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Synthesis and application of TiO2/SiO2/Fe3O4 nanoparticles as novel

adsorbent for removal of Cd(II), Hg(II) and Ni(II) ions from water samples

Article  in  Clean Technologies and Environmental Policy · June 2017

DOI: 10.1007/s10098-017-1374-5

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Clean Techn Environ Policy
DOI 10.1007/s10098-017-1374-5

ORIGINAL PAPER

Synthesis and application of TiO2/SiO2/Fe3O4 nanoparticles

as novel adsorbent for removal of Cd(II), Hg(II) and Ni(II) ions
from water samples
Soheil Sobhanardakani1 • Raziyeh Zandipak2

Received: 16 March 2016 / Accepted: 25 May 2017

 Springer-Verlag Berlin Heidelberg 2017

Abstract In the current study, SiO2/Fe3O4 core–shell Introduction

nanoparticles functionalized with TiO2, using a simple
method and application for removal of Cd(II), Hg(II) and Among environmental pollutants, heavy metals are con-
Ni(II) ions from aqueous solution. The structure of the sidered to be the most important that cause major public-
resulting product was confirmed by X-ray diffraction health concerns owing to their high stability and bioaccu-
spectrometry, transmission electron microscopy (TEM), mulation (Du et al. 2016; Wu et al. 2016). Heavy metals
pHpzc and Brunauer, Emmett and Teller methods. The are discharged into aquatic environments from various
average diameter of TiO2/SiO2/Fe3O4 nanoparticles sources including urbanism, mining, agriculture, industrials
according to TEM was obtained around 48 nm. In batch and electronics plating (Boparai et al. 2011; Ghasemi et al.
tests, the effects of pH, initial metal concentration, contact 2015). Toxic heavy metal (e.g., Cd, Cr, Hg and Pb) ions
time and temperature were studied. Adsorption of metal have serious adverse health effects to human health in even
ions was studied from both kinetics and equilibrium point very low concentrations. Exposure to the low amounts of
of view. Maximum adsorption capacity of Cd(II), Hg(II) these elements can cause harmful effects on the central
and Ni(II) on TiO2/SiO2/Fe3O4 nanoparticles was 670.9, nervous system, kidney, skin, teeth, liver or lung. However,
745.6 and 563.0 mg g-1, respectively. Adsorption–des- long-term exposure to high levels of them may even lead to
orption results showed that the reusability of nanoparticles death (Zhang et al. 2013; Shan et al. 2015; Zeng et al.
was encouraging. This adsorbent was successfully applied 2015). Cadmium, Hg and Ni are known as toxic heavy
to removal Cd(II), Hg(II) and Ni(II) ions in real samples metals. In this regard, the maximum limit (mg L-1)
including tap water, electronic wastewater and medical established by USEPA for Cd, Hg and Ni in drinking water
wastewater. was 0.003, 0.001 and 0.10 mg L-1, respectively, and for
wastewater was 0.01, 0.005 and 0.10, respectively (Sob-
Keywords Heavy metal ions  TiO2/SiO2/Fe3O4 hanardakani and Zandipak 2015).
nanoparticles  Adsorption efficiency  Isotherm Nowadays, the conventional techniques used for heavy
metal removal from aqueous solutions are precipitation,
membrane filtration, ion exchange, reverse osmosis, elec-
trochemical reduction, ultrafiltration, ionization and
adsorption. Many of these methods are expensive, exhibit
average removal efficiency and are performed in sequential
steps (Al-Zoubi et al. 2015; Guo et al. 2014; Zandipak and
& Soheil Sobhanardakani Sobhanardakani 2016). Adsorption is generally considered
[email protected]
to be one of the most frequently used and promising
1
Department of the Environment, College of Basic Sciences, techniques due to its low cost, easy operation, high effi-
Hamedan Branch, Islamic Azad University, Hamedan, Iran ciency, simplicity of the equipment and easy regeneration
2
Young Researchers and Elite Club, Hamedan Branch, Islamic (Sobhanardakani et al. 2013a, b).
Azad University, Hamedan, Iran

