Chemical Engineering Journal 185186 (2012) 120126

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Journal

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

Magnetic Fe3 O4 /ZnCr-layered double hydroxide composite with enhanced

adsorption and photocatalytic activity
Dan Chen , Yang Li, Jia Zhang, Ji-zhi Zhou, Yun Guo, Hong Liu
School of Environmental and Chemical Engineering, Shanghai University, No.99 Shangda Road, Shanghai 200444, PR China

a r t i c l e

i n f o

Article history:
Received 9 November 2011
Received in revised form 10 January 2012
Accepted 10 January 2012
Keywords:
Layered double hydroxide
Fe3 O4
Adsorption
Photocatalysis
Organic dyes

a b s t r a c t
The novel magnetic Fe3 O4 /ZnCr-layered double hydroxide (LDH) composite has been successfully fabricated via two-step microwave hydrothermal method. The characterization by X-ray diffraction (XRD),
Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and transmission
electron microscope (TEM) reveals the Fe3 O4 nanoparticle in size of around 10 nm distributed on the surface of ZnCr-LDH. This provided the magnetic property of the composite, which improved the separation
of the composite from aqueous solution. Moreover, the composite adsorbed 528 mg/g of methyl orange
(MO) as well as decomposed 95% of methylene blue (MB) under UV irradiation. The results reveal a
higher removal of dye on the composite, compared to that on ZnCr-LDH under the same conditions.
Therefore, our work suggests the novel magnetic Fe3 O4 /ZnCr-LDH composite to be applicable for organic
dyes wastewater treatment.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The dyes are widely used in industries including textile, cosmetics, leather and food. However, many organic dyes are harmful to
human being and toxic to microorganisms, so the removal of dyes
has gained more attention in the past few years [1]. Various physical
and chemical technologies, such as coagulating sedimentation [2],
adsorption [3], chemical oxidation, have been developed to remove
the organic dyes from wastewaters. Among these approaches,
adsorption and photocatalysis are two widely used methods for
the removal of organic dyes in aqueous water [46].
As an anionic clay, layered double hydroxide (LDH) is generally
expressed as [M1x 2+ Mx 3+ (OH)2 ]x+ (An )x/n mH2 O, where M2+ represents divalent metal cation, M3+ trivalent metal cation and An
an anion [7,8]. x was denoted as the molar ratio of M3+ to total
metal, ranging from 0.15 to 0.33 for pure LDH formation. LDH has
exhibited its promising application in the adsorption of dye anions
due to its high surface area and the anion exchange property of
its host An [911]. Besides, the photo-decomposition of organic
compounds was found on those LDH composed of various metals
such as Zn, Ni, and Cr [1214]. It is attributed to the well distribution of metals in the brucite-like layer of LDH that allows the dye
sorption inside the particle and high light absorption on the structure of LDH in the spectral range [15]. Despite, it is still an issue
that the separation of LDH from water is difcult in the industrial

Corresponding author. Tel.: +86 21 66137784; fax: +86 21 66137756.

E-mail address: dchen@shu.edu.cn (D. Chen).
1385-8947/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2012.01.059

applications, especially in the treatment of river, lake and other

natural water.
On the other hand, magnetic separation is a very convenient approach for removing and recycling magnetic particles/composites [16,17]. For this purpose, magnetic Fe3 O4 is
prepared and widely used due to its unique magnetic response
and large surface area [1820]. Accordingly, the combination of
Fe3 O4 nanoparticle and LDH has developed recently to enhance
separation and re-dispersion performance of LDH in aqueous solution [21,22]. To the best of our knowledge, the magnetic Fe3 O4 /LDH
composite for enhanced photocatalytic applications has not been
reported.
Therefore, the objectives of our work are to (1) prepare a
magnetic Fe3 O4 /ZnCr-LDH composite via two-step microwave
hydrothermal method; (2) characterize the structure of the asprepared composite under various conditions; (3) investigate the
adsorption capacity and photocatalytic activity of the composite in
the dye removal. Our results show that the Fe3 O4 /ZnCr-LDH composite can be easily prepared and was suggested to be more efcient
in the removal of dye than ZnCr-LDH.
2. Materials and methods
2.1. Synthesis of Fe3 O4
Ferrite with molar Fe3+ /Fe2+ = 2 was prepared by microwave
hydrothermal method described elsewhere [23]. Typically,
Fe(NO3 )3 9H2 O (0.02 mol) and Fe(NO3 )2 6H2 O (0.01 mol) were
dissolved in 25 mL of deionized water. The pH value was adjusted

