacity towards Pb(II)
ions. In the current study, the adsorbent was used to remove two
other metal ions, namely Cu(II) and Cd(II), from aqueous solution. The
solubility and swelling of the material was investigated in addition to
its physio-chemical properties. In addition, the adsorption process was
studied with regard to the effect of initial pH, isotherms, and kinetics.
The mechanism of the adsorption was also elucidated by XPS analysis.
2. Materials and methods
2.1. Materials
Chitosan (medium molecular weight), methacrylamide (MAm), glu-
taraldehyde (50% v/v) and ammonium persulfate (APS) were obtained

Fig. 2. FTIR spectra of (a) unmodified chitosan and (b) crosslinked chitosan-g-PMAm.
 Z.A. Sutirman et al. / International Journal of Biological Macromolecules 116 (2018) 255–263 257

Table 1 2.4. Fourier transform infrared spectroscopy (FTIR)

Solubility of chitosan beads and crosslinked chitosan-g-PMAm beads.

Adsorbent Solubility FTIR spectra of chitosan and crosslinked chitosan-g-PMAm were re-
Medium Distilled water 0.10 M NaOH
corded on a Perkin Elmer Spectrum™ 400 model (USA) using KBr pellet,
1% (w/v) in the range of 4000–400 cm−1.
acetic acid

Chitosan beads Soluble Insoluble Insoluble 2.5. X-ray photoelectron spectroscopy (XPS)
Crosslinked chitosan-g-PMAm beads Insoluble Insoluble Insoluble
XPS analyses of crosslinked chitosan-g-PMAm before and after metal
ions adsorption were carried out on XPS Axis Ultra DLD (Shimadzu,
Japan) with Mg and Al Kα as the excitation source. The main elements,
from Sigma-Aldrich Co (St. Louis, USA). Acetone was purchased from
namely C, O and N of each sample were scanned and CASA XPS software
RCI Labscan Limited (Bangkok, Thailand). Sodium hydroxide pellet
was used to fit the XPS peaks to determine the different oxidation states
and standard solutions of copper and cadmium (certipur ®) were pur-
of each element. The binding energy was calibrated against the C1s peak
chased from Merck (Darmstadt, Germany). Acetic acid was from QRëc
at 284.6 eV.
(Selangor, Malaysia). All reagents were used without further
purification.
2.6. Adsorption experiment
2.2. Preparation of crosslinked chitosan beads
Experiments on adsorption of Cu(II) and Cd(II) ions onto crosslinked
chitosan-g-PMAm in single-ion system were performed by batch equil-
Crosslinked chitosan-g-PMAm was prepared as reported earlier [9].
ibration. Standard stock solution of metal ions (1000 mg L−1) was di-
Briefly, chitosan (1 g) was dissolved in 100 mL of acetic acid (1% v/v)
luted using deionized water to obtain desired concentrations. For each
and stirred constantly to obtain a homogenous solution. The solution
experiment, a certain amount of adsorbent was placed in 50-mL Erlen-
was added dropwise into a NaOH solution (2 M) and the formed
meyer flask containing 20 mL of aqueous solution of metal ions. The
beads were left overnight to neutralize the acid. The beads were then
content was agitated thoroughly using mechanical orbital shaker at a
washed with distilled water to remove residual NaOH. The wet chitosan
speed of 200 rpm at room temperature. The experiments were con-
beads were crosslinked with glutaraldehyde at a ratio of 1.5 mL of glu-
ducted in duplicates and average of the determinations was used for cal-
taraldehyde to 1 g of beads. After stirring for 24 h, the resultant
culations. The amount of metal ion adsorbed was calculated according
crosslinked chitosan beads were rinsed thoroughly with distilled water.
to the following equation;
Graft copolymerization of crosslinked chitosan with
methacrylamide was performed by free radical mechanism. Initially,
1 g of crosslinked chitosan bead and 0.6 g of APS in 10 mL of distilled Ci −C f
Removal efficiency ð%Þ ¼  100
water were placed in a 250-mL three-necked flask equipped with a re- Ci
flux condenser, a gas inlet system and nitrogen atmosphere. The mix-
ture was stirred magnetically for 30 min to facilitate radical formation
where Ci is the initial concentration of the metal ions in solution
on chitosan. Then, 3 g of MAm (20 mL) was added. The polymerization
(mg L−1) and Cf is the concentration of remaining ions after adsorption
was allowed to take place at 60 °C for 3 h. The modified chitosan beads
(mg L−1).
were thoroughly washed with distilled water to remove unreacted re-
agents. The proposed structure of crosslinked chitosan-g-PMAm is
2.6.1. Effect of pH solution
shown in Fig. 1.
The influence of pH on the adsorption of metal ions was studied in
the pH range of 2–6. The pH was adjusted by adding a few drops of ei-
2.3. Dissolution and swelling tests
ther 0.1 M NaOH or 0.1 M HCl. Crosslinked chitosan-g-PMAm (0.05 g)
was placed in each metal ion solution with initial concentration of
Swelling studies was performed according to a previous report [10].
100 mg L−1. The pH of the solution in the flask was not controlled dur-
Chitosan beads (0.05 g) were placed in each of the solvents, namely dis-
ing the adsorption process to avoid introduction of additional ions into
tilled water (pH 8.2), 1% (w/v) acetic acid (pH 3.5), and 0.10 M NaOH
the solution. After 1 h, the residual concentration of metal ion was mea-
(pH 12.8). After 24 h, the beads were filtered out and weighed. The
sured by atomic absorption spectrophotometry (AAS) (Perkin-Elmer
same procedure was repeated using crosslinked chitosan and
AAnalyst400).
crosslinked chitosan-g-PMAm. The percentages of swelling were calcu-
lated using the following equation;
100
W s −W
Removal efficiency (%)

