Kavosirakati 2019

International Journal of Biological Macromolecules 130 (2019) 1025–1045
Contents lists available at ScienceDirect
International Journal of Biological Macromolecules
journal homepage: http://www.elsevier.com/locate/ijbiomac
Preparation and characterization of poly aniline modified chitosan

embedded with ZnO-Fe3O4 for Cu(II) removal from aqueous solution
Khodadad Kavosi Rakati, Masoomeh Mirzaei ⁎, Sarah Maghsoodi, Amirhossein Shahbazi
Department of Chemical Engineering, Mahshahr Branch, Islamic Azad University, Mahshahr, Iran
a r t i c l e i n f o a b s t r a c t
Article history: Poly aniline modified chitosan embedded with ZnO/Fe3O4 nanocomposites were synthesized using a precipita-
Received 1 December 2018 tion method and applied to the removal of Cu(II) from aqueous solution. The synthesized nanocomposite was
Received in revised form 2 February 2019 characterized by FT-IR, XRD, FESEM, TEM, EDS, TGA, BET and zeta-potential analyses. The adsorption batch exper-
Accepted 5 February 2019
iments were conducted as a function of five effective parameters including pH, contact time, initial concentration
Available online 1 March 2019
of copper, temperature, and adsorbent dosage using a central composite design (CCD) in response surface meth-
Keywords:
odology (RSM). Contour and surface plots were used to determine the interaction effects of main factors and op-
Chitosan timum conditions of process. The regression equation coefficients were calculated and the data confirmed the
Magnetic nanoparticle validity of second-order polynomial equation for the removal of Cu(II) with novel absorbent. Analysis of variance
Heavy metal removal (ANOVA) showed a high coefficient of determination value (R2) for copper removal being 0.99. The optimum
Adsorption response surface methodology level of the pH, temperature, initial concentration of copper, adsorbent dosage and contact time for maximum
(RSM) Cu(II) removal (94.51%) were found to be 6.5, 31 °C, 82 mg L−1, 0.81 g L−1, and 51 min, respectively. It was con-
firmed from XPS and EDS analyses that heavy metal ions were present on the surface of nanocomposite after ad-
sorption. The adsorption equilibrium data fitted well with the Langmuir isotherm model and the adsorption
process followed the pseudo-second-order and intra-particle diffusion kinetic model. The saturated adsorption
capacity is found to be 328.4 mg/g. Thermodynamics analysis suggests that the adsorption process is endother-
mic, with increasing entropy and spontaneous in nature. Further recycling experiments show that nanocompos-
ite still retains 95% of the original adsorption following the 5th adsorption-desorption cycle. The effects of coexist
cation ions on the adsorption of Cu(II) was also investigated under optimal condition. All the results demonstrate
that nanocomposite is a potential recyclable adsorbent for hazardous metal ions in wastewater.
© 2019 Published by Elsevier B.V.
1. Introduction traditional techniques have their own internal limitations such as less re-
moval efficiency, sensitive operating conditions, high operational cost and
Industrialization has led to an increase in the release of toxic effluents, production of secondary sludge which requires an additional treatment.
including toxic chemicals such as heavy metals. Some of the most com- Most of the existing heavy metal removal technologies are limited due
mon heavy metals are lead, nickel, copper, mercury, chromium, cadmium, to their high cost. It has become necessary to evolve new technologies
and arsenic, which are being released by dental operation, textile, tanning, using widely available low cost materials for the removal of heavy
electroplating, and the paper and pulp industry [1]. These heavy metals metal ions [17–19]. Among all of these approaches, the adsorption pro-
cause serious environmental problems by entering into the food chain cess is considered more efficient and economical because of its flexibility
leading to severe health disorders in humans who are at the top of the in design, simplicity of operation, facile handling, and in many cases gen-
food chain [2]. There is an urgent need to safeguard water and food re- eration of high-quality treated effluent [1]. An effective adsorbent should
sources from heavy metals. It has also become essential to purify water generally possess a high surface area, small diffusion resistance and short
contaminated by heavy metal ions. A large number of strategies are adsorption equilibrium time, so that it can be used to remove larger
available currently to decontaminate water to make it potable, including amounts of contaminants in a shorter time [20]. In addition, it should gen-
reverse osmosis [3] ion exchange [4,5], cyanide treatment [6], electro- erate a minimum amount of sludge. Thus, developing an adsorbent with
chemical precipitation [7,8], adsorption [9–16]. However, these large surface area and small diffusion resistance is of great significance
in practical engineering applications [21].
⁎ Corresponding author. With the developments in nanotechnology, nanoscale materials
E-mail address: [email protected] (M. Mirzaei). have gained attention to solve the environmental problems. Among
https://doi.org/10.1016/j.ijbiomac.2019.02.033
0141-8130/© 2019 Published by Elsevier B.V.
1026 K. Kavosi Rakati et al. / International Journal of Biological Macromolecules 130 (2019) 1025–1045
Table 1 Although many scholars have made a lot of efforts for removing
Actual and coded values of the test variables. heavy metal ions using magnetic chitosans in a laboratory scale, several
Name Units Low High -alpha +alpha questions still needed to be solved:
pH 4 6 3 7 1- The preparation method of magnetic chitosan should be simplified
t min 40 60 30 70
D g/L 0.4 0.8 0.2 1
and easily-controlled, and a single step or one-pot synthesis should
C0 mg/l 60 100 40 120 be encouraged;
T C 20 40 10 50 2- To find optimize process parameters and obtain the maximum ad-
sorption capacities of heavy metal ions onto MCS, modern optimiza-
tion methods (such as the response surface methodology,
polynomial-based RSM, artificial neural network, and genetic algo-
the available adsorbents, nanosized metal oxides (NMOs), including rithm) should be applied;
nanosized ferric oxides, manganese oxides, aluminum oxides, titanium 3- For the actual wastewater treatment, it's quite necessary to study the
oxides, magnesium oxides and cerium oxides, are classified as the adsorption behavior of a multiple solute system, and the influence of
promising ones for heavy metals removal from aqueous systems [22]. co-existing ions in the solution on the target ions;
This is partly because of their large surface areas and high activities 4- Most importantly, adsorption capacity of reported MCS needs to
caused by the size quantization effect [23,24]. Recent studies suggested improve.
that many NMOs exhibit very favorable sorption to heavy metals in
terms of high capacity and selectivity, which would result in deep re- Trying to modify Chitosan for overcoming its restrictions
moval of toxic metals to meet increasingly strict regulations [25]. How- (i.e., difficult separation and secondary pollution) and to extend its ad-
ever, as the size of metal oxides reduces from micrometer to nanometer sorption capabilities, Fe3O4/ZnO/chitosan composite was prepared
levels, the increased surface energy inevitably leads to their poor stabil- using a facile chemical co-precipitation method. The higher specific sur-
ity. Consequently, NMOs are prone to agglomeration due to Van der face area can be obtained by loading ZnO nanoparticle on Chitosan
Waals forces or other interactions [26], and the high capacity and selec- which may provide an alternative method to improve the adsorption
tivity of NMOs would be greatly decreased or even lost. Moreover, capacity for heavy metals removal. To our best knowledge, the study
NMOs are unusable in fixed beds or any other flow through systems be- of Cu2 + adsorptive removal with this innovative composite have not
cause of the excessive pressure drops (or the difficult separation from been studied well. Polyanilinie was used to improve the mechanical
aqueous systems) and poor mechanical strength. To improve the appli- strength of chitosan, chemical resistance of chitosan in acidic media
cability of NMOs in real wastewater treatment, they were then impreg- and increase its adsorption capacity. The principle is based on the che-
nated into porous supports of large size to obtain composite adsorbents lating properties attributed to the electron-donating groups (amine
[9,10,27,28]. The widely used porous supports include activated carbon, and secondary amino groups) on the polyaniline polymer. The compos-
natural materials, synthetic polymeric hosts, etc. ite was characterized by using various techniques and its potential was
Compared to other host materials, porous polymeric hosts are a par- evaluated for the removal of Cu2 +. In the other part of this study, re-
ticularly attractive option partly because of their controllable pore size sponse surface methodology (RSM) based on a central composite de-
and surface chemistry as well as their excellent mechanical strength sign (CCD) has been used for the identification and optimization of
for long-term use [29]. Chitosan, a known biosorbent, is a derivative of the copper ions removal by synthesized nanocomposite. Investigated
chitin, which is the second most abundant natural polymer after cellu- experimental factors were the amount of adsorbent, initial pH, initial
lose [30]. Chitosan has been explored extensively for many applications ions concentration, temperature and contact time. All the parameters
because of its low cost, hydrophilicity, biodegradability, and antimicro- were simultaneously used in order to calculate their relative effects. Fur-
bial properties [31]. It has been proven to be an effective adsorbent for thermore, the experimental data of Cu2 + removal were fitted via differ-
heavy metals because of the amino and hydroxyl functional groups ent isotherm and kinetic models. Finally, the thermodynamic study of
present in its structure. Amine groups form complex reactions with cat- Cu2 + adsorptive removal was performed. Finally, kinetic, isotherm
ionic metal ions, while anionic ions are adsorbed by electrostatic attrac- and thermodynamics of adsorption were evaluated. The reusability of
tion [32]. Despite the favorable characteristics of chitosan, it has poor chitosan/ZnO/Fe3O4 adsorbent was examined after four cycles of
mechanical strength and is unstable, which hinder its practical applica- adsorption-desorption.
tions. To improve the mechanical properties of chitosan, the synthetic
polymers such as poly (ethylene oxide), poly (vinyl alcohol), cellulose, 2. Material and methods
and nylon-6 is blended with chitosan [17,29,33,34]. The blends of men-
tioned polymers with chitosan cannot have significant effect in improv- Chitosan (95% degree of deacetylation) was purchased from Pelican
ing adsorption process efficiency. Therefore, the blending of chitosan Biotech and Chemicals Labs. Zinc nitrate hexahydrate (Zn(NO3)3.6H2O),
with efficient material can improve the adsorption capacity of chitosan.
Recently, nano-sized particles such as zinc oxide nanoparticles, nano
Table 2
zerovalent iron particles and titanium oxide nanoparticles have been The SBET, total pore volumes, and average diameters of CS/ZnO and CS/ZnO/Fe3O4 nano-
explored to remove heavy metal ions [35]. composites.
The recovery of chitosan adsorbents from treated water by ordinary
Sample SBET Vtotal Average diameter
methods, such as filtration and centrifugation, may result in loss of the (m2/g) (cm3/g) (nm)
adsorbents and secondary pollutions, also, waste of time and high
Chitosan/ZnO(0.1 g) 61.4 0.0358 2.833
cost. An efficient improvement is the combination of chitosan with Chitosan/ZnO(0.3 g) 78.5 0.0424 2.652
magnetic cores, which possessed the features of both magnetic cores Chitosan/ZnO(0.6 g) 93.6 0.0489 2.481
(ease of magnetic separation) and chitosan [16,36–39]. Furthermore, Chitosan/ZnO(0.9 g) 96.3 0.0511 2.435
the magnetic separation techniques are convenient and more amenable Chitosan/ZnO(1.2 g) 86.7 0.0492 2.516
Chitosan/ZnO/Fe3O4 (0.25 g) 101.35 0.0536 2.426
to automation, which makes these magnetic core–chitosan hybrid ad-
Chitosan/ZnO/Fe3O4 (0.5 g) 110.84 0.0576 2.401
sorbents attractive in practical applications. Magnetic chitosan adsor- Chitosan/ZnO/Fe3O4 (0.75 g) 117.25 0.0605 2.367
bents are generally prepared using the water/oil (W/O) emulsion Chitosan/ZnO/Fe3O4 (1 g) 126.94 0.0632 2.224
cross-linking technique inside which the most commonly used mag- Chitosan/ZnO/Fe3O4 (1.25 g) 121.52 0.0610 2.291
netic cores are based on magnetite (Fe3O4, [40]. Chitosan/ZnO/Fe3O4 (1.5 g) 114.23 0.0599 2.305
K. Kavosi Rakati et al. / International Journal of Biological Macromolecules 130 (2019) 1025–1045 1027
ferric chloride hexahydrate (FeCl3·6H2O) and ferrous sulfate centrifuged and washed with deionized water. The magnetite powder
heptahydrate (FeSO4.7H2O) (both AR analytical grade, Merck Chemical obtained was then dispersed into deionized water and used for the ex-
Company) were used as ZnO and Fe3O4 sources for the preparation of periment. In the case of ZnO nanoparticles, the fixed molar ratio (Zn
the nanocomposite. Other reagents were analytical grade and pur- (NO3)3·6H2O:C2H2O4:CO(NH2)2 = 1:2:3) was prescribed to prepare
chased locally. Double distilled water was used throughout the study. 1 M mixed solution. Then pH of the mixed solution was adjusted to suit-
Furthermore, Cu(NO3)2 were bought from Merck company. Other able value by HCl 0 .1M. The adjusted solution went through stirring-
chemicals were taken from Sigma Aldrich (USA). time of 2 h. Next the stirred solution was poured into 35 mL autoclave
and heated to 140 °C for 2 h. With that, the obtained precipitate was col-
2.1. Nanocomposite preparation lected by centrifugation, and washed using ethanol and distilled water
for several times. Finally, the final participate was converted to ZnO
The ZnO and Fe3O4nanoparticles were synthesized by a co- nanoparticles through the calcination at 400 °C for 3 h.
precipitation method reported by [21,41]. In the case of Before nanocomposite synthesis, chitosan was modified with poly
Fe3O4nanoparticles, the concentrations of ferrous sulphate:ferric chlo- aniline. 2.5 g of chitosan was dissolved in aqueous acetic acid (2% (v/
ride precursors are 0.75 M each. The precursors are taken in 2:1 mol v)), and the solution was stirred for 24 h at room temperature. To this
ratio and stirred well for 15 min. After 15 min of stirring, sodium hy- about 0.01 M of aniline, dissolved in 1 M HCl, was added and stirred
droxide is added at regular intervals to the precursor solution. Upon ad- for 15 min to form a homogenous solution. Ammonium peroxydisulfate
dition of NaOH, the solution turned black, indicating the formation of solution in 1 M HCl was dropped into the above solution with constant
magnetite nanoparticles. Further stirring is continued for 1 h to uni- stirring at 5 °C. After complete addition of the oxidizing agent, the reac-
formly disperse the magnetic nanoparticles. The nanoparticles were tion mixture was kept under constant stirring for 6 h. The greenish-
Fig. 1. XRD patterns of a:Fe3O4 b:ZnO c:Chitosan d:CS/ZnO/Fe3O4.