D. Chen et al. / Chemical Engineering Journal 185186 (2012) 120126

121

to 10.0 by adding NH3 H2 O. The microwave hydrothermal treatment of this mixed solution was carried out in the sealed reactor
with Teon liner at 150 C and pressure of 30 psi for 30 min. After
cooling down, the precipitate was collected by ltering, washing
repeatedly with deionized water, and drying in the oven at 80 C
overnight.
2.2. Synthesis of Fe3 O4 /ZnCr-LDH composite
Zn(NO3 )2 6H2 O (0.08 mol) and Cr(NO3 )3 9H2 O (0.04 mol) were
dissolved in 25 mL of deionized water. Fe3 O4 nanoparticle of 0.2 g
was dispersed to this ZnCr solution with ultrasonic treatment
for 15 min at room temperature. Synchronously, NH3 H2 O was
pumped to adjust the pH to 8.0. After ultrasonication, the suspension was poured into the sealed reactor with Teon liner. The
microwave hydrothermal treatment was performed at 150 C, pressure 30 psi for 30 min. The as-obtained particle was separated by a
magnet. Subsequently, the as-prepared Fe3 O4 /ZnCr-LDH composite was dried at 80 C in a vacuum oven for 12 h. In comparison,
the pure ZnCr-LDH was prepared in the similar way without Fe3 O4
addition.

Fig. 1. A representative low magnication TEM images of Fe3 O4 /ZnCr-LDH.

All the experiments were carried out in triplicate with the reproducibility within 5%.

2.3. Adsorption tests

Kinetic study was conducted to nd out the equilibrium time
of MO sorption on the Fe3 O4 /ZnCr-LDH composite at room temperature. The solid/solution ratio was 0.25 g/L and the initial
concentration of MO was 100 mg/L. Suspensions were stirred for
different time interval (5 min to 24 h). The dye concentration in the
solution was recorded on a UVvis spectrophotometer at 462 nm
after the separation of particles by a magnet. For comparison, the
removal of dye was performed in the similar way on the physical mixture of Fe3 O4 and ZnCr-LDH (75 wt.% ZnCr-LDH and 25 wt.%
Fe3 O4 , Fe3 O4 + ZnCr-LDH), the pure ZnCr-LDH and Fe3 O4 .
The sorption isotherms were established on Fe3 O4 /ZnCr-LDH
and the physical mixture of Fe3 O4 and ZnCr-LDH in the MO solution
(solid/solution ratio = 0.25 g/L) with its initial concentration from
50 to 500 mg/L. The suspensions were stirred during equilibrium
times. The dye concentration in the solution was monitored with
the UVvis spectrophotometer at 462 nm after the separation of
particles by a magnet.
The quantity of dye adsorbed at equilibrium was calculated by
the following expression:

2.5. Characterization

where m is mass of sorbent (g), V is the volume of the solution (L),

Co is the initial concentration of sorbate (mg/L), Ce is the equilibrium sorbate concentration (mg/L) and qe is the quantity of sorbate
adsorbed at equilibrium (mg of MO per g of sorbent).

Morphologies images of Fe3 O4 /ZnCr-LDH were taken on the

scanning electron microscope (SEM, JEOLJSM6700) with gold coating and transmission electron microscope (TEM, Hitachi H-800).
The samples for TEM were prepared by dispersing the powder
in ethanol and coating a very dilute suspension on carbon-coated
Cu grids. N2 adsorptiondesorption isotherms were measured by
using Micromeritics Tristar 3000 at 77 K. The specic surface areas
were evaluated using BrunauerEmmettTeller (BET) method values based on the absorption isotherm. The X-ray diffraction (XRD)
were recorded on the powder X-ray diffractometer (Model XD-3A,
Shinaduzu Co., Japan) using Cu K radiation ( = 0.154 nm, 34 kV,
20 mA) at a scanning rate of 8 min1 from 2 = 5 to 2 = 80 .
Fourier transform infrared (FTIR) spectra are collected on a Thermo
Nicolet FTIR 8700 instrument in the range of 4304000 cm1 with
resolution of 4 cm1 using the KBr pellet technique. The inductively coupled plasma atomic emission spectrometry (ICP-AES,
Shimadzu, ICPS-7510) was used to determine the concentration of
heavy metals in the solution after the dissolution of the precipitate
in 0.1 M of HNO3 solution. Vibrating sample magnetometer (VSM,
7407 type, LakeShore Company, America) was used to measure the
magnetic properties of synthesized materials. The UVvis spectra
were recorded by an UV-spectrophotometer (ET99731, Tintometer
GmbH, Germany).