Sð%Þ ¼  100
W 90
where S is the percentage of swelling, Ws is the height of swollen beads 80
and W denotes the weight of dry beads.
70
Cu(II)
Table 2 60
Swelling behavior of chitosan beads and crosslinked chitosan-g-PMAm beads in different Cd(II)
media.
50
Adsorbent Percentage of swelling (%)

Medium Distilled water 0.10 NaOH

40
1% (w/v) 2 3 4 5 6
acetic acid
pH
Chitosan beads – 238.8 219.4
Crosslinked chitosan-g-PMAm beads 121.8 105.2 87.4
Fig. 3. Effect of solution pH on adsorption of Cu(II) and Cd(II) ions.
258 Z.A. Sutirman et al. / International Journal of Biological Macromolecules 116 (2018) 255–263

strong acidic
pH repulsion
NH2 NH3 M2
crosslinked chitosan-g-PMAm

M2 = Cu(II) or Cd(II)
Fig. 4. Schematic of the protonation of amine groups in acidic solution at pH 2–3.

O O attraction
(a)
C NH2 C NH2 M2
delocalization

M2 O
O C NH2
(b)
C NH2 and
M2

M2 = Cu(II) or Cd(II)
Fig. 5. Schematics of (a) delocalized resonance structures of O-bonded amide groups, (b) possible coordination modes of PMAm chains in acidic solution.

M2
low acidic
pH
NH2 or/and OH NH2 HO
chelation

M2 = Cu(II) or Cd(II)
Fig. 6. Schematic of the chelation of metal ions with amino and hydroxyl groups.

Table 3
Langmuir and Freundlich isotherm parameters for the adsorption of Cu(II) and Cd(II) ions
2.6.2. Adsorption equilibrium study
onto crosslinked chitosan-g-PMAm.
Adsorption equilibrium study in a single-metal system was con-
ducted by adding 0.1 g of the adsorbent to each series of Erlenmeyer Metal ion Langmuir Freundlich
flasks containing solutions with different initial metal ion concentra- qmax (mg g−1) b (L mg−1) R2 KF (mg g−1) n R2
tions (200, 300, 400, 500 and 600 mg L−1). These solutions were ad-
Cu(II) 140.9 0.005 0.982 2.284 1.535 0.978
justed to optimum pH. After agitation for 5 h at room temperature, Cd(II) 178.6 0.015 0.971 6.052 1.561 0.964
the filtrates were analyzed by AAS.
 Z.A. Sutirman et al. / International Journal of Biological Macromolecules 116 (2018) 255–263 259

