Chemical Engineering Journal 347 (2018) 574–584

Contents lists available at ScienceDirect

Chemical Engineering Journal

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

Synthesis of Schiff base functionalized superparamagnetic Fe3O4 composites T

for effective removal of Pb(II) and Cd(II) from aqueous solution
⁎
Jianjian Zhao, Yuzhong Niu , Bing Ren, Hou Chen, Shengxiao Zhang, Juan Jin, Yao Zhang
School of Chemistry and Materials Science, Ludong University, Yantai 264025, PR China

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• Schiff-base functionalized magnetic

Fe O composites were synthesized by
3 4
different methods.
• The magnetic composites were pro-
mising adsorbents for the removal of
Pb(II) and Cd(II).
• Kinetic adsorption followed pseudo-
second-order model and dominated by
film diffusion process.
• The adsorption process was sponta-
neous, endothermic, random increase,
and chemical in nature.
• The adsorption mechanism was re-
vealed combined experimental and
theoretical method.

A R T I C LE I N FO A B S T R A C T

Keywords: Schiff-base functionalized superparamagnetic Fe3O4 composites (Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S)

Synthesis were synthesized by homogeneous and heterogeneous method, respectively. Their structures were characterized
Superparamagnetic Fe3O4 composites by FTIR, elemental analysis, SEM, TEM, TGA, XRD, and porous structure analysis. The feasibility of Fe3O4@SiO2-
Schiff base HO-S and Fe3O4@ SiO2-HE-S for the removal of Pb(II) and Cd(II) from aqueous solution was systematically
Adsorption
investigated. The effects of pH, time, temperature, and initial metal ions concentration on the adsorption were
DFT
determined. Results demonstrated that the optimal adsorption pH for both Pb(II) and Cd(II) is 6. Adsorption
kinetic showed that the adsorption equilibrium time for Pb(II) and Cd(II) are 270 and 210 min, respectively.
Adsorption kinetic followed pseudo-second order model and dominated by film diffusion process. Isotherm
adsorption indicated that the adsorption capacity increased with the increase of metal ion concentration and
temperature. The isotherm adsorption process can be well depicted by Langmuir isotherm model.
Thermodynamic parameters indicated that the adsorption process is spontaneous, endothermic, and random-
ness-increasing process. FTIR and DFT calculation demonstrated the interaction between N atom and metal ion
dominated the adsorption of Pb(II) and Cd(II), while O atom also participated in the coordination. Charge
transfer occurred from Schiff base ligand to Pb(II) and Cd(II) during the adsorption process.

1. Introduction during the past few years [1,2]. Among these metal ions, Pb(II) and Cd
(II) are considered to be high toxic due to the non-biodegradability and
With the development of industrialization, water pollution aroused poisonousness to human and living beings [3]. The uptake of Pb(II)
by heavy metal ions had become a serious environmental problem would increase blood pressure and cause damage to the kidneys,

⁎
Corresponding author.
E-mail address: niuyuzhong@126.com (Y. Niu).