123
 S. Sobhanardakani, R. Zandipak

In recent years, great attention has been devoted to the Materials and methods
application of nano-structure materials in analytical chem-
istry, especially magnetic nanoparticles (Sobhanardakani Apparatus and reagents
et al. 2014). Magnetic nanoparticles (MNPs) with the general
formula MFe2O4 (M = Fe, Co, Cu, Mn, etc.) such as mag- All reagents were analytical reagent grade or the highest
netite (Fe3O4) and maghemite (c-Fe2O3) are a special kind of purity purchased from Merck (Darmstadt, Germany).
nano-sized materials which used in the fields of biotech- Double-distilled water (ddH2O) was used throughout the
nology and biomedicine and as an efficient adsorbent. Fe3O4 study. Stock solutions of Cd(II), Hg(II) and Ni(II)
nanoparticles with magnetic property, high surface area and (1000 mg L–1) were prepared by dissolving appropriate
large adsorption capacity have been developed to remove amount of Cd(NO3)24H2O, Hg(NO3)26H2O and
heavy metals from aqueous solutions, which can be easily Ni(NO3)26H2O in ddH2O. Metal solutions of different
separated and recycled via an external magnetic field initial concentrations were prepared by dilution of
(Afkhami and Moosavi 2010). However, bare Fe3O4 1000 mg L–1.
nanoparticles are easily oxidized in air and corroded in acidic The concentration of metal ions was determined by
environment and also prone to aggregation via magnetic inductively coupled plasma optical emission spectrometry
force. As a result, the magnetic property and adsorption (ICP-OES) (JY138 ultrace, France). All pH measurements
capacity will be significantly reduced. Thus, surface pro- were taken with a 780 pH meter (Metrohm, Switzerland)
tection and modification of Fe3O4 nanoparticles are required combined with a glace-calomel electrode. The crystal
to inhibit the aggregation, which will also endow the structure of synthesized materials was determined by an
nanoparticles with high dispersity, antioxidant ability and XRD [38066 Riva, d/G.Via M. Misone, 11/D (TN) Italy] at
acid/alkali resistance. Silica has been known to be one of the ambient temperature. The structure of the nanoparticles
most ideal shell materials due to its reliable chemical sta- was characterized by TEM (Philips, CM10, 100 kV).
bility, biocompatibility and facile surface modification. Specific surface area and porosity were defined by N2
Hence, silica-coated Fe3O4 nanoparticles could be used for adsorption–desorption porosimetry (77 K) using a
rapid separation (Wang et al. 2010; Lai et al. 2016). porosimeter (BEL Japan, Inc.).
Additionally, in order to improve the adsorption
capacity and selectivity of silica-coated magnetic Preparation of magnetite nanoparticles (Fe3O4)
nanoparticles for removal of heavy metal ions, surface
modification with new functional groups, such as ferric The magnetite nanoparticles were prepared by the con-
oxides, aluminum oxides, titanium oxides and cerium ventional co-precipitation method with minor modifica-
oxides, has been widely investigated. Among various metal tions. In this method, ultrasonic vibration by an ultrasonic
oxides, titanium dioxide (TiO2) for favorable characteris- bath was used instead of magnetic stirring. For this pur-
tics such as high surface area, biological and chemical pose, 11.68 and 4.30 g of FeCl36H2O and FeCl24H2O,
inertness, high adsorption capacity, photoreactivity and respectively, were dissolved in 200 mL ddH2O under
low toxicity is suitable for high removal inorganic and nitrogen gas in an ultrasonic bath at 85 C for a few min
organic pollutants (Sun et al. 2015; Wei et al. 2016). which led to smaller and more homogenized particles.
In this study, silica-coated magnetic nanoparticles Then, 20 mL of 27% NH3 was added to the solution. The
functionalized with TiO2 (TiO2/SiO2/Fe3O4) were synthe- color of bulk solution changed from orange to black
sized for the first time as a novel adsorbent for the removal immediately. The magnetite precipitates were washed
of Cd(II), Hg(II) and Ni(II) ions from contaminated real twice with ddH2O and once with 0.02 mol L-1 sodium
water samples by two steps. First, the SiO2/Fe3O4 chloride and were separated from solution with a magnet
nanoparticles were synthesized using Fe3O4 as the core and (Sobhanardakani and Zandipak 2015).
tetraethoxysilane (TEOS) as silica source. In the second
step, the anatase TiO2 was coated on the SiO2/Fe3O4 Preparation of silica-coated magnetite nanoparticles
nanoparticles surface using tetrabutyl titanate (TBOT) as (SiO2/Fe3O4)
titanium source. For this purpose, SiO2 was used to stabi-
lize the Fe3O4 nanoparticles and inhibit their aggregation, 0.5 g of obtained MNPs was dispersed into the mixture of
while the TiO2 group was applied to functionalize the 100 mL of ethanol, 20 mL of ddH2O, and 1.0 mL of
SiO2/Fe3O4 nanoparticles so as to obtain selective and concentrated ammonia aqueous solution (28 wt%). After
rapid metal adsorption. Also, the effects of pH and tem- this, the mixture solution was homogenized by ultrasoni-
perature on the adsorption efficiency were studied. Finally, cation for 30 min to form a uniform dispersion. Subse-
kinetic and isotherm of adsorption were evaluated. quently, 0.4 mL of TEOS was added dropwise into the

123
Synthesis and application of TiO2/SiO2/Fe3O4 nanoparticles as novel adsorbent for removal of…

solution with vigorous stirring. After stirred at room tem- final pH was measured after 24 h. The pHpzc is the point
perature for 6 h, the silica-coated magnetite was separated where the pHinitial = pHfinal.
with a permanent magnet, washed 3 times with ddH2O and
dried for 12 h in vacuum at 50 C. Equilibrium adsorption studies

Preparation of TiO2 loading on the silica-coated Adsorption equilibrium experiments were carried out by
magnetite nanoparticles (TiO2/SiO2/Fe3O4) adding 10 mL of different initial concentration of Cd(II)
(15–200 mg L–1), Hg(II) (20–250 mg L–1) and Ni(II) (20–
SiO2/Fe3O4 nanoparticles were dispersed in 40 mL of 250 mg L–1) solution to 0.007 g of adsorbent at 25 C. The
ethanol and homogenized by ultrasonication for 30 min. samples were shaken in a water bath shaker at 180 rpm for
Then, 2.0 mL of TBOT and glacial acetic acid (5:1 v/v) 24 h. Then, metal loaded TiO2/SiO2/Fe3O4 nanoparticles
was orderly introduced to the solution under vigorous were separated with magnetic decantation and the equi-
mechanical stirring at room temperature for 4 h. In the next librium concentration of Cd(II), Hg(II) and Ni(II) in the
step, 15 mL of ethanol and 3 mL of ddH2O were added bulk (Ce) was determined using an ICP-OES analysis
dropwise to the suspension, and then the suspension was (Scheme 1b). The amount of adsorbed Cd(II), Hg(II) and
heated at 45 C. Finally, TiO2/SiO2/Fe3O4 nanoparticles Ni(II) per unit mass of adsorbent at equilibrium qe (mg g–1)
was dried in vacuum at 50 C and calcined in nitrogen was calculated according to Eq. 1:
protection for 3 h at 500 C (Scheme 1a). ðC0  Ce ÞV
qe ¼ ð1Þ
W
Point of zero charge of the adsorbent (pHPZC) where C0 and Ce (mg L–1) are the initial and equilibrium
contents, respectively, V (L) is the volume of the solution,
The point of zero charge (PZC) is a characteristic of metal and W (g) is the mass of adsorbent used.
oxides (hydroxides) and of fundamental importance in
surface science. It is a concept relating to the phenomenon Kinetic adsorption studies
of adsorption and describes the condition when the elec-
trical charge density on a surface is zero. In the current The adsorption kinetic experiments were carried out at
study, the pHPZC of the adsorbent was determined by three different initial concentrations of (20, 50, 80 mg L–1)
introducing 0.007 g of adsorbent into 100-mL Erlenmeyer studied metals. In each concentration, 10 mL of metal
flasks containing 0.01 mol L-1 NaNO3 solutions. The pH solution was added to 0.007 g of adsorbent and was shaken
values of the solutions were adjusted to 2.0, 3.0, 4.0, 5.0, at 180 rpm at room temperature (25 C). Then, samples
6.0, 7.0, 8.0, 9.0, 10.0 using 0.01 mol L-1 solutions of were withdrawn at different time intervals and the equi-
HNO3 and NaOH. The solution mixtures were allowed to librium concentration of metal ions was determined by the
equilibrate in an isothermal shaker (25 C) for 24 h. The ICP-OES method. The amount of metal ions adsorbed at