2.4. Photocatalytic tests

3. Results and discussion

Photocatalytic activity of the samples was determined by the

degradation of MB solution under UV light irradiation. In this experiment, the reaction mixture was stirred in the dark for 1 h to ensure
that MB was adsorbed to saturation on the catalysts. Afterwards,
the solutions were irradiated with UV light with a 500 W medium
Hg lamp. Photocatalyst of 50 mg was added into 50 mL MB (5 mg/L)
solution with a solid/water ratio of 1 g/L. At a given time interval
of irradiation, 5 mL aliquots was withdrawn and then magnetically
separated to remove essentially all the catalysts. The concentrations of the remnant dye were spectrophotometrically monitored
by measuring the absorbance of solutions at 655 nm during the
photodegradation process. The blank reaction was carried out following the same procedure without adding the catalyst.

3.1. Physicochemical characterization of Fe3 O4 /ZnCr-LDH

composite

qe =

(Co Ce )V
m

(1)

Fig. 1 shows TEM image of Fe3 O4 /ZnCr-LDH composite, which

illustrates the dark spot of Fe3 O4 dispersed on the plate-like LDH
via two-step microwave hydrothermal method. They are approximately hexagonal and wide nature, with an average diameter close
to 50150 nm. These were commonly observed for typical LDH
compounds. Moreover, the sizes of Fe3 O4 nanoparticle are around
10 nm, without free-standing ones in the structure. It is also worth
noting that the composite was found stable when subjected to stirring or ultrasound treatment. SEM images of the ZnCr-LDH (A and
C) and Fe3 O4 /ZnCr-LDH (B and D) are shown in Fig. 2. It can be

122

D. Chen et al. / Chemical Engineering Journal 185186 (2012) 120126

Fig. 2. SEM images of ZnCr-LDH (A and C) and Fe3 O4 /ZnCr-LDH (B and D).

(440)

(511)

(422)

(400)

iii

10

20

30

(113),(110)

(018)

(006)

(012),(009)

ii
(003)

Relative intensity (a.u.)

(220)

(311)

seen that Fe3 O4 /ZnCr-LDH has a bigger diameter than ZnCr-LDH.

Fe3 O4 /ZnCr-LDH shows a plate-like morphology with agglomerated Fe3 O4 nanoparticle onto the plate surfaces, compared to the
relatively smooth surface of ZnCr-LDH. All these prove the successful synthesis of Fe3 O4 /ZnCr-LDH composite and indicate that the
surface of ZnCr-LDH was modied by Fe3 O4 nanoparticle in the
composite.
XRD patterns for ZnCr-LDH (curve i), Fe3 O4 (curve iii) and
Fe3 O4 /ZnCr-LDH (curve ii) are shown in Fig. 3. The peaks located at
(0 0 3), (0 0 6), (0 0 9)/(0 1 2), (0 1 8) and (1 1 0)/(1 1 3) are ascribed
to the characteristic peaks of the rhombohedral phase of LDH

40

50

60

i
70

2 (degree)
Fig. 3. XRD patterns of (i) ZnCr-LDH, (ii) Fe3 O4 /ZnCr-LDH and (iii) Fe3 O4 .