Table 4 1636 cm−1 indicates the stretching of C_O. The shifting of this fre-
RL values based on Langmuir equation. quency compared to that of chitosan is due to the introduction of
Initial concentration (mg L−1) RL values MAm, subsequently confirming the graft copolymerization. The spec-
Cu(II) Cd(II)
trum also shows peaks that refer to C\\N stretching vibrations at 1120
and 1023 cm−1. The findings in this study are consistent with other pre-
200 0.495 0.251
vious works [13,14].
300 0.395 0.183
400 0.329 0.144
500 0.282 0.118
600 0.246 0.101 3.2. Solubility and swelling behavior

The solubility of the material is another important criterion for bio-

polymer sorbent. It was observed that the chitosan beads were soluble
in 1% acetic acid, but insoluble in distilled water and 0.10 M NaOH
2.6.3. Kinetic adsorption study
(Table 1). Pristine chitosan or chitosan beads contain free amine groups
For batch kinetic studies, 0.1 g of crosslinked chitosan-g-PMAm was
on the C-2 position of the D-glucosamine repeating unit. The solubiliza-
immersed in 100 mg L−1 solution of metal ions. The flask was shaken
tion occurs when these \\NH2 functions are protonated and converted
thoroughly at 200 rpm under optimum pH conditions as has been deter-
the polysaccharide to a polyelectrolyte in acidic media [15]. Therefore,
mined in the previous step. About 10 mL of sample solution was re-
modification of chitosan is necessary to enhance its chemical stability,
moved at different intervals in the range of 10–100 min to determine
making it useful in removing pollutants from acidic effluent. Mean-
the current metal ion concentrations.
while, crosslinked chitosan-g-PMAm was not soluble in the three
media. This could be attributed to the reduced number of protonated
3. Results and discussions amine after the reaction of amine groups of chitosan in the crosslinking
and grafting reactions.
3.1. FTIR analysis Table 2 shows the percentage of swelling of chitosan and crosslinked
chitosan-g-PMAm beads in three different media. It can be seen that
The FTIR spectrum of unmodified chitosan (Fig. 2a) displays a strong swelling behavior of chitosan significantly changed upon modifications.
broad peak at 3434 cm−1 which was attributed to the overlapping be- The less swelling of the beads improves its adsorption performance [16].
tween \\NH2 and \\OH stretching vibrations and inter hydrogen Chitosan beads were dissolved in acidic solution (as mentioned above)
bonds of the polysaccharide. The characteristic peaks of symmetric but they showed higher percentages of swelling in distilled water and
and asymmetric\\CH2 groups can be observed at 2923 cm−1. It clearly basic solution of 238.8% and 219.4%, respectively. Meanwhile, the per-
shows the absorption peak of chitin moiety in the chitosan at centages of swelling for crosslinked chitosan-g-PMAm under identical
1649 cm−1 (C_O stretching). The peaks at 1423 cm−1 and conditions were 121.8%, 105.2% and 87.4%, respectively. Modification
1380−1 cm are assigned to the C\\N bond stretching and deformation of chitosan improves its insolubility in water and organic solvents and
of C\\H, respectively, while the peak at 1080 cm−1 corresponds to also its swelling behavior [4]. Therefore, it can be concluded that modi-
C\\O stretching vibration [11]. fication on chitosan is not only reinforcing its chemical strength but also
Meanwhile, the spectrum of crosslinked chitosan-g-PMAm showed decreases the swelling of the beads.
variation in intensity and shifting of the significant peaks (Fig. 2b). Ab-
sorption peak at 3439 cm−1 is attributable to typical stretching vibra-
tions of \\OH and \\NH2 groups. A slight change in intensity of this 3.3. Effect of pH on adsorption of Cu(II) and Cd(II) ions
peak with respect to chitosan shows that appreciable amount of OH/
NH2 at chitosan were involved in the crosslinking and grafting reactions. The pH of a solution is an important regulating factor in adsorption
A new peak at 1731 cm−1 is due to C_O stretching vibration of alde- of heavy metal ions. It is not only affecting the surface charge of the ad-
hyde [12]. The presence of this group might be a result of unreacted sorbent but also the degree of ionization and speciation of adsorbate
end of glutaraldehyde or self-polymerization. Moreover, the peak at during the reaction [17]. Fig. 3 shows the effect of pH on adsorption of