Fig. 1 (continued).
black precipitate obtained was washed with water followed by metha- to this solution with vigorous stirring until the pH reached 7.0. Finally,
nol until the filtrate become colorless. The final composite was dried at the solution A was filtrated and washed with ethanol and deionized
60 °C for 24 h. To synthesis nanocomposite, Firstly, 2.5 g of modified chi- water and dried at 60 °C for 48 h. The resulting samples were
tosan was added to 150 mL of 1% (v/v) acetic acid under stirring for 4 h chitosan/ZnO-composites. To prepare the primary solution of Chito-
and sonicated for 20 min to remove the bubbles. After that, different san/ZnO/Fe3O4 nano-composite, various amounts of iron oxide (0.25,
contents of ZnO nanoparticles (0.1, 0.3, 0.6, 0.9, 1.2) were dispersed in 0.5, 0.75, 1.0, 1.25 and 1.5 g) were dispersed in chitosan/ZnO solution
chitosan solution under stirring for 3 h to obtain a homogeneous solu- (solution A) under stirring for 3 h to get solution B. 0.1 M NaOH
tion (solution A). 0.1 M NaOH (Sigma Aldrich, UK) was added slowly (Sigma Aldrich, UK) was added slowly to this solution with vigorous
Fig. 2. The FTIR spectra of the chitosan and nanocomposite.
Fig. 3. SEM image of a:ZnO nanoparticle b:Fe3O4 nanoparticle c:CS/ZnO/Fe3O4 nanocomposite d:TEM image of CS/ZnO/Fe3O4 nanocomposite.
Fig. 4. Magnetic hysteresis loop (M–H) of CS/ZnO/Fe3O4.
stirring until the pH reached 7.0. The operations of filtration, washing +20,000 Oe at room temperature. Thermal stability and decomposition
and drying were similar to those of mentioned above. of prepared chitosan, chitosan/ceria and chitosan/ceria/Fe3O4 nano-
composite adsorbents were studied by using a Mettler Toledo TGA-851
2.2. Characterization thermogravimetric analyzer (Mettler, Switzerland). The functional
groups of nano-composites were determined using FTIR analysis
The prepared materials were characterized by X-ray diffraction (XRD) (Perkin-Elmer, RXI model). The surface area, average pore volume and
using a Philips X'Pertpro Pan-analytical instrument. The data were taken average pore diameter of samples were determined by Brunauer–
for the 2θ range of 0–80° with a step of 0.02°. Transmission Electron Mi- Emmert–Teller (BET) method (BELSORP model, Japan). The point of
croscopy (TEM) imaging was performed using a Zeiss-EM10C-100 KV zero charge (pHpzc) of Chitosan/ZnO/Fe3O4 nano-composite adsorbent
model, Germany, the samples for TEM were prepared by sonication of was determined by a Malvern ZEN2600 Zetasizer Nano Z.
the samples in ethanol and depositing onto a copper coated carbon grid
and letting the solvent to evaporate. The Field Emission Scanning Electron 2.3. Swelling behavior of nano-composite adsorbent
Microscopy (FE-SEM) images were obtained using SIGMA VP-500 model,
Zeiss. Magnetic measurement was carried out using magnetometer using The dry polymeric Chitosan/ZnO/Fe3O4 adsorbent was immersed
VSM Unit (LakeShore 7410) with the filed sweeping from −20,000 to in deionized water at various times to reach the equilibrium
120
100 CS/ZnO/Fe3O4
CS
80
Weight(%)
60
40
20
0
0 100 200 300 400 500 600 700 800 900
Temperature (oC)
Fig. 5. TGA curves of CS and CS/ZnO/Fe3O4 nanocomposite.