with lattice parameters a of 2.977 A and c of 26.84 A [24], indicating the formation of ZnCr-LDH. There is a series of characteristic
peaks at 2 = 30.1, 35.6, 43.4, 70.0, 62.7, being similar to the
previously reported data for Fe3 O4 nanoparticle [25,26]. No characteristic peaks of other materials were detected, so it is believed
that Fe3 O4 /ZnCr-LDH is a composite of ZnCr-LDH with Fe3 O4 .
Moreover, the intensities of the characteristic reections for both
ZnCr-LDH and ferrite phases in Fe3 O4 /ZnCr-LDH are not obviously
changed compared to those in pure ZnCr-LDH and Fe3 O4 nanoparticle, respectively. It demonstrates that the combination of Fe3 O4
nanoparticle and ZnCr-LDH was accepted as a physical process [21].
FTIR spectroscopy (Fig. 4) was proven to be characterized by
Fe3 O4 /ZnCr-LDH, ZnCr-LDH and Fe3 O4 . The absorption of the characteristic groups of ZnCr-LDH in Fe3 O4 /ZnCr-LDH is similar to
the pure ZnCr-LDH. The strong and broad bands centered around
3400 cm1 are associated with the O H stretching vibrations of
the hydroxyl groups in the layers and interlayer water molecules
[27]. The water deformation band is observed at 1635 cm1 . D3h
of interlayer NO3 vibration appears at 1384 cm1 and 826 cm1 .
The shoulder at 520 cm1 is assigned to M O lattice vibrations. In
addition, it is found that the band at 579 cm1 is due to the lattice vibrations of Fe O in the Fe3 O4 /ZnCr-LDH phase [28]. Infrared
analysis not only strongly conrms that the Fe3 O4 assembled on
ZnCr-LDH, but also indicated that no obvious interaction existed
from ZnCr-LDH and Fe3 O4 by microwave hydrothermal method.
Table 1 summarizes the elemental information of the two
particles (ZnCr-LDH, Fe3 O4 /ZnCr-LDH). The Zn:Cr molar ratio
in ZnCr-LDH and Fe3 O4 /ZnCr-LDH is measured around 1.81.9,
which approximates the ratio in the precursor solution (2.0). In
Fe3 O4 /ZnCr-LDH, the mass ratio of two constituent compounds was
approximately 3:1, which corresponds to molar Fe/Zn ratio of 1:1
as designed.

D. Chen et al. / Chemical Engineering Journal 185186 (2012) 120126

123

Table 1
Summarizes the elemental analysis data for samples ZnCr-LDH and Fe3 O4 /ZnCr-LDH.
Zn (wt%)a

Sample

Cr (wt%)a

Fe (wt%)a

N (wt%)b

H2 O (wt%)c

Zn:Cr

Zn:Fe

(Calculated molar ratio)

ZnCr-LDH
Fe3 O4 /ZnCr-LDH
a
b
c

32.00
21.13

14.06
8.89

14.53

3.185
2.612

3.08
4.03

1.81
1.89

1.24

The weight percentage of zinc, chromium, iron obtained from ICP measurements.
The weight percentage of N obtained from CHNS elemental analysis.
The weight loss percentage of dry sample from TG analysis between 25 and 200 C.

be the reaction site. Fig. 6 shows the N2 sorption hysteresis loop of

the materials at 77 K. It can be calculated by the BET method that
the surface area of ZnCr-LDH is 45 m2 /g, while that of Fe3 O4 /ZnCrLDH is higher at 114 m2 /g. This result implies that Fe3 O4 /ZnCr-LDH
would result in a better catalytic and adsorption activity than that
for ZnCr-LDH.

Fe O
3 4

Transmittance (a.u.)

Fe O /ZnCr-LDH
3 4

3.2. Adsorption capacity of Fe3 O4 /ZnCr-LDH composite

Fig. 7(A) shows the removal of MO in aqueous solution with the
different dosages of Fe3 O4 /ZnCr-LDH. At the dosage of 0.8 g/L, the
sample rapidly (within 10 min) adsorbed 99% of MO with its initial

ZnCr-LDH

1635
1384

826

3400

4000

3500

570
520

3000

2500

2000

1500

1000

500

70

Wavenumber (cm-1)

60

Volume (cm3/g)

Fig. 4. FTIR spectra of ZnCr-LDH, Fe3 O4 and Fe3 O4 /ZnCr-LDH.

The curve exhibits a ferromagnetic behavior of the composite

with values of saturation magnetization (Ms ), remnant magnetization (Mr ), and coercivity (Hc ) of about 22.6 emu/g, 1.09 emu/g
and 45.0 G. The complete separation of the composite with magnet
was shown in Fig. 5. The magnetic separability of such a magnetic
composite was tested in water by placing a magnet near the glass,
clearly demonstrating the magnetic properties of composite (the
inset of Fig. 5). Therefore, separating the magnetic Fe3 O4 /ZnCr-LDH
composite rapidly becomes positive for the environmental protection and other applications.
The low temperature N2 sorption analysis was conducted to
compare the adsorption and photocatalytic activity of Fe3 O4 /ZnCrLDH and ZnCr-LDH by studying the specic surface area, which can

80

50
40
30

Surface area = 114 m /g

20
10
0.0

0.2

0.4

0.6

0.8

1.0

0.8

1.0

Relative pressure (p/po)

B
30
2

Surface area = 45 m /g

Volume (cm3/g)

25

20

15

10

5
0.0

0.2

0.4

0.6

Relative pressure (p/po)

Fig. 5. Magnetization characteristic curve of Fe3 O4 /ZnCr-LDH, the inset of gure is
the photographs of the magnetic composite in aqueous solution.

