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Advanced Powder Technology 25 (2014) 17151720

Contents lists available at ScienceDirect

Advanced Powder Technology


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

Original Research Paper

Monodisperse nanostructured Fe3O4/ZnO microrods using for waste


water treatment
Mengmeng Xu, Qiang Li , Huiqing Fan
State Key Laboratory of Solidication Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xian 710072, China

a r t i c l e

i n f o

Article history:
Received 16 March 2014
Received in revised form 9 June 2014
Accepted 23 June 2014
Available online 5 July 2014
Keywords:
Microwave hydrothermal synthesis
Fe3O4/ZnO heterostructures
Photocatalyst
Waste water treatment

a b s t r a c t
Monodisperse nanostructured Fe3O4/ZnO microrods were successfully prepared by an economic one-step
synthesis route. The formation of nanostructured Fe3O4/ZnO microrods was evident from the detailed
structural and elemental analysis by eld emission scanning electronic microscopy, transmission electron
microscopy, Raman spectra and X-ray photoelectron spectroscopy measurements. The formation mechanism of the hexagonal Fe3O4/ZnO microrods was carefully discussed. The removal of toxic metal ions
experiments display that Fe3O4/ZnO heterostructures show the best removal efciency compared with
pure ZnO and Fe3O4 structures, and the photocatalytic experiments show that the Fe3O4/ZnO heterostructures display the excellent photocatalytic activity decomposing Rhodamine B (100% after 40 min).
2014 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved.

1. Introduction
Todays world is facing a tremendous set of environmental
problems related to the remediation of hazardous wastes [13],
contaminated groundwater, and the control of toxic air contaminants [46]. Moreover, evidence is mounting that such problems
threaten human health and have already become a serious public
concern. Therefore, emerging techniques with reference to the
treatment of wastewater and toxic air have been developed,
including adsorption, photodegradation, ion exchange, reverse
osmosis, chemical precipitation and membrane. Among them,
adsorption and photodegradation had been proven to be successful
techniques to remove toxic contaminants from water. In most
cases, these are semiconductor metal oxides [79], porous materials [1013], magnetic oxides [14]. Meanwhile, the steady and fast
development of nanoscience and nanotechnology provide opportunities for improving the performance of these adsorbents and
photocatalysts.
Zinc oxide (ZnO) one-dimensional (1D) nanostructure [1518] has
become promising photocatalyst for their high surface-to-volume
ratio, high photosensitivity, good quantum efciency, chemical
stability and non-toxic nature. Many techniques including chemical
vapor deposition (CVD), template-guided growth, electrospinning
and thermal evaporation have been widely employed over the past
years to synthesize ZnO 1D nanostructure ZnO. In general, these
Corresponding author. Tel.: +86 29 88494463; fax: +86 29 88492642.
E-mail addresses: qli@nwpu.edu.cn, jerrylee57318@hotmail.com (Q. Li).

synthetic methods involve complex procedures, sophisticated


equipments and rigorous experimental conditions. However, these
techniques always require high temperatures and long processing
time. Therefore, large-scale and low-cost controllable growth of
ZnO 1D nanostructure via a one-step synthetic approach is still crucially expected for novel applications. Moreover, Fe3O4 nanoparticles
have superparamagnetic properties and essential functionality
[1922]. The combination of magnetic oxides and ZnO nanocrystals
may lead to high adsorption efciency including metal ions, organic
contaminants, meanwhile promote electronhole pair separation in
the process of photodegradation.
In this paper, nanostructured Fe3O4/ZnO microrods were
fabricated by an economic one-step synthesis route. The removal
efciency of toxic metal ions and photocatalytic performance were
investigated. Compared with pure ZnO and other oxides/ZnO heterostructures, Fe3O4/ZnO microrods show enhanced efciency for
the removal of multiple toxic metal ions (Co2+, Ni2+, Cu2+, Cd2+,
Pb2+, Hg2+ and Fe3+) and the photocatalytic degradation of organic
pollutant. We expect such a monodisperse Fe3O4/ZnO heterostructures will nd its industrial application in the future to remove
undesirable contaminants from the waste water.
2. Experimental
2.1. Synthesis
All the chemicals were of analytical reagent (AR) grade and
used without further purication. In a typical procedure,

http://dx.doi.org/10.1016/j.apt.2014.06.019
0921-8831/ 2014 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.