https://doi.org/10.1016/j.cej.2018.04.151
Received 3 March 2018; Received in revised form 20 April 2018; Accepted 21 April 2018
Available online 23 April 2018
1385-8947/ © 2018 Elsevier B.V. All rights reserved.
J. Zhao et al.
nervous, and immune system [4]. While Cd(II) could cause renal da-
mage, hypertension, and skeletal malformation [5]. Therefore, it is
essential to remove Pb(II) and Cd(II) from aqueous solution.
Traditional methods including chemical precipitation, electro-
plating, ion exchange, and membrane separation have been adopted for
the treatment of heavy metal ions [4]. Compared with these methods,
absorption is identified as one of the most promising methods due to its
simplicity, high efficiency, and cost-effectiveness [4,6]. Hence, various
adsorbents have been constructed for the remediation of Pb(II) and Cd
(II) pollution [7,8]. Superparamagnetic Fe3O4 has attracted extensive
attention due to its large surface area, high efficiency, low-cost, easy
functionalization and separation [9,10]. Therefore, the design and
synthesis of Fe3O4 based adsorbents still attract enormous interests.
However, naked Fe3O4 particle usually suffers the drawbacks of
poor stability, aggregation and surface oxidation, which limit their
application in metal ion separation and remediation [11,12]. To over-
come these disadvantages, Fe3O4 particles are usually coated with
suitable substances to enhance their stability [13]. Such coating agents
include silica, carbon, graphene oxide, and chitosan, etc. [14–17].
Among them, coating Fe3O4 by silica is widely employed as silica ex-
hibited excellent thermal and chemical stability, well-modified surface
property to construct adsorbents to meet diverse requirements in
practical applications [12,18]. For example, Li et al. synthesized ami-
doxime-functionalized silica coated Fe3O4 (Fe3O4@SiO2) and used for
the removal of U(VI) from aqueous solutions, which exhibited enhanced
adsorption amount compared with bare Fe3O4@SiO2 [19]. Roto et al.
described the introduction of thiol group on the surface of Fe3O4@SiO2
for effective chloroauric ([AuCl4]−) adsorption [20]. Schiff base ligand
that formed by the reaction of amine group with active carbonyl group
bears both nitrogen and oxygen donor atoms, have been proved to have
excellent binding ability for metal ions [21–23]. Thus, the introduction
of Schiff base ligand to the surface of Fe3O4 would combine the virtues
of both components, which provide the feasibility to construct ad-
sorbents with high efficiency. The diversity of amine and carbonyl
compounds enables to construct various Schiff base functionalized
Fe3O4 adsorbents. For example, Yuvaraja et al. reported the synthesis of
superparamagnetic Fe3O4 supported chitosan-4-((pyridin-2-ylimino)
methyl)benzaldehyde Schiff base for the removal of Pb(II) [24]. Mor-
adinasab et al. reported the use of Schiff base modified Fe3O4@SiO2
that formed by salicylaldehyde to remove Cu(II), Zn(II), and Ni(II) [25].
Setoodehkhah et al. synthesized water soluble Schiff base functiona-
lized Fe3O4 nanoparticles by sodium salicylaldehyde-5-sulfonate to re-
move Pb(II) and Cu(II) [26]. The present method adopted for the
synthesis of Schiff base functionalized Fe3O4 composites generally in-
volves two steps reaction with the solid Fe3O4@SiO2, which attributed
to heterogeneous method. The method involves the introduction of
amino group by the reaction of 3-aminopropyltriethoxysilane (APTES)
with Fe3O4@SiO2 and the subsequent reaction of amino group with
active carbonyl compounds [25,26]. As an alternative method, homo-
geneous method allows the reaction of APTES with active carbonyl
compounds first to form Schiff base ligand, and then the resulting Schiff
Scheme 1. Synthesis route of Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S.
575
Chemical Engineering Journal 347 (2018) 574–584
base ligand was anchored on the surface of Fe3O4@SiO2. Homogeneous
method involves one step reaction with solid support, has been proved
to be more efficient for the synthesis of silica gel adsorbents with better
adsorption properties [27,28]. However, little attention has been paid
to the synthesis of Schiff base functionalized Fe3O4 composites by
homogeneous method and the adsorption behavior of the resulting
adsorbents.
In the present study, Schiff base functionalized superparamagnetic
Fe3O4 composites (Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S) were
synthesized by homogeneous and heterogeneous methods, and their
structures were fully characterized. The obtained adsorbents were ap-
plied to remove Pb(II) and Cd(II) from aqueous solution by batch
method. The effects of pH, time, temperature, and initial concentration
on the adsorption of Pb(II) and Cd(II) were investigated systematically.
The adsorption mechanism was revealed on the basis of experimental
and theoretical calculation.
2. Experimental
2.1. Materials and methods
Superparamagnetic Fe3O4 was prepared via co-precipitation method
according to the similar procedure described in the reference [20,29].
Tetraethoxysilane (TEOS), Salicylicaldehyde (SA), and other regents
were analytical grade and purchased from Sinopharm Chemical Re-
agent Co., Ltd. APTES was provided by Qufu Wanda Chemicals Factory.
Toluene need to be distilled before use, while other regents were used
as received.
Fourier Transform Infrared Spectroscopy (FTIR) was performed on a
Nicolet iS50 (Thermo Fisher Scientific). The morphology of the ad-
sorbents was observed on Hitachi S-4800 field emission scanning
electron microscope (SEM) and field emission transmission electron
microscope (TEM, FEI TF 20). Elemental analysis was conducted by
Elementar vario EL cube. Thermogravimetric analysis (TGA) was per-
formed on NETZSCH STA409PC. The wide-angle X-ray diffraction
(XRD) was recorded by Rigaku D/max-2500VPC. Porous structure
analysis was determined by the ASAP 2020 analyzer. The concentration
of metal ion was detected by VARIAN AA240 atomic adsorption spec-
trophotometer (AAS).
2.2. Synthesis of Schiff base functionalized superparamagnetic Fe3O4
composites (Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S)
Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S were prepared according
to the procedures depicted in Scheme 1.
2.2.1. Synthesis of Fe3O4@SiO2
Fe3O4@SiO2 was synthesized according to the similar procedure
described in previous report [13]. 5.0 g Fe3O4 was dispersed in a mix-
ture of 100 mL distilled water and 100 mL ethanol by ultrasonication
for 1 h. The pH of the suspension was adjusted to 10 by ammonia
J. Zhao et al.
Fig. 1. FTIR spectra of Fe3O4 (1), Fe3O4@SiO2 (2), Fe3O4@SiO2-NH2 (3),
Fe3O4@SiO2-HE-S (4), and Fe3O4@SiO2-HO-S (5).
solution, and then 5.0 mL TEOS were added. The mixture was stirred
for 8 h at 60 °C. Finally, Fe3O4@SiO2 was obtained by magnetic se-
paration and soxhlet extraction with anhydrous ethanol for 12 h.
2.2.2. Synthesis of Fe3O4@SiO2-NH2
The amino group was introduced on the surface of Fe3O4@SiO2
using our previous method with suitable modification [18]. Typically, a
suspension of 4.0 g Fe3O4@SiO2 and 5.0 mL APTES was charged into
80 mL toluene under nitrogen atmosphere. The mixture was dispersed
by ultrasonication and stirred at 60 °C for 8 h. Fe3O4@SiO2-NH2 was
obtained after magnetic separation and soxhlet extraction with anhy-
drous ethanol for 12 h.
2.2.3. Synthesis of Fe3O4@SiO2-HE-S
Under nitrogen atmosphere, 5.0 mL SA and 3.0 g Fe3O4@SiO2-NH2
was suspend into 30 mL anhydrous ethanol by ultrasonication. The
mixture was stirred at 70 °C for 8 h, and Fe3O4@SiO2-HE-S was
achieved after magnetic separation and soxhlet extraction by anhydrous
ethanol for 12 h.
2.2.4. Synthesis of Fe3O4@SiO2-HO-S
A mixture of 5.0 mL SA, 7.0 mL APTES, and 70 mL of anhydrous
ethanol was stirred and refluxed for 3 h under nitrogen atmosphere.
Then, 4.0 g Fe3O4@SiO2 and 50 mL toluene were added and dispersed
by ultrasonication. The suspension was stirred for 8 h at 70 °C, and
Fe3O4@SiO2-HO-S was obtained after magnetic separation and extrac-
tion.
2.3. Adsorption performance of Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S
2.3.1. Adsorption kinetic
The adsorption kinetic was carried out using batch method by
charging a series of 20 mg adsorbent into 20 mL−1 Pb(II) or Cd(II) so-
lution (pH = 6, 0.002 mol·L−1 and 0.004 mol·L−1). The mixture was
shaken at 25 °C and the residual concentration of metal ion was mea-
sured at various time intervals by AAS. The adsorption capacity was
calculated by Eq. (1):
(C0−C ) V
q=
W (1)
−1
where q (mmol·g ) is the adsorption amount; C0 and C are the initial
and equilibrium Pb(II) or Cd(II) concentration (mmol·mL−1), respec-
tively; W (g) is the mass of the adsorbent; and V (mL) is the volume of
576
Chemical Engineering Journal 347 (2018) 574–584
the solution.
2.3.2. Effect of pH on the adsorption
The effect of pH on the adsorption was performed by charging
20 mg adsorbent and 20 mL Pb(II) or Cd(II) solution with varying pH
(1.0–6.0) into a series of flasks [4]. The mixture was shaken at 25 °C for
12 h, and the concentration of metal ion was determined. The adsorp-
tion capacity was calculated according to Eq. (1).
2.3.3. Isotherm adsorption
Isotherm adsorption were carried out by mixing 20 mg of adsorbent
with 20 mL−1 Pb(II) or Cd(II) solution with different concentration at
pH 6.0. The mixture was shaken at different temperatures for 12 h.
After that, the concentration of metal ions was determined and the
adsorption capacity was calculated.
2.4. Adsorption mechanism
The adsorption mechanism was investigated combined FTIR and
DFT calculation. DFT calculation was carried out by Gaussian 03 pro-
gram using B3LYP functional [30,31]. The geometries of the complexes
that formed during the adsorption were optimized using the basis set of
6-31+G(d) for C, H, N, O atoms, and LANL2DZ for metal ion. The in-
teraction between adsorbent and metal ion was revealed on the basis of
NBO analysis by DFT calculation at B3LYP/6-311++G (d, p)
(LANL2DZ for metal ions) level [30].
3. Results and discussion
3.1. Characterization of Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S
The FTIR spectra of Fe3O4@SiO2-HO-S, Fe3O4@SiO2-HE-S, and their
intermediate products were shown in Fig. 1. In the spectrum of Fe3O4,
Fe-O exhibited the characteristic vibration absorption peak at
586 cm−1. After the sol-gel reaction with TEOS, the strong absorption
peak appeared at 1096 cm−1 attributed to the stretching vibration of
Si–O–Si, and the absorption peak of hydroxyl group at 3430 cm−1 was
greatly enhanced, demonstrated the successfully coating of Fe3O4 by
silica [12]. For Fe3O4@SiO2-NH2, the new absorption peak presented at
2922 cm−1 and 2850 cm−1 belongs to the asymmetric and symmetry
absorption of CH2 band, indicating the successful introduction of ami-
nopropyl group onto Fe3O4@SiO2. In the spectra of Fe3O4@SiO2-HO-S
and Fe3O4@SiO2-HE-S, the band appeared at 1461 cm−1 attributes to
the aromatic salicylic rings, suggesting Schiff base functional group was
introduced onto the surface of Fe3O4 composites successfully. The ni-
trogen content of Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S determined
by elemental analysis was 1.15% and 0.80%, respectively, which fur-
ther indicated the successful functionalization of Fe3O4@SiO2 with
Schiff base functional group by both homogeneous and heterogeneous
methods. It was observed that the nitrogen content of Fe3O4@SiO2-HO-
S is higher than Fe3O4@SiO2-HE-S, indicating homogeneous method
was more efficient for the attaching of functional group on the surface
of Fe3O4. Similar results were also observed for the modification of
silica gel and other solid matrixs [27,32,33].
The morphology of the adsorbents was detected via SEM and TEM
by selecting Fe3O4@SiO2-HO-S as representative. As shown in Fig. 2a,
Fe3O4@SiO2-HO-S exhibited relatively uniform spherical morphology.
The appearance of agglomeration owes to the superparamagnetic
property of Fe3O4, which is agreed with previous reports [26,34,35].
TEM clearly showed the core-shell structure of Fe3O4@SiO2-HO-S with
an outer side light contrast silica shell and a dark contrast Fe3O4 inner
core, further suggesting the successful functionalized of Fe3O4 with
Schiff base ligand. The lattice fringes of Fe3O4@SiO2-HO-S were dis-
played in Fig. 2c, the lattice fringes spacing of 0.297 and 0.485 nm
corresponding to the (0 0 2) and (1 1 1) planes, respectively [36].
The thermal stability of Fe3O4@SiO2-HO-S, Fe3O4@SiO2-HE-S, and
J. Zhao et al.
Fig. 2. The SEM (a), TEM (b) images and lattice fringes (c) of Fe3O4@SiO2-HO-S.
Fig. 3. TGA curves of Fe3O4 (1), Fe3O4@SiO2 (2), Fe3O4@SiO2-HE-S (3), and
Fe3O4@SiO2-HO-S (4).
intermediates evaluated by TGA was shown in Fig. 3. It can be seen that
Fe3O4 displayed the weight loss of 2.69% in the range of 25–700 °C due
to the loss of physically adsorbed water, which is similar to previous
studies [37,38]. Fe3O4@SiO2, Fe3O4@SiO2-HE-S, and Fe3O4@SiO2-HO-
S also showed the first stage dehydration loss in the range of 25–110 °C
for about 2.04%, 1.65%, and 1.26%, respectively. The second stage
weight loss of Fe3O4@SiO2 from 110 to 700 °C attributed to the loss of
water due to the condensation of silanol groups, while the same weight
loss could also be observed in the range of 110–340 °C for Fe3O4@SiO2-
HE-S and Fe3O4@SiO2-HO-S. An obvious weight loss ascribed to the
decomposition of Schiff base ligand and the condensation of residual
silanol groups appeared from 340 °C to 700 °C for Fe3O4@SiO2-HE-S
and Fe3O4@SiO2-HO-S [18]. The total weight loss of Fe3O4@SiO2-HE-S
and Fe3O4@SiO2-HO-S were 8.57% and 10.21%, further indicating the
content of Schiff base functional group of Fe3O4@SiO2-HO-S was higher
than Fe3O4@SiO2-HE-S, which was in consist with the result of ele-
mental analysis.
XRD is a valuable technique to identify crystal structure of the
materials. XRD patterns of Fe3O4, Fe3O4@SiO2, Fe3O4@SiO2-HO-S, and
Fe3O4@SiO2-HE-S were illustrated in Fig. 4. It is apparent that the XRD
spectrum of Fe3O4 exhibited the characteristic peaks at 2θ values of
30.1°, 35.4°, 43.1°, 53.5°, 57.2°, and 62.7°, which attributed to (2 2 0),
(3 1 1), (4 0 0), (4 2 2), (5 1 1), and (4 4 0) crystal planes, respectively
[39,40]. After functionalization, a relative low peak appeared at about
22° in the XRD spectra of Fe3O4@SiO2, Fe3O4@SiO2-HO-S, and Fe3O4@
SiO2-HE-S, which belonged to the amorphous diffraction peak of silica
[18]. The position of the characteristic peaks of Fe3O4 was not changed
577
Chemical Engineering Journal 347 (2018) 574–584
Fig. 4. XRD patterns of Fe3O4, Fe3O4@SiO2, Fe3O4@SiO2-HO-S, and Fe3O4@
SiO2-HE-S.
after functionalization, indicating the introduction of Schiff base func-
tional group did not affect the crystal structure of Fe3O4. However, the
relative strength of the diffraction peaks became stronger after func-
tionalized as compared with bare Fe3O4 due to the change of the crystal
size during the functionalization.
The porous structure analysis of Fe3O4@SiO2, Fe3O4@SiO2-HO-S,
and Fe3O4@SiO2- HE-S were determined. The nitrogen adsorption-
desorption isotherm curves were shown in Fig. 5 and the porous
parameters were presented in Table 1. It can be seen that the curves of
Fe3O4@SiO2, Fe3O4@SiO2-HO-S, and Fe3O4@SiO2-HE-S displayed ty-
pical IV isotherms. The BET surface area and BJH desorption cumula-
tive volume of Fe3O4@SiO2 were 71.8 m2·g−1 and 0.23 cm3·g−1, re-
spectively. The BET surface area of Fe3O4@SiO2-HO-S and Fe3O4@
SiO2-HE-S were 31.02 and 42.02 m2·g−1, while the cumulative volume
were 0.15 and 0.20 cm3·g−1, respectively. The decrease of surface area
and cumulative volume was mainly attributed to the modification of
Fe3O4@SiO2 with schiff base ligand on the surface and in the pore
channels, which can be proved by the decrease of BJH desorption
average pore radius. The BET surface area, desorption cumulative vo-
lume and desorption average pore radius of Fe3O4@SiO2-HO-S were all
smaller than Fe3O4@SiO2-HE-S, implying more functional groups were
attached on the surface of Fe3O4@SiO2, which were in agreement with
the result of elemental analysis and TGA analysis.
J. Zhao et al. Chemical Engineering Journal 347 (2018) 574–584

