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Adsorption of methylene blue onto Fe3O4/activated montmorillonite

nanocomposite

Article  in  Applied Clay Science · July 2015

DOI: 10.1016/j.clay.2015.06.038

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 Applied Clay Science 119 (2016) 132–140

Contents lists available at ScienceDirect

Applied Clay Science

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

Adsorption of methylene blue onto Fe3O4/activated

montmorillonite nanocomposite
Jiali Chang a, Jianchao Ma b,1, Qingliang Ma c, Duoduo Zhang a, Nannan Qiao a, Mengxiao Hu a, Hongzhu Ma a,⁎
a
School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, Shaanxi, PR China
b
College of Mining Technology, Taiyuan University of Technology, Taiyuan 030024, Shanxi, PR China
c
Key Laboratory of Coal Science and Technology, Taiyuan University of Technology, Ministry of Education and Shanxi Province, Taiyuan 030024, Shanxi, PR China

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

Article history: A Fe3O4/activated montmorillonite (Fe3O4/Mt) nanocomposite was prepared by a coprecipitation method. The
Received 22 November 2014 morphology and structure of the Fe3O4/Mt nanocomposite are explored using X-ray powder diffraction, Fourier
Received in revised form 26 June 2015 transform infrared spectroscopy, N2 adsorption–desorption isotherm and scanning electron microscopy. The
Accepted 28 June 2015
adsorption capacity of Fe3O4/Mt for methylene blue (MB) was evaluated. Within 25 min, the Fe3O4/Mt nanocom-
Available online 14 July 2015
posite (0.5 g) removed 99.47% of the MB from a 120 mg L−1 solution at 293 K and at an original solution pH of
Keywords:
7.37. The experimental adsorption data followed a pseudo-second-order kinetic model and Langmuir isotherm.
Fe3O4/Mt nanocomposite The reusability of the Fe3O4/Mt was tested and still over 83.73% color removal of MB was obtained after five
Methylene blue cycles. The Fe3O4/Mt nanocomposite has good stability and reusability.
Adsorption © 2015 Elsevier B.V. All rights reserved.
Kinetics
Isotherm

1. Introduction
Dyes and pigments are the main organic pollutant compounds in
wastewater released from various industries, especially the textile dyeing
and processing factories. The presence of dyes in the effluents, even at
low concentrations, is very harmful to human beings and microorgan-
isms (Weng and Pan, 2007). Various technologies developed for the
removal of dye contaminants from wastewater, include adsorption,
coagulation/flocculation, advanced oxidation processes, ozonation,
membrane filtration and biological treatment (Fatimah et al., 2011;
Zhou et al., 2012; Peng et al., 2013; Cottet et al., 2014). Due to the high
efficiency, cost effectiveness, and simple operation, adsorption of dye
contaminants from wastewater has received a great deal of attention
(Sivakumar and Palanisamy, 2009). Some adsorbents, such as activated
carbon, clays, zeolites and other porous materials, are widely investigated
(Nandi et al., 2009; Houndonougbo et al., 2013). Especially activated
carbon is frequently used since it is effective for the removal of dissolved
organic matter. However, difficulties in regenerating it and its higher
processing cost limit its applications (Lin et al., 2014).
Clay minerals are ubiquitous in nature (Zhang et al., 2010; Bergaya
and Lagaly, 2013). Most clay minerals are composed of tetrahedral and
⁎ Corresponding author.
E-mail address: hzmachem@snnu.edu.cn (H. Ma).
1
The author contributed equally to this work. SNNU and TYUT contributed equally to
this work.
octahedral sheets, which are normally classified into two groups with
structural arrangements in 1:1 or 2:1 layers. For example, montmorillon-
ites are a class of 2:1 clay minerals consisting of one Al3+ octahedral sheet
sandwiched between two Si4+ tetrahedral sheets (Bailey et al., 1980;
Bergaya and Lagaly, 2013). The isomorphous substitution of Al3+ for
Si4+ in the tetrahedral layer and the substitution of Mg2+ or Zn2+ for
Al3+ in the octahedral layer results in permanent negative charge on
the clay mineral surface (Zhou, 2011a). The layers are held together by
van der Waals forces (Lee and Tiwari, 2012). Due to these weak forces
and the charge deficits in the structure, water can easily penetrate into
the layers and some inorganic cations (Na+, Ca2+ ions, etc.) balance the
negative charge (Kaya and Oren, 2005; Zhou et al., 2011b). With lower
charge density types of surfaces, clay minerals can play an important
role in the attraction of neutral organic contaminants, thus, there has
been an interest in utilizing clay minerals such as montmorillonite,
kaolinite, illite, and saponite as adsorbents (DiazGomez-Trevino et al.,
2013; Zhou and Keeling, 2013).
However, because of the hydrophilicity of their interlayer surfaces,
the adsorption capacity of natural clay minerals for hydrophobic organic
compounds is limited. So, surfactant-modified clay minerals have been
extensively studied to improve the hydrophobicity of their surfaces
(Tong et al., 2010; Wu et al., 2013; Zaghouane-Boudiaf et al., 2014). It
has also been demonstrated that Fe3+ and Cu2+-modified montmorillon-
ite interacts strongly with organic matter (Polubesova et al., 2008).
Magnetic separation is a quick and effective technique for separating
magnetic particles (Ai et al., 2011a). Recently, a magnetic Fe3O4@
graphene composite was developed and then utilized for dye removal