3.5
2.5
Swelling Rao (g/g)

2
1.5
0.5
0
0 100 200 300 400 500 600 700 800 900
Time(min)
1.5
y = 0.5719x - 2.1015
1 R² = 0.9501
0.5
Ln(Mt/M∞)
-0.5
-1
-1.5
0 1 2 3 4 5 6 7 8
Ln(t)
Fig. 6. a The swelling behavior of CS/ZnO/Fe3O4 nano-composite adsorbent. b the straight line of Ln(Mt/M∞) versus Lnt.
swelling. The swelling ratio (SR, g/g) was measured by the following adsorptive solutions was adjusted using nitric acid (1 M) and sodium
equation [42]: hydroxide (1 M) when needed.
Wt −Wd 2.5. Design of experiments

SR ¼ ð1Þ
Wd
Response surface methodology (RSM) was used to evaluate the ef-
where Wd is dry weight of sample and Wt is the swollen sample at time fects of different operating parameters on the removal efficiency of Cu
t. (II) ions. It not only shows the optimum conditions, but it also proposes
fitted regression models. A 5-level, 5-factor Central Composite Design
2.4. Adsorption experiments (CCD) was used to evaluate the effect of the selected parameters on
the removal efficiency of Cu(II) ions from aqueous solutions by CS/
The adsorption of copper on nanocomposite was studied by a batch ZnO/Fe3O4. The four parameters affecting heavy metal removal, namely
technique. A certain amount of adsorbent was equilibrated with 50 mL solution pH, time, temperature, initial contaminant concentration and
of the heavy metals solution of known concentration in 100 mL Erlen- adsorbent dosage were selected as independent variables, and the re-
meyer flasks. The flasks were agitated in an incubator shaker at moval efficiency of Cu(II) was considered as the dependent variable(re-
150 rpm for 120 min. After that, the suspension of the adsorbent was sponse). Variables were coded in accordance with the following
separated from the solution by a 0.22 μm cellulosic filter. The concentra- equation:
tion of heavy metal ions remaining in solution was measured by AAS
(Perkin-Elmer 700) using the flame method. The effect of several pa-
rameters, such as pH, temperature, time, contaminant concentration X i −X 0
xi ¼ ð2Þ
and adsorbent dose on the adsorption was investigated. The pH of the ΔX i
Table 3 The experimental results were analyzed using Design Expert 7.0 and
ANOVA results of the regression model for optimization of Cu adsorption. a regression quadratic polynomial model was proposed as follows:
Parameter Cu
Source F-value p-Value X

k X
k X
k
Y ¼ α0 þ α i xi þ α ii x2ii þ α ij xi x j þ ε ð4Þ
Model 312.60 b0.0001 Significant i¼1 i¼1 i¼1
A-pH 1701.06 b0.0001
B-t 1175.20 b0.0001
C-D 2562.80 b0.0001 where, α0 is the constant coefficient, αi, αii and αij are the regression
D-C0 711.33 b0.0001 coefficient and Xi, Xj indicate the independent variables. ε represents
E-T 9.58 0.0043 the random error.
AB 0.4119 0.5261
AC 4.75 0.0375
AD 6.67 0.0151 3. Results and discussion
AE 0.0566 0.8137
BC 5.99 0.0207 3.1. CS/ZnO/Fe3O4 characterization
BD 0.6837 0.4151
BE 2.64 0.1148
CD 0.7185 0.4036 BET analysis was used to find the best CS:ZnO and CS/ZnO:
CE 0.2346 0.6318 Fe3O4ratios. The results were presented in Table 2. Based on the results,
DE 0.0449 0.8337 increasing ZnO content up to 0.9 g improves total surface area (SBET) and
A2 11.35 0.0021 total pore volume and then decrease specific surface area of chitosan/
B2 17.56 0.0002
C2 34.64 b 0.0001
ZnO nanocomposite. CS/ZnO SBET and average total pore volume in-
D2 5.89 0.0217 crease with addition of Fe3O4 nanoparticles up to 1.25 g. Further in-
E2 0.3064 0.5841 crease in Fe3O4contents (1.4 g) resulted in a decrease in total surface
Lack of fit 8.23E−03 0.912 Not significant area. The reduction of the SBET and average total pore volume of
nano-composites with high contents of ZnO (1 .2g) and Fe3O4 (1 .5g)
can be due to the instability of nanoparticles leading to blockage of
the adsorbent pores by agglomeration of nanoparticles. Among the
where xi is the coded value of an independent variable, Xi is the real nano-composites, the highest surface area and average pore volume
value of an independent variable, X0 is the real value of an independent were found to be 118.7 (m2/g) and 0.0603 (cm3/g), respectively, for
variable at the center point and ΔXi is the step change value. The re- CS/ZnO/Fe3O4 with 0.9 g of ZnO and 1.25 g of Fe3O4 nanoparticles.
moval efficiency of each contaminant (Yi) was calculated according to The X-ray diffraction pattern of magnetic nanoparticles (Fig. 1a)
the following equation: shows the identical peaks for Fe3O4, which were located at 30.1°,
35.5°, 43.1°, 53.4°, 57.0°, and 62.6° corresponding to their indices (2 2
0), (3 1 1), (4 0 0), (4 2 2), (5 1 1), and (4 4 0) [22]. In addition, a search
C 0 −C t match on the library of the instrument was held and confirmed
Y ðiÞ ¼ 100 ð3Þ
C0 matching with the Fe3O4. ZnO NPs Fig. 1.b) exhibited strong diffraction
peaks at 31.76° (1 0 0), 34.47° (0 0 2), 36.26° (1 0 1), 47.57° (1 0 2),
56.65° (1 1 0), 62.95° (1 0 3) and 67.94° (2 0 0) corresponding to the
where, Y is the heavy metal removal efficiency (%), and C0 and Ct are the
hexagonal wurtzite structure of ZnO (JCPDS card no. 36–1451)
initial and residual concentrations of metal in solution (mg/L). The ex-
[36,37]. The XRD pattern of CS (Fig. 1c) exhibited characteristics reflec-
perimental range and levels of independent variables for metal ion re-
tions at 2θ = 9.80 and 19.86, which is consistent with previous studies
moval were given in Table 1.
reporting the reflection pattern of chitosan [29]. Two broad diffraction
peaks appeared at 2θ = 20.0 and 25.3 are the characteristics peaks of
the polyaniline, corresponding to the periodicity parallel and perpen-
dicular to polymer chains [43]. XRD pattern of CS/ZnO/Fe3O4 nano-
Table 4 composite is illustrated in Fig. 2d. The corresponding diffraction peaks
The regression coefficient values. of ZnO and Fe3O4 were observed which confirmed the presence of
R_Cu = Fe3O4 and ZnO nanoparticles in the nano-composite structure. The re-
sults indicates that that the crystalline structure of ZnO and Fe3O4
+84.33
+4.26 A does not destroyed during the formation of the nanocomposite.
+3.54 B The FTIR spectra of the chitosan and composite is shown in Fig. 2. As
+5.23 C observed, the band located at 512 cm−1 attributed to the Zn\\O
−2.76 D stretching mode of the ZnO lattice [44]. The strong characteristic ad-
+0.3200 E
sorption peak at 585 cm−1 corresponding to the Fe\\O bond vibration
−0.0742 AB
−0.2520 AC of Fe3O4 [45]. The absorption peaks in the range of 1050–1150 cm−1
+0.2985 AD were related to C\\O stretching vibrations. The band at
+0.0275 AE 1550–1640 cm−1 was assigned to the stretching vibrations of amide
+0.2830 BC
(C=N) groups [46,47]. The absorption peak at 2925 cm−1 and absorp-
+0.0956 BD
+0.1880 BE tion peaks at about 1050–1150 cm−1 were related to C\\H and C\\O
+0.0980 CD stretching vibrations, respectively [48]. The absorption peak at
+0.0560 CE 3430 cm−1 was attributed to the stretching vibrations of O\\H and
+0.0245 DE N\\H groups [48,49].
−0.3895 A2
Morphological structure of as-synthesized ZnO, As observed, the
−0.4845 B2
−0.6805 C2 band located at 512 cm−1 attributed to the Zn\\O stretching mode of
+0.2805 D2 the ZnO lattice [44]. The strong characteristic adsorption peak at
+0.0640 E2 585 cm−1 corresponding to the Fe\\O bond vibration of Fe3O4 and CS/
ZnO/As observed, the band located at 512 cm−1 attributed to the
Table 5 presence of Fe, Zn and O composition in the CS–ZnO- Fe3O4 nanocom-