Fig. 6. N2 sorption isotherms of (A) Fe3 O4 /ZnCr-LDH and (B) ZnCr-LDH.

124

D. Chen et al. / Chemical Engineering Journal 185186 (2012) 120126

A
1.6

1.4

Q (mmol/g)

Intensity (a.u.)

0 g/L
0.1 g/L

0.4 g/L
0.8 g/L

1.2

Fe3O4+ZnCr-LDH
Fe3O4/ZnCr-LDH

1.0

0.8
0.6

0
200

300

400

500

600

0.0

700

0.2

0.4

Wavelength(nm)

0.6

0.8

1.0

1.2

Ce (mmol/L)

100

0.8
0.7
0.6
0.5

60

Fe3O4/ZnCr-LDH
Fe3O4+ZnCr-LDH

40

ZnCr-LDH
Fe3O4

20

Ce/Q

Removal of MO %

80

0.4
0.3

Fe3O4+ZnCr-LDH
Fe3O4/ZnCr-LDH

0.2
0.1

10

15

20

25

0.0
0.0

0.2

Time (h)
Fig. 7. (A) UVvis adsorption spectra of MO before and after adsorption by
Fe3 O4 /ZnCr-LDH at different dosages. Initial MO concentration: 100 mg/L, contact
time: 10 min and (B) MO adsorption kinetics over Fe3 O4 /ZnCr-LDH, Fe3 O4 + ZnCrLDH, ZnCr-LDH and Fe3 O4 .

concentration of 100 mg/L, and at the lower dosage of 0.4 g/L, 67%
of the adsorption capacity are achieved in less than 10 min.
The removal process as the function of time is shown in Fig. 7(B).
The adsorption behavior of Fe3 O4 /ZnCr-LDH is similar to that of
Fe3 O4 + ZnCr-LDH with a rapid initial uptake and a subsequent
stable stage. Compared with Fe3 O4 + ZnCr-LDH, Fe3 O4 /ZnCr-LDH
takes more time to reach the adsorption equilibrium. After stirring for about 2.5 h, the MO loading (90.4 mg/L) become almost
constant, indicating attainment of equilibrium. However, the equilibrium removal of MO by Fe3 O4 /ZnCr-LDH is nearly 90%, higher
than that for Fe3 O4 + ZnCr-LDH (about 85%) in 24 h. Furthermore,
the removal efciency of MO using pure Fe3 O4 and ZnCr-LDH,
which are used with their respective dosages, are shown in Fig. 7(B).
The MO removal over Fe3 O4 + ZnCr-LDH is approximately equal to
the sum of MO removal over ZnCr-LDH and Fe3 O4 . Therefore, in
the case of Fe3 O4 /ZnCr-LDH, the modication of Fe3 O4 on the LDH
surface improves the adsorption capacity of the composite.
The equilibrium sorption experimental data of MO by
Fe3 O4 /ZnCr-LDH and Fe3 O4 + ZnCr-LDH phases are presented in
Fig. 8(A).
Adsorption isotherms are an important way of probing the
mechanism of adsorption of MO on the adsorbent surface and
several adsorption equilibrium models are used to describe the
adsorbent interface phase of isotherm at constant temperatures,

0.4

0.6

0.8

1.0

1.2

Ce (mmol/L)
Fig. 8. (A) MO adsorption isotherms and (B) Langmuir adsorption isotherms over
Fe3 O4 /ZnCr-LDH and Fe3 O4 + ZnCr-LDH.

such as the Langmuir, Freundlich, and RedlichPeterson [29,30].