http://dx.doi.org/10.1016/j.clay.2015.06.038
0169-1317/© 2015 Elsevier B.V. All rights reserved.
 J. Chang et al. / Applied Clay Science 119 (2016) 132–140
(Yao et al., 2012). Fe3O4 coated with different amounts of soluble
biobased materials were prepared for the removal of the cationic azo
dye crystal violet (Magnacca et al., 2014). Magnetic γ-Fe2O3 carbon
composite was synthesized through the thermal pyrolysis of hydrochar
and used for pollutant removal (Zhu et al., 2014). Thus, combining clay
materials with magnetic property to fabricate magnetic adsorbents is a
promising method to remove dyes from wastewater.
The main objective of this research was to investigate the ability of a
magnetite Fe3O4/activated montmorillonite (Fe3O4/Mt) nanocomposite
to remove the cationic dye methylene blue (MB) from aqueous solutions.
The Fe3O4/Mt nanocomposite was synthesized by a coprecipitation
method and characterized by X-ray powder diffraction (XRD), Fourier
transform infrared spectroscopy (FT-IR), Brunauer–Emmett–Teller
(BET) specific surface area and scanning electron microscopy (SEM).
The effects of temperature, initial pH, contact time, adsorbent dosage
and initial MB concentration on the MB removal efficiencies and the
lifespan of the Fe3O4/Mt nanocomposite were investigated. Finally, the
physical and chemical characteristics of the Fe3O4/Mt nanocomposite in
batch adsorption experiments were examined in order to gain a deeper
understanding of the adsorption process.
2. Materials and methods
2.1. Materials
Activated montmorillonite (Huangshan, Baiyue activated montmo-
rillonite Co. Ltd, China), methylene blue (Zhengzhou, Paini Chemical
Reagent Co. Ltd, China), 30% ammonia solution, HCl, HNO3, NaNO3,
FeCl3·6H2O, FeCl2·4H2O, ethanol and all other chemicals were reagent
grade and purchased from Sinopharm Chemical Reagent Co. Ltd.
Hexaammine cobalt chloride was prepared from ammonium chloride
and cobalt chloride hexahydrate (Bjerrum and McReynolds, 1946).
The Fe3O4/Mt nanocomposite was synthesized by a coprecipitation of
FeCl3·6H2O and FeCl2·4H2O with ammonia solution in the presence of
Mt. In detail, 30% ammonia solution was added dropwise to the iron so-
lution (nFe2+: nFe3+ = 1:1.8) at 363 K with constant stirring to adjust
the pH to 9–10 so that Fe2+/Fe3+ ions precipitated. The Mt powder was
then added and the solution was stirred for 4 h. Then the solution was
cooled to room temperature, a dark black solution formed which was
then filtered. The precipitate was washed with distilled water/ethanol
(1/1) and dried in vacuum at 343 K, to obtain the Fe3O4/Mt nanocompos-
ite. The weight ratio of Fe3O4 to Mt was 1:3.
Fig. 1. X-ray diffraction patterns of (a) Mt, (b) Fe3O4 and (c) Fe3O4/Mt.
133
2.2. Characterization
The Fe3O4/Mt nanocomposite was analyzed by XRD using a Rigaku
apparatus with Cu Kα radiation. The morphologies were identified
using JCPDS data files. SEM measurements were collected using a Philips
Quanta 200 scanning electron microscope at 20 kV. The BET specific
surface areas and pore structures were obtained from nitrogen ad-
sorption data at 77 K using a Micromeritics ASAP2020 system. FTIR
spectra were taken on a Tensor 27 (Bruker, Germany) instrument
in the range of 4000–400 cm − 1 . The cation-exchange capacities
(CEC) and zero charge points (pHzpc) of the nanocomposite were deter-
mined using a titrimetric method, according to the literature (Davranche
et al., 2003).
2.3. Adsorption isotherms
Adsorption experiments were carried out in a batch equilibrium
mode. Typically, 0.5 g of Fe3O4/Mt nanocomposite and 200 mL of dye so-
lution (120 mg L−1 MB) were added to a 250 mL glass flask at 293 K
under an agitation speed of 200 rpm. At predetermined time intervals,
the Fe3O4/Mt nanocomposite was removed from the solution using a
magnet and MB concentration in the solution was then determined by
measuring the absorbance of the solution at 665 nm (λmax for MB),
using a UV–vis spectrophotometer (UVT6, Beijing Purkinje General In-
strument Co. Ltd, China). The equilibrium amount of adsorption (qe),
the amount of adsorption (qt) and the color removal were calculated
based on the following equations:
ðC 0 −C e ÞV
qe ¼ ð1Þ
W
ðC 0 −C t ÞV
qt ¼ ð2Þ
W
ðC 0 −C t Þ
color removalð%Þ ¼  100% ð3Þ
C0
where C0 (mg L−1), Ce (mg L−1) and Ct (mg L−1) are MB concentrations
at the initial, equilibrium time and time t (min), V (L) is the volume of
the solution, and W (g) is the weight of the Fe3O4/Mt nanocomposite.
All the experimental data were averages of duplicate or triplicate
determinations.
Fig. 2. FT-IR spectra of Fe3O4, Mt and Fe3O4/Mt.
134 J. Chang et al. / Applied Clay Science 119 (2016) 132–140

Fig. 3. Nitrogen adsorption–desorption isotherms and pore size distributions of (a) Fe3O4, (b) Mt and (c) Fe3O4/Mt.