Scheme 1 Schematic diagram

for a synthesis of the TiO2/SiO2/
Fe3O4 nanoparticles and b the
adsorption mechanism of metal
ions

123
 S. Sobhanardakani, R. Zandipak

each time interval per unit mass of the adsorbent qt addition, XRD patterns of SiO2/Fe3O4 are similar to that of
(mg g–1) was calculated using Eq. 2: Fe3O4 nanoparticles. The peak at around 2h = 15–25 in
ðC0  Ct ÞV the XRD pattern (Fig. 1) is according to the amorphous
qt ¼ ð2Þ silica shell on the surface of the magnetite nanoparticles.
W
The characteristic diffraction peaks of Fe3O4 are weakened
here C0 and Ct (mg L–1) are the liquid phase concentrations because of the silica coat, and the diffraction peak of
of metal ions at initial and any time t, respectively. amorphous silica can be observed. According to Fig. 1,
TiO2/SiO2/Fe3O4 sample obtained has the characteristic
Preparation of real samples peaks of anatase TiO2 agreed well with the standard ana-
tase TiO2 XRD spectrum (PDF #71-1166).
In order to demonstrate the applicability and reliability of The TEM images of Fe3O4, SiO2/Fe3O4 and TiO2/SiO2/
the method for real samples, three samples, including tap Fe3O4 nanoparticles are shown in Fig. 2. As shown in
water, electronic wastewater and medical wastewater, were Fig. 2a, Fe3O4 nanoparticles were spherical shape with
prepared and analyzed. Tap water samples were taken from average diameter of about 20 nm and the aggregation of
our research laboratory (Hamedan Branch, Islamic Azad the nanoparticles can be discerned clearly. However, in
University, Hamedan, Iran); electronic wastewater and Fig. 2b, the coated silica layer as the typical core–shell
medical wastewater were collected in a 2.0-L PTFE bottle. structure of the SiO2/Fe3O4 nanoparticles can be observed.
All samples filtered through a filter paper (Whatman No. Therefore, due to surface coated of silica on the shell, and
40) to remove suspended particulate matter. the average thickness of the homogeneous SiO2 layer is
about 3 nm, it can be concluded that the dispersity of SiO2/
Fe3O4 nanoparticles is improved, and also the average size
Results and discussion increased to about 30 nm. According to Fig. 2c, the aver-
age diameter of TiO2/SiO2/Fe3O4 nanoparticles is 48 nm
Characterization of adsorbents and the average thickness of the homogeneous anatase
TiO2 layer is about 9 nm. Also, the aggregation of the
The XRD pattern of Fe3O4, SiO2/Fe3O4 and TiO2/SiO2/ Fe3O4 nanoparticles is more evident than the SiO2/Fe3O4
Fe3O4 nanoparticles is shown in Fig. 1. In Fig. 1, the rel- nanoparticles.
atively strong diffraction peaks at 2h = 30.3, 35.5, 43.2, Specific surface areas are commonly treated according
53.7, 57.3, 62.7 and 74.5 could be assigned to the to the Brunauer, Emmett and Teller (BET) theory as a
(220), (311), (400), (422), (511), (440) and (533) planes, standard procedure to nitrogen adsorption/desorption iso-
which agreed well with the database of magnetite (JCPDS therms measured at 77 K. The specific surface area of the
card, File No. 79–0418). It indicated the presence of Fe3O4 sample is determined by physical adsorption of a gas on the
phase with highly crystalline cubic spinel structure. In surface of the solid and by measuring the amount of
adsorbed gas corresponding to a monomolecular layer on
the surface (Brunauer et al. 1938; Venkatesha et al. 2012).
The results of the BET method showed that the average
specific surface areas of magnetite were 100.2 m2 g-1.
After the coating procedure, the SiO2/Fe3O4 exhibits a
relatively higher BET surface area of 158.4 m2 g-1
because of the coating of SiO2 component. However, after
the functionalization of the surface of SiO2/Fe3O4 core–
shell nanoparticles with TiO2, the specific surface area of
TiO2/SiO2/Fe3O4 decreased to 149.8 m2 g-1. It should be
noted that the decrease in surface area may be resulted
from the increase in the size of particles and also the
agglomeration of particles.
As observed in Fig. 3, the pHPZC was found to be 6.0,
4.3 and 5.0 for Fe3O4, SiO2/Fe3O4 and TiO2/SiO2/Fe3O4,
respectively. The surface charge is positive at pH values
lower than pHPZC, neutral at pHPZC and negative at pH
values higher than it. Surface coverage of the magnetite
Fig. 1 XRD patterns of Fe3O4, SiO2/Fe3O4 and TiO2/SiO2/Fe3O4 with silica, reasonably, leads to a decrease in the pHPZC of
nanoparticles the surface approaching the respective value of pure silica.

