Chemistry Research Journal, 2017, 2(3):160-169

Available online www.chemrj.org

ISSN: 2455-8990
Research Article CODEN(USA): CRJHA5

Investigation of Adsorptive Properties of Modified Sepiolite as an Efficient Magnetically

Recoverable Clay for Removal of Azo Dye from Aqueous Solutions

Nahid Rasouli*, Somayea Batavani

Department of Chemistry, Payame Noor University, P.O. Box 19395-3697, Tehran, Iran

Abstract In this research, the natural clay of sepiolite (Mg4Si6O15(OH)2·6H2O) were modified by magnetic metal
oxide ofNi0.5Zn0.5Fe2O4 to obtain an efficient and magnetically recoverable adsorbent (Ni0.5Zn0.5Fe2O4/sepiolite).
The synthesized adsorbent (Ni0.5Zn0.5Fe2O4/sepiolite) was characterized by X-ray diffraction (XRD), Fourier
transform infrared (FT-IR), UV-Vis spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-
ray analysis (EDX).In this study, the adsorption properties of the prepared sample was evaluated for the removal of
Congo red (CR) dye in aqueous solution and the reusability of the sample was also investigated. The effect of initial
dye concentration, pH and temperature on adsorption capacity of modified clay (Ni 0.5Zn0.5Fe2O4/sepiolite) for Congo
red were investigated. Also, the results of adsorption kinetic of CR dye in aqueous solution followed pseudo- first
order model.

Keywords Azo dye; adsorption kinetic; sepiolite; Magnetic; recoverable clay

Introduction
Dyes are widely used in industries such as textiles, leather, printing, food, and plastics, etc. The removal of dyes
from industrial wastewaters is a major problem [1-2]. Conventional methods for the removal of dyes from
wastewater include adsorption onto solid substrates, chemical coagulation, oxidation, filtration and biological
treatment. Adsorption is one of the effective separation techniques to remove dilute pollutants [3-4]. Therefore,
researches have been continued a search for cheaper, easily obtainable materials for the adsorption of dye. Natural
clays for dye removal from wastewater such as sepiolite are investigated as low-cost and readily available
adsorbents. The adsorption capacity of clays results from high surface area and a net negative charge on their
structure, which attracts and holds cations such as heavy metals [5]. Sepiolite is a natural hydrated magnesium
silicate with a wide range of industrial applications derived mainly from its adsorptive properties. It has a fibrous
structure formed by an alteration of blocks and channels that grow up in the fiber direction. Each block is
constructed of two tetrahedral silica sheets enclosing a central magnesia sheet. Adsorption is due to the presence of
active adsorption centers on sepiolite surfaces (oxygen atoms in the tetrahedral sheet, water molecules coordinated
with the Mg2+ ions at the edge of thestructure, and silanol groups caused by the break-up of Si―O―Si bonds) [6-7].
The ability of sepiolite for adsorption of cationic dyes has been reported [8–11]. Regarding anionic dyes, natural
sepiolite provided relatively low adsorbed amounts of an azo acid dye [12]. In its untreated form, sepiolite was not
also able to remove anionic dyes, requiring a chemical modification [13]. Recently, studies on magnetic
nanoparticles has grown intensely. It is believed that magnetic nanoparticles can used as modifier which exhibit high
adsorption, chemical and thermal stability. In addition, the easy separation of magnetic adsorbent from solution can
be achieved using an external magnetic field [14–16]. So, the aim of this work is to examine the effectiveness of

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sepiolite modified by magnetic metal oxide (Ni0.5Zn0.5Fe2O4/sepiolite) as low cost material in removing high
concentration of Congo red from aqueous solution. Also, the adsorption rates were determined quantitatively and
simulated with the pseudo-first order and pseudo second order kinetic models.