Model summary statistic. posite. The elemental composition of iron, zinc, oxygen, nitrogen and
Std. Dev. 0.72 carbon is 32.2, 21.8, 19.9, 3.5 and 22.5%, respectively. No other peak re-
Mean 79.97 lated to any impurity has been detected in the EDS, which confirms that
C.V. % 1.91 the grown nanoparticles in the nanocomposite are composed only with
R2 0.99
iron, zinc, oxygen and carbon. Thus, the presence of iron and zinc con-
Adjusted R2 0.98
Predicted R2 0.99 tent in the nanocomposite was confirmed from the EDS results.
Adeq precision 69.93 The magnetic properties of magnetic nanoparticles and nanocom-
posite were investigated at room temperature using Vibrating sample
magnetometer (VSM) system. Fig. 4 shows the magnetic hysteresis
Zn\\O stretching mode of the ZnO lattice [44]. The strong characteristic curves measured at 300 K, with the field sweeping from −20,000 to
adsorption peak at 585 cm−1 corresponding to the Fe\\O bond vibra- 20,000 Oe. From the obtained data, it was found that both samples ex-
tion of Fe3O4 nanocomposite were illustrated in Fig. 3. Irregular struc- hibit a super-paramagnetic characteristics and the saturation magneti-
ture of ZnO nanoparticles was observed in Fig. 3a. As shown, the ZnO zation of magnetic nanoparticles was 44.8 emu/g where the
nanoparticles were well synthesized. High proportion of ZnO nanopar- nanocomposite was 12.5 emu/g respectively. This decrease in the mag-
ticles had a spherical shape and also their size was in the range of netic property, in case of nanocomposite relative to pure magnetic
18–25 nm. FESEM analysis (Fig. 3b) proved the uniformly distributed nanoparticles, is due to the lower amount of magnetite present in the
As observed, the band located at 512 cm−1 attributed to the Zn\\O nanocomposite matrix and the impregnation of the magnetite nanopar-
stretching mode of the ZnO lattice [44]. The strong characteristic ad- ticles inside the polymer matrix which most probably shields the mag-
sorption peak at 585 cm−1 corresponding to the Fe\\O bond vibration netic property of magnetic nanoparticles. Thus it can be seen that the
of Fe3O4 nanoparticles with spherical morphology in which the size of nanocomposite materials obtained by this synthesis route possess a
nanoparticles was in nano scale (25–30 nm). In the case of the nano- moderate saturation magnetization. This feature is beneficial for their
composite (Fig. 3c), the iron oxide and zinc oxide nanoparticles had application as adsorbents as the nanocomposite could be quickly
been uniformly distributed on the chitosan surface with a spherical moved along the magnetic field and completely separated from the
structure and high density. The average diameter of nanocomposite treated water.
structure was 40–50 nm. TEM image of CS/As observed, the band lo- Thermal stabilities of the samples were determined by TGA. The TGA
cated at 512 cm−1 attributed to the Zn\\O stretching mode of the ZnO curves of the CS and CS/ZnO/Fe3O4 are illustrated in Fig. 5. The pure CS
lattice [44]. The strong characteristic adsorption peak at 585 cm−1 cor- exhibited a weight loss of 5% below 100 °C and a rapid and main weight
responding to the Fe\\O bond vibration of Fe3O4/ZnO nano-composite loss at 280–500 °C, referring to the removal of physically adsorbed
(Fig. 3d) displayed good dispersion of the ZnO NPs. TEM analysis con- water and the decomposition of the pure CS, respectively. No significant
firmed the results of FESEM analysis. The spherical morphology and uni- weight change was observed above 500 °C. However, the TGA curve of
form distribution of nanoparticles were clearly observed and also As observed, the band located at 512 cm−1 attributed to the Zn\\O
average particle size of nanoparticles was 46 nm. The electron disper- stretching mode of the ZnO lattice [44]. The strong characteristic ad-
sive spectroscopy (EDS) analysis of these particles indicates the sorption peak at 585 cm−1 corresponding to the Fe\\O bond vibration
Fig. 7. Predicted vs actual removal efficiency.

Fig. 8. Normal residual plot.
of Fe3O4/ZnO/CS was very different from that of the pure CS. Three 200 °C, as a result of the evaporation of adsorbed water. The other two
stages of weight loss were observed in the TGA curve of Fe3O4/ZnO/ stages of main weight loss at 200–400 °C and 600–750 °C were caused
CS. The first stage was about 7% weight loss from room temperature to by the decomposition of the cross-linking CS in Fe3O4/ZnO/CS. In the
Fig. 9. 3D plots for interactive effect of pH and initial Cu(II) concentration on the removal efficiency.
Fig. 10. 3D plots for interactive effect of time and nanocomposite dosage on the removal efficiency.
course of the reaction, Fe3O4, ZnO and CS were connected together chitosan in Fe3O4/ZnO/CS. Thus, the final temperature of decomposi-
through the chelation between Fe3+ and CS and Zn2+and CS. The con- tion for Fe3O4/ZnO/CS was higher than that for the pure CS.
formational changes of chitosan and the addition Fe3O4/ZnO/CS al Time-dependent swelling behavior of CS/ZnO/Fe3O4 nano-
bridging between Fe3O4 and CS enhanced the thermal stability of composite adsorbent is indicated in Fig. 6. As shown, the swelling
Fig. 11. 3D plots for interactive effect of temperature and nanocomposite dosage on the removal efficiency.
Fig. 12. 3D plots for interactive effect of pH and nanocomposite dosage on the removal efficiency.
ratio (SR) of nano-composite increases rapidly within 500 min and then coefficient of determination (R2). Model terms are evaluated by the P-
the curve leveled off, approximately. Finally, the equilibrium SR was value (probability) with 95% confidence level. The analysis of variance
found to be 2.82. In general, SR greater than one means that CS/ZnO/ (ANOVA) for removal efficiency (Y) is represented in Table 3. All of
Fe3O4 nano-composite is hydrophilic. It can be due to the surface hy- the response surface quadratic models for parameters in this table are
droxyl groups of chitosan and nanoparticles. The water-transfer mech- significant at the 5% confidence level since the P-values are b0.05. The
anism and swelling kinetics are key factors to explain the swelling correlation coefficient (R2) is 0.99, which it is N0.80, the cut-off for a
properties in detail because water diffuses into the polymer sample model with good fit. A high coefficient (R2) value ensures a satisfactory
and the sample swells. There are three types of sorption mechanisms adjustment of the quadratic model to the experimental data and illus-
of polymer sample. The penetration of the water into the polymer trates good agreement between the calculated and observed results
network, relaxation of polymer chains and stretch of whole polymer and shows that a desirable and reasonable agreement with the adjusted
structure in solution are the first, second and third process, respectively. R2. If the model terms have the P-value (probability) N0.05, they are
The following equation was used to interpret the penetrating considered limited influence [50]. So, they must be excluded from the
mechanism [42]: study to improve the models. The model of removal efficiency is consid-
ered significant using the F-test at 5% significant level (Prob b0.05). In-
Mt n significant model terms, which have limited influence, are excluded
¼ kt ð3Þ
M∞ from the study to improve the models. Based on the results obtained,
the response surface models for predicting removal efficiency is consid-
where Mt and M∞ represent the amount of water adsorbed at time t and ered reasonable. The final regression model is presented in terms of its
equilibrium, respectively; k represents the swelling rate front factor and coded factors (Table 4). Model summary statistic is listed in Table 5.
n is the kinetic exponent which clarifies the mode of the penetrant The pred R-squared of 0.99 was in reasonable agreement with the “adj
transport. The values of n and k determined from slope and intercept Rsquared” of 0.98 because the difference between these values is within
of linear form of eq. 3, Ln(Mt/M∞) = Ln(k) + n Lnt. If a Fickian mecha- 0.01 which confirmed good predictability of the model. Moreover, the
nism dominates, the penetrating diffusion rate of will be rate-limiting standard deviation for the model was 0.72 and it has been confirmed
and n equals 0.5. When n is between 0.5 and 1.0, a typical non-Fickian that smaller the value of standard deviation the better is the model be-
mechanism occurs during the swelling and transport of the solute will cause the predicted value obtained will be found closer to the actual
be anomalous. If n equals 1, the relaxation controlled mechanism will
be rate-limiting. In this study the results indicated that the swelling of Table 6
CS/ZnO/Fe3O4 nano-composite adsorbent obeyed from non-Fickian Optimization results.
mechanism because n value was N0.5 (0.57). Name Units Values
pH 6.5
3.2. Adsorption experiments t min 51
D g/L 0.71
The analysis of variance (ANOVA) is used for graphical analysis of C0 mg/l 82.5
data to obtain the interaction among the process variables and the re- T C 30.3
Removal efficiency % 94.51
sponse. The quality of the fit polynomial model is expressed by
Table 7
Kinetic parameters for the Cu(II) adsorption onto the nanocomposite adsorbent.
Pseudo-first-order model Pseudo-second-order model Intra-particle diffusion model
k1 qe R2 k2 qe R2 kid C R2
(min−1) (mg/g) (g/mg min) (mg/g) (g mg−1 min0.5)
0.193 208.25 0.956 0.00148 228.95 0.999 k1 k2 k3 1.86 0.976