The Langmuir model is the most general and effective for monolayer adsorption onto surface with a nite number of identical
sites. The Langmuir model is based on the assumptions that all
the adsorption sites are equivalent (i.e. the surface of the adsorbent is uniform); all adsorption occur by the same mechanism; the
adsorption occurs in a monolayer form and there is no interaction
between adsorbed molecules [31,32]. The expression for Langmuir
adsorption isotherms, after applying the Langmuir linear regression
is:
1
Ce
Ce
+
=
Q
Qm
Qm KL

(2)

where Ce (mmol/L) is the equilibrium concentration of MO in the

solution, Q (mmol/g) is the amount of MO removed per gram of
adsorbent, and Qm (mmol/g) is the maximum amount adsorbed
per unit mass of the solid. KL (L/mmol) is the Langmuir constant
related to adsorption energy. Langmuir adsorption curves are presented in Fig. 8(B). The calculated Langmuir model parameters
(KL , Qm ) and linearization coefcients (R2 ) are given in Table 2.
It can be seen from Table 2 that the linearization coefcient R2
values of Fe3 O4 /ZnCr-LDH for Langmuir model are higher than
those of Fe3 O4 + ZnCr-LDH. Furthermore, the results point out
that the theoretical Langmuir maximum adsorption capacity of

D. Chen et al. / Chemical Engineering Journal 185186 (2012) 120126

Table 2
Langmuir parameters Qm , KL and linearization coefcient R2 for the adsorption of
MO by Fe3 O4 /ZnCr-LDH and Fe3 O4 + ZnCr-LDH.
Sample

Qm (mmol/g)

KL (L/mmol)

R2

Fe3 O4 /ZnCr-LDH
Fe3 O4 + ZnCr-LDH

1.636
1.527

308.711
164.542

0.9999
0.9998

125

process, the composite showed enhanced adsorption and photocatalytic activity. The adsorption capacity was up to 1.64 mmol/g, and
around 95% of dyes were photodegraded in 3 h. Magnetic measurement shows that Fe3 O4 /ZnCr-LDH is magnetic with a saturation
magnetization of 22.6 emu/g and a coercive force of 45.0 G. Finally,
it means that the magnetic composite can be widely applied as ideal
candidates for the treatment of organic dyes polluted wastewater.

100

only UV
UV+ZnCr-LDH
UV+Fe3 O4 /ZnCr-LDH

% MB removed

80

Acknowledgments
This study was carried out under the key subject of Shanghai Municipality (S30109), as well as been supported by National
Nature Science Foundation of China no. 50704023, no. 50974086
and Shanghai University Excellence Youth Fund.

60

40

References

20

0
0.0

0.5

1.0

1.5

2.0

2.5

3.0

Irradiation Time (min)

Fig. 9. The photodegradation of MB by Fe3 O4 /ZnCr-LDH and ZnCr-LDH photocatalysts as a function of UV light irradiation time.

Fe3 O4 /ZnCr-LDH (1.64 mmol/g) is larger than that of Fe3 O4 + ZnCrLDH (1.53 mmol/g).
3.3. Photocatalytic activity of Fe3 O4 /ZnCr-LDH composite
MB is applied as a model dye which is widely used for photocatalytic investigations. The MB stability against photocatalysis
increases as the pH decreases, but the correction of the pH to lower
values than 5.4 (the pH of the as-prepared solution) will lead to
the dissolution of hydrotalcite [33]. Thus, pH value was around 5.4.
The curves of the degradation efciency with irradiation time are
shown in Fig. 9. Compared to the low degradation of MB in the
blank test, 95% of MB was decomposed on Fe3 O4 /ZnCr-LDH within
3 h, indicating the expected performance of the composite in photocatalysis. In contrast, 58.1% MB can be photodegraded by pure
ZnCr-LDH under UV-light in 3 h. This result indicates that the modication of Fe3 O4 nanoparticle on the LDH surface contributed to
the enhanced photocatalytic capacity of ZnCr-LDH. The improvement of photocatalysis was probably attributed to the following
two factors: rst, adsorption capability is very crucial to photocatalytic reactions. Fe3 O4 /ZnCr-LDH has a higher adsorption capability
than the pure ZnCr-LDH. Second, Fe3 O4 /ZnCr-LDH has a special coupled nanostructure: a spot of Fe3 O4 nanoparticle coupled to the
surface of ZnCr-LDH and therefore any transferred charge carriers have more opportunities to be accessible for either oxidants or
reductants in the solution [34].
4. Conclusion
In this work, Fe3 O4 /ZnCr-LDH composite, as adsorbent and
photocatalyst, has been synthesized via two-step microwave
hydrothermal method. The material composition and stoichiometry, as well as its magnetic and optical properties, have been
examined and veried by various characterization techniques.
Meanwhile, adsorption capacity and photodegradation activity
were tested on Fe3 O4 /ZnCr-LDH. During the whole construction