correlation coefficient (R22) of pseudo-second-order model are all

higher than the corresponding values of pseudo-first-order model,
suggesting pseudo-second-order model could be well described the
adsorption kinetic process of Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S
for Pb(II) and Cd(II). In addition, the theoretical adsorption capacities
calculated (qe,cal) from pseudo-second-order model are much closer to
the experimental value (qe,exp), further demonstrate the adsorption ki-
netic process can be well described by pseudo-second-order model.
In order to distinguish whether intraparticle diffusion or film dif-
fusion process is the rate controlling step, Boyed film diffusion model
described by Eq. (4) was employed to analyze the kinetic data [45].
∞
6 1
F = 1−
π2
∑ n2
exp[−n2Bt ]
n=1 (4)

where B is time constant, n is the integer that defines the infinite series
solution and F is the equilibrium fractional attainment at time t. F can
be calculated by Eq. (5):
Fig. 5. Nitrogen adsorption–desorption isotherms of Fe3O4@SiO2, Fe3O4@SiO2- qt
HO-S, and Fe3O4@SiO2-HE-S. F=
qe (5)

Table 1 where qe and qt are the equilibrium and the adsorption amount at time t
The parameters of porous structure of Fe3O4@SiO2, Fe3O4@SiO2-HO-S, and (mmol·g−1), respectively.
Fe3O4@SiO2-HE-S. The Bt value can be obtained by the corresponding F value [46]. The
fitting plots of Bt versus t can be used to determine the rate controlling
Adsorbent BET surface BJH desorption BJH desorption
area (m2·g−1) cumulative volume of average pore radius
step. If the fitting curve exhibits good linearity and pass through the
pores (cm3·g−1) (nm) origin, the adsorption is controlled by intraparticle diffusion process.
Otherwise, if the fitting curve do not pass through the origin, film
Fe3O4@SiO2 71.58 0.23 71.87 diffusion process is the rate controlling step [46]. The linear equations
Fe3O4@SiO2- 42.02 0.20 57.67
HE-S
and the corresponding parameters of Bt versus t plots were shown in
Fe3O4@SiO2- 31.02 0.15 33.71 Table 3. It is evident that the lines of the Bt versus t plot exhibited
HO-S excellent linearity and do not pass through the origin, indicating the
adsorption process of Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S for Pb
(II) and Cd(II) was controlled by film diffusion mechanism.
3.2. Adsorption kinetic
3.3. The effect of pH on the adsorption
The adsorption kinetic curves of Fe3O4@SiO2-HO-S and Fe3O4@
SiO2-HE-S for Pb(II) and Cd(II) at different concentration were shown in
The effect of pH on the adsorption of Pb(II) and Cd(II) was shown in
Fig. 6. As can be seen from Fig. 6, the equilibrium adsorption capacity
Fig. 7. It is evident that the adsorption capacity of Fe3O4@SiO2-HO-S
of Fe3O4@SiO2-HO-S for both Pb(II) and Cd(II) are higher than Fe3O4@
and Fe3O4@SiO2-HE-S for Pb(II) and Cd(II) increased with the increase
SiO2-HE-S at different concentration due to higher content of functional
of solution pH, and the maximum adsorption for both ions appeared at
group Fe3O4@SiO2-HO-S possessed. It can also observed that the ad-
pH 6. At low pH, the functional groups of –N] and –OH was proto-
sorption of Pb(II) and Cd(II) was very rapidly in the first 150 min, then
nated due to the presence of H+, the electrostatic repulsion between
the adsorption rate gradually slow down and equilibrium was reached
positively charged functional group and metal ion prevented the con-
at about 270 and 210 min for Pb(II) and Cd(II), respectively. In the
tact of Pb(II) and Cd(II) to coordinate with the adsorbents, resulting in
initial adsorption stage, the rapid adsorption rate attributed to the
the low adsorption capacity [18,47]. With the increase of pH, the
higher concentration of metal ion and abundant available binding sites
concentration of H+ decreased and the protonation of functional group
of the adsorbent, which facilitate the binding of metal ion with ad-
decreased accordingly, leading to the increase of available binding
sorbent. With the adsorption proceeding, both the metal ion con-
sites. Hence, the adsorption capacity increased accordingly. However,
centration and available binding sites were decreased. The decreased
when pH was more than 6, Pb(II) and Cd(II) would be hydrolyzed to
concentration gradient made it difficult for metal ion to diffusion to the
produce hydroxide precipitation [4,48]. Therefore, this condition is
surface of the adsorbent, leading to the decrease of adsorption rate
often not desirable and the optimum adsorption pH is 6 for both Pb(II)
gradually until the equilibrium was reached.
and Cd(II).
The kinetic data were fitted by pseudo-first-order, pseudo-second-
order, and Boyed film diffusion models to reveal the adsorption kinetic
mechanism. The linear forms of pseudo-first-order and pseudo-second- 3.4. Isotherm adsorption
order model can be described as Eqs. (2) and (3) [41–44].
The isotherm adsorption data is very important for describing the
ln(qe−q) = lnqe−k1 t (2) state of adsorption equilibrium, and it provides the basic information
about thermodynamic performance [4]. The isotherm adsorption
t 1 1 curves of Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S for Pb(II) and Cd(II)
= + t
q k2 qe2 qe (3) were showed in Fig. 8. It is clearly shown that the adsorption amount
increased with the increase of initial metal ion concentration and
where qe and q are the equilibrium and instant adsorption amount temperature. The adsorption amount increased with the increase of
(mmol·g−1), k1 (min−1) and k2 (g·mmol−1·min−1) are the rate constant temperature indicated the adsorption process was endothermic process.
of pseudo-first-order and pseudo-second-order model, respectively. The The increased of adsorption capacity associate with initial metal ion
fitting results were listed in Table 2. According to Table 2, The concentration suggested the adsorption favored high concentration due