53.85 13.62 0.54
value for the response. Adequate precision is a measure of the signal to concentrations on the surface of the nanocomposite. In the higher
noise ratio and a value greater than or equal to 4 is always desirable. In range of adsorbate concentration, the surface of adsorbent began to
the present analysis, a value of 69.93 indicated sufficient model discrim- get saturated and results in decreasing the adsorption efficiency of Cu
ination. On the other hand, a relatively lower value of the coefficient of (II) ions. Copper ions needed to diffuse to the adsorbent sites by
variation (CV = 1.91%) indicated dependability and reproducibility of intraparticle diffusion. In addition, steric repulsion between the copper
the model [50]. ions could slow down the adsorption process and thereby decreases
Predicted versus actual plot of the response was presented in Fig. 7. the removal rate. The solution pH is an important operational parameter
The values predicted by the model and the results obtained by the ex- in the adsorption process because it affects the solubility of the metal
periments are distributed uniformly around a 45° line. Normal Probabil- ions, concentration of the counter ions on the functional groups of the
ity Plots for is shown in Fig. 8. Normal probability plots of the adsorbent and the degree of ionization of the adsorbent during reaction
studentized residuals and diagnostics are provided by Design Expert [31].
software program (a statistical software package from Stat-Ease Inc) The adsorption efficiency increases with increasing solution pH.
to confirm that the selected model provides an adequate approximation Electrostatic attraction is considered as the main adsorption mechanism
of the real system. Plot of Normal probability aid in evaluating the at pH values higher than the pHpzc. Metal ions can also adsorb on the
models. The normal probability plot predicts that if the residuals follow surface of nanocomposite through the ion exchange process at pH
a normal distribution, as shown in Fig. 8, then the points will fall along a values less than the pHzpc. Nanocomposite pHpzc was obtained around
straight line for each case. However, some scattering is expected even 6.7. Notably, the efficiency of adsorption increases remarkably with in-
with normal data; thus, the data can be considered to be normally dis- creasing pH value of the solution when it is below the value of 5.5 and
tributed in the responses of certain model. then it increases smoothly until the pH value of 7. When the pH is higher
Response surface plots were used to determine the individual and than 7.0, the OH– in the system and the functional groups on the surface
interaction effects of the input variables on the target responses. They of the cell wall compete for heavy metal ions, which decrease sorption
analyze the geometric nature of the surface, the maxima and minima capacity. Under lower pH, NH2 and OH functional groups in nanocom-
of the response and the significance of the coefficients of the equation. posite are protonated and thus resulted in positively charged surface
of absorbent. That is to say, electrostatic repulsion will occur between
3.3. Sensitivity analysis cationic metal ions and positively charged nanocomposite surface at
low pH [51]. The protonated groups showed relatively lower complex-
The response surface plots were obtained by varying two factors ation with metal ions and ion-exchange capacity, and thus the
while keeping the other constant. Fig. 9 represents the effect of initial adsorption capacity was decreased. However, the NH3+ groups were
concentration of metals and pH on Cu(II) removal. Metal adsorption is converted to NH2 groups, which have stronger complexing and ex-
a mass transfer process that can generally be defined as the accumula- changing capabilities to metal ions [31]. Meanwhile, a mass of H+ and
tion of metal at the interface between the solid/liquid phases. The H3O+ present in the aqueous solution also compete with the cationic
Figure shows that the initial Cu(II) concentration had a negative effect metal ions for the available adsorption sites on CS/Fe3O4/ZnO, which re-
on the removal efficiency of Cu (II) ions, in which by increasing the ini- sults in a lower adsorption at low solution pH. Thus, more active sites
tial concentration of Cu (II) from 40 to 120 mg/L, the Cu (II) removal ef- are available for the adsorption of Cu2+ ions at higher pH conditions.
ficiency decreased from 89.3% to 75.4%. This behavior could be related to In addition, almost no Cu2+ ions were adsorbed at pH 2, which is to
the complexity of competitive adsorption of the metal ions at different say all binding sites were occupied by proton.
Fig. 13. Intraparticle-diffusion kinetic model fits for the adsorption of Cu2+ ions on nanocomposite.
Fig. 14. Isotherm models for Cu2+ adsorption by CS/Fe3O4/ZnO nanocomposite.
The simultaneous influence of contact time and absorbent dosage on the swelling property of adsorbents and the mobility of metal ions.
removal efficiency was illustrated in Fig. 10. The contact time of the ab- Increasing temperature had a significant positive effect on the removal
sorbent and adsorbate will greatly affect the efficiency of the adsorption efficiency of Cu(II) ions in which increased with the increase in temper-
process. Besides, in the practical usage of absorbents, the contact time ature. Increasing the temperature of solutions would increase the mo-
directly reflects the economical efficiency of the process, which is re- bility of metal ions and also produces a swelling effect within the
lated to the adsorption kinetics. So we can come to a conclusion that internal structure of nanocomposite, thus, enabling the large metal mol-
the contact time of the adsorption process is a fairly important influen- ecules to penetrate further [45,52,53] .The temperature also affects the
tial factor. It is evidently that longer contact time is favorable for increas- adsorption rate by altering the molecular interactions and the solubility.
ing the adsorption efficiency until equilibrium adsorption is established. The higher removal due to the high temperature may be attributed to
The adsorption efficiency can reach up in a short period and then it in- the chemical reaction taking place between the functional groups of
creases mildly with extending agitation time. Such a fast adsorption the adsorbate and adsorbent molecules. Higher absorbent dosage
rate may due to the fact that the adsorption sites are open and the leads to higher removal efficiency. This behavior could be ascribed to a
metal ions interacts easily with the active sites at first and the following greater surface area and the more availability of adsorption sites at the
slower rate can be contributed to the slower diffusion of Cu2+ ions into higher adsorbent dosage. However, if the adsorption capacity was
the interior of the adsorbent during chelating process. Adsorbent dosage expressed by milligram adsorbed per gram of nanocomposite, the ca-
is another important factor which must be carefully investigated for re- pacity would decrease with the increasing amount of adsorbent. This
moval process. To maximize the interactions between metal ions and may be attributed to overlapping or aggregation of adsorption sites
adsorption sites of the adsorbent, getting an optimum dosage of the ad- that results in the increase of diffusion path length and decreases the
sorbent is necessary. Based on the Fig. 10, initially, a rapid removal of Cu total adsorbent surface area which is available to the metal ions. It
(II) with the increasing adsorbent dosage was observed [40]. The in- shows that the nanoabsorbent dosage is more significant than temper-
crease in adsorption with adsorbent dosage can be attributed to the ature under the high concentration of CS/ZnO/Fe3O4.
higher adsorbent surface and availability of more adsorption sites for The interactive effects of pH and adsorbent dosage were shown in
metal ions. However, if the adsorption capacity was expressed by milli- Fig. 12. It shows that increasing in adsorbent dosage has higher effect
gram adsorbed per gram of nanocomposite, the capacity would on the adsorption of Cu(II) ions. This behavior could be ascribed to a
decrease with the increasing amount of adsorbent. This may be attrib- greater surface area and the more availability of adsorption sites at the
uted to overlapping or aggregation of adsorption sites that results in higher adsorbent dosage. Although the increase in each of pH and ad-
the increase of diffusion path length and decreases the total adsorbent sorbent dosage parameters individually had a positive effect on the re-
surface area which is available to the metal ions. A further increase in moval efficiency of Cu(II) ions, the simultaneous increase of these
the nano composite dosage did not show much increase in the removal parameters showed a negative synergistic effect on the removal.
rate and adsorption equilibrium.
Fig. 11 show the interaction between temperature and nanocom- 3.4. Optimization
posite dosage. Temperature is perceived as an important parameter
for the adsorption of metal ions by adsorbents. That's mostly because Maximum removal efficiency for adsorbate and the corresponding
the temperature of the solution may affect the solid/liquid interfaces, optimal conditions of variables were determined and the model was
Table 8
Isotherm parameters for the Cu(II) adsorption onto the nano-composite adsorbent.
Freundlich model Langmuir model Temkin model D-R model