[1] T. Robinson, G. McMullan, R. Marchant, P. Nigam, Remediation of dyes in textile

efuent: a critical review on current treatment technologies with a proposed
alternative, Bioresour. Technol. 77 (2001) 247255.
[2] V. Golob, A. Vinder, M. Simonic, Efciency of the coagulation/occulation
method for the treatment of dyebath efuents, Dyes Pigments 67 (2005) 9397.
[3] S. Papic, N. Koprivanac, A.L. Bozic, A. Metes, Removal of some reactive dyes
from synthetic wastewater by combined Al (III) coagulation/carbon adsorption
process, Dyes Pigments 62 (2004) 291298.
[4] V.K. Gupta, P.J.M. Carrott, M.M.L. Ribeiro Carrott, Suhas, Low cost adsorbents:
growing approach to wastewater treatmenta review, Crit. Rev. Environ. Sci.
Technol. 39 (2009) 783842.
[5] M.R. Hoffmann, S.T. Martin, W. Choi, D.W. Bahnemann, Environmental applications of semiconductor photocatalysis, Chem. Rev. 95 (1995) 6996.
[6] B. Tryba, A.M. Morawski, T. Tsumura, M. Toyoda, M. Inagaki, Hybridization of
adsorptivity with photocatalytic activity-carbon-coated anatase, J. Photochem.
Photobiol. A 167 (2004) 127135.
[7] F.Z. Zhang, X. Xiang, F. Li, X. Duan, Layered double hydroxides as catalytic
materials: recent development, Catal. Survey Asia 12 (2008) 253265.
[8] P.A. Terry, Characterization of Cr ion exchange with hydrotalcite, Chemosphere
57 (2004) 541546.
[9] X. Duan, D.G. Evans (Eds.), Layered Double Hydroxides: Structure and Bonding
(Berlin), Springer-Verlag, Berlin, 2006, p. 119.
[10] A.I. Khan, D. OHare, Intercalation chemistry of layered double hydroxides:
recent developments and applications, J. Mater. Chem. 12 (2002) 31913198.
[11] E. Alvarez-Ayuso, H.W. Nugteren, Purication of chromium (VI) nishing
wastewaters using calcined and uncalcined MgAlCO3 hydrotalcite, Water
Res. 39 (2005) 25352542.
[12] C.G. Silva, Y. Bouizi, V. Fornes, H. Garcia, Layered double hydroxides as highly
efcient photocatalysts for visible light oxygen generation from water, J. Am.
Chem. Soc. 131 (2009) 1383313839.
[13] P. Benito, M. Herrero, F.M. Labajos, V. Rives, C. Royo, N. Latorre, A. Monzon, Production of carbon nanotubes from methane use of Co-Zn-Al catalysts prepared
by microwave-assisted synthesis, Chem. Eng. J. 149 (2009) 455462.
[14] G.J. Cui, X.Y. Xu, T.J. Lin, D.G. Evans, D.Q. Li, Synthesis and UV absorption
properties of 5,5 -methylenedisalicylic acid-intercalated ZnAl layered double
hydroxides, Ind. Eng. Chem. Res. 49 (2010) 448453.
[15] M. Vernic, B. Graciela, A. Norma, L. Miguel, Ethanol steam reforming using
Ni(II)Al(III) layered double hydroxide as catalyst precursor kinetic study,
Chem. Eng. J. 138 (2008) 602607.
[16] S.K. Li, F.Z. Huang, Y. Wang, Y.H. Shen, L.G. Qiu, A.J. Xie, S.J. Xu, Magnetic
Fe3 O4 @C@Cu2 O composites with bean-like core/shell nanostructures: synthesis, properties and application in recyclable photocatalytic degradation of dye
pollutants, J. Mater. Chem. 21 (2011) 74597466.
[17] J. Xie, K. Chen, H.Y. Lee, C. Xu, A.R. Hsu, S. Peng, X. Chen, S. Sun, Ultrasmall c(RGDyK)-coated Fe3 O4 nanopatticles and their specic targeting to
integrinv 3 -rich tumor cells, J. Am. Chem. Soc. 130 (2008) 75427543.
[18] J.L. Arias, M.A. Ruiz, V. Gallardo, Tegafur loading and release properties of magnetite/poly (alkylcyanoacrylate) (core/shell) nanoparticles, J. Control. Release
125 (2008) 5058.
[19] W.R. Zhao, J.L. Gu, L.X. Zhang, H.R. Chen, J.L. Shi, Fabrication of uniform magnetic nanocomposite spheres with a magnetic core/mesoporous silica shell
structure, J. Am. Chem. Soc. 127 (2005) 89168917.
[20] W. Chiu, P. Khiew, M. Cloke, D. Isa, H. Lim, T.T. Nan, N. Huang, S. Radiman, R.
Abd-Shukor, M.A.A. Hamid, C. Chia, Heterogeneous seeded growth: synthesis
and characterization of bifunctional Fe3 O4 /ZnO core/shell nanocrystals, J. Phys.
Chem. C 114 (2010) 82128218.
[21] C.P. Chen, P. Gunawan, R. Xu, Self-assembled Fe3 O4 -layered double hydroxide
colloidal nanohybrids with excellent performance for treatment of organic dyes
in water, J. Mater. Chem. 21 (2011) 12181225.
[22] Z.P. Yang, X.Y. Gong, C.J Zhang, Recyclable Fe3 O4 /hydroxyapatite composite nanoparticles for photocatalytic applications, Chem. Eng. J. 165 (2010)
117121.