Table 1 2.4. Adsorption isotherm models

Porosity parameters of Fe3O4, Mt and Fe3O4/Mt.

Samples BET specific surface area Total pore volume Average pore size To determine the interactive behavior between the adsorbent and
(m2 g−1) (cm3 g−1) (nm) the adsorbate, adsorption isotherm models, including the Langmuir,
Fe3O4 91.92 0.2967 22.50 Freundlich and Temkin models were tested. The nonlinear mathematical
Mt 187.30 0.2261 47.41 expression of the Langmuir model (Langmuir, 1916) can be expressed
Fe3O4/Mt 147.92 0.3169 46.39 as:

qm K L C e
qe ¼ ð4Þ
1 þ K L Ce

Fig. 4. SEM images of (a) Fe3O4, (b) Mt and (c) Fe3O4/Mt.

 J. Chang et al. / Applied Clay Science 119 (2016) 132–140 135

where Ce is the equilibrium concentration of the adsorbate (mg L− 1), The value of RL indicates the category of the isotherm: unfavorable
qe (mg g− 1) is the amount of dye adsorbed by the nanocomposite at (RL N 1), linear (RL = 1), irreversible (RL = 0) or favorable (0 b RL b 1).
equilibrium, qm (mg g−1) signifies the maximum adsorption capacity The nonlinear form of the Freundlich model can be expressed as:
and the Langmuir constant KL (L mg−1) relates to the free energy and
affinity of the adsorption. The feasibility of the adsorption process is
qe ¼ K F C e1=n ð6Þ
determined using the separation factor (RL) (Fan et al., 2012), which is
defined by:
where KF (mg g−1) represents the adsorption capacity and n represents
1 the degree of dependence of the adsorption at equilibrium concentration
RL ¼ ð5Þ
1 þ K L C0 (Freundlich, 1906).

Fig. 5. Effect of parameters on MB removal by the Fe3O4/Mt nanocomposite. (a) pH, (b) contact time, (c) temperature, (d) adsorbent dosage and (e) initial dye concentration.
136 J. Chang et al. / Applied Clay Science 119 (2016) 132–140

2.5. Adsorption kinetics

Kinetic models can predict the adsorption rate (k) and equilibrium
adsorption capacity (qe), which play an important role in the adsorption
mechanism. Two kinetic models were used to investigate the adsorption
kinetics, the Lagergren pseudo-first-order model and the pseudo-second-
order model. The former is based on the assumption that the rate-
limiting step is a physical adsorption process that occurs via van der
Waals forces, π–π interactions, and hydrogen bonding between the ad-
sorbent and the adsorbate. The latter is based on the assumption that
the rate-limiting step is a chemical adsorption that occurs via the sharing
or exchange of electrons between the adsorbent and the adsorbate (Li
et al., 2013).
The Lagergren equation describes the adsorption of solid–liquid
phases and can be expressed as follows:

k1
logðqe −qt Þ ¼ log qe − t ð8Þ
2:303

Fig. 6. Recycling of Fe3O4/Mt.

where qe and qt are the amounts of MB (mg g−1) adsorbed on the adsor-
bent at equilibrium and at a given time t (min), respectively, and k1 is the
rate constant of adsorption (g mg−1 min−1) (Lagergren, 1898).
The nonlinear Temkin isotherm is represented as: The pseudo-second-order rate model can be expressed as:

qe ¼ A þ B lnC e ð7Þ t 1 t
¼ þ ð9Þ
qt k2 q2e qe
where B = RT/β, is related to the heat of adsorption β (J mol−1), A is the
Temkin constant and Ce is the equilibrium concentration of the adsor- where k2 is the rate constant for the pseudo-second-order adsorption
bate (mg L−1) (Temkin and Pyzhev, 1940). process (Ho and McKay, 1999).

Fig. 7. Modeling of MB adsorption kinetics using pseudo-first-order (a–b) and pseudo-second-order (c–d) models.
 J. Chang et al. / Applied Clay Science 119 (2016) 132–140 137

Table 2
Kinetic parameters of the pseudo-first-order and pseudo-second-order models for the adsorption of MB onto Fe3O4/Mt.

Pseudo-first-order model Pseudo-second-order model

T (K) co (mg L−1) qe,exp (mg g−1) q1e (mg g−1) k1 (min−1) R21 RMS q2e (mg g−1) k2 (L mg−1 min−1) R22 RMS

293 100 39.96 0.0388 0.0859 0.8139 0.1645 40.00 11.1607 0.9999 0.0000
150 59.96 0.0948 0.1113 0.8668 0.1747 59.88 2.0738 0.9999 0.0003
200 79.95 1.9191 0.1599 0.7754 0.3449 80.00 0.2418 0.9999 0.0013
250 99.85 7.3672 0.1843 0.9644 0.1420 100.00 0.0902 0.9999 0.0006
293 120 47.97 0.0508 0.1576 0.9436 0.0820 47.98 1.2884 0.9999 0.0002
303 120 47.96 0.0304 0.1293 0.9564 0.0340 47.96 1.6756 0.9999 0.0000
313 120 47.97 0.0550 0.1461 0.9649 0.0850 47.96 4.2333 0.9999 0.0000