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M. Xu et al. / Advanced Powder Technology 25 (2014) 17151720

2.5 mmol of Zinc nitrate hexahydrate (Zn(NO3)2  6H2O), 2 mmol


of hexamethylene tetramine (HMTA) and 1.25 mmol of urea
were added to 40 mL deionized water with stirring for 10 min
at room temperature, correspondingly. Then, ve different
molars (0, 0.125, 0.167, 0.25, 0.5 mmol) of Iron (III) chloride
hexahydrate (FeCl36H2O) were dispersed in the solution. In
order to obtain superparamagnetic Fe3O4, 3.6 mmol of glucose
(C6H12O6  H2O) acting as a reducing agent [23,24] was simultaneously added to the solution. After being vigorously stirred
for another 30 min at room temperature, the resulting clear solution was transferred to a Teon vessel of the MDS-6 (Microwave
Digestion/Extraction System, Shanghai Sineo Microwave Chemical Technology Co., Ltd.). A temperature program was established
to make the desired reaction temperature (150 C). The asprepared powders were rinsed several times with deionized
water and pure ethanol and collected by centrifugation, and then
vacuum-dried at 80 C for 8 h. Finally, the Fe3O4/ZnO heterostructures were obtained by calcining the precursor at 500 C
for 2 h in air.

2.2. Characterization
The phase composition and structure of the samples were
characterized by X-ray diffraction (XRD; Xpert, Philips, Holland)
with Cu Ka1 radiation (k = 1.5406 ) at 40 kV and 30 mA over 2h
of range 2060. The morphology of the obtained samples was
investigated using eld emission scanning electronic microscopy
(FE-SEM; JSM-6701F, JEOL, Japan) and transmission electron
microscopy (TEM; JEM-3010, Questar, New Hope, USA). The
X-ray photoelectron spectroscopy (XPS) measurements were performed using Omicron energy analyser (PHI-5400, Perkin Elmer,
USA) instrument with Al Ka as radiation X-ray source. Rhodamine B (RhB) was employed as a representative dye indicator
to evaluate the UV photocatalytic activity of all samples. For
each condition, 30 mg of photocatalyst was ultrasonically dispersed in dye indicator aqueous solution (10 mg/L, 30 mL) and
magnetically stirred in the dark for 30 min to ensure the adsorption/desorption equilibrium of dye indicator on the photocatalyst
surface. Then, UV irradiation was carried out with a 300500 W
uorescent Hg lamp. After a given irradiation time, about 5 mL
of the mixture was withdrawn and the photocatalysts were separated by centrifugation. Photocatalytic degradation process was
monitored using a UVvis spectrophotometer (UV-2450; Shimadzu, Tokyo, Japan) to measure the absorption of RhB at
554 nm. In order to investigate the simultaneous removal of
toxic metal ions, the waste-water was prepared by mixing
40 ml of water containing different toxic metal ions (290.1 mg/
L Ni2+, 290.2 mg/L Co2+, 240.8 mg/L Cu2+, 340.2 mg/L Pb2+,
170 mg/L Ag+). The adsorption experiments were conducted by
mixing 30 mL waste-water with 30 mg of Fe3O4, ZnO and
Fe3O4/ZnO heterostructures. The above mixture was kept in a
water shaker for 24 h at room temperature (30 C) with a continuously magnetically stirring. The nanoadsorbents with adsorbed
metal ions were separated from the mixture by a permanent
magnet. The concentrations of metal ions were measured by
inductively coupled plasma atomic emission spectrometry (ICPAES, Thermo Electron Corporation, New York, USA). The removal
efciency (%) and equilibrium adsorbed concentration of the
metal ions were calculated as follows:

Removal efficiency% C 0  C t =C t  100

where C0 and Ct are the initial and residual concentration of metal


ions (mg/L) in aqueous solution.