2 2 2
n KF R qm KL R RL AT KT R qm kDR R2
−1 −1 2 2 7
(mg/g) (mg/g) (L mg ) (J mol ) (L/g) (mg/g) (mol /J ) × 10
Cu(II) 2.362 24.65 0.901 328.46 0.0192 0.999 0.969 64.85 0.245 0.895 4.150 1.142 0.946
Table 9 Table 11
Thermodynamic parameters for the adsorption of Cu(II) onto the nanocomposite. Cu(II) removal by using different adsorbents.
T (°C) Nanocomposite Type of adsorbent Operating Uptake References

condition (mg/g)
ΔG° (kJ mol−1) ΔH° (kJ mol−1) ΔS° (J mol−1 K−1)
Carbonaceous nanofibers T = 5.5 ± 0.2 204.00 [75]
Cu(II) 15 −2.985 12.24 124.84
Live yeast (Y. lipolytica) pH = 6.4 204.10 [76]
25 −4.712
Graphene oxide pH = 5 45.20 [77]
35 −5.438
kaolinite- zerovalent iron NP pH = 6.0 49.00 [78]
Bare NZVI pH = 6.5 250.00 [79]
MWCNT- nanofibrous NZVI pH = 5.5 107.80 [80]
confirmed by some further experimental runs. Numerical optimization Ecklonia maxima — marine alga pH = 6 90.00 [81]
was done to find a maximum point for the desirability function by set- Spirogyra (green alga) pH = 5 133.00 [82]
ting the values of pH, temperature, concentration of initial ions and ad- Iron oxide coated eggshell powder pH = 6 44.00 [83]
Non-crosslinked chitosan pH = 5 85.00 [84]
sorbent dosage within their ranges and maximizing the removal Crosslinked chitosan (EPI) pH = 5 62.40 [85]
efficiencies of Cu(II) ions. The results listed in Table 6. The desirability Crosslinked chitosan (TPP) pH between 5 and 6 200.00 [86]
value was found to be 0.93. This optimum condition was checked exper- Chitosan/Fe3O4/ZnO pH = 6.5 328.46
imentally. The results showed the removal efficiency of 94.32 ± 1.65 for
Cu(II) ions. The high degree of agreement between the predicted
optimum conditions and the repeated experimental results indicated where qt and qe (mmol g−1) represent the amount of metal ions
that the CCD RSM could be employed as an effective and reliable adsorbed on the adsorbents at time t (min) and equilibrium, respec-
tool for evaluation and optimization of the effects of adsorption tively. k1 (min−1) is the rate constant of the pseudo-first order model,
parameters on the removal efficiency of heavy metals using CS/ZnO/ while k2 (g mmol−1 min−1) is the rate constant of pseudosecond
Fe3O4nanocomposite. order model.
The kinetics parameters and correlation coefficients are listed in
3.5. Adsorption kinetic Table 7. The higher correlation coefficients showed that the pseudo-
second-order model was more applicable to describe the metal ions ad-
Adsorption is a process of dynamic balance, and the adsorption rate sorption, implying that second order chemisorption controlled the ad-
depends on many factors such as the physical and chemical properties sorption process rather
of adsorbent, the concentration and the characteristics of heavy metal than mass transport. And the theoretical value of qe obtained from
ions and the combination ability of heavy metal ions and adsorbent. the pseudo-second-order kinetic model was in close agreement with
The solution was investigated at the initial metal ion concentration of the experimental value. Several studies in the literature involving ad-
80 mg/ L, the adsorbent dosage of 0.71 g/L, and pH of 6.5. Several kinetic sorption of Cu(II), Cd (II) and Pb (II) ions, as well as other metal ions,
models such as pseudo-first-order, pseudo second-order and intra- onto chitosan or modified chitosan, have also shown that the PSO kinet-
particle diffusion model have been applied to find out the adsorption ics model gave the best fit for the experimental data [51,54].
mechanism. The pseudo-first-order kinetic model presumes that the The intraparticle diffusion model is used to explain diffusion mecha-
binding is from physical adsorption, while the pseudo-second order ki- nism of adsorption process [53]. The intraparticle diffusion model can be
netic model presumes that the binding is based on chemical adsorption. described as follows [54]:
logðqt −qe Þ ¼ logqe −k1 t ð4Þ qt ¼ kid t 0:5 þ C ð6Þ
where Kid is the intraparticle diffusion rate constant (mg/g h0.5) and C is
t=qt ¼ 1= k2 qe 2 þ t=qe ð5Þ the intercept. The value of C relates to the thickness of the boundary
Table 10
Comparison of adsorption capacities of various chitosan-based adsorbents for Cu(II) ions.
Adsorbent Adsorption condition qm Isotherm Kinetic Thermodynamic Ref
Raw chitosan 25 °C, pH 5.5 80.17 Langmuir PSOa [61]

Magnetic chitosan microcapsules pH 7.0, 30 °C 104 Langmuir PSO [62]
Epichlorohydrin cross-linked xanthate chitosan pH 5.0, 30 °C 43.47 Langmuir PSO Endothermic [63]
Magnetic chitosan nanoparticles pH 5.0, 35 °C 35.5 Langmuir [64]
Xanthate-modified magnetic chitosan 25 °C, pH 5.0 34.5 Langmuir [65]
Magnetic chitosan modified by melamine 25 °C, pH 5.0 163.9 Langmuir [66]
S-doped Fe3O4@Chitosan 46.6 Freundlich [67]
EDTA-modified chitosan/sio2/Fe3O4 25 °C, pH 5.0 31.4 Langmuir PSO Endothermic [40]
Chitosan coated cotton fiber 25 °C, pH 6.5 18.08 Langmuir [68]
Porous chitosan-oxalate 30 °C, pH 5.0 227.27 Langmuir PSO Endothermic [69]
Non-porous chitosan-oxalate 30 °C, pH 5.0 175.44 Langmuir PSO Endothermic [69]
Thiourea-modified magnetic chitosan microspheres 28 °C, pH 5.0 66.7 Langmuir PSO [70]
Magnetic chitosan/cellulose microsphere 30 °C 88.21 Langmuir [71]
Chitosan-modified mnfe2o4 pH 6.5 65.1 Langmuir [59]
Magnetic chitosan nanoparticles 25 °C, pH 5.0 33.7 Langmuir PSO [64]
Chitosan/poly(acrylic acid) magnetic pH 5.5, 30 °C 174.0 Langmuir PSO [72]
Magnetic chitosan pH 5.5, 25 °C 216.6 Langmuir PSO Endothermic [73]
Magnetic chitosan bead pH 4.0, 30 °C 147.0 Langmuir [30]
Carboxymethyl chitosan–hemicellulose resin pH 4.0, 25 °C 333.3 Langmuir PSO [74]
Fe3O4-CS/EDTA pH 3.0, 30 °C 225 Langmuir PSO Endothermic [45]
Chitosan/Fe3O4/zno pH:6.5 328.46 Langmuir PSO/ID Endothermic
31 °C
a
PSO: pseudo-second-order ID: intraparticle diffusion.
sites are occupied, adsorption cannot be achieved on the same sites.

