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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
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.
All the experiments were carried out in triplicate with the reproducibility within 5%.
2.5. Characterization
qe =
(Co Ce )V
m
(1)
122
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)
(220)
(311)
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.
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
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.
Fe O
3 4
Transmittance (a.u.)
Fe O /ZnCr-LDH
3 4
ZnCr-LDH
1635
1384
826
3400
4000
3500
570
520
3000
2500
2000
1500
1000
500
70
Wavenumber (cm-1)
60
Volume (cm3/g)
80
50
40
30
0.2
0.4
0.6
0.8
1.0
0.8
1.0
B
30
2
Surface area = 45 m /g
Volume (cm3/g)
25
20
15
10
5
0.0
0.2
0.4
0.6
124
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.
(2)
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
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
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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
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