3. Results and discussion


3.1. Morphology and composition characterization
Fig. 1(ae) show the FE-SEM images of samples with different
added amount (0, 0.125, 0.167, 0.25, 0.5 mmol) of FeCl3  6H2O
denoted as ZF1, ZF2, ZF3, ZF4, ZF5, respectively. The insets are
the higher magnication SEM images. As shown in Fig. 1a, pencil-like ZnO rods consist of a hexagonal trunk and two hexagonal
tips on one side. The trunk has a diameter of about 2 lm in the
middle and a length of about 10 lm. Nanostructured ZnO microrods with a regular hexagonal shape and at end can be clearly
observed in Fig. 1(bd) when FeCl36H2O is added. In addition,
ZnO hexagonal microrods are covered with many nanoparticles.
Moreover, with the amount of FeCl3  6H2O increases, the covered
nanoparticles occur to accumulate. The diameter and length of
these microrods are in the ranges of 100200 nm and 12 lm,
respectively. Especially, when 0.25 mmol FeCl3  6H2O was added,
monodisperse nanostructured Fe3O4/ZnO microrods were
obtained. Further increase the amount of FeCl36H2O to 0.5 mmol,
the regular morphology of ZnO microrods was destroyed (Fig. 1e),
and we ascribe the results to the introduction of Fe element which
may enter the ZnO lattice or product oxides leading to the change
of nal morphology.
To identify the composition of the heterostructures, HRTEM and
selected-area electron diffraction (SAED) pattern images are shown
in Fig. 2. The HRTEM image in the Fig. 2(a) displays that the hexagonal rods have a lattice spacing of about 0.52 nm, corresponding to
the distance between the (0 0 2) planes in the ZnO crystal lattice,
which demonstrates that the hexagonal rods are composed of well
crystallized ZnO. The nanoparticles covered the surface of the hexagonal rods have a diameters of about 1020 nm and a lattice spacing of about 0.295 nm, corresponding to the distance between the
(2 2 0) planes in the Fe3O4 crystal lattice. Moreover, we can clearly
observe the bonding of the crystal lattice between the nanoparticles and microrods from the HRTEM images. In addition, the SAED
pattern is composed of single-crystalline pattern spots and pattern
rings (Fig. 2(b)), which can be assigned to ZnO microrods and Fe3O4
nanoparticles, respectively. Similar results were obtained by
energy dispersive spectroscopy (EDS) analysis (Fig. 2(c and d)).
The content of Fe in the square region is about seven times greater
than that of hexagonal region, indicating the heterojunction
formed at the interface.
In order to understand the assembling process of the heterogeneous nanostructured Fe3O4/ZnO microrods, we studied the inuence of different parameters on the morphology and phase of
products systematically and found that the content of HMTA and
urea added determine the morphology of the nal products. Firstly,
the role of HMTA was investigated. The SEM images of samples
obtained with different amounts of HMTA (a) 0, (b) 0.5 g added
and the other conditions unchanged from ZF4 are shown in
Fig. 3(a and b), respectively. Compared with ZF4, when no HMTA
was added, pencil-like ZnO rods with a diameter of about
12 lm in the middle and a length of about 1020 lm were
achieved (Fig. 3(a)), and further increasing the quantity of HMTA
to 0.5 g, the length to diameter ratio increased (Fig. 3(b)). Additionally, the amount of urea also plays a crucial role in determining the
morphology of the products. Several experiments with different
amounts of urea such as 0, 0.151 g with the other conditions
unchanged from ZF4 were conducted. The results are shown in
Fig. 3(c and d). As can be seen, without urea added, irregularly
shaped hexagonal rods with a mass of agglomeration are obtained
(Fig. 3(c)). Compared with ZF4, double amount of urea addition
does not make obvious effect on the morphology of hexagonal
rods, but the rods aggregate together. In the reaction process, the

M. Xu et al. / Advanced Powder Technology 25 (2014) 17151720

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Fig. 1. (ae) Show the SEM images of ZF1, ZF2, ZF3, ZF4, ZF5. The insets are the higher magnication SEM images.

Fig. 3. SEM images of samples obtained with different amounts of HMTA or urea
added and other conditions unchanged from ZF4 were conducted: (a and b) 0 g,
0.5 g HMTA added; (c and d) 0 g, 0.151 urea added.
Fig. 2. (a and b) Show the HRTEM and SAED images of ZF4; (c and d) EDS spectra in
the edge and central areas of ZF4.