Several stages are involved in the adsorption process, including the
diffusion of the dye from the aqueous phase to the adsorbent surface
and then into the interior of the adsorbent pores. The rate-limiting
step of the adsorption can be determined using an intraparticle diffusion
model, which was developed by Weber and Morris (Weber and Morris,
1963), the most commonly used intraparticle diffusion model and
represented as:
qt ¼ kid t 0:5 þ C
where kid is the rate constant (mg g−1 min−0.5) and C (mg g−1) is the
boundary layer thickness.
3. Results and discussion
3.1. Characterization
The raw material is mainly composed of montmorillonite (JCPDS file
no. 29-1498) and quartz (JCPDS file no.46-1045, Fig. 1a). The reflection
of Fe3 O4 (Fig. 1b) can be indexed as cubic phase Fe3O 4 (JCPDS file
no.19-0629) (Zhang et al., 2008). In the XRD pattern of the Fe3O4/Mt
nanocomposite, the reflections corresponding to Mt are present at
2θ = 19.891°, 20.859°, 26.639°, 39.464°, 50.138° and 54.231°, but with
lower intensities than those in the pure Mt. The reflections at 17.170°,
35.022° and 36.543° are not seen and no significant shifts in the Fe3O4
reflections are observed. More importantly, loading Fe3O4 onto the Mt
changed the d001-value from 1.54 nm for the parent Mt to 1.23 nm, in-
dicating that Mg2 + and Ca2 + metal ions were replaced by hydrogen
ions which intercalated into the silicate layers and that the interlayer
water was lost during the synthesis procedure (Lee and Tiwari, 2012).
In addition, the ferriferrous oxide particles may be dispersed on the
external surfaces of Mt instead of being in the interlayer spaces.
FT-IR spectroscopy was employed to further confirm the structure of
the Fe3O4/Mt nanocomposite (Fig. 2). The absorption bands at 3430,
2370 and 1640 cm− 1 can be ascribed to the vibrations of the water
molecules (Wu et al., 2014a). The three absorption bands at 1030, 791
and 528 cm−1 are Si\\O stretching vibrations (Hajjaji and Arfaoui,
2009; Wu et al., 2014b). The characteristic bands at 573 and 663 cm−1
are due to Fe\\O stretching vibrations (Magnacca et al., 2014). The inten-
sity of the Si\\O bands in the Fe3O4/Mt nanocomposite is weaker than
those in Mt, indicating that the Fe\\O bonds may interact with the
Si\\O bonds on the surface of Mt. Fe3O4 is probably bonded to the surface
ð10Þ of Mt during the synthesis procedure.
The average pore diameter of Mt and Fe3O4/Mt suggests that both
Mt and the Fe3O4/Mt nanocomposites comprised macropores and
mesopores (Randelovic et al., 2014) (Fig. 3). The type IV isotherms
with apparent hysteresis loops in the P/Po range of 0.4–1.0 are observed,
indicating that mesopores are present (Liu et al., 2014). The total pore
volumes in the Fe3O4/Mt nanocomposite are bigger than those in the
Mt (Table 1), which is beneficial for adsorption efficiency.
The micrographs of Mt and Fe3O4/Mt are very similar (Fig. 4), the
Fe3O4 particles are well dispersed on the surface of Mt with no agglom-
eration (Zhao et al., 2014).
3.2. Optimization of the adsorption conditions
A high MB removal efficiency was achieved for the entire pH range
3–11 (Fig. 5a). This can be explained by the electrostatic interactions
between the cationic dye MB and the negatively charged surface of
the Fe3O4/Mt nanocomposite (Da Fonseca et al., 2006). A little lower
MB removal was obtained at acidic pH values than at alkaline pH values.
This is caused by the fact that excess H+ ions compete with the dye
cations for the available adsorption sites at acidic pH values (Bestani
et al., 2008). Moreover, the adsorption of MB onto the Fe3O4/Mt nano-
composite was most favorable at pH N pHpzc (7.56), which is consistent
with the results reported (Salleh et al., 2011). Since color removal was
not significantly affected by pH, the original solution pH (7.37) was se-
lected for all subsequent MB adsorption experiments.

Fig. 8. Modeling of MB adsorption kinetics using intraparticle diffusion model.