Cu(II) and Cd(II) ions on crosslinked chitosan-g-PMAm in the pH
range of 2–6. In very strong acidic solution (pH 2–3), amine groups
(which do not involve in crosslinking) on the beads surface are easily
Table 5
Comparison of the maximum adsorption capacities of some chitosan-based adsorbents on
protonated using the excessive protons and thus, induced electrostatic
Cu(II) and Cd(II) removal. repulsion to metal cations (Fig. 4). Moreover, these protons would com-
pete with metal ions for binding sites on adsorbent, leading to a reduc-
Chitosan adsorbent qmax References
(mg g−1)
tion of metal ions adsorption. Yet, adsorption of metal ions still occurred
due to the addition of amido groups (grafting of MAm) but with low
Cu Cd
percentage removal [18]. The possible interactions between adsorbent
(II) (II)
and metal ions at this pH range can be shown in Fig. 5.
Chitosan microspheres 80.7 – 16
Pristine chitosan – 85.4 35
Polyaniline graft chitosan beads 83.3 – 19 Table 6
Polyaniline grafted crosslinked chitosan beads – 98.4 28 Kinetic parameters for the adsorption of Cu(II) and Cd(II) ions onto crosslinked chitosan-
Itaconic acid grafted crosslinked chitosan beads 19.6 – 36 g-PMAm.
Halomonas BVR1 immobalized in chitosan – 23.9 37
Thiosemicarbazide chitosan 142.9 – 38 Kinetic equation Cu(II) Cd(II)
Preparation of poly(chitosan-acrylamide) 196.8 – 39 Pseudo-first order
Surfactant-modified chitosan beads – 125 40 K1 (min−1) 0.471 0.028
Poly(maleic acid)-grafted cross-linked chitosan – 39.2 41 R2 0.938 0.945
microspheres
Crosslinked-chitosan graft poly 122 – 42 Pseudo-second order
(N-vinyl-2-pyrrolidone) K2 (g mg−1 min−1) 0.134 3.646
Crosslinked chitosan-g-PMAm 140.9 178.6 This study R2 0.988 0.999
260 Z.A. Sutirman et al. / International Journal of Biological Macromolecules 116 (2018) 255–263
Fig. 7. Wide scan XPS spectra of (a) crosslinked chitosan-g-PMAm; (b) Cu-loaded crosslinked chitosan-g-PMAm and (c) Cd-loaded crosslinked chitosan-g-PMAm.
As the pH is increased to 4–5, the number of protonated amine is re-
duced and the repulsive forces are also weakened, thereby increasing
the metal ions adsorption onto crosslinked chitosan-g-PMAm [19].
Two types of interactions are suggested; (i) the chelation between un-
charged amine groups (NH2) or hydroxyl groups (OH) and metal ions
(Fig. 6); and (ii) an electrostatic attraction between carboxylate ions
(originating from PMAm chains) and metal cations.
At higher pHs (N6), precipitation of insoluble metal hydroxide can
occur which makes the true metal adsorption studies impossible
[20,21]. The maximum removal efficiencies for Cu(II) and Cd(II) ions
were found to be 67.2% at pH 5 and 89.7% at pH 4, respectively.
3.4. Adsorption equilibrium study
Adsorption isotherms help one to understand the interactive behav-
iors between the solutes and adsorbent while the two phases are
reaching the equilibrium state. It is also important in the design and op-
timization of the adsorption system. In this study, the experimental data
were analyzed using the widely used Langmuir and Freundlich isotherm
models.
Langmuir isotherm is based on the assumption of structurally homo-
geneous adsorbent and all adsorption sites have equivalent energy. At
the point of maximum adsorption, only a monolayer of adsorbate is
formed and there is no interaction between adsorbed molecules. The
linear form of Langmuir isotherm is written as follows [22]:
Ce Ce 1
¼ þ
qe qmax qmax b
where qe (mg g−1) is the amount of metal ions adsorbed at equilibrium,
Ce (mg L−1) is the metal ion concentration at equilibrium. qmax
(mg g−1) is the maximum adsorption capacity of the adsorbent and b
(L mg−1) is the Langmuir constant. The values of qmax and b are ob-
tained from the slope and intercept of Ce/qe versus Ce plot, respectively.
The essential characteristics of the Langmuir can be expressed in
terms of a dimensionless constant, RL, which is defined as follow:
1
RL ¼
1 þ bC 0
where value of RL indicates that the type of the isotherm either to be un-
favorable (RL N 1), linear (RL = 1), favorable (0 b RL b 1), or irreversible
(RL = 0)
The Freundlich model was first developed in 1906 by Herbert F.
Freundlich when he studied the sorption of a material onto animal
 Z.A. Sutirman et al. / International Journal of Biological Macromolecules 116 (2018) 255–263 261

