Beruflich Dokumente
Kultur Dokumente
a r t i c l e
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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).
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.
1716
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:
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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.
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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Fig. 5. (ac) Show the high-resolution spectra for O, Zn, and Fe elements of ZF1, ZF4,
respectively.
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].
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.
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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