123
Synthesis and application of TiO2/SiO2/Fe3O4 nanoparticles as novel adsorbent for removal of…

Fig. 2 TEM images of Fe3O4 (a), SiO2/Fe3O4 (b) and TiO2/SiO2/Fe3O4 nanoparticles (c)

7 improve adsorption capacity compared with unmodified

adsorbent.

6 Adsorption isotherms

The effect of initial metal concentration on the amount of

5 adsorbed heavy metal ions was investigated in the initial
p H fin al

concentration range of 20–250 mg L–1. The results indi-

cated that the value of qe increases sharply at lower metal
4 concentration, whereas at higher values of Ce, the increase
of qe is slowed down, which means TiO2/SiO2/Fe3O4
nanoparticles could be completely saturated with heavy
3 metal ions at enough high initial concentrations.
The adsorbent capacity and the driving force of
adsorption are essential data for designing an appropriate
2
adsorption treatment process. Adsorption isotherm models
0 2 4 6 8 10 12
were used to describe the equilibrium relationship between
pHinitial
the solid adsorbent and liquid adsorbate. In the present
Fig. 3 pH variation in terms of initial pH of solution for determi- study, the equilibrium adsorption data were correlated with
nation of point of zero charge pH different isotherm models, such as Langmuir (L), Fre-
undlich (F), Temkin (T), Redlich–Peterson (R–P), Lang-
muir–Freundlich (L–F) and Brouers–Sotolongo (B–S) for
Differences reported in the synthesis procedures, aqueous investigation of the adsorption mechanism at 25 C.
medium conditions and measuring methods are likely to be Langmuir isotherm is often used to describe adsorption
the cause of the different pHPZC. Actually, lower concen- of solute from liquid solutions, and this model assumes
trations of TEOS in the silanization procedure described monolayer adsorption onto a homogeneous surface with
above gave rise to higher pHPZC for the produced silica- finite number of identical sites (Langmuir 1918). The
coated magnetite. The incomplete surface coating results in nonlinear form of Langmuir isotherm model is given as
a non-homogeneous surface chemical composition, which follows:
affects the pHPZC of the silanized magnetite. qm KL Ce
In this study, the structure of new adsorbent is like the qe ¼ ð3Þ
1 þ KL Ce
core–shell nanoparticles, in which the structure from inner
to outer is sequentially comprised of a magnetic core, As shown in Eq. 3, qm (mg g–1) and KL (L mg–1) are
passive film of silica and functional groups of TiO2. The known as Langmuir constants and referred to maximum
advantages of this magnetic adsorbent are as follows: (1) adsorption capacity and affinity of adsorption, respectively.
The magnetic core can provide a convenient platform for In order to predict the favorability of the adsorption pro-
the facile separation; (2) the silica shell can efficiently cess, the essential characteristic of Langmuir equation can
prevent the aggregation and chemical decomposition of be described using the dimensionless separation factor RL,
Fe3O4 in a harsh environment; and (3) TiO2 used to which can be defined as follows:

123
 S. Sobhanardakani, R. Zandipak

1 here qm is the maximum adsorption capacity, Ce and KBS

RL ¼ ð4Þ
1 þ KL C0 are equilibrium concentration (mg L–1) and Brouers–So-
here C0 represents the maximal initial concentration of tolongo isotherm constant, respectively. The exponent a is
metal ion (mg L–1). RL is the nature of the adsorption a measure of the width of the adsorption energy distribu-
process. In this regard, if RL [ 1, the isotherm is unfa- tion and therefore of the energy heterogeneity of the
vorable, RL = 1, the isotherm is linear, 0 \ RL \ 1, the adsorbent surface.
isotherm is favorable, RL = 0, the isotherm is irreversible. The constant parameters of the isotherm equations
The Freundlich model assumes that the uptake or which were obtained by nonlinear method for this
adsorption of solute occurs on the heterogeneous surface adsorption process and the correlation coefficient (r2) for
(Freundlich and Heller 1939). The nonlinear form of Fre- all applied isotherms are summarized in Table 1. Based on
undlich isotherm presented as follows: the obtained correlation coefficients (r2 [ 0.99) and RMS
error values, the L–F model describes the adsorption of
qe ¼ KF ðCe Þ1=n ð5Þ heavy metal ions by TiO2/SiO2/Fe3O4 nanoparticles better
where KF (mg1-(1/n) L1/n/g) is Freundlich constant and n is than the other isotherm models. The L–F model represents
adsorption heterogeneity.
The Temkin isotherm shows the effects of indirect Table 1 Obtained parameters for adsorption of metal ions onto TiO2/
interactions between adsorbate molecules based on the SiO2/Fe3O4 nanoparticles (pH = 20, dose of TiO2/SiO2/Fe3O4
assumption that the heat of adsorption of all molecules in nanoparticles = 0.007 g, contact time = 40 min, temperature =
the layer would decrease linearly with surface coverage 25 C)
(Temkin and Pyzhev 1940). Temkin isotherm model is Isotherm Parameters Metal cations
presented in Eq. 6:
Cd(II) Hg(II) Ni(II)
qe ¼ B lnðACe Þ ð6Þ
L qm (mg g-1) 435.5 736.19 553.5
where B = RT/b and b (J mol-1) is the Temkin constant KL (L mg-1) 0.122 0.326 0.045
related to the heat of adsorption; and A (L mg–1) is the RL 0.353 0.132 0.526
Temkin isotherm constant. r2 0.9779 0.9931 0.9960
Redlich and Peterson (R–P) proposed an isotherm RMS error 22.04 20.025 9.834
compromising the features of the Langmuir and the Fre- F KF (L mg (1-(1/n))
/g) 122.3 233.3 71.24
undlich isotherms. Redlich–Peterson is one of the three- n 0.351 0.303 0.411
parameter equations (Mane et al. 2007): r2 0.9733 0.9112 0.9597
KRP Ce RMS error 29.43 75.337 31.50
qe ¼ ð7Þ
1þ / Ceb T B 91.73 127.7 114.1
A (L mg–1) 3.138 5.771 0.539
here KR–P (L g–1), , b are the Redlich–Peterson constants. 2
r 0.9900 0.9693 0.9915
b is the parameter which is between 0 and 1.
RMS error 18.017 44.26 14.47
The other isotherm model used for modeling of equi-
B–S qm (mg g-1) 555.0 682.8 484.0
librium adsorption data is Langmuir–Freundlich isotherm.
a 0.572 0.766 0.803
This model is obtained by introducing a power law
KB–S (L mg-1)a 0.205 0.314 0.069
expression of the Freundlich isotherm into the Langmuir
r2 0.9902 0.9913 0.9944
isotherm. At low adsorbate concentrations, it reduces to
RMS error 19.262 21.932 12.68
Freundlich isotherm; while at high concentrations, it pre-
L–F qm (mg g-1) 670.9 745.6 563.0
dicts a monolayer adsorption capacity characteristic of the
Langmuir isotherm (Azizian et al. 2007): KL–F (L mg-1) 0.073 0.315 0.043
n 1.498 1.039 1.028
qm ðKLF Ce Þ1=n r 2
0.9951 0.9949 0.9961
qe ¼ ð8Þ
1 þ ðK C Þ1=n
LF e
RMS error 13.278 19.961 9.654
R–P KR–P (L g-1) 173.6 237.4 27.00
where KL–F (L mg–1) and n are constants. a0 (L mg-1)1/b 0.740 0.315 0.085
Brouers–Sotolongo proposed an isotherm for heteroge- B 0.806 1.005 0.962
neous surface containing micro-cores (Brouers et al. 2005). r2 0.9923 0.9928 0.9959
Its expression is given as follows: RMS error 17.325 21.235 10.540



qe ¼ qm 1  exp KBS Cea ð9Þ

123
Synthesis and application of TiO2/SiO2/Fe3O4 nanoparticles as novel adsorbent for removal of…

the adsorbent with heterogeneous surface with a different adsorption and also that in the equilibrium amounts of ad-
distribution of adsorption energies. This means a hetero- species (qe) are verifiable. It is clear that Cd(II), Hg(II) and
geneous adsorption in all studied systems, which is in Ni(II) ions adsorption onto TiO2/SiO2/Fe3O4 nanoparticles
agreement with the results from kinetic studies for Cd(II), is rapid at the first 40 min and then approaches equilibrium
Hg(II) and Ni(II). after a few minutes. The results of these experiments show
The obtained adsorption capacities of ions on the TiO2/ that the rate of adsorption of studied heavy metal ions by
SiO2/Fe3O4 nanoparticles (mg g–1) were 670.9 for Cd(II), adsorbent is fast.
745.6 for, Hg(II) and 563 for Ni(II), and the adsorption The prediction of batch adsorption kinetics is one of the
capacities of the prepared SiO2/Fe3O4 nanoparticles for significant aspects which can explicate the mechanism of
Cd(II), Hg(II) and Ni(II) ions were 200, 187.5, 142 mg g–1, adsorption and its potential rate-limiting steps that include
respectively. The obtained maximum adsorption capacities, mass transport and chemical reaction processes. In order to
qm, for TiO2/SiO2/Fe3O4 nanoparticles were higher or com- explain the adsorption kinetic data, different models,
parable with SiO2/Fe3O4 nanoparticles. Also, the comparison including pseudo-first-order (PFO), pseudo-second-order
of adsorption capacity of other adsorbents for the removal of (PSO), Elovich (E), mixed 1,2-order (MOE), exponential
Cd(II), Hg(II) and Ni(II) ions from water is presented in (EXP) and fractal-like-pseudo-second-order (FL-PSO),
Table 2. As shown in Table 2, higher adsorption capacity was were used.
observed by the adsorbent prepared in the current study. This Pseudo-first-order equation is one of the most popular
indicates that TiO2/SiO2/Fe3O4 nanoparticles are suitable ad- and empirical models for adsorption kinetics which pre-
sorbent for removal of metal ions from aqueous solution. sented by Lagergren (Azizian 2004). The integrated form
On the other hand, adsorption capacity increased in the of this model can be given as follows:
sequence of Hg(II) [ Cd(II) [ Ni(II), where the different qt ¼ qe ð1  expðk1 tÞÞ ð10Þ
adsorption capacity may be due to related to their size,
degree of hydration and the value of their binding constant where qt and qe (mg g–1) are the amount of adsorbed
with the adsorbent. species per unit mass of adsorbent at any time (t) and at
equilibrium, respectively. k1 (min-1) represents the
Adsorption kinetics pseudo-first-order rate constant.
Another simple and well-known kinetic model which is
The effect of the contact time on the adsorption of studied used extensively in recent years is pseudo-second-order
heavy metal ions by the TiO2/SiO2/Fe3O4 nanoparticles at equation (Azizian 2004). The integrated form of this
different initial concentrations was investigated, and the equation is:
results are depicted in Fig. 4. The results showed that, by k2 q2e t
increase in initial concentration, an increase in the rate of qt ¼ ð11Þ
1 þ k 2 qe t