2. Experimental
2.1. Materials and characterization
All the analytical chemicals (Fe(NO3)3.9H2O, Ni(NO3)2.6H2O, Zn(NO3)2.6H2O, sodium hydroxide and Congo red
dye were purchased from Merck and used without further purification. The sepiolite clay used in this study was
provided from Neishabour Region, Iran. Congo red dye used in this study was obtained from Sigma. The molecular
structure of this dye is shown in Fig.1. The structural analysis of the samples was performed by powder X-ray
Diffraction (Holland Philips Expert, X-ray diffractometer with Cu-Kα radiation) and FT-IR analysis using a Fourier
transmission infrared spectrometer (JASCO FTIR-4200, Japan) in KBr pellet, in the range of 4000-400 cm-1. The
morphology of the samples was characterized by scanning electron microscopy, SEM (VEGA3, TESCAN). The
UV-Vis absorption spectra were recorded using a Shimadzu UV-2550 spectrophotometer.
NH2

- +
N SO3Na
N N
- +
SO3Na N

NH2

Figure 1: The chemical structure of CR dye

2.2. Synthesis of the modifiedSepiolite (Ni0.5Zn0.5Fe2O4/sepiolite)
The modified sepiolite was prepared by co-precipitation method. In this method, 3 g sepiolite was added into 100 ml
of distilled water containing Ni(NO3)2.6H2O (0.02 mol), Zn (NO3)2.6H2O (0.02 mol) and Fe(NO3)3.9H2O (0.04
mol).Then, the pH of solution was adjusted to 10 by adding NH 4OH solution (4 mol L-1). The suspension was left to
settle down and filtrated. Finally, the obtained solid was washed with distilled water three times and dried at 80ºC
for 12 h.
2.3. Adsorption experiments
In order to investigate the behavior of the natural sepiolite and Ni 0.5Zn0.5Fe2O4/sepiolite, dark adsorption
experiments were carried out. The amount of adsorbed dye per gram of adsorbent (mg/g) at time t (min) was
calculated using the following equation [17]:
C 0 −C t V
qt = (1)
m
−1
Where qt (mgg ) is the amount of adsorbed Congo red per gram of adsorbent at time t (min), C 0 is the initial
concentration of Congo red solution (mgL-1), Ct is the concentration of Congo red solution (mgL-1) at time t (min), V
is the volume of the solution (L) and m is the mass of the adsorbent (g). The initial concentrations of dye solutions
were in the range of 40 to 100 mg /L and experiments were performed at 25 °C. The initial dye concentration, pH,
and temperature were selected as experimental parameters. The effects of pH on the dye adsorption were determined
over a range of pH 7-13. The pH of the solution was adjusted with NaOH or HNO 3 solution by using a pH-meter.
After the adsorption equilibrium is reached, the suspensions were centrifuged at 15000 rpm and the concentration of
dye remaining in the supernatant determined using UV-vis spectrophotometer at λmax= 498 nm. The amount of
adsorbed dye was calculated from the concentrations in the solution both before and after the adsorption. The
calibration curve was plotted from the dye solutions prepared in the concentrations of 40–100 mg/L. All experiments
were repeated at least twice.
2.4. Kinetic studies
The Adsorption kinetics was determined by analyzing the adsorptive uptake of dye from aqueous solution at several
times intervals. In this work, 100 cc of aqueous solution of CR dye with an initial concentration of 80mg/L were
poured in glass tube and mixed with 0.05g of adsorbent at room temperature. Then, at time intervals between 15 to
180 min, the solid phase was separated by centrifugation at 1500 rpm. The dye concentration in the supernatant

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liquid was determined by UV-vis spectrophotometer. The measurements were carried out at the wavelength
λmax=498 nm for CR dye.