126

D. Chen et al. / Chemical Engineering Journal 185186 (2012) 120126

[23] Y.B. Khollam, S.R. Dhage, H.S. Potdar, Microwave hydrothermal preparation
of submicron-sized spherical magnetite (Fe3 O4 ) powders, Mater. Letters 56
(2002) 571577.
[24] R.R. Delgado, M.A. Vidaurre, C.P.D. Pauli, M.A. Ulibarri, M.J. Avena, Surfacecharging behavior of ZnCr layered double hydroxide, J. Colloid Interface Sci.
280 (2004) 431441.
[25] H. Yan, J. Zhang, C. You, Z. Song, B. Yu, Y. Shen, Inuences of different synthesis
conditions on properties of Fe3 O4 nanoparticles, Mater. Chem. Phys. 113 (2009)
4652.
[26] H.P. Klug, L.E. Alexander, X-Ray Diffraction Procedures for Polycrystalline and
Amorphous Materials, Wiley, New York, 1962, pp. 491538.
[27] M. Bouraada, M. Lafjah, M.S. Ouali, L.-C. de Mnorval, Basic dye removal
from aqueous solutions by dodecylsulfate- and dodecyl benzene sulfonateintercalated hydrotalcite, J. Hazard. Mater. 153 (2008) 911918.
[28] M. Racuciu, Synthesis protocol inuence on aqueous magnetic uid properties,
Curr. Appl. Phys. 9 (2009) 10621066.

[29] G.A. Walker, L.R. Weatherley, Adsorption of acid dyes from aqueous solution
the effect of adsorbent pore size distribution and dye aggregation, Chem. Eng.
J. 83 (2001) 201206.
[30] R. Marangoni, M. Bouhent, C. Taviot-Guho, F. Wypych, F. Lerouxc, Zn2 Al layered double hydroxides intercalated and adsorbed with anionic blue dyes: a
physico-chemical characterization, J. Colloid Interface Sci. 333 (2009) 120127.
[31] A.R. Auxilio, C. Philip, P.C. Andrews, P.C. Junk, The adsorption behavior of C.I.
Acid blue 9 onto calcined MgAl layered double hydroxides, Dyes Pigments 81
(2009) 103112.
[32] Y.W. You, H.T. Zhao, Selenium adsorption on MgAl and ZnAl layered double
hydroxides, Appl. Clay Sci. 20 (2001) 1325.
[33] E. Dvininova, M. Ignata, P. Barvinschib, M. Smithersc, E.A. Popovicia,
New SnO2 /MgAl-layered double hydroxide composites as photocatalysts for
cationic dyes bleaching, J. Hazard. Mater. 177 (2010) 150158.
[34] L. Zhang, W.Z. Wang, L. Zhou, M. Shang, S.M. Sun, Fe3 O4 coupled BiOCl: a highly
efcient magnetic photocatalyst, Appl. Catal. B 90 (2009) 458462.