3.2. Crystal structure and elements analysis


controlled hydrolysis of HMTA and urea in aqueous solutions, it not
only provides the basic alkaline environment for the growth of
ZnO, but also acts as surfactant which can tune the growth rates
along different growing directions. It is proposed that HMTA, being
a long chain polymer and a nonpolar chelating agent, will preferentially attach to the nonpolar facets of the ZnO crystal, thereby cutting off the access of Zn2+ ions to them leaving only the polar (0 0 1)
face for epitaxial growth. Meanwhile, urea can promote the growth
of the six side facets of hexagonal rods.

The XRD study in Fig. 4(a) shows that two sets of diffraction
peaks mixed together can be observed from the spectrum of
samples, which can be indexed to hexagonal wurtzite ZnO (JCPDS
File No. #36-1451) and cubic Fe3O4 (JCPDS File No. #88-0315).
Moreover, the XRD peaks of ZF2ZF5 shift obviously towards
higher diffraction angles compared to those of ZF1, indicating that
iron Fe are introduced into the ZnO host lattice. The calculated
average crystal sizes (D) of Fe3O4 for ZF3 and ZF4 using the
DebyeScherrer formula from XRD patterns are 14.1(1) and

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M. Xu et al. / Advanced Powder Technology 25 (2014) 17151720

Fig. 5. (ac) Show the high-resolution spectra for O, Zn, and Fe elements of ZF1, ZF4,
respectively.

3.3. Photodegradation and removal of toxic metal ions experiments


Fig. 4. (a) XRD and (b) room temperature Raman spectra of all samples (ZF1ZF5).

13.5(6) nm. The result is consistent with that of TEM image.


DebyeScherrer formula for nding the crystallite size (D) is given
as:

D Kk=b cos h

where K is the Scherrers constant and has the value of 0.9 for hexagonal crystal structure, k is the wavelength of the radiation
(1.5418 ), b is the forward width at half maximum radian (FWHM)
and h is the half value of the Bragg diffraction angle in the XRD pattern (degree). The room temperature Raman scattering spectra of
ZF1, ZF2, ZF3, ZF4, ZF5 are presented in Fig. 4(b). For pure ZnO,
the Raman scattering spectrum consists of conventional modes centered at 333, 383, 438 and 583 cm1, which can be attributed to the
processes E2 (H)  E2 (L), A1 (TO), E2 (high), E1 (LO) [2527], respectively. The results demonstrate that the ZnO crystal structure still
retains its wurtzite lattice character. Furthermore, compared with
pure ZnO, Fe3O4/ZnO heterostructures show an additional peak 1
and the gradually disappeared peak 3. The additional and disappeared mode relate to the formation of Fe3O4/ZnO heterostructures.
In addition, as the increase of the ratio of Fe/Zn, the positions of
peak 14 are all shifted towards lower frequencies. Once again, it
proves that a little amount of Fe is incorporated into the ZnO host
lattice.
Then, the XPS analysis is carried out to investigate the surface
feature of ZF1 and ZF4 as shown in Fig. 5. The high-resolution spectra for O, Zn, and Fe species are shown in Fig. 5(ac), respectively.
The typical O1s peak on the surface can be consistently tted by a
strong peak A and a medium partially overlapped peak B. The
peaks of A and B can be assigned to lattice oxygen and weakly
bound oxygen O2 ions in the oxygen decient region, such as
OH groups [2830], respectively. In addition, it is worth mentioning that the surface hydroxyls can produce primary active hydroxyl
radicals, which are capable of trapping photoinduced electrons and
holes. Thus, the surface hydroxyls are very important for photocatalysis. Compared with ZF1, the O1s peaks obviously shift towards
low binding energy. The high-resolution spectra for Fe elements
(Fig. 5b) shows binding energy of 710.48 eV, corresponding to Fe
2p1/2 [31], in good agreement with the values reported for Fe3O4
in the handbook and literature [3234].