Hence, a maximum adsorption capacity is reached when all sites are oc-
cupied. The Dubinin–Radushkevich isotherm equation is more general
than the Langmuir equation because it does not assume a homogeneous
surface or constant adsorption potential. It was used to distinguish be-
tween the chemical and physical adsorption. The model is based on
the adsorption potential theory by Polanyi. Dubinin suggested that the
adsorption proceeds in the volume of adsorbent micropores as opposed
to layer-by-layer adsorption on micropore walls. The Freundlich iso-
therm is another empirical equation. It assumes that adsorbates are
adsorbed to the heterogeneous surface of adsorbents, both monolayer
and multilayer adsorption occur during the adsorption. Temkin model
accepts the following conditions: (i) the adsorption hea.t of all mole-
cules present in the layer linearly decreases wi.th the covera.ge whi.ch
is because of adsorbent-adsorbate interactions; (ii.) a uniform distribu-
tion of binding energies, up to maximum binding energy, is used to
characterize the adsorption. The Temkin isotherm proposes tha.t the
decrea.se in the hea.t of adsorption is more linear rather than logarith-
Fig. 15. Magnetic separation photos of CS/Fe3O4/ZnO nanocomposite.
mic as already suggested implicitly by the Freundli.ch equation. The iso-
therms curves for removal of Cu(II) by CS/ZnO/Fe3O4at optimum
layer. The larger C implies the greater effect of theboundary layer [55]. condition were depicted in Fig. 14. It is found that uptake capacities of
Fig. 13 and Table 7 show the intra-particle diffusion plots for the metal pollutant on adsorbent raised with increasing of initial adsorbate con-
ion adsorption on CS/Fe3O4/ZnO nanocomposite. It is observable that centration at beginning, and then reached the equilibrium.
more than one linear portion appear in the plot, which indicates that
the adsorption is affected by two or more steps [38]. Moreover, the dif- qe ¼ ðqo KL Ce Þ=ð1 þ KL Ce Þ ð7Þ
fusion rate constants in every step follow the order of ki,1 N ki,2 N ki,3,
which are depicted in Table 7. This can be illustrated as follows: the qe ¼ K F ðCe Þ1=n ð8Þ
first portion with steep slope represents the instant diffusion stage, in
which large numbers of metal ions from bulk phase were adsorbed rap- qe ¼ B ln ðKT Ce Þ where B ¼ ðRT=AT Þ: ð9Þ
idly by the surface functional groups of CS/Fe3O4/ZnO. After almost all
the exterior active points were occupied, the metal ions got ready to qe ¼ qm exp −kDR ε2 where ε ¼ RTlnð1 þ 1=Ce Þ ð10Þ
enter into the pores of the adsorbents [33], and then were adsorbed
by the interior surface of pores, which arose in the second stage. In the where Ce (mg/L) represents concentration of pollutant in aqueous solu-
third portion, the intra-particle diffusion rate constants were close to tion at equilibrium; qe (mg/g) is adsorption amount of pollutant at
zero, indicating equilibrium state reached at last. As a summary of the equilibrium, and qmax (mg/g) is the maximum uptake capacity of adsor-
kinetic studies, it is implied that both the intra-particle diffusion and bent, respectively. KL (L mg−1) is a Langmuir constant concerning ad-
the chemical chelating reaction between metal ions and active points sorption energy; n and KF represent Freundlich constants associated
of the adsorbents had effects on the adsorption processes [33]. Some with sorption intensity and sorption capacity, respectively. KT, At and
previous kinetic studies showed similar results. Bt are Temkin constant, initial adsorption heat constant (mg/g), and sur-
face heterogeneity of the adsorbent constant (mg/g), respectively. kDR is
3.6. Adsorption isotherm the D-R constant (mol2 kJ−2) and ε shows the Polanyi potential
(J mol−1). R represent the gas constant (J mol−1 K−1) [55].
The adsorption isotherms could reflect the interaction pattern be- The obtained values for isotherm constants and correlation coeffi-
tween adsorbent and adsorbate, further explaining the adsorption cients are listed in Table 8. Compared with the Freundlich and Temkin
mechanisms [43]. For the adsorption isotherm studies, the tested condi- isotherm models, the Langmuir model fits better with the experimental
tions were as follows: adsorbent dosage 0.71 g/L, temperature 30 °C and data due to the higher correlation coefficients (N0.990), which suggests
pH 6.5. The isotherms data of Cu(II) on nanocomposite was simulated a monolayer adsorption. These results indicated that adsorbent have a
by four well-known isotherm models, i.e., Langmuir (Eq. (7)) and homogeneous surface with identical sorption sites. As is shown in
Freundlich (Eq. (8)), Temkin (Eq. (9)) and Dubinin-Radushkevich ،Table 8 for the Langmuir isotherm, the maximum Cu(II) adsorption
(Eq. (10)) models. The Langmuir isotherm presumes that adsorption oc- capacity of the anilined CS/Fe3O4/ZnO was found to be 328.46 mg/ g,
curring on homogenous sites on the surface of adsorbents. Once the which is much higher than the capacities of previously described
Fig. 16. EDS spectra of CS/Fe3O4/ZnO nanocomposite before and after adsorption of Cu2+.
materials for Cu(II) [56–60]. The high adsorption capacity of the 3.8. Regeneration and reusability of nanocomposite
anilined CS/Fe3O4/ZnO could be explained by two factors. Firstly, the
large numbers of functional groups (including OH and NH2) on the sur- Generally, the adsorbed metal ions can be desorbed and concen-
faces of the nanocomposite will provide large numbers of adsorption trated by eluant. However, acids such as HCl and HNO3 may react with
sites. Secondly, the large numbers of ZnO nanoparticles and amino Fe3O4, which is the magnetic component of magnetic CS/ZnO.
and hydroxyl groups on the chitosan chains will make the nanocompos- Ethylendiamine tetraacetic acid (EDTA) is known as a very strong che-
ite very hydrophilic and dispersible. Effective dispersion of the anilined lating agent for many heavy metal ions and was proposed to replace
CS/Fe3O4/ZnO will ensure that the adsorbent has full access to dissolved the active groups on magnetic CS/ZnO nanoparticles and preferentially
Cu(II). In addition, a separation factor constant (RL) was applied to eval- complex with metal ions. Consequently, EDTA was chosen as the eluant
uate the degree of suitability of adsorbent towards investigated adsor- for metal ions. At a concentration of 0.02 M EDTA and with the contact
bate [45]. And the RL is defined as follows. time of 1 h, it is possible to desorb 88% of Cu(II) ions adsorbed on CS/
ZnO/Fe3O4 into the solution. Increasing EDTA concentration to 0.1 M re-
1 sulted in 95% desorption of Cu(II). And the adsorption capacity of the
RL ¼ ð11Þ nanoparticles could still be maintained N90% after four cycles. After
1 þ K L Co
the copper ions were desorbed, hydrogen ions of EDTA became avail-
able and adhered onto the surface of the sorbent. The important func-
where KL (L mg−1) and C0 (mg/L) represent Langmuir constant and ini-
tional groups on the sorbent, such as NH2 and OH, are protonated,
tial concentration of adsorbate, respectively. Thus, magnitude of RL
leading to less metal binding on the sorbent. Thus, 0.1 mol/L NaOH
value represents the feasibility of adsorption. It was shown in Table 8,
was applied to neutralize the hydrogen ions in the regeneration. The
the values of 0 b RL b 1 suggests the adsorption of Cu(II) by CS/Fe3O4/
amount of copper ions adsorbed and the desorption efficiency in five
ZnO is favorable.
consecutive sorption-desorption cycles using EDTA are presented in
Fig. 15. The desorption efficiency of each cycle is as high as 93.7% to
3.7. Adsorption thermodynamics
97.2%. Besides the high desorption ratio, the sorption and degradation
capacities were barely affected by the number of cycles, implying the
The thermodynamic parameters including Gibbs free energy change
higher possibility of this adsorbent to recover copper ions.
(G°), entropy change (S°) and enthalpy change (H°) for the adsorption
Fig. 15 shows photographs of the CS/Fe3O4/ZnO nanocomposite solu-
of Cu(II) ions using synthesized CS/ZnO/Fe3O4 adsorbent were evalu-
tion with Cu2+ ions before and after magnetic separation using an exter-
ated by the following equations:
nal magnetic field. Nanocomposite could be easily isolated from treated
solution under magnetic field within several seconds. The enough mag-
ΔG∘ ¼ −RT lnK L ð12Þ
netic response of resulting adsorbents meets the demand of fast solid/liq-
uid separation after adsorption equilibrium was achieved.
ΔH ∘ ΔS∘
ln K L ¼ − þ ð13Þ
RT R 3.9. Adsorption mechanism
where R (8.314 J mol−1 K−1) is the gas constant, T (K) is the absolute The EDS spectra of resulting adsorbent with adsorbate was per-
temperature, and KL (Lmol−1) is the Langmuir constant. ΔG, ΔH and formed to verify whether adsorption process occurred or not. As pre-
ΔS are the changes in Gibbs free energy, enthalpy and entropy, respec- sented in Fig. 16, compared with the EDS result of CS/Fe3O4/ZnO, the
tively. After calculating equilibrium constant and related ΔG° at various characteristic elemental peak corresponding to Cu was observed from
temperatures, as represented in Table 9; The values of ΔH° and ΔS° the EDS spectra of Cu(II) loaded nanocomposite. These results indicated
which are slope and intercept of ln KD versus 1/T plot were evaluated. that CS/Fe3O4/ZnO can efficiently adsorb Cu(II). From XPS survey spec-
The negative values of ΔG° confirm the spontaneous nature of the ad- tra of resulting adsorbent with and without adsorbate shown in
sorption of Cu2+ on the CS/Fe3O4/ZnO nanocomposite. Generally, the Fig. 17, new peak with binding energy of 932.0 eV for Cu 2p appeared
change in free energy for physisorption is between −20 and in adsorbent, which indicates that Cu(II) were successfully adsorbed
0 kJ mol−1, but chemisorption is in the range of −80 to −400 by CS/Fe3O4/ZnO adsorbent. To further illustrate the uptake mechanism,
kJ mol−1. The values of ΔG obtained in this study are within the ranges the high resolution XPS spectra of N 1 s and O 1 s of adsorbent before
of the physisorption mechanism. As the temperature of the system in- and after adsorption of target pollutants were also conducted. As
creased, the negativity of ΔG° also increased, and proved that the tem-
perature has a synergistic effect on the favorability. The positive value
of ΔH° indicates that the adsorption reaction is endothermic. The posi-
tive value of ΔS° further confirms that the “disorder” of the system in-
creases as a result of Cu2+adsorption on the surface of CS/Fe3O4/ZnO
nanocomposite.
Results of Cu(II) ions adsorption onto chitosan-based adsorbents re-
ported in the literature are shown in Table 10. It can be seen that the
maximum adsorption capacities of CS/Fe3O4/ZnO for copper ions was
comparable and even higher than that of other chitosan based adsor-
bents except for carboxymethyl chitosan–hemicellulose resin which
may be attributed to the higher specific surface area of the nanocompos-
ite. In addition, the results of different types of adsorbents including nat-
ural material, modified biopolymers, industrial by-products, and
modified biological wastes were compared with CS/Fe3O4/ZnO nano-
composite. The maximum capacity at different operating conditions
for each adsorbent have been presented in Table 11. Based on the re-
ported results, CS/Fe3O4/ZnO showed better performance compared to
other absorbents due to the different advantages such as excellent me- Fig. 17. XPS Cu 2p spectra CS/Fe3O4/ZnO nanocomposite before and after adsorption of Cu
chanical stability, good hydrophilic nature and high surface area. (II).
Fig. 18. XPS a:N 1s b:O 1s spectra of Chitosan/Fe3O4/ZnO before and after adsorption of Cu(II).
Yan et al. [72] Zhang et al. [68]
shown in Fig. 18(a), XPS spectra of O 1 s of nanocomposite before and