578
J. Zhao et al. Chemical Engineering Journal 347 (2018) 574–584

Fig. 6. Adsorption kinetic curves of Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S for Pb(II) and Cd(II) at different concentration.

to the larger driving force arise from high concentration gradient. Table 3
In order to reveal the isotherm adsorption mechanism, Langmuir, The linear equations and corresponding parameters of Bt versus t plots.
Freundlich, and Dubinin-Radushkevich (D-R) models were employed to Adsorbent Ion C(mol·L−1) Linear equation Intercept R2
analyze the isotherm adsorption data [18,30]. Langmuir model describe error
single molecular layer adsorption on the uniform surface with a finite
number of identical sites of the adsorbent, the linear equation of Fe3O4@ Cd(II) 0.002 Bt = 0.0082 t + 0.1827 0.0409 0.9768
SiO2- 0.004 Bt = 0.0052 t + 0.0631 0.0158 0.9914
Langmuir model can be described by Eq. (6): HE-S Pb(II) 0.002 Bt = 0.0129 t − 0.4601 0.0529 0.9878
0.004 Bt = 0.0168 t − 0.3820 0.0678 0.9801
Ce C 1
= e + Fe3O4@ Cd(II) 0.002 Bt = 0.0120 t − 0.2722 0.0855 0.9894
qe qm qm KL (6) SiO2- 0.004 Bt = 0.0111 t − 0.3638 0.0844 0.9756
HO-S Pb(II) 0.002 Bt = 0.0173 t − 0.5311 0.1325 0.9892
where Ce (mmol·ml−1) and qe (mmol·g−1) are the equilibrium con- 0.004 Bt = 0.0112 t − 0.1620 0.0601 0.9788
centration of metal ion and adsorption amount, respectively; qm
(mmol·g−1) is the maximum adsorption amount; KL (mL·mmol−1) is the
Langmuir constant.
Freundlich model is used to describe the multilayer adsorption of

Table 2
The fitting parameters of pseudo-first-order and pseudo-second-order model.
Adsorbent Ion C (mol·L−1) qe,exp (mmol·g−1) Pseudo-first-order Pseudo-second-order

qe, cal (mmol·g−1) k1 (min−1) R12 qe,cal (mmol·g−1) k2 (mmol·g−1·min−1) R22

Fe3O4@SiO2-HE-S Cd(II) 0.002 0.18 0.71 0.0382 0.6312 0.17 0.2101 0.9984
0.004 0.21 1.34 0.0378 0.5785 0.21 0.0082 0.9716
Pb(II) 0.002 0.23 1.54 0.0420 0.6420 0.27 0.0874 0.9812
0.004 0.24 2.21 0.0436 0.7574 0.31 0.0347 0.9930

Fe3O4@SiO2-HO-S Cd(II) 0.002 0.24 2.46 0.0381 0.6235 0.33 0.0405 0.9815
0.004 0.33 3.56 0.0413 0.5887 0.40 0.0321 0.9860
Pb(II) 0.002 0.25 0.62 0.0374 0.7128 0.27 0.0903 0.9910
0.004 0.36 3.59 0.0490 0.7139 0.41 0.0562 0.9890

579
J. Zhao et al. Chemical Engineering Journal 347 (2018) 574–584

Fig. 7. The effect of pH on the adsorption of Pb(II) and Cd(II).

non-uniform surfaces, the linear equation of Freundlich model can be
expressed by Eq. (7):
lnCe
lnqe = lnKF +
n (7)
where KF (mmol·g−1) is the Freundlich constant and n is adsorption
intensity index (dimensionless) related to the adsorption intensity.
The fitting parameters of Langmuir and Freundlich models were
listed in Table 4. It can be seen that the correlation coefficient of
Langmuir model (RL2) were all higher than Freundlich model (RF2),
indicating the uptake of Pb(II) and Cd(II) can be well described by
Langmuir model with monolayer adsorption behavior. In addition, the
qm calculated from Langmuir model was much closer to the experi-
mental value, further demonstrate the adsorption process could be well
fitted by Langmuir model. The comparison of qm with other alternative
adsorbents was presented in Table 5. It can be seen that Fe3O4@SiO2-
HO-S and Fe3O4@SiO2-HE-S exhibited relative larger adsorption capa-
city than most of the adsorbents, and could be potentially used as
promising candidates for the separation and preconcentration of Pb(II)
and Cd(II) from aqueous solution.
D-R model was employed to identify whether the adsorption is
physical or chemical in nature [59,60]. The linear equation of D-R

Fig. 8. The isotherm adsorption curves for Pb(II) and Cd(II).