The photodegradation of organic pollutant can be considered as


a pseudo-rst-order reaction [35] and its kinetics can be expressed
as follows:

C C 0 ekt

where k is the degradation rate constant, C0 and C are the initial concentrations of organic pollutant and that at the reaction time t,
respectively. Fig. 6(a) displays the ln (C/C0)  t plots for photodegradation of Fe3O4/ZnO heterostructures photocatalysts with different Fe3O4/ZnO ratios compared with commercial TiO2. The ZF3
photocatalysis can rapidly decompose RhB completely in 40 min
showing the highest photocatalytic activity, and the degradation rate
constant k = 0.053(3). Fig. 6(b) shows the time dependent absorption
spectra of RhB degradation over ZF4 photocatalysis under UV irradiation. Evidently, the absorbance of RhB decreases rapidly with the
reaction time, which is indicative of the reduction of RhB from colored aqueous solution to colorless. Moreover, the results of the
simultaneous removal experiments of toxic metal ions are shown
in Fig. 6(c). It demonstrates that Fe3O4/ZnO heterostructures show

Fig. 6. (a) The RhB degradation curves of C/C0 versus time for photodegradation of
Fe3O4/ZnO heterostructures photocatalysts with different Fe3O4/ZnO ratios compared with commercial TiO2; (b) the time dependent absorption spectra of RhB
degradation of ZF4 under UV irradiation; and (c) removal efciency of toxic metal
ions (Co2+, Ni2+, Cu2+, Pb2+, Ag+) of pure ZnO, Fe3O4, and Fe3O4/ZnO heterostructures.

M. Xu et al. / Advanced Powder Technology 25 (2014) 17151720

much better removal activity for metal ions than pure Fe3O4 and ZnO.
It is very encouraging to see that almost 100% removal efciency was
achieved for Ag+, Pb2+ ions and 80%, 89.7%, 91.6% removal efciency
for Co2+, Cu2+, Ni2+ using Fe3O4/ZnO heterostructures from wastewater, respectively. It is obvious that the availability of active surface
sites for the adsorption of metal ions increases with the formation of
Fe3O4/ZnO heterostructures. In general, the preference of common
hydrous solids for metals has been related to the metals electronegativity. The electronegativity values of Co2+, Ni2+, Cu2+, are 1.88, 1.91,
1.90, respectively. Due to high electronegativity, Pb2+ and Ag+ exhibit
stronger attraction towards the Fe3O4/ZnO heterostructures and
hence better removal efciency.
The reasons why Fe3O4/ZnO heterostructures have a good
efciency of removal toxic metal ions and photodegradation have
been widely discussed. The better performances of Fe3O4/ZnO
heterostructures over pure ZnO and Fe3O4 could be attributed to
their synergistic effect which provides additional surface active
sites for the adsorption of toxic metal ions. In the case of Fe3O4/
ZnO heterostructures, the presence of magnetic Fe3O4 nanoparticles in the ZnO network provides additional surface active sites
for the adsorption of toxic metal ions and organic pollutants. The
enhanced photocatalytic performance can be ascribed to the different band gaps (ZnO: Eg = 3.37 eV; Fe3O4: Eg = 0.1 eV) and work
functions of ZnO and Fe3O4, which promotes interfacial electron
hole separation in the photocatalytic process, thereby increasing
the number of live photocharges and improving the photocatalytic activity. However, the excess Fe3O4 affects the morphology
of the Fe3O4/ZnO heterostructures, and also reduces the photocatalytic active sites on the surface of ZnO microrods. Therefore, we
can get optimal photocatalytic activity only when the appropriate
Fe content is added.

4. Conclusions
We successfully fabricated the heterogeneous nanostructured
Fe3O4/ZnO microrods via an economic method. The morphology
and composition were carefully characterized by SEM, TEM, XRD,
Raman, XPS, and the results showed the formation of the hexagonal nanostructured Fe3O4/ZnO microrods. Both photocatalysis and
removal of toxic metal ions experiments indicated that Fe3O4/ZnO
heterostructures display the highest efciency. The present work
indicates the suitable nano-heterostructures, increased activity of
ZnO nanocrystals and combination of magnetic oxides, should nd
industrial application in the future to remove undesirable contaminants from the waste water. Certainly, the lm technology should
be developed to overcome the drawbacks related to the use of
powder materials.
Acknowledgements
This work was supported by National Nature Science Foundation (51172187), the SPDRF (20116102130002), the Doctoral fund
of Ministry of Education of China (20116102120016), 111 Program
(B08040) of MOE, Aeronautical Science Foundation of China
(2013ZF53072), Xian Science and Technology Foundation
(CX12174, XBCL-1-08), Shaanxi Province Science Foundation
(2013KW12-02), Shaanxi Province Foundation for Returned Scholars, High-level start-up Funding of NWPU.
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