3. Results and Discussion

3.1. Characterization of the modified sepiolite (Ni0.5Zn0.5Fe2O4/sepiolite)
Fig. 2 (a-c) shows the XRD patterns of Ni0.5Zn0.5Fe2O4/sepiolite, Ni0.5Zn0.5Fe2O4 and sepiolite, respectively. The
XRD pattern of Ni0.5Zn0.5Fe2O4/sepiolite show that the Ni0.5Zn0.5Fe2O4with cubic phase was obtained (JCPDS
No.08-0234), and the distinctive peaks at 29.92°, 35.27°, 42.85°, 53.11°, 56.63° and 62.21° matched well with the
(220), (311), (400), (422), (511) and (440) crystal planes of Ni 0.5Zn0.5Fe2O4 [18]. Other crystal phases corresponding
to peaks at 7.18, 19.70, 20.58, 23.74, 26.65, 27.98, 34.74, 36.81 and 39.86 were compared with the 2Ɵ values
reported for sepiolite [19]. However, it could be noticed that the characteristic diffraction peak of sepiolite in the
Ni0.5Zn0.5Fe2O4/sepiolite composite was weak, which could be attributed to the low amount of the sepiolite is used in
the synthesis of composite. The chemical structure of the Ni0.5Zn0.5Fe2O4/sepiolite composite was confirmed by FT-
IR analysis. The FT-IR spectrum of sepiolite has the characteristic bands at 3691 cm−1 related to stretching
vibrations of hydroxyl groups attached to octahedral Mg ions located in the interior blocks, 3581 cm −1 related to H–
O–H stretching vibrations of water molecules weakly hydrogen bonded to the Si–O surface, and 3452 cm−1 and 1663
cm−1 related to the water –OH stretch and bending vibration, respectively. In addition, the spectrum of natural
sepiolite had also the characteristic lattice vibrations at 1211, 1090 and 984 cm −1 (the Si–O combination bands),
1017 cm−1 (the basal plane of the tetrahedral units exhibiting the Si–O–Si plane vibrations), 450 cm−1 (Si–O–Mg of
the octahedral–tetrahedral linkage) and 650 cm−1 (Mg3OH-bending vibration) [19-21]. The morphology of sepiolite
can be seen in the SEM images (Fig.3(a)). SEM image of the sepiolite showed that it has a fibrous structure that
there is possibility for dye to trapped and adsorbed into this structure. However, SEM image of the
Ni0.5Zn0.5Fe2O4/sepiolite sample is different from sepiolite sample (Fig.3(b)). The EDX spectrum of
Ni0.5Zn0.5Fe2O4/sepiolite is shown in Fig. 4(b). The atomic weight ratio of O: Mg: Si: Fe: Ni: Zn was 66.74: 8.52:
12.95: 5.07: 0.99: 0.92 which indicates that the natural sepiolite are successfully modified by Ni 0.5Zn0.5Fe2O4
sample.Based on the results of XRD, FT-IR, SEM and EDAX confirmed the synthesis of the
Ni0.5Zn0.5Fe2O4/sepiolite composite.

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Figure 2: The XRD patterns of (a) Ni0.5Zn0.5Fe2O4/sepiolite, (b) Ni0.5Zn0.5Fe2O4and (c) sepiolite samples

Figure 3: SEM images of the (a) sepiolite and (b) Ni0.5Zn0.5Fe2O4/sepiolite samples

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Figure 4: EDAX spectrum of (a)sepiolite and (b) Ni0.5Zn0.5Fe2O4/sepiolite samples

3.2. Adsorption properties
The adsorption kinetic experiments were carried out at different experimental conditions and the results obtained are
discussed below.
3.2.1. Effect of dye concentration
The initial concentration provides an important driving force to overcome all mass transfer resistances of all
molecules between the aqueous and solid phases. Fig. 5 shows the plot of amount of dye adsorbed versus time at
different initial dye concentrations. From the figure it was observed that the amount of dye adsorbed gets increased.
Dye removal is highly concentration dependent. The rate of adsorption also increases with the increase in initial dye
concentration due to increase in the driving force. In fact, the more concentrated the solution, the better the
adsorption.

160 40 ppm 60 ppm

140
120
100
qt(mg/g)

80
60
40
20
0
0 20 40 60 80 100 120 140
Time (min)

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Figure 5: The effect of initial dye concentration on the adsorption rate of CR dye on Ni 0.5Zn0.5Fe2O4/sepiolite
3.2.2. Effect of solution pH
Generally, the adsorption capacity increases with increasing pH for cationic dyes, while it decreases with increasing
pH for anionic dyes. We had previously shown that sepiolite had an isoelectrical point at pH 6.6 and exhibited
positive zeta potential values at the lower pH values from pH 6.6, and negative zeta potential values at the higher pH
values from pH 6.6. Fig. 6 demonstrates that the adsorption decreases with increasing pH because of the electrostatic
repulsion between the chromophore groups of dye and the negatively charged sepiolite surface. The higher
adsorption of CR dye on sepiolite at neutral pH result due to the neutralization of the negative sites at the surface of
sepiolite.