Table 2 Comparison of maximum adsorption capacity (qm) of different adsorbents for Cd(II), Hg(II) and Ni(II)
Adsorbent Maximum adsorption pH Temperature References
capacity (mg g-1)
Cd(II) Hg(II) Ni(II)

Novel chelating sponge 125.11 – 65.39 6.5–8.5 35 Cheng et al. (2014)

Magnetic graphenes 163.6 – 158.5 6.0 20 Guo et al. (2014)
Mercaptoethylamino homopolymer-modified maghemite nanoparticles 91.5 237.6 – 6.0 25 Madrakian et al.
(2015)
Multi-carboxyl functionalized silica gel 43.84 – 31.92 6.0 25 Li et al. (2014)
Magnetite nano-rods 88.39 – 95.42 5.5 25 Karami (2013)
Thiol modified Fe3O4@SiO2 – 148.8 – 6.5 30 Zhang et al. (2013)
Ca(BO2)2 microspheres 110.6 – – 7.5 – Zhang et al. (2016)
Zinc oxide nanoparticles 387 714 – 5.5 30 Sheela et al. (2012)
Polyampholyte hydrogel 153.8 – – 6.0 30 Zhou et al. (2016)
Resin loaded magnetic b-cyclodextrin bead and graphene oxide sheet – 88.43 – 7.1 50 Cui et al. (2015)
(MCD-GO-R)
TiO2/SiO2/Fe3O4 nanoparticles 670.9 745.6 563 7.0 25 This work

123
 S. Sobhanardakani, R. Zandipak

350
350
(a) (b)
300 300

250 250

200
q t (m g g -1 )

200

q t (m g g -1 )
150 150

100 20 mg L-1 100 20 mg L-1

50 mg L-1 50 mg L-1
80 mg L-1 80 mg L-1
50 FL-PSO-Cd(II) 50
FL-PSO-Hg(II)

0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300

t (min) t (min)

250
(c)

200

150
q t (m g g -1 )

100
20 mg L-1
50 mg L-1
50 80 mg L-1
FL-PSO-Ni(II)

0
0 50 100 150 200 250 300

t (min)

Fig. 4 Experimental kinetic data for the adsorption of a Cd(II), b Hg(II) and c Ni(II) by TiO2/SiO2/Fe3O4 nanoparticles at different initial
concentrations. Lines represent the FL-PSO model fitted to the data

where k2 (g mg–1 min) is the rate coefficient. where a and b are equation constants. Mainly, Elovich
The mixed 1,2-order, that is the combination of first- and equation is applied to describe chemical adsorption onto
second-order equation, is expressed by (Marczewski 2010): heterogeneous adsorbent surfaces.
1  expðk1 tÞ Exponential model is one of the new empirical models
qt ¼ qe ð12Þ which are suitable for modeling of adsorption kinetic onto
1  F2 expðk1 tÞ
both homogeneous and heterogeneous solid surfaces
here F2 (F2 \ 1) is determining the share of second-order (Haerifar and Azizian 2013). Its integrated form is:
term in the order rate equation. 

qt ¼ qe Ln 2:72  1:72 exp k10 t ð15Þ
k2 qe
F2 ¼ ; F 1 þ F2 ¼ 1 ð13Þ where k10 is constant.
k 1 þ k 2 qe
Fractal-like-pseudo-second-order model is one of the
In order to investigate the adsorption of pollutants from recently developed kinetic models for adsorption, which
aqueous solution, Elovich rate equation has been widely was presented for the systems with different paths of
used (Plazinski et al. 2009). The integrated form of Elovich adsorption (Haerifar and Azizian 2012). The integrated
equation is expressed as follows: form of this equation is:
1 k20 q2e t/
qt ¼ Lnð1 þ abtÞ ð14Þ qt ¼ ð16Þ
a 1 þ k20 qe t/

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Synthesis and application of TiO2/SiO2/Fe3O4 nanoparticles as novel adsorbent for removal of…

Table 3 Constant of kinetic models for adsorption of metal ions onto TiO2/SiO2/Fe3O4 nanoparticles (pH = 20, dose of TiO2/SiO2/Fe3O4
nanoparticles = 0.007 g, contact time = 40 min, temperature = 25 C)
Isotherm Parameters Metal cations
Cd(II) Hg(II) Ni(II)
20 50 80 20 50 80 20 50 80