580
J. Zhao et al. Chemical Engineering Journal 347 (2018) 574–584

Table 4
The fitting parameters of Langmuir and Freundlich model.
Adsorbent Ion T (°C) Langmuir Freundlich

−1 −1
qm (mmol·g ) KL (mL·mmol ) RL 2
KF (mmol·g−1) n RF2

Fe3O4@SiO2-HE-S Cd(II) 15 0.33 198.41 0.9949 13.91 1.25 0.9374

25 0.56 210.08 0.9940 27.49 1.11 0.9236
35 0.68 378.79 0.9859 38.41 1.26 0.8799

Fe3O4@SiO2-HE-S Pb(II) 15 0.33 531.90 0.9868 7.610 1.62 0.8952

25 0.47 595.24 0.9890 12.20 1.55 0.9286
35 0.56 606.06 0.9940 12.90 1.60 0.9110

Fe3O4@SiO2-HO-S Cd(II) 15 0.46 121.79 0.9806 15.89 1.28 0.8946

25 0.80 139.04 0.9836 27.34 1.21 0.9085
35 1.18 195.32 0.9847 29.62 1.21 0.9151

Fe3O4@SiO2-HO-S Pb(II) 15 0.84 94.16 0.9921 26.59 1.08 0.8979

25 0.86 115.12 0.9947 42.43 1.20 0.9250
35 1.18 115.58 0.9987 45.34 1.12 0.9063

Table 5 where T (K) is temperature, R is gas constant, and KL is the Langmuir

Comparison of the maximum adsorption capacity with other alternative ad- constant. The calculated thermodynamic parameters were listed in
sorbents. Table 7. It can be seen that the values of ΔG are all negative, indicating
Ion Adsorbent qm References the adsorption process of Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S for
Pb(II) and Cd(II) was spontaneous. In addition, the values of ΔG de-
Pb(II) Fe3O4@SiO2-HO-S 0.86 This study creased with the increase of temperature, implying the adsorption fa-
Fe3O4@SiO2-HE-S 0.47 This study
vored high temperature, which is consistent with the results of the
Multi-walled carbon nanotubes 0.08 [49]
Amino functionalized magnetic graphenes 0.13 [50]
isotherm adsorption. The positive values of ΔH and ΔS indicating that
Fe3O4 microroses 0.22 [51] the adsorption process is endothermic and randomness-increasing
Magnetic porous ferrospinel MnFe2O4 0.33 [52] process. The positive change of entropy can be reasonably interpreted
Amino-functionalized Fe3O4 0.37 [53] by the release of hydration H2O molecules during the adsorption pro-
EDTA modified mesoporous SiO2 0.71 [54]
cess. Due to the solvation effect, Pb(II) and Cd(II) exist in solvation form
Graphene/activated carbon composite 1.05 [55]
with H2O molecules surrounded in aqueous solution before adsorption.
Cd(II) Fe3O4@SiO2-HO-S 0.80 This study
With the adsorption proceeding, Pb(II) and Cd(II) were chelated by the
Fe3O4@SiO2-HE-S 0.56 This study
Magnesium-activated carbon composite 0.09 [56] functional groups of the adsorbents, leading to the release of H2O
Citric acid coated magnetite nanoparticles 0.10 [57] molecules that primarily combined Pb(II) and Cd(II) in the hydration
Mesoporous activated carbon 0.24 [58] shell. Hence, the randomness increased and the entropy change was
Amino functionalized magnetic graphenes 0.25 [50] positive [64].
Magnetic Fe3O4/chitosan nanoparticles 0.32 [38]
L-Arginine modified magnetic Fe3O4 1.07 [48]

3.5. Adsorption mechanism

model can be described by Eqs. (8):

lnqe = lnqm−βε 2
where ε (kJ2·mol−2) is Polanyi potential and can be obtained by ε = RT
ln(1 + 1/Ce), β (mol2·J−2) is the activity coefficient related to the mean
free energy (E, kJ·mol−1) of the adsorption.
The E value can be derived by Eq. (9):
1 groups of Schiff base ligand involved in the adsorption due to the
E=
2β
The E value can be used to determine whether the adsorption is
physical or chemical. If E value falls in the range of 8–16 kJ·mol−1, the
adsorption is chemical adsorption. Or else, if it below 8 kJ·mol−1, it is
physical adsorption. The fitting parameters of D-R model were pre-
sented in Table 6, it clearly shown that the E values at different tem-
peratures were all between 8 and 16 kJ·mol−1, which indicated the
adsorption of Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S for Pb(II) and
Cd(II) was chemical adsorption in nature.
Thermodynamic parameters of the adsorption process including
Gibbs free energy change (ΔG, kJ·mol−1), enthalpy change (ΔH,
kJ·mol−1), and entropy change (ΔS, J·mol−1·K−1) were calculated by
Eqs. (10) and (11): [61–63]:
ΔG = −RT lnKL
lnKL =
ΔS ΔH
− electron configuration of Cd(II) in the complex was 5s0.324d9.996p0.01,
R RT
The adsorption mechanism were investigated combined the FTIR
(8) technique and DFT calculation. The FTIR spectra of Fe3O4@SiO2-HO-S
and Fe3O4@SiO2-HE-S before and after adsorption were illustrated in
Fig. 9. It is evident that the absorption peak at 1402 cm−1 associated
with C]N groups became weaker after adsorption, indicating the in-
volvement of C]N groups for the adsorption process of Pb(II) and Cd
(II). However, FTIR spectra could not confirm whether the hydroxyl
(9) overlap of hydroxyl and silanol group absorption peak at 3430 cm−1.
Therefore, DFT calculation was employed to further reveal the ad-
sorption mechanism. The Schiff base ligand was selected as computa-
tional model to coordinate with Pb(II) and Cd(II). The optimized geo-
metries of the complexes with Pb(II) and Cd(II) were shown in Fig. 10.
Schiff base ligand tends to coordinate with Pb(II) and Cd(II) by nitrogen
and hydroxyl oxygen atoms to form stable chelates. The bond lengths of
N–Pb and N–Cd were 2.217 and 2.166 Å, while those of O–Pb and O–Cd
were 2.308 and 2.219 Å. The nature of the interaction between ligand
and metal ion was further investigated by NBO analysis. The NBO
partial charge of Pb(II) and Cd(II) in the complexes were 1.69 and 1.67,
which was smaller than 2, indicating the existence of charge transfer
from Schiff base ligand to metal ion during the adsorption. Compared
with bare Pb(II), the electron configuration of Pb(II) in the complex was
(10) 6s1.946p0.37, suggesting the electron mainly transfer from Schiff base
ligand to the 6s and 6p empty orbital of Pb(II). As for Cd(II), the
(11) demonstrating the electron transfer from Schiff base ligand to 5s empty

581
J. Zhao et al. Chemical Engineering Journal 347 (2018) 574–584

Table 6
The fitting parameters of D-R model.
Adsorbent Ion T (°C) Linear equation qm (mmol·g−1) k (mol2·J−2) E (kJ·mol−1) R2

Fe3O4@SiO2-HE-S Cd(II) 15 y = −3.02 · 10−9x + 0.17 1.21 3.02 · 10−9 12.81 0.9861
25 y = −4.65 · 10−9x + 0.60 1.83 4.06 · 10−9 11.11 0.9974
35 y = −4.06 · 10−9x + 0.81 2.20 4.25 · 10−9 10.92 0.9986

Fe3O4@SiO2-HE-S Pb(II) 15 y = −3.83 · 10−9x + 0.01 1.02 3.83 · 10−9 11.45 0.9665
25 y = −4.66 · 10−9x + 0.44 1.62 4.66 · 10−9 10.42 0.9280
35 y = −3.74 · 10−9x + 0.53 1.71 3.74 · 10−9 11.67 0.9834

Fe3O4@SiO2-HO-S Cd(II) 15 y = −3.86 · 10−9x + 0.28 1.31 3.86 · 10−9 11.45 0.9867
25 y = −2.20 · 10−9x + 0.64 1.92 4.22 · 10−9 10.93 0.9957
35 y = −3.98 · 10−9x + 0.70 2.01 3.98 · 10−9 11.38 0.9923

Fe3O4@SiO2-HO-S Pb(II) 15 y = −3.67 · 10−9x + 0.78 2.27 3.67 · 10−9 11.68 0.9996
25 y = −3.86 · 10−9x + 0.80 2.29 3.86 · 10−9 11.45 0.9954
35 y = −4.89 · 10−9x + 0.94 2.61 4.89 · 10−9 10.17 0.9967