138 J. Chang et al. / Applied Clay Science 119 (2016) 132–140

Table 3 (Fig. 5d), maybe due to the availability of more adsorption sites. As the
Kinetic parameters of the intraparticle diffusion model for the adsorption of MB onto dosage of adsorbent increased further (N 2.5 g L−1), the color removal
Fe3O4/Mt.
did not change much, indicating the splitting effect of flux (concentration
T (K) c0 (mg L−1) C (mg g−1) Kid (mg g−1 min−0.5) R2 RMS gradient) between adsorbent and adsorbate (Zhang et al., 2012). In order
293 100 39.91 0.0090 0.7593 0.0089 to make full use of the adsorbent, 2.5 g L−1 was considered to be the
150 59.84 0.0228 0.6147 0.8613 optimum dose.
200 77.04 0.5657 0.5228 0.8133 The MB removal declined from 99.28% to 79.92% with the initial con-
250 94.17 1.0722 0.6696 1.1635
centration of MB increased from 120 to 1000 mg L− 1 (Fig. 5e). This
293 120 47.87 0.0173 0.8772 0.0100
303 120 47.76 0.0360 0.7529 0.0320 trend might be explained by the fact that at lower MB concentrations,
313 120 47.70 0.0499 0.6439 0.0573 a maximum amount of dye molecules can adsorb onto the Fe3O4/Mt
nanocomposite, which ensured a higher MB removal. In contrast, at
higher dye concentrations, the active adsorption sites became saturated
In the first 10 min the color removal increased sharply and thereafter and lower removal efficiency was observed (Toor and Jin, 2012). Based
gradually slowed down as the equilibrium approached in about 25 min on all these results, the optimized conditions for the maximum removal
(Fig. 5b). Initially there was a very rapid uptake of MB molecules on the of MB were: the solution's original pH (7.37); contact time, 25 min;
external surfaces which was then followed by slow intraparticle diffusion temperature, 293 K; adsorbent dosage, 2.5 g L−1 Fe3O4/Mt; initial dye
into the interior of the Fe3O4/Mt nanocomposite (Yagub et al., 2012). concentration, 120 mg L−1.
After 25 min, a dynamic equilibrium was reached between the adsorp- The color removal of MB by Fe3O4/Mt was still over 83.73% after five
tion and desorption of the dye. A contact time of 25 min was used for times (Fig. 6). Furthermore, the Fe3O4/Mt nanocomposite maintained
all further experiments. good magnetic separation effect in an external magnetic field (Fig. 6
With the temperature increased from 293 to 303 K, the color removal inset), indicating that Fe3O4/Mt has relatively good stability and
decreased from 99.47% to 99.05% (Fig. 5c). The slight drop of adsorption reusability.
capacity at higher temperature may be attributed to the weakening of
the physical interactions between the dye and the adsorbent (Cottet 3.3. Adsorption kinetics
et al., 2014). Since there is only a slight change in the color removal
with temperature, it is most practicable to adsorb the dye at room The adsorption kinetics were investigated using two kinetic models
temperature. (Fig. 7). Table 2 summarized the pseudo-first-order and pseudo-second-
An initial rapid increase in color removal from 65.23% to 99.41% with order kinetic constants that were obtained from a linear regression
increasing adsorbent dosage from 0.625 to 2.5 g L− 1 was detected analysis. For the pseudo-second-order kinetics model, high correlation

Fig. 9. Various isotherm models for the adsorption of MB on Mt and Fe3O4/Mt nanocomposite.
 J. Chang et al. / Applied Clay Science 119 (2016) 132–140 139

Table 4
Isotherm parameters for the adsorption of MB onto Fe3O4/Mt at 293 K.

Langmuir Freundlich Temkin

Absorbent qmax (mg g−1) RL KL (L mg−1) R2 RMS KF (mg g−1) n R2 RMS A B R2 RMS

Mt 64.43 0.0054–0.0430 0.185 0.9953 0.8336 14.24 2.63 0.9878 0.9992 13.13 10.66 0.9324 4.0154
Fe3O4/Mt 106.38 0.0025–0.0208 0.393 0.9580 2.2328 31.69 3.01 0.9358 3.4938 35.70 15.51 0.8826 8.1453