160 Ph=13 Ph=11

140
120
100
qt(mg/g)

80
60
40
20
0
0 50 100 150 200
Time (min)
Figure 6: The effect of pH on the adsorption rate of CR dye on Ni0.5Zn0.5Fe2O4/sepiolite.
3.2.3. Effect of temperature
The temperature has two major effects on the adsorption process. Increasing the temperature is known to increase
the rate of diffusion of the adsorbate molecules across the external boundary layer and in the internal pores of the
adsorbent, owing to the decrease in the viscosity of the solution. In addition, changing the temperature will change
the equilibrium capacity of the adsorbent for a particular adsorbate. As seen in Fig. 7, the adsorbed amount of CR at
equilibrium has increased with increase in temperature. This may be a result of increase in the mobility of the large
dye ion with temperature. An increasing number of molecules may also acquire sufficient energy to underground an
interaction with active sites at the surface. Therefore, it can be said that the adsorption process is endothermic

160 55C 45C

140
120
100
qt(mg/g)

80
60
40
20
0
0 50 100 150 200
Time (min)
Figure 7: The effect of temperatureon the adsorption rate of CR dye on Ni0.5Zn0.5Fe2O4/sepiolite

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3.3.4. Adsorption kinetic models

The kinetic of adsorption can be described using several models. In the present study, the lagergren pseudo- first-
and pseudo- second order model was tested. The Lagergren’s pseudo- first order model for liquid-solid adsorption is
generally expressed as: [23, 24]
dq t
= k1 qe − qt (2)
dt
Here k1 is rate constant for pseudo- first order adsorption. After definite integration by applying the initial conditions
qt=0 at t=0 and qt=qt at t=t, Eq. (2) becomes:
ln qe − qt = ln(qe ) − k1 t (3)
The above linear equation can usually be used be estimated equilibrium adsorption capacity (q e) from intercept and
k1 from the slope. A pseudo- second order equation can be expressed as follows [25, 26]:
dqt
= k 2 (qe − qt )2 4
dt
Where k2 is rate constant for pseudo- second order adsorption. After definite integration by applying the initial
conditions, we have a linear form as:
t 1 1
= 2
+ t (5)
qt k 2 qe qe
The plot of t/qt versus time gives straight lines. The values for q e and k2 can be calculated from the slope and
intercept. The pseudo- second order equation is often successfully used to describe the kinetics of pollutants on the
adsorbent. This model assumes that chemisorption might be the rate limiting step in adsorption processes [27, 28].
Fig. 8 (a) & (b) represents a pseudo- first and pseudo- second order kinetic model for adsorption of CR at 25 ◦C for
the Ni0.5Zn0.5Fe2O4/sepiolite sample. The correlation coefficient (R 2) for the pseudo- second order model did not fit
very well for the Ni0.5Zn0.5Fe2O4/sepiolite sample and calculated qe value was near to the experimental data. For
pseudo- first order kinetic, the R2 is closer to unity. These results show that the pseudo- first order model is
predominant. This model assumes that chemisorption might be the rate limiting step in adsorption processes. The
stability of the samples was investigated during four cycles of experiment for adsorption of CR dye. This properties
is very important in the application of the Ni0.5Zn0.5Fe2O4/sepiolite sample in environmental technology. The
reusability of theNi0.5Zn0.5Fe2O4/sepiolite sample after several consecutive uses was obtained to be 98, 93, 90, 85 %,
respectively (Fig.9).
180
160 y = 0.597x + 58.09
R² = 0.602
140
120
100
t/qt

80
60
40
20
0
0 20 40 60 80 100 120 140 160 180 200

Time (min)

Fig.8 (a)

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1.5
y = -0.01x + 1.420
R² = 0.889

1
ln (qe-qt)

0.5

0
0 50 100 150 200

-0.5 Time (min)

Fig.8 (b)
Figure 8(a): The plots of ln(qe-qt) and (b) t/qt versus time for Ni0.5Zn0.5Fe2O4/sepiolite samples

120

100
Adsorption (%)

80

60
98 93 90 85
40

20

0
1 2 3 4

Run number

Figure 9: The reusability Ni0.5Zn0.5Fe2O4/sepiolite samples after four consecutive uses

4. Conclusion
In our study, Ni0.5Zn0.5Fe2O4 /sepiolite as an adsorbent has a high potential for removing of Congo red from the
aqueous solution. The kinetics of Congo red adsorption was examined by using the pseudo-first order and pseudo-
second order kinetic models under different conditions. The results of adsorption kinetic of CR dye in aqueous
solution followed pseudo- first order model.

Acknowledgments
We are grateful to the Research Council of Payame Noor University for their financial supports.

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