Table 7 between N atom and Pb(II) dominated the adsorption, while O atom
The thermodynamic parameters of the adsorption. also participate in the coordination. Similar phenomenon was observed
Adsorbent Ion T (°C) ΔG (kJ·mol−1) ΔH (kJ·mol−1) ΔS (J·mol−1·K−1)
in the complex of Cd(II), the E(2) stabilization energies of LP(N) →
LP∗(Pb) and LP(O) → LP∗(Pb) were 47.93 and 10.78 kcal/mol, respec-
Fe3O4@ Cd(II) 15 −11.50 22.11 116.45 tively. It can observed that the E(2) stabilization energies of Pb(II)
SiO2- 25 −12.23 complex were higher than Cd(II) complex, implying the binding ability
HO-S 35 −13.16
of the adsorbent for Pb(II) was stronger than Cd(II), which is consistent
Fe3O4@ Pb(II) 15 −10.89 12.96 82.80 with the experimental results as both Fe3O4@SiO2-HO-S and Fe3O4@
SiO2- 25 −11.76
SiO2-HE-S exhibited relative higher adsorption capacity for Pb(II).
HO-S 35 −11.85
In order to make the DFT calculation more close to the adsorption
Fe3O4@ Cd(II) 15 −12.67 27.35 138.53
process, the coordination geometries of Pb(II) and Cd(II) with two
SiO2- 25 −13.26
HE-S 35 −14.82 Schiff base ligands were optimized and presented in Fig. 11. It is clearly
that the two Schiff base ligands also tend to bind Pb(II) and Cd(II) by
Fe3O4@ Pb(II) 15 −15.04 7.89 79.57
SiO2- 25 −15.84
nitrogen and oxygen atoms to form quadri-coordianted complexes,
HE-S 35 −15.99 which is similar to the complexes formed by single Schiff base ligand.
The bond distances of N–Pb, N–Cd, O–Pb, and O–Cd become longer
than the single Schiff base ligand complexes due to the steric hindrance
caused by the presence of two Schiff base ligands. The NBO partial
charge of Pb(II) and Cd(II) in the complexes were 1.55 and 1.68, and
the electron configuration of Pb(II) and Cd(II) were 6s1.916p0.537p0.01
and 5s0.324d9.985p0.01, respectively. The results further indicated charge
transfer from Schiff base ligand to metal ion occurred during the ad-
sorption. The transferred electron was mainly from Schiff base ligands
to the 6s and 6p empty orbital of Pb(II), and the 5s empty orbital of Cd
(II), which is consistent with the result obtained from the complex of
single Schiff base ligand with Pb(II) and Cd(II).

4. Conclusion

Schiff base functionalized superparamagnetic Fe3O4 composites

Fig. 9. The FTIR spectra of the adsorbents before and after adsorption for Pb(II)
and Cd(II).
orbital of Cd(II) dominate the coordination.
The interaction between donor atom and metal ion was revealed by
second-order perturbation theory analysis of the Fock matrix in NBO
basis, and the corresponding E(2) stabilization energy was employed to
measure the donor-acceptor interaction [30,65]. For the complex of Pb
(II), σ donation of lone pair electrons of N and O to unoccupied orbital
of Pb(II) was responsible for the interaction. The E(2) stabilization
energies of LP(N) → LP∗(Pb) and LP(O) → LP∗(Pb) were 54.49 and
16.94 kcal/mol, respectively. The results demonstrated the interaction
(Fe3O4@SiO2-HO-S and Fe3O4@SiO2-HE-S) have been synthesized by
homogeneous and heterogeneous method, respectively. Their structures
were characterized by FTIR, elemental analysis, SEM, TEM, TGA, XRD,
and porous structure analysis. FTIR spectra indicated Fe3O4@SiO2-HO-
S and Fe3O4@SiO2-HE-S were successfully synthesized. Elemental
analysis and TGA implied the content of functional group of Fe3O4@
SiO2-HO-S was higher than Fe3O4@SiO2-HE-S. SEM and TEM revealed
that the composites exhibited typical core-shell structure with relatively
uniform spherical shape. XRD spectroscopy indicated the coating of the
silica and further functionalization did not affect the crystal structure of
Fe3O4. The adsorption experiments demonstrated the optimal adsorp-
tion pH for Pb(II) and Cd(II) was 6. Adsorption kinetic followed pseudo-
second-order model and dominated by film diffusion process. Isotherm
adsorption indicated that the adsorption capacity increased with the
increase of metal ion concentration and temperature. The isotherm
adsorption process can be well depicted by Langmuir model and pro-
ceed chemically. Thermodynamic parameters indicated that the ad-
sorption process was spontaneous, endothermic, and randomness-in-
creasing process. FTIR and DFT calculation demonstrated the