coefficients (R2 N 0.999) and low root mean square errors (RMS b 0.0015)
were obtained for all dye concentrations and temperatures. Moreover,
the theoretical qe values agreed well with the experimental data, indi-
cating that this adsorption process conformed to pseudo-second-order
kinetics.
The qe values increased with an increase in the initial dye concentra-
tion, while the rate constants (k2) decreased. This might be attributed to
less competition for the sorption surface sites at lower concentrations.
At higher concentrations, the competition for the surface active sites
was high, and consequently lower k2 values were obtained. The rate
constants (k2) increased with temperature, indicating that the reaction
rate was accelerated at higher temperatures.
The Weber intraparticle diffusion model was employed to identify the
steps that occurred during the adsorption process. The linear plots at
various initial concentrations did not pass through the origin (Fig. 8),
suggesting that intraparticle diffusion is not the only rate-controlling
step (Huang et al., 2011). The values of the intercept, C, are an indication
of the thickness of the boundary layer, which play a significant role in the
uptake of the dye (Eskandarian et al., 2014). Generally, a larger C value
represents a greater boundary layer effect (Dogan et al., 2007). The C
values (39.91–94.17 mg g−1) increased with initial dye concentration
(100–250 mg L−1,Table 3) increasing, demonstrating that an increase
in the initial dye concentration promoted a boundary layer diffusion
effect. Thus it can be concluded that surface adsorption (pseudo-
second-order) and intraparticle diffusion took place concurrently
(Ghorai et al., 2013).
3.4. Adsorption isotherms
The regression coefficient (R2) obtained from the Langmuir isotherm
is higher than those from the Freundlich and Temkin isotherms (Fig. 9
and Table 4), and the relative value of RMS is lower. This indicates that
the Langmuir isotherm is a better fit and that adsorption occurred in the
interlayer pores (Bouzid et al., 2015). The RL values are 0.0054–0.043
and 0.0025–0.021 for Mt and Fe3O4/Mt, respectively, since the values
are 0 b RL b 1, this indicates that the adsorptions of MB on Mt and
Fe3O4/Mt are favorable adsorption processes.
Based on Langmuir isotherm, the maximum MB adsorption amount
qm is 64.43 mg g−1 for Mt and 106.38 mg g−1 for Fe3O4/Mt. Modifying
the Mt with Fe3O4 was beneficial for the adsorption of MB. A comparison
with other reported adsorbents (Table 5) shows that the qm value for
the Fe3O4/Mt nanocomposite is one of the highest, suggesting that the
Fe3O4/Mt nanocomposite is a good candidate for dye removal from
aqueous solutions.
Table 5
Comparison of adsorption capacity (qm, mg g−1) of MB on various adsorbents.
Material Maximum adsorption References
capacity qm (mg g−1)
Chitosan/bentonite 95.24 Bulut and Karaer (2015)
Raw ball clay 34.65 Auta and Hameed (2012)
Phoenix tree leaves 80.90 Han et al. (2007)
Montmorillonite modified 69.11 Cottet et al. (2014)
with iron oxide
Mt/CoFe2O4 composite 97.75 Ai et al. (2011b)
Spent activated clay 127.50 Weng and Pan (2007)
Mt 64.43 This study
Fe3O4/Mt 106.38 This study
4. Conclusions
The Fe3O4/Mt nanocomposite was prepared by a chemical coprecipi-
tation method and used as adsorbent for MB removal. The characteriza-
tion of Fe3O4/Mt revealed that Fe3O4 particles are present on the surface
of Mt. The magnetic mesoporous Fe3O4/Mt nanocomposite had large
total pore volumes and good adsorption efficacy (99.47%) in MB removal.
A pseudo-second-order adsorption model fits well with the experimental
data (R22 = 0.9999). The equilibrium adsorption isotherm followed a
Langmuir model (qm = 106.38 mg g−1) better than Freundlich or Temkin
model. The Fe3O4/Mt nanocomposite might be a promising adsorbent for
the selective removal of cationic dye pollutants from aqueous solutions.
These results prove that the design and production of adsorbents with
magnetic properties are becoming very attractive and are beginning to
find applications in the fields of environmentology.
Acknowledgments
The authors are grateful to be supported by the Fundamental
Research Funds for the Central Universities (GK201302013), the
National Natural Science Foundation of China (no. 51204119) and Nat-
ural Science Foundation of Shanxi (nos. 2014021015-4, 2015021107).
References
Ai, L.H., Zhang, C.Y., Chen, Z.L., 2011a. Removal of methylene blue from aqueous solution
by a solvothermal-synthesized graphene/magnetite composite. J. Hazard. Mater. 192,
1515–1524.
Ai, L.H., Zhou, Y., Jiang, J., 2011b. Removal of methylene blue from aqueous solution by
montmorillonite/CoFe2O4 composite with magnetic separation performance. Desali-
nation 266, 72–77.
Auta, M., Hameed, B., 2012. Modified mesoporous clay adsorbent for adsorption isotherm
and kinetics of methylene blue. Chem. Eng. J. 198–199, 219–227.
Bailey, S.W., Brindely, G.W., Brown, G. (Eds.), 1980. Crystal structures of clay minerals and