after adsorption of Cu(II) ions indicated that the binding energy position
of O 1 s did not show any noticeable change after Cu(II) ion adsorption. Table 12
This result revealed that the coordination between O atoms of –OH and Absorption capacity of Cu2+ on CS/Fe3O4/ZnO nanocomposite in presence of other metal
cations.
Cu(II) ions did not occur in the adsorption process. But the computer
deconvolution XPS spectra of N 1 s shows significant binding energy qm,exp(mg g−1) Removal (%)
shits (Fig. 18(b)). A significant N 1 s binding energy shift from 398.57 Cu 2+
328.46 91.2
to 399.83 eV for amine and a shift from 399.20 to 400.29 eV for amide Pb2+ 310.33 89.9
groups of CS/Fe3O4/ZnO are attributed to a pair of lone electrons from Co2+ 260.73 79.1
Ni2+ 201.38 66.7
the N atom which is shared with the copper ions, and hence the electron
Table 13 3.11. Application of the method for general comparison

Interference study of copper binding to nanocomposite in the presence of Na+, K+, Ca2+,
and Mg2+.
The position of a magnetic material is displayed on a coordinate
Concentration Cu2+ Removal(%) All Cations depicted using normalized Q and M. The purpose of normalization is
Na+ K+ Ca2+ Mg2+ to eliminate the influence of the unit of Q and Ms. The normalized scores
(x') are calculated by using min–max normalization:
0.3 92.20 91.86 92.52 91.89 91.80
3 92.06 91.52 93.05 91.30 90.25
30 91.41 92.34 92.14 92.41 92.14 x‐xmin
x¼ ð14Þ
300 91.10 92.41 91.85 90.86 89.64 xmax ‐xmin
where x is the value of studied index; xmin and xmax are the minimum
cloud density of the N atom is reduced, leading to a higher binding en-
and maximum value of the index, respectively; x′ is the normalized
ergy (BE) peak.
scores of the indexes. The normalized Ms and Q are noted as Ms′ and
Q′. The value of Ms′ or Q′ is in the range of 0 to 1. The best possible sit-
3.10. Effects of coexisting cations uation is when both Ms′ and Q′ are 1, corresponding to MCBs has the
maximum adsorption capacity and magnetic recoverability at the
The effect of metal cations Co2+, Ni2+ and Pb2+on the binding of same time. It is target (1, 1) on the two-dimensional coordinate. For a
copper to CS/Fe3O4/ZnO has been studied in optimum condition and given absorbent (i), the effort-vector(EVi) could be express as:
the results are shown in Table 12. The maximum adsorption capacity
obtained for Cu2+ which was higher than the values found for Pb2+, EV i ¼ ð1; 1Þ− M0s;i ; Q 0i ¼ 1−M0s;i ; 1−Q 0i ð15Þ
Co2+ and Ni2+, showing the following adsorption capacity order:
Cu2+ N Pb 2+ N Co2+ N Ni2+. These data is in agreement with the
study carried out by Vold et al. [87], where CS adsorbed Cu2+ selec- Distance between the coordinate of i and the target is defined as the
tively in the presence of Ni2+, Zn2+, and Cd2+ ions, even though no effort distance(EDi) of i, which can be calculated as:
selectivity was observed for the other ions in the absence of Cu2+. rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2 2
Varma et al. [88] reported that CS derivatives containing nitrogen
EDi ¼ 1−M0s;i þ 1−Q 0i ð16Þ
as heteroatom, presented the order of affinity for divalent metal
ions Cu2+ N Cd 2+ N Ni2+ which agrees with the one observed in
this study. Also, taking into account the high stability constants of The distance shows the improvement room for nanocomposite, and
Cu2+ with ammonia molecules having nitrogen atom, nanocompos- the shorter the distance, the better the performance is. At boundary
ite is expected as a selective chelating resin for Cu2+ over both Co2+ condition, i.e. points located on the x-axis or y-axis, the nanocomposite
and Ni2+. On the other hand, the higher affinity for Cu2+ than that of performance is not favorable because it has poorest adsorption property
Co2+, Ni2+ may be attributed to Jahn–Teller effect which is predom- or magnetization property. The optimal nanocomposite should be lo-
inant for copper complexes [40]. The effect of naturally occurring in- cated as close as possible to (1, 1).
terfering cations ions Na +, K +, Ca 2+ , or Mg2+ on the binding of Effort-vector data visualization was applied to compare nanocom-
copper to nanocomposite was presented in Table 13. that the pres- posite prepared in this work and magnetic materials reported in litera-
ence of all of the coexisting ions has little to no effect on the absorp- tures [30,62,64,89,90]. Effort-vector data of all magnetic materials are
tion of copper to nanocomposite. Even in extremely high amounts of shown in Fig. 19. This method uses the distance of the data point to
cations present in solution the Cu 2+ binding was still above 90%, the target (1, 1), was used to assess the overall performance of MCB.
which indicates a strong affinity of Cu2+ ions to the nanocomposite. The closer the distance, the better the performance is.
Zhang et al.[89]
0.8
Present work
Fan et al.[30]
0.6
Q
Chen and Wang[64] Fan et al.[30]

0.4
0.2
Yan et al.[72]
Zhang et al.[68]
0
0 0.2 0.4 0.6 0.8 1
M s
Fig. 19. Evaluation of the materials for Cu2+ removal with effort-vector data visualization.
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International Journal of Biological Macromolecules 130 (2019) 1025–1045

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

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

Preparation and characterization of poly aniline modiﬁed chitosan

Fig. 1. XRD patterns of a:Fe3O4 b:ZnO c:Chitosan d:CS/ZnO/Fe3O4.

Fig. 2. The FTIR spectra of the chitosan and nanocomposite.

Fig. 4. Magnetic hysteresis loop (M–H) of CS/ZnO/Fe3O4.

Fig. 5. TGA curves of CS and CS/ZnO/Fe3O4 nanocomposite.

Swelling Rao (g/g)

Wt −Wd 2.5. Design of experiments

Source F-value p-Value X

Table 5 presence of Fe, Zn and O composition in the CS–ZnO- Fe3O4 nanocom-

Fig. 7. Predicted vs actual removal efﬁciency.

Fig. 8. Normal residual plot.

Pseudo-ﬁrst-order model Pseudo-second-order model Intra-particle diffusion model

(min−1) (mg/g) (g/mg min) (mg/g) (g mg−1 min0.5)

0.193 208.25 0.956 0.00148 228.95 0.999 k1 k2 k3 1.86 0.976

Fig. 14. Isotherm models for Cu2+ adsorption by CS/Fe3O4/ZnO nanocomposite.

Freundlich model Langmuir model Temkin model D-R model

T (°C) Nanocomposite Type of adsorbent Operating Uptake References

logðqt −qe Þ ¼ logqe −k1 t ð4Þ qt ¼ kid t 0:5 þ C ð6Þ

Adsorbent Adsorption condition qm Isotherm Kinetic Thermodynamic Ref

Raw chitosan 25 °C, pH 5.5 80.17 Langmuir PSOa [61]

sites are occupied, adsorption cannot be achieved on the same sites.

shown in Fig. 18(a), XPS spectra of O 1 s of nanocomposite before and

Table 13 3.11. Application of the method for general comparison

Chen and Wang[64] Fan et al.[30]

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