582
J. Zhao et al.
Fig. 10. Optimized geometries of Schiff base ligand with Pb(II) and Cd(II) complexes.
Fig. 11. Optimized geometries of Pb(II) and Cd(II) complexes with two Schiff base ligands.
interaction of N atom with Pb(II) and Cd(II) dominated the adsorption,
while O atom also participate the coordination. Charge transfer oc-
curred from Schiff base ligand to Pb(II) and Cd(II) during the adsorp-
tion.
Acknowledgements
The authors are grateful for the financial support by the National
Natural Science Foundation of China (No. 21307053), A Project of
Shandong Province Higher Educational Science and Technology
Program (No. J15LD01), Natural Science Foundation of Shandong
Province (Nos. ZR2018MB039, ZR2017PB006), Science and
Technology Research Program of Yantai (2017ZH060), Innovation
Foundation for Students of Ludong University (Nos. ld17l042,
ld17l044).
References
[1] L. Ma, Q. Wang, S.M. Islam, Y. Liu, S. Ma, M.G. Kanatzidis, Highly selective and
efficient removal of heavy metals by layered double hydroxide intercalated with the
MoS42− ion, J. Am. Chem. Soc. 138 (2016) 2858–2866.
[2] L.L. Ling, W.J. Liu, S. Zhang, H. Jiang, Magnesium oxide embedded nitrogen self-
doped biochar composites: fast and high-efficiency adsorption of heavy metals in an
aqueous solution, Environ. Sci. Technol. 51 (2017) 10081–10089.
[3] J. Liang, X.M. Li, Z.G. Yu, G.M. Zeng, Y. Luo, L.B. Jiang, Z.X. Yang, Y.Y. Qian,
H.P. Wu, Amorphous MnO2 modified biochar derived from aerobically composted
swine manure for adsorption of Pb(II) and Cd(II), ACS Sustainable Chem. Eng. 5
(2017) 5049–5058.
[4] Y. Niu, R. Qu, C. Sun, C. Wang, H. Chen, C. Ji, Y. Zhang, X. Shao, F. Bu, Adsorption
of Pb(II) from aqueous solution by silica-gel supported hyperbranched poly-
amidoamine dendrimers, J. Hazard. Mater. 244–245 (2013) 276–286.
[5] Y. Shen, H. Li, W. Zhu, S.H. Ho, W. Yuan, J. Chen, Y. Xie, Microalgal-biochar im-
mobilized complex: a novel efficient biosorbent for cadmium removal from aqueous
solution, Bioresour. Technol. 244 (2017) 1031–1038.
[6] N. Bordoloi, R. Goswami, M. Kumar, R. Kataki, Biosorption of Co (II) from aqueous
solution using algal biochar: kinetics and isotherm studies, Bioresour. Technol. 244
(2017) 1465–1469.
[7] H. Wang, X. Wang, J. Ma, P. Xia, J. Zhao, Removal of cadmium (II) from aqueous
solution: a comparative study of raw attapulgite clay and a reusable waste–struvite/
583
Chemical Engineering Journal 347 (2018) 574–584
attapulgite obtained from nutrient-rich wastewater, J. Hazard. Mater. 329 (2017)
66–76.
[8] J. Ma, F. Li, T. Qian, H. Liu, W. Liu, D. Zhao, Natural organic matter resistant
powder activated charcoal supported titanate nanotubes for adsorption of Pb(II),
Chem. Eng. J. 315 (2017) 191–200.
[9] X. Qiu, N. Li, S. Yang, D. Chen, Q. Xu, H. Li, J. Lu, A new magnetic nanocomposite
for selective detection and removal of trace copper ions from water, J. Mater. Chem.
A 3 (2015) 1265–1271.
[10] S. Zhang, Y. Zhang, J. Liu, Q. Xu, H. Xiao, X. Wang, H. Xu, J. Zhou, Thiol modified
Fe3O4@SiO2 as a robust, high effective, and recycling magnetic sorbent for mercury
removal, Chem. Eng. J. 226 (2013) 30–38.
[11] J. Zhao, Z. Lu, X. He, X. Zhang, Q. Li, T. Xia, W. Zhang, C. Lu, Fabrication and
characterization of highly porous Fe(OH)3@cellulose hybrid fibers for effective
removal of congo red from contaminated water, ACS Sustainable Chem. Eng. 5
(2017) 7723–7732.
[12] R. Yi, G. Ye, D. Pan, F. Wu, M. Wen, J. Chen, Novel core-shell structured super-
paramagnetic microspheres decorated with macrocyclic host molecules for specific
recognition and magnetic removal of Pb(II), J. Mater. Chem. A 2 (2014)
6840–6846.
[13] M.S. Moorthy, D.J. Seo, H.J. Song, S.S. Park, C.S. Ha, Magnetic mesoporous silica
hybrid nanoparticles for highly selective boron adsorption, J. Mater. Chem. A 1
(2013) 12485–12496.
[14] M. Cheng, Z.K. Wang, Q. Lv, C.L. Li, S.Q. Sun, S.Q. Hu, Preparation of amino-
functionalized Fe3O4@mSiO2 core-shell magnetic nanoparticles and their applica-
tion for aqueous Fe3+ removal, J. Hazard. Mater. 341 (2018) 198–206.
[15] D.L. Zhao, X. Gao, C.N. Wu, R. Xie, S.J. Feng, C.L. Chen, Facile preparation of amino
functionalized graphene oxide decorated with Fe3O4 nanoparticles for the adsorp-
tion of Cr(VI), Appl. Surf. Sci. 384 (2016) 1–9.
[16] M.A. Habila, Z.A. Alothman, A.M. El-Toni, S.A. Al-Tamrah, M. Soylak, J.P. Labis,
Carbon-coated Fe3O4 nanoparticles with surface amido groups for magnetic solid
phase extraction of Cr(III), Co(II), Cd(II), Zn(II) and Pb(II) prior to their quantita-
tion by ICP-MS, Microchim. Acta 184 (2017) 2645–2651.
[17] D.L. Kong, N. Wang, N. Qiao, Q. Wang, Z. Wang, Z.Y. Zhou, Z.Q. Ren, Facile pre-
paration of ion-imprinted chitosan microspheres enwrapping Fe3O4 and graphene
oxide by inverse suspension cross-linking for highly selective removal of copper(II),
ACS Sustainable Chem. Eng. 5 (2017) 7401–7409.
[18] Y. Niu, R. Qu, H. Chen, L. Mu, X. Liu, T. Wang, Y. Zhang, C. Sun, Synthesis of silica
gel supported salicylaldehyde modified PAMAM dendrimers for the effective re-
moval of Hg(II) from aqueous solution, J. Hazard. Mater. 278 (2014) 267–278.
[19] Y. Zhao, J. Li, L. Zhao, S. Zhang, Y. Huang, X. Wu, X. Wang, Synthesis of ami-
doxime-functionalized Fe3O4@SiO2 core–shell magnetic microspheres for highly
efficient sorption of U(VI), Chem. Eng. J. 235 (2014) 275–283.
[20] R. Roto, Y. Yusran, A. Kuncaka, Magnetic adsorbent of Fe3O4@SiO2 core-shell na-
noparticles modified with thiol group for chloroauric ion adsorption, Appl. Surf. Sci.
377 (2016) 30–36.
J. Zhao et al.
[21] P. Kaur, R. Singh, V. Kaur, D. Talwar, Reusable Schiff base functionalized silica as a
multi-purpose nanoprobe for fluorogenic recognition, quantification and extraction
of Zn2+ ions, Sens. Actuators, B 254 (2018) 533–541.
[22] M. Monier, D.A. Abdel-Latif, Y.G. Abou El-Reash, Ion-imprinted modified chitosan
resin for selective removal of Pd(II) ions, J. Colloid Interface Sci. 469 (2016)
344–354.
[23] M.R. Awual, G.E. Eldesoky, T. Yaita, M. Naushad, H. Shiwaku, Z.A. AlOthman,
S. Suzuki, Schiff based ligand containing nano-composite adsorbent for optical
copper(II) ions removal from aqueous solutions, Chem. Eng. J. 279 (2015) 639–647.
[24] Y. Gutha, V.S. Munagapati, Removal of Pb(II) ions by using magnetic chitosan-4-
((pyridin-2-ylimino)methyl)benzaldehyde Schiff’s base, Int. J. Biol. Macromol. 93
(2016) 408–417.
[25] M.B. Sheida Moradinasab, Removal of heavy metals from aqueous solution using
Fe3O4 nanoparticles coated with Schiff base ligand, Desalin. Water Treat. 57 (2016)
4028–4036.
[26] M. Setoodehkhah, S. Momeni, Water soluble Schiff Base functinalized Fe3O4 mag-
netic nano-particles as a novel adsorbent for the removal of Pb(II) and Cu(II) metal
ions from aqueous solutions, J. Inorg. Organomet. Polym Mater. 28 (2018)
1098–1106.
[27] Y. Niu, H. Liu, R. Qu, S. Liang, H. Chen, C. Sun, Y. Cui, Preparation and char-
acterization of thiourea-containing silica gel hybrid materials for Hg(II) adsorption,
Ind. Eng. Chem. Res. 54 (2015) 1656–1664.
[28] D. Pérez-Quintanilla, I.D. Hierro, M. Fajardo, I. Sierra, 2-Mercaptothiazoline mod-
ified mesoporous silica for mercury removal from aqueous media, J. Hazard. Mater.
134 (2006) 245–256.
[29] M. Zhu, W. Zhang, Y. Li, L. Gai, J. Zhou, W. Ma, Multishell structured magnetic
nanocomposites carrying a copolymer of pyrrole-thiophene for highly selective Au
(III) recovery, J. Mater. Chem. A 4 (2016) 19060–19069.
[30] X. Song, Y. Niu, P. Zhang, C. Zhang, Z. Zhang, Y. Zhu, R. Qu, Removal of Co(II) from