their X-ray identification, 5. Monography-Mineralogical Society, London, pp. 1–124.
Handbook of Clay Science. In: Bergaya, F., Lagaly, G. (Eds.), Developments in Clay Science,
5, 2nd ed. Elsevier, Amsterdam, pp. 1–813.
Bestani, B., Benderdouche, N., Benstaali, B., Belhakem, M., Addou, A., 2008. Methylene
blue and iodine adsorption onto an activated desert plant. Bioresour. Technol. 99,
8441–8444.
Bjerrum, J., McReynolds, J.P., 1946. Hexamminecobalt(III) salts. Inorg. Synth. 2, 216–221.
Bouzid, S., Khenifi, A., Bennabou, K.A., Trujillano, R., Vicente, M.A., Derriche, Z., 2015. Re-
moval of orange II by phosphonium-modified Algerian bentonites. Chem. Eng.
Commun. 202, 520–533.
Bulut, Y., Karaer, H., 2015. Adsorption of methylene blue from aqueous solution by
crosslinked chitosan/bentonite composite. J. Dispers. Sci. Technol. 36, 61–67.
Cottet, L., Almeida, C.A.P., Naidek, N., Viante, M.F., Lopes, M.C., Debacher, N.A., 2014.
Adsorption characteristics of montmorillonite clay modified with iron oxide with re-
spect to methylene blue in aqueous media. Appl. Clay Sci. 95, 25–31.
Da Fonseca, M.G., De Oliveira, M.M., Arakaki, L.N.H., 2006. Removal of cadmium, zinc,
manganese and chromium cations from aqueous solution by a clay mineral.
J. Hazard. Mater. B137, 288–292.
Davranche, M., Lacour, S., Bordas, F., Bollinger, J.C., 2003. An easy determination of the sur-
face chemical properties of simple and natural solids. J. Chem. Educ. 80, 76–78.
DiazGomez-Trevino, A.P., Martinez-Miranda, V., Solache-Rios, M., 2013. Removal of
remazol yellow from aqueous solutions by unmodified and stabilized iron modified
clay. Appl. Clay Sci. 80–81, 219–225.
Dogan, M., Ozdemir, Y., Alkan, M., 2007. Adsorption kinetics and mechanism of cationic
methyl violet and methylene blue dyes onto sepiolite. Dyes Pigments 75, 701–713.
Eskandarian, L., Arami, M., Pajootan, E., 2014. Evaluation of adsorption characteristics of
multiwalled carbon nanotubes modified by a poly(propylene imine) dendrimer in
single and multiple dye solutions: isotherms, kinetics, and thermodynamics.
J. Chem. Eng. Data 59, 444–454.
Fan, L.L., Luo, C.N., Li, X.J., Lu, F.G., Qiu, H.M., Sun, M., 2012. Fabrication of novel magnetic
chitosan grafted with graphene oxide to enhance adsorption properties for methyl
blue. J. Hazard. Mater. 215, 272–279.
Fatimah, I., Wang, S., Wulandari, D., 2011. ZnO/montmorillonite for photocatalytic and
photochemical degradation of methylene blue. Appl. Clay Sci. 53, 553–560.
140 J. Chang et al. / Applied Clay Science 119 (2016) 132–140
Freundlich, H.M.F., 1906. Uber die adsorption in Losungen. Z. Phys. Chem. 57, 385–470.
Ghorai, S., Sarkar, A.K., Panda, A.B., Pal, S., 2013. Effective removal of Congo red dye from
aqueous solution using modified xanthan gum/silica hybrid nanocomposite as adsor-
bent. Bioresour. Technol. 144, 485–491.
Hajjaji, M., Arfaoui, H.E., 2009. Adsorption of methylene blue and zinc ions on raw and
acid-activated bentonite from Morocco. Appl. Clay Sci. 46, 418–421.
Han, R.P., Zou, W.H., Yu, W.H., Cheng, S.J., Wang, Y.F., Shi, J., 2007. Biosorption of methylene
blue from aqueous solution by fallen phoenix tree's leaves. J. Hazard. Mater. 141,
156–162.
Ho, Y.S., McKay, G., 1999. Pseudo-second order model for sorption processes. Process
Biochem. 34, 451–465.
Houndonougbo, Y., Signer, C., He, N., Morris, W., Furukawa, H., Ray, K.G., Olmsted, D.L.,
Asta, M., Laird, B.B., Yaghi, O.M., 2013. A combined experimental-computational in-
vestigation of methane adsorption and selectivity in a series of isoreticular zeolitic
imidazolate frameworks. J. Phys. Chem. C 117, 10326–10335.
Huang, X.Y., Bu, H.T., Jiang, G.B., Zeng, M.H., 2011. Cross-linked succinyl chitosan as an adsor-
bent for the removal of Methylene Blue from aqueous solution. Int. J. Biol. Macromol. 49,
643–651.
Kaya, A., Oren, A.H., 2005. Adsorption of zinc from aqueous solutions to bentonite.
J. Hazard. Mater. B 125, 183–189.
Lagergren, S., 1898. About the theory of so called adsorption of soluble substances. K.
Svenska Vetenskapsakad. Handl. 24, 1–39.
Langmuir, I., 1916. The constitution and fundamental properties of solids and liquids.
J. Am. Chem. Soc. 38, 2221–2295.
Lee, S.M., Tiwari, D., 2012. Organo and inorgano-organo-modified clays in the remedia-
tion of aqueous solutions: an overview. Appl. Clay Sci. 59–60, 84–102.
Li, H.Q., Huang, G.H., An, C.J., Hu, J.T., Yang, S.Q., 2013. Removal of tannin from aqueous so-
lution by adsorption onto treated coal fly ash: kinetic, equilibrium, and thermody-
namic studies. Ind. Eng. Chem. Res. 52, 15923–15931.
Lin, S.L., Song, Z.L., Che, G.B., Ren, A., Li, P., Liu, C.B., Zhang, J.S., 2014. Adsorption behavior
of metal-organic frameworks for methylene blue from aqueous solution. Micropo-
rous Mesoporous Mater. 193, 27–34.
Liu, H.C., Chen, W., Liu, C., Liu, Y., Dong, C.L., 2014. Magnetic mesoporous clay adsorbent:
preparation, characterization and adsorption capacity for atrazine. Microporous
Mesoporous Mater. 194, 72–78.