PFO k1 (min-1) 0.062 0.069 0.035 0.052 0.037 0.043 0.070 0.107 0.121
qe (mg g-1) 71.28 170.13 276.43 72.83 182.09 272.92 63.25 137.8 204.7
r2 0.9943 0.9864 0.9800 0.9697 0.9823 0.9879 0.9448 0.8968 0.8511
RMS error 1.774 6.217 13.07 4.936 9.551 10.64 5.061 14.53 25.74
PSO k2 (g mg-1 min) 0.001 0.000 0.000 0.012 0.031 0.000 0.001 0.001 0.000
-1
qe (mg g ) 78.81 187.18 317.5 82.47 212.2 310.54 68.92 148.3 220.2
r2 0.9621 0.9961 0.9936 0.9287 0.9510 0.9961 0.9860 0.9665 0.9426
RMS error 4.598 3.328 7.395 7.574 15.88 5.999 2.545 8.262 15.95
E a 0.077 0.034 0.015 0.060 0.021 0.015 0.091 0.047 0.033
b 26.77 93.07 29.18 10.82 15.01 35.23 33.55 75.2 99.0
r2 0.8872 0.9574 0.9808 0.8504 0.8963 0.9722 0.9836 0.9900 0.9944
RMS error 7.934 11.014 12.79 10.97 23.11 16.13 2.751 4.512 4.958
EXP k10 044 0.048 0.024 0.036 0.025 0.029 0.055 0.076 0.083
qe (mg g-1) 71.91 166.12 270.26 73.70 180.14 283.3 64.00 139.3 209.49
r2 0.9862 0.9936 0.9906 0.9548 0.9697 0.9949 0.9628 0.9231 0.8831
RMS error 2.774 4.260 8.940 6.030 12.48 6.885 4.149 12.53 22.79
MOE F2 1.136 1.293 1.250 3.054 3.842 1.363 1.064 0.999 0.999
k1 (min-1) 0.098 0.021 0.000 0.165 0.085 0.014 0.010 0.000 0.000
qe (mg g-1) 70.46 227.9 368.7 70.64 181.06 389.6 70.21 151.86 227.6
r2 0.9973 0.9976 0.9938 0.9980 0.9954 0.9964 0.9723 0.9616 0.9332
RMS error 1.258 2.729 7.576 1.312 5.031 6.035 3.747 9.255 18.00
FL-PSO  1.908 1.200 0.920 2.575 2.049 1.053 0.713 0.545 0.402
k20 0.000 0.000 0.000 0.001 0.021 0.000 0.002 0.001 0.000
qe (mg g-1) 71.32 169.0 274.8 73.70 177.61 290.6 66.30 146.3 218.0
r2 0.9992 0.9982 0.9951 0.9990 0.9988 0.9969 0.9988 0.9970 0.9960
RMS error 0.8012 2.354 6.580 0.903 2.579 5.568 1.267 2.956 4.345
Experimental data qe (exp) 70.84 167.1 270 72.21 176.78 286.2 64.2 142.2 212.0

where k20 is a constant. concentration and approaching to unity. This means that by
The obtained constants by nonlinear method for Cd(II), increasing of heavy metals concentration, the number of
Hg(II) and Ni(II) adsorption by TiO2/SiO2/Fe3O4 paths for adsorption decreases and at high concentrations,
nanoparticles are listed in Table 3. The highest correlation the adsorbates directly adsorb onto active sites.
coefficient (r2 [ 0.99) and lower RMS error found for FL-
PSO model. Also, the obtained qe values by FL-PSO model Effect of solution pH
are very close to the experimental value. The results of
fitting by the FL-PSO model are shown by solid lines in The pH of the aqueous solution was an important variable;
Fig. 5. Modeling of adsorption kinetic data with this model it is well known that pH influences the adsorption pro-
indicates that the rate constant of this system is time cesses significantly by affecting both the protonation of the
dependent which is due to the presence of different active surface groups and the degree of the ionization of the
site for adsorption (heterogenous surface) and therefore adsorbates. The effect of varying pH (3.0 to 11.0) on the
changing of favorable active sites of adsorption with time. adsorption of heavy metal ions onto TiO2/SiO2/Fe3O4
Comparison of a value of the FL-PSO model at different nanoparticles was investigated using 0.1 mol L-1 of HCl
concentrations indicates a small increase of a with or NaOH solutions for pH adjustment with 20 mg L–1 of

123
 S. Sobhanardakani, R. Zandipak

100 Further, increases in the pH of solution were shown to

exhibit different effects on the adsorption process, espe-
cially in the basic region where deposition plays a pre-
80
dominant role in metal ion removal. When the pH value
increased from 7.0 to 11.0, the adsorption amount of
Removal efficiency (% )

Cd(II), Hg(II) and Ni(II) decreased by TiO2/SiO2/Fe3O4

60
nanoparticles, which could be explained by the fact that
Cd(II), Hg(II) and Ni(II) species start to hydrolyze and
40 precipitate into Cd (OH)2, Hg (OH)2 and Ni (OH)2 at
Cd(II) pH [ 7.0. Also, in pHs lower than 3.0, the TiO2/SiO2/
Hg(II) Fe3O4 nanoparticles were dissolved.
Ni(II)
20
Effect of temperature