fuel ethanol by silica-gel supported PAMAM dendrimers: combined experimental
and theoretical study, Fuel 199 (2017) 91–101.
[31] A.Y. Mehandzhiyski, E. Riccardi, T.S. van Erp, H. Koch, P.O. Åstrand, T.T. Trinh,
B.A. Grimes, Density functional theory study on the interactions of metal ions with
long chain deprotonated carboxylic acids, J. Phys. Chem. A 119 (2015)
10195–10203.
[32] W.L. Sun, J. Xia, Y.C. Shan, Comparison kinetics studies of Cu(II) adsorption by
multi-walled carbon nanotubes in homo and heterogeneous systems: effect of nano-
SiO2, Chem. Eng. J. 250 (2014) 119–127.
[33] Y. Zhang, R. Qu, C. Sun, H. Chen, C. Wang, C. Ji, P. Yin, Y. Sun, H. Zhang, Y. Niu,
Comparison of synthesis of chelating resin silica-gel-supported diethylenetriamine
and its removal properties for transition metal ions, J. Hazard. Mater. 163 (2009)
127–135.
[34] Y. Liu, R. Fu, Y. Sun, X. Zhou, S.A. Baig, X. Xu, Multifunctional nanocomposites
Fe3O4@SiO2-EDTA for Pb(II) and Cu(II) removal from aqueous solutions, Appl.
Surf. Sci. 369 (2016) 267–276.
[35] M.E. Mahmoud, M.F. Amira, A.A. Zaghloul, G.A.A. Ibrahim, Microwave-enforced
sorption of heavy metals from aqueous solutions on the surface of magnetic iron
oxide-functionalized-3-aminopropyltriethoxysilane, Chem. Eng. J. 293 (2016)
200–206.
[36] C. Li, Y. Wei, A. Liivat, Y. Zhu, J. Zhu, Microwave-solvothermal synthesis of Fe3O4
magnetic nanoparticles, Mater. Lett. 107 (2013) 23–26.
[37] X. Wan, Y. Zhan, Z. Long, G. Zeng, Y. Ren, Y. He, High-performance magnetic poly
(arylene ether nitrile) nanocomposites: co-modification of Fe3O4 via mussel in-
spired poly(dopamine) and amino functionalized silane KH550, Appl. Surf. Sci. 425
(2017) 905–914.
[38] H.L. Fan, S.F. Zhou, W.Z. Jiao, G.S. Qi, Y.Z. Liu, Removal of heavy metal ions by
magnetic chitosan nanoparticles prepared continuously via high-gravity reactive
precipitation method, Carbohydr. Polym. 174 (2017) 1192–1200.
[39] X.L. Wu, L. Wang, C.L. Chen, A.W. Xu, X.K. Wang, Water-dispersible magnetite-
graphene-LDH composites for efficient arsenate removal, J. Mater. Chem. 21 (2011)
17353–17359.
[40] L. Zhou, G. Zhang, J. Tian, D. Wang, D. Cai, Z. Wu, Functionalized Fe3O4@C na-
nospheres with adjustable structure for efficient hexavalent chromium removal,
ACS Sustainable Chem. Eng. 5 (2017) 11042–11050.
[41] Y.S. Ho, Second-order kinetic model for the sorption of cadmium onto tree fern: a
comparison of linear and non-linear methods, Water Res. 40 (2006) 119–125.
[42] Y.S. Ho, G. McKay, Sorption of dye from aqueous solution by peat, Chem. Eng. J. 70
(1998) 115–124.
[43] Y.S. Ho, G. McKay, Kinetic models for the sorption of dye from aqueous solution by
wood, Process Saf. Environ. Prot. 76 (1998) 183–191.
[44] X. Song, Y. Niu, Z. Qiu, Z. Zhang, Y. Zhou, J. Zhao, H. Chen, Adsorption of Hg(II)
584
Chemical Engineering Journal 347 (2018) 574–584
and Ag(I) from fuel ethanol by silica gel supported sulfur-containing PAMAM
dendrimers: kinetics, equilibrium and thermodynamics, Fuel 206 (2017) 80–88.
[45] G.E. Boyd, A.W. Adamson, L.S. Myers, The exchange adsorption of ions from aqu-
eous solutions by organic zeolites. II. Kinetics, J. Am. Chem. Soc. 69 (1947)
2836–2848.
[46] D. Reichenberg, Properties of ion-exchange resins in relation to their structure. III.
Kinetics of exchange, J. Am. Chem. Soc. 75 (1953) 589–597.
[47] H.T. Fan, J.X. Liu, H. Yao, Z.G. Zhang, F. Yan, W.X. Li, Ionic imprinted silica-sup-
ported hybrid sorbent with an anchored chelating Schiff base for selective removal
of cadmium(II) ions from aqueous media, Ind. Eng. Chem. Res. 53 (2014) 369–378.
[48] S. Guo, P. Jiao, Z. Dan, N. Duan, G. Chen, J. Zhang, Preparation of L-arginine
modified magnetic adsorbent by one-step method for removal of Zn(II) and Cd(II)
from aqueous solution, Chem. Eng. J. 317 (2017) 999–1011.
[49] X. Ren, D. Shao, S. Yang, J. Hu, G. Sheng, X. Tan, X. Wang, Comparative study of Pb
(II) sorption on XC-72 carbon and multi-walled carbon nanotubes from aqueous
solutions, Chem. Eng. J. 170 (2011) 170–177.
[50] X. Guo, B. Du, Q. Wei, J. Yang, L. Hu, L. Yan, W. Xu, Synthesis of amino functio-
nalized magnetic graphenes composite material and its application to remove Cr
(VI), Pb(II), Hg(II), Cd(II) and Ni(II) from contaminated water, J. Hazard. Mater.
278 (2014) 211–220.
[51] L. Han, Y. Wei, Low-temperature synthesis of Fe3O4 microroses and their applica-
tion in water treatment, Mater. Lett. 70 (2012) 1–3.
[52] Y. Ren, N. Li, J. Feng, T. Luan, Q. Wen, Z. Li, M. Zhang, Adsorption of Pb(II) and Cu
(II) from aqueous solution on magnetic porous ferrospinel MnFe2O4, J. Colloid
Interface Sci. 367 (2012) 415–421.
[53] J. Wang, S. Zheng, Y. Shao, J. Liu, Z. Xu, D. Zhu, Amino-functionalized Fe3O4@SiO2
core–shell magnetic nanomaterial as a novel adsorbent for aqueous heavy metals
removal, J. Colloid Interface Sci. 349 (2010) 293–299.
[54] Y. Liu, Z. Lou, Y. Sun, X. Zhou, S.A. Baig, X. Xu, Influence of complexing agent on
the removal of Pb(II) from aqueous solutions by modified mesoporous SiO2,
Microporous Mesoporous Mater. 246 (2017) 1–13.
[55] N. Saeidi, M. Parvini, Z. Niavarani, High surface area and mesoporous graphene/
activated carbon composite for adsorption of Pb(II) from wastewater, J. Environ.
Chem. Eng. 3 (2015) 2697–2706.
[56] H. Yanagisawa, Y. Matsumoto, M. Machida, Adsorption of Zn(II) and Cd(II) ions
onto magnesium and activated carbon composite in aqueous solution, Appl. Surf.
Sci. 256 (2010) 1619–1623.
[57] D. Singh, R.K. Gautam, R. Kumar, B.K. Shukla, V. Shankar, V. Krishna, Citric acid
coated magnetic nanoparticles: synthesis, characterization and application in re-
moval of Cd(II) ions from aqueous solution, J. Water Process Eng. 4 (2014)
233–241.
[58] E. Asuquo, A. Martin, P. Nzerem, F. Siperstein, X. Fan, Adsorption of Cd(II) and Pb
(II) ions from aqueous solutions using mesoporous activated carbon adsorbent:
equilibrium, kinetics and characterisation studies, J. Environ. Chem. Eng. 5 (2017)
679–698.
[59] A. Kayvani Fard, G. McKay, Y. Manawi, Z. Malaibari, M.A. Hussien, Outstanding
adsorption performance of high aspect ratio and super-hydrophobic carbon nano-
tubes for oil removal, Chemosphere 164 (2016) 142–155.
[60] M. Jahandar Lashaki, M. Fayaz, S. Niknaddaf, Z. Hashisho, Effect of the adsorbate
kinetic diameter on the accuracy of the Dubinin-Radushkevich equation for mod-
eling adsorption of organic vapors on activated carbon, J. Hazard. Mater. 241–242
(2012) 154–163.
[61] S. Yuan, J. Gu, Y. Zheng, W. Jiang, B. Liang, S.O. Pehkonen, Purification of phenol-
contaminated water by adsorption with quaternized poly(dimethylaminopropyl
methacrylamide)-grafted PVBC microspheres, J. Mater. Chem. A 3 (2015)
4620–4636.
[62] Y. Zou, X. Wang, Y. Ai, Y. Liu, Y. Ji, H. Wang, T. Hayat, A. Alsaedi, W. Hu, X. Wang,
β-Cyclodextrin modified graphitic carbon nitride for the removal of pollutants from
aqueous solution: experimental and theoretical calculation study, J. Mater. Chem. A
4 (2016) 14170–14179.
[63] X. Li, W.C. Cao, Y.G. Liu, G.M. Zeng, W. Zeng, L. Qin, T.T. Li, Property variation of
magnetic mesoporous carbon modified by aminated hollow magnetic nanospheres:
synthesis, characterization, and sorption, ACS Sustainable Chem. Eng. 5 (2017)
179–188.
[64] B. Gao, Y. Gao, Y. Li, Preparation and chelation adsorption property of composite
chelating material poly(amidoxime)/SiO2 towards heavy metal ions, Chem. Eng. J.
158 (2010) 542–549.
[65] G. Yuan, Y. Tian, J. Liu, H. Tu, J. Liao, J. Yang, Y. Yang, D. Wang, N. Liu, Schiff base
anchored on metal-organic framework for Co (II) removal from aqueous solution,
Chem. Eng. J. 326 (2017) 691–699.