Magnacca, G., Allera, A., Montoneri, E., Celi, L., Benito, D.E., Gagliardi, L.G., Gonzalez, M.C.,
Martire, D.O., Carlos, L., 2014. Novel magnetite nanoparticles coated with waste-
sourced biobased substances as sustainable and renewable adsorbing materials.
ACS Sustainable Chem. Eng. 2, 1518–1524.
Nandi, B.K., Goswami, A., Purkait, M.K., 2009. Removal of cationic dyes from aqueous so-
lutions by kaolin: kinetic and equilibrium studies. Appl. Clay Sci. 42, 583–590.
Peng, Y.G., Chen, D.J., Ji, J.L., Kong, Y., Wan, H.X., Yao, C., 2013. Chitosan-modified
palygorskite: preparation, characterization and reactive dye removal. Appl. Clay Sci.
74, 81–86.
Polubesova, T., Chen, Y., Navon, R., Chefetz, B., 2008. Interactions of hydrophobic fractions
of dissolved organic matter with Fe3+- and Cu2+-montmorillonite. Environ. Sci.
Technol. 42, 4797–4803.
Randelovic, M.S., Purenovic, M.M., Matovic, B.Z., Zarubica, A.R., Momcilovic, M.Z.,
Purenovic, J.M., 2014. Structural, textural and adsorption characteristics of
bentonite-based composite. Microporous Mesoporous Mater. 195, 67–74.
Salleh, M.A.M., Mahmoud, D.K., Karim, W.A.W.A., Idris, A., 2011. Cationic and anionic dye
adsorption by agricultural solid wastes: a comprehensive review. Desalination 280,
1–13.
View publication stats
Sivakumar, P., Palanisamy, P.N., 2009. Adsorption studies of basic red 29 by a non-
conventional activated carbon prepared from Euphorbia antiquorum L. J. Chem.
Tech. Res. 1, 502–510.
Temkin, M.J., Pyzhev, V., 1940. Recent modifications to Langmuir isotherms. Acta
Physicochem. 12, 217–222 (URSS).
Tong, D.S., Zhou, C.H., Lu, Y., Yu, H.Y., Zhang, G.F., Yu, W.H., 2010. Adsorption of Acid Red G
dye on octadecyl trimethylammonium montmorillonite. Appl. Clay Sci. 50, 427–431.
Toor, M., Jin, B., 2012. Adsorption characteristics, isotherm, kinetics, and diffusion of mod-
ified natural bentonite for removing diazo dye. Chem. Eng. J. 187, 79–88.
Weber, W.J., Morris, J.C., 1963. Kinetics of adsorption on carbon from solution. J. Sanit.
Eng. Div. ASCE 89 (SA2), 31–59.
Weng, C.H., Pan, Y.F., 2007. Adsorption of a cationic dye (methylene blue) onto spent ac-
tivated clay. J. Hazard. Mater. 144, 355–362.
Wu, Q., Li, Z., Hong, H., 2013. Adsorption of the quinolone antibiotic nalidixic acid onto
montmorillonite and kaolinite. Appl. Clay Sci. 74, 66–73.
Wu, L.M., Tong, D.S., Zhao, L.Z., Yu, W.H., Zhou, C.H., Wang, H., 2014a. Fourier transform
infrared spectroscopy analysis for hydrothermal transformation of microcrystalline
cellulose on montmorillonite. Appl. Clay Sci. 95, 74–82.
Wu, L.M., Zhou, C.H., Tong, D.S., Yu, W.H., 2014b. Novel hydrothermal carbonization of
cellulose catalyzed by montmorillonite to produce kerogen-like hydrochar. Cellulose
21, 2845–2857.
Yagub, M.T., Sen, T.K., Ang, H.M., 2012. Equilibrium, kinetics, and thermodynamics of
methylene blue adsorption by pine tree leaves. Water Air Soil Pollut. 223, 5267–5282.
Yao, Y.J., Miao, S.D., Liu, S.Z., Ma, L.P., Sun, H.Q., Wang, S.B., 2012. Synthesis, characteriza-
tion, and adsorption properties of magnetic Fe3O4@graphene nanocomposite. Chem.
Eng. J. 184, 326–332.
Zaghouane-Boudiaf, H., Boutahala, M., Sahnoun, S., Tiar, C., Gomri, F., 2014. Adsorption
characteristics, isotherm, kinetics, and diffusion of modified natural bentonite for re-
moving the 2,4,5-trichlorophenol. Appl. Clay Sci. 90, 81–87.
Zhang, Z.J., Chen, X.Y., Wang, B.N., Shi, C.W., 2008. Hydrothermal synthesis and self-
assembly of magnetite (Fe3O4) nanoparticles with the magnetic and electrochemical
properties. J. Cryst. Growth 310, 5453–5457.
Zhang, D., Zhou, C.H., Lin, C.X., Tong, D.S., Yu, W.H., 2010. Synthesis of clay minerals. Appl.
Clay Sci. 50, 1–11.
Zhang, J.X., Zhou, Q.X., Ou, L.L., 2012. Kinetic, isotherm, and thermodynamic studies of the
adsorption of methyl orange from aqueous solution by chitosan/alumina composite.
J. Chem. Eng. Data 57, 412–419.
Zhao, D., Cheng, J., Chen, J.W., 2014. One-step synthesis of bentonite-supported nanoscale
Fe/Ni bimetals for rapid degradation of methyl orange in water. Environ. Chem. Lett.
12, 461–466.
Zhou, C.H., 2011a. An overview on strategies towards clay-based designer catalysts for
green and sustainable catalysis. Appl. Clay Sci. 53, 97–105.
Zhou, C.H., Keeling, J., 2013. Fundamental and applied research on clay minerals: from
climate and environment to nanotechnology. Appl. Clay Sci. 74, 3–9.
Zhou, C.H., Shen, Z.F., Liu, L.H., Liu, S.M., 2011. Preparation and functionality of clay-
containing films. J. Mater. Chem. 21, 15132–15153.
Zhou, C.H., Zhang, D., Tong, D.S., Wu, L.M., Yu, W.H., Ismadji, S., 2012. Paper-like compos-
ites of cellulose acetate-organo-montmorillonite for removal of hazardous anionic
dye in water. Chem. Eng. J. 209, 223–234.
Zhu, X.D., Liu, Y.C., Luo, G., Qian, F., Zhang, S.C., Chen, J.M., 2014. Facile fabrication of magnetic
carbon composites from hydrochar via simultaneous activation and magnetization for
triclosa adsorption. Environ. Sci. Technol. 48, 5840–5848.