0
Temperature is an important factor to enhance the
2 4 6 8 10 12
adsorption process as it affects the adsorption capacity by
pH
altering the molecular interactions and the solubility
Fig. 5 Effect of solution pH on the removal percentage of metal ions potential of the adsorbate. In order to determine the effect
by TiO2/SiO2/Fe3O4 nanoparticles (C0 = 20 mg L-1, dose of TiO2/ of temperature on the removal of studied heavy metal ions
SiO2/Fe3O4 nanoparticles = 0.007 g, contact time = 40 min, by TiO2/SiO2/Fe3O4 nanoparticles, adsorption experiments
temperature = 25 C)
were tested at four temperatures (25, 35, 45 and 55 C)
with metal ion concentrations of 20 mg L-1. Figure 6
shows the removal percentage of Cd(II), Hg(II) and Ni(II)
initial metal concentration. Effect of solution pH on the by TiO2/SiO2/Fe3O4 nanoparticles at different tempera-
removal percentage of Cd(II), Hg(II) and Ni(II) ions by tures. It is clear that the removal percentage of all heavy
TiO2/SiO2/Fe3O4 nanoparticles is shown in Fig. 5. As can metal ions decreases with increase in temperature. By
be seen from Fig. 5, adsorption amount of the three metal increasing of temperature from 25 to 55 C, the removal
ions increased with increasing the pH values up to 7.0 and percentage decreases from 98.5 to 89% for Cd(II), from
then decreased at higher pHs. The changes in removal 99.8 to 92.5% for Hg(II) and from 86 to 45% for Ni(II).
percentage are mainly due to the different speciation of These results indicate that the adsorption of these metals
Cd(II), Hg(II) and Ni(II) in solution and the change in onto TiO2/SiO2/Fe3O4 nanoparticles is exothermic. Since
surface charges on the TiO2/SiO2/Fe3O4 nanoparticles. the effect of temperature on the removal percentage of
In general, at the lower pH values, adsorption was low, Ni(II) ions is higher than Cd(II), Hg(II) ions, it can be
which suggests that a weak attraction between the adsor- suggested that the adsorption of Ni(II) onto TiO2/SiO2/
bent surface and the positive ions took place. The phe- Fe3O4 nanoparticles is more exothermic than Cd(II),
nomenon could be explained by the fact that the amount of Hg(II).
removal at a low pH was considerably lower may be due to
the competition between the metal ions and H? on the Desorption and reusability
active sites of the adsorbent surface, which prevented the
metal ions from approaching the binding sites. In addition, The reusability of adsorbents is of great importance factor
the positive surface charge might lead to electrostatic in evaluating their potential applications. Therefore, it is
repulsion of the metal ions. However, with increasing of necessary to repeated use of an adsorbent under proper
pH value, the competition from the hydrogen ions conditions. In order to investigate the regeneration capacity
decreased and metal ions can be adsorbed on the adsorbent of adsorbent, desorption experiments were performed
and the adsorption amount has reached maximum at pH 7.0 under batch experimental conditions. In this study,
for all metal ions. At low pHs (pH \ pHpzc), the surface of methanol, acetic acid, sodium hydroxide, acetonitrile and
the adsorbent presents in positive form and has less mixture of methanol and sodium hydroxide were chosen as
adsorption. As the alkalinity of solution increases, the the eluent. After adsorption of the metal ions, the adsorbent
carboxylic acid functional groups turn into carboxylate was magnetically separated. Then, 15 mL of desorbent
anions and the adsorption increases gradually until solution was added to the 0.007 g of metal loaded TiO2/
pH [ pHpzc. After then, carboxylic acid functional groups SiO2/Fe3O4 nanoparticles in a beaker. The nanoparticles
completely turn into carboxylate anions, with almost no were collected magnetically from the solution after 5, 10,
change in adsorption. 20, 30 and 40 min contact times with the eluent. The

123
Synthesis and application of TiO2/SiO2/Fe3O4 nanoparticles as novel adsorbent for removal of…

Fig. 6 Effect of temperature on

the removal percentage of metal
ions by TiO2/SiO2/Fe3O4
nanoparticles
(C0 = 20 mg L-1, pH = 20,
dose of TiO2/SiO2/Fe3O4
nanoparticles = 0.007 g,
contact time = 40 min)

Fig. 7 Effect of type of eluting

agent on recovery (%) for metal
ions adsorbed on TiO2/SiO2/
Fe3O4 nanoparticles

concentration of metals in the desorbed solution was ions during these five cycles. Furthermore, the results
measured by ICP-OES. The results are given in Fig. 7. showed that the efficiencies of the recycled adsorbent for
Results showed that mixture of methanol and sodium removing metal ions are nearly the same as those for the
hydroxide is more effective at desorption time of 20 min fresh ones even after five times recycling.
and could be used for the quantitative recovery of the metal
ions. The metal cations at pH 7.0 are attracted electro- Adsorption of metal ions in real samples
statically by the TiO2/SiO2/Fe3O4 nanoparticles. This
interaction was corrupted with the sodium hydroxide The applicability of the prepared TiO2/SiO2/Fe3O4
solution. Also, there are some interactions between the nanoparticles was tested by adsorption of amounts of
metal cations and the TiO2/SiO2/Fe3O4 nanoparticles. For Cd(II), Hg(II) and Ni(II) ions in real samples including tap
breaking these interactions, it was required methanol to water, electronic wastewater and medical wastewater
improve the elution efficiency. The reusability and stability samples. The samples were analyzed after spiking with
of TiO2/SiO2/Fe3O4 nanoparticles for the removal of the different concentrations of metals. The recovery studies of
metal ions were assessed by performing fifteen consecutive the spiked Cd(II), Hg(II) and Ni(II) ions in water samples
separations/desorption cycles under the optimized condi- (tap water, electronic wastewater and medical wastewater)
tions. The results showed that there was no significant showed average values in the range from 94 to 102%
change in the performance of the adsorbent during the first (Table 4), suggesting the method is suitable for the
five cycles, indicating that the fabricated adsorbent is a removal of metal ions. Also, the results presented in
reusable solid-phase adsorbent for the removal of the metal Table 4 indicated that the efficiency of TiO2/SiO2/Fe3O4

123
 S. Sobhanardakani, R. Zandipak

Table 4 Results of adsorption

Sample Metals Added (lg-1) Found (lg-1) Recovery (%)
of metal ions in various water
samples under the optimum Tap water Cd(II) 25 24.9 99.6
conditions (n = 3)
50 49.8 99.6
Hg(II) 25 25.2 100.8
50 49.5 99
Ni(II) 25 24.1 96.4
50 48.9 97.8
Electronic wastewater Cd(II) 25 24.7 98.8
50 50.1 100.2
Hg(II) 25 24.8 99.2
50 49.9 99.8
Ni(II) 25 24.5 98
50 47.8 95.6
Medical wastewater Cd(II) 25 25.1 100.4
50 49.7 99.4
Hg(II) 25 25.5 102
50 49.6 99.2
Ni(II) 25 23.5 94
50 45.5 91

nanoparticles is satisfactory for the adsorption of metal Acknowledgements Funding was provided by Hamedan Branch,
ions from various samples. Islamic Azad University (Grant No. 34200).

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