charcoal [23]. This model describes the adsorbent surface as heteroge-
neous and multilayer adsorption occurs in the process. The Freundlich
isotherm can be expressed as the following equation:
1 cording to the two kinetic models, namely pseudo-first order kinetic
logqe ¼ logK F þ logC e
n and pseudo-second order kinetic. The best fit model was selected
where Ce (mg L−1) is the liquid-phase concentration at equilibrium, KF
is the Freundlich isotherm constant and n is the heterogeneity factor
which is related to the capacity and intensity of the adsorption. The pa-
rameters of Freundlich model can be calculated from the linear plot of
log qe versus log Ce.
From the values of the coefficient of determination, R2 (Table 3), it is
clear that the experimental adsorptions were well described by the
Langmuir model over the concentration range studied. The results sug-
gested that the adsorption has monolayer coverage and the interaction
between the adsorbed metal ions is negligible [24]. It was found that the
qmax values for Cu(II) and Cd(II) at room temperature were
140.9 mg g−1 and 178.6 mg g−1, respectively. In addition, the separation
factors (RL) for these two metal ions were in the range of 0–1 (Table 4),
which was less than unity, indicating that the adsorption of metal ions
onto crosslinked chitosan-g-PMAm was a favorable process. Table 5
provides a comparison of the qmax of crosslinked chitosan-g-PMAm for
Cu(II) and Cd(II) ions with several previously-reported chitosan-based
adsorbents [16,19,28,35–42]. It shows that the prepared adsorbent is a
promising candidate for practical wastewater treatment.
3.5. Kinetic adsorption study
Adsorption kinetic helps elucidate the mechanism of adsorption
process. The adsorption data of Cu(II) and Cd(II) ions were evaluated ac-
based on how close the linear regression coefficient of determination
(R2) to 1.
Pseudo-first order model was the first kinetic model expressed by
Lagergren in 1989. The equation is generally given as [25]:
K1
logðqe −qt Þ ¼ logðqe Þ−t
2:303
where qe and qt represent the amounts of solutes adsorbed on adsorbent
(mg g−1) at equilibrium and at time t, respectively. K1 (min−1) is the
rate constant of pseudo-first order kinetic. The values of K1 and correla-
tion coefficient, R2 obtained from the straight-line plot of log (qe − qt)
versus t are shown in Table 6. It can be seen that the coefficient of deter-
mination for Cu(II) and Cd(II) ions were slightly lower, indicating the
model was not suitable to be used to interpret the adsorption of metal
ions onto crosslinked chitosan-g-PMAm. Moreover, the pseudo-first
order model is not favorable over the whole range of contact time in
the adsorption experiment. It would only be applicable over the initial
stage of the adsorption process [26].

Fig. 8. XPS spectra of adsorbent. (a) C 1s of crosslinked chitosan-g-PMAm; (b) C 1s of Cu-loaded crosslinked chitosan-g-PMAm and (c) C 1s of Cd-loaded crosslinked chitosan-g-PMAm.
262 Z.A. Sutirman et al. / International Journal of Biological Macromolecules 116 (2018) 255–263

Many studies have shown that the pseudo-second order kinetic
model gives a better fit for adsorption data. This model describes the ki-
netic behavior over the whole range of adsorption and is in agreement
with chemisorption [27]. The pseudo-second order rate expression is
as follows:
 
t 1 1 peak at 284.6 eV was assigned to C\\C in the adsorbent and the peak
¼ þ t
qt K 2 qe 2 qe
where K2 is the pseudo-second order rate constant. The straight-line
plot of t/qt versus t was used to determine the values of K2 and coeffi-
cient of determination, R2. Based on the results (Table 5), the pseudo-
second order gave a better fit for adsorption data than pseudo-first
order with respect to linearity coefficients obtained with 0.998 and
0.999 for Cu(II) and Cd(II) ions, respectively. Therefore, it can be as-
sumed that the dominant mechanism for metal ions adsorption by
crosslinked chitosan-g-PMAm was chemisorption or strong surface
complexation which involved electron transfer between adsorbent
and adsorbate [28].
3.6. Adsorption mechanism of crosslinked chitosan-g-PMAm
XPS analysis was conducted to understand the interactions between
the target metal ions and adsorbent based on the binding energy (BE) of
the species involved. Fig. 7 represents typical wide scan XPS spectra of
crosslinked chitosan-g-PMAm. It can be seen that peaks of Cu(II) and
Cd(II) appeared at 935.1 eV and 402.0 eV, respectively after adsorption,
indicating the distribution of the metal ions on the surface of the adsor-
bent [29,30].
Curve fitting XPS spectra of C 1s are shown in Fig. 8. The resolved C 1s
spectrum prior to adsorption can be convoluted into four peaks. The
at 286.3 eV can be attributed to the C\\NH2 from the glucosamine
unit. Meanwhile, the peak at 287.6 eV was assigned to C\\O, C\\O\\C
and C_N which resulted from crosslinking reaction, and the peak at
289.3 eV was assigned to the O\\C\\O and C_O chemical binding
[31]. However, the BE of C\\NH2, C\\O and C_O were slightly shifted
to the BE values of 286.7, 288.7 and 289.8 eV, respectively, after Cu(II)
ion adsorption (Fig. 8b) and BE values of 286.6, 287.9 and 289.9 eV, re-
spectively, after Cd(II) ion adsorption (Fig. 8c). These changes suggested
the formation of adsorbent-metal complexes and thus, reduced the
electron density at the adjacent carbon atoms in C\\NH2, C\\O and
C_O [32].
Fig. 9 shows high resolution XPS N 1s spectra for crosslinked
chitosan-g-PMAm before and after adsorption of Cu(II) and Cd(II)
ions. The peak at the BE value of 397.3 eV can be assigned to the nitro-
gen atom in\\NH2 or/and\\NH\\ while the peak at 499.4 eV was at-
tributed to protonated amino, NH+ 3 [33]. The increase in the binding
energies after adsorption (Fig. 9b and c) indicated that the surface com-
plexes of R-NH2Cu(II)/Cd(II) were formed, in which a lone pair of

Fig. 9. XPS spectra of adsorbent. (a) N 1s of crosslinked chitosan-g-PMAm; (b) N 1s of Cu-loaded crosslinked chitosan-g-PMAm and (c) N 1s of Cd-loaded crosslinked chitosan-g-PMAm.
 Z.A. Sutirman et al. / International Journal of Biological Macromolecules 116 (2018) 255–263
electrons in N atom was donated to the covalent bond between N and
Cu(II)/Cd(II). As a result, the electron density in N atom was decreased
and it consequently led to higher BE values [32,34].
3.7. Conclusion
The newly prepared crosslinked chitosan-g-PMAm has showed abil-
ity to remove Cu(II) and Cd(II) ions from aqueous solution. The adsorp-
tion of both metal ions was highly pH dependent with the highest
removal at pH 5 and pH 4 for Cu(II) and Cd(II), respectively. The exper-
imental results were found to be in better agreement with Langmuir
isotherm than Freundlich isotherm, indicating monolayer adsorption
processes. Further, the kinetic studies can be well explained by
pseudo-second order with coefficients of determination (R2) value
close to unity. This demonstrates that the adsorption process occurred
through chemisorption mechanism. XPS analysis clearly showed that
C\\NH2, C\\O and C_O groups on the adsorbent were involved in the
formation of surface complexes with metal ions and the mechanism
can also be supported by the effect of pH. Thus, it can be concluded
that crosslinked chitosan-g-PMAm would be a very promising material
as a low-cost alternative for the adsorption of metal ions in wastewater
treatment.
Acknowledgement
This work was supported by Ministry of Higher Education Malaysia
through research grant number (R.J130000.7809.4F177).
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