ARTICLE

pubs.acs.org/JPCC

Synthesis of Porous Fe3O4 Nanospheres and Its Application for the

Catalytic Degradation of Xylenol Orange
Maiyong Zhu and Guowang Diao*
College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002, P. R. China
bS Supporting Information
ABSTRACT: Porous magnetite (Fe3O4) nanospheres composed
of primary nanocrystals have been successfully synthesized by
solvothermal method with FeCl3 3 6H2O serving as the single iron
resource, polyvinylpyrrolidone (PVP) as the capping agent, and
sodium acetate as the precipitation agent. To understand the
formation mechanism of the porous Fe3O4 nanospheres, the
reaction conditions such as the concentration of the precursor,
capping agent, precipitation agent, the reaction temperature, and
reaction time were investigated. The characterization of the as-
prepared product was identified with transmission electronic micro-
scopy (TEM), field emission scanning electronic microscopy (FE-SEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray
photoelectron spectroscopy (XPS), vibrating sample magnetometer (VSM), N2 adsorption
desorption technique, and Fourier
transform infrared spectroscopy (FTIR). The results indicate that the porous Fe3O4 nanospheres display excellent magnetic properties at
room temperature, which allows them to be easily separated from the reaction system with the help of external magnet when they serve as
catalysts. Catalytic activity studies show that the as-prepared porous Fe3O4 nanospheres are highly effective catalysts for the degradation
of xylenol orange (XO) in aqueous solution with H2O2 as oxidant. The degradation reaction is first-order, its rate constant at room
temperature being 0.056 min
1. Furthermore, the catalytic activity of Fe3O4 nanospheres decreases very slightly after seven cycles of the
catalysis experiment. Therefore, porous Fe3O4 nanospheres can serve as effective recyclable catalysts for the degradation of XO.

1. INTRODUCTION temperature, which can be a great challenge for many groups.

During the past few decades, magnetic nanoparticles with
peculiar size and structure have attracted wide attention because
of their unique physical and chemical properties.1
5 Many
strategies have been developed to get a variety of magnetic
nanomaterials, such as iron, cobalt, nickel, alloys, iron oxide,
metal ferrite, and so on.6
8 Of all magnetic materials, magnetite
(Fe3O4) is the most important and most widely used one in many
fields. When prepared into well-defined nanoscale structures,
Fe3O4 may be practically or potentially applied in a wide range
of fields, such as biomolecular separation,9 chemical sensor,10
energy storage,11 catalysis,12
14 microwave absorption,15 biome-
dicine/biotechnology,16
23 and environmental remediation.24
29
Generally speaking, Fe3O4 nanoparticles could be prepared with
different methods including coprecipitation of Fe2+ and Fe3+,
thermal decomposition, microemulsion, and hydrothermal/
solvothermal.30
35 Of all these methods, coprecipitation is a
preferred choice for most researchers because the reaction could
be performed under a mild condition by using water as solvent.
However, the shape of the outcome product is hard to control.7,36
Thermal decomposition is considered to be the best route in
obtaining nanomaterials with controllable size and morphology.
However, the precursors of the product are organometallic com-
pounds, such as Fe(CO)5, metal cupferronates,37 and metal
acetylacetonates,38 which are poisonous. In addition, thermal
decomposition of organometallic compound often requires high
Microemulsions can also be used to synthesize nanoparticles
with specific morphology and uniform size. Unfortunately, this
method consumes a large amount of organic solvent; besides,
organic surfactants are needed to control the size and shape of
the product.39 Compared with other options, solvothermal is
often characterized by low yield, yet with this method almost all
materials can be solubilized by heating and pressurizing the
solvent system to its critical point, allowing the synthesis of high-
quality nanostructured materials.40
Hydrothermal/solvothermal has become one of the most
popular methods to get inorganic nanostructured materials,
especially metals and their oxides, despite low yield.41 Higher
pressure and higher temperature (sometimes even above critical
point of the solvent) occurred in this method and can increase
the solubility of solids and accelerate reactions between solid
species. Regarding magnetic nanomaterials, many research
groups have employed solvothermal method. Gao et al. prepared
water-soluble magnetite nanocrystals with different sizes, that is,
4, 12, and 60 nm, by refluxing 2-pyrrolidone solution of FeCl3.42 Li
and his coworkers reported a generalized hydrothermal method
for synthesizing various nanocrystals by liquid
solid
solution
Received: January 14, 2011
Revised: August 24, 2011
Published: August 26, 2011

r 2011 American Chemical Society 18923 dx.doi.org/10.1021/jp200418j | J. Phys. Chem. C 2011, 115, 18923–18934
The Journal of Physical Chemistry C
reaction.43,44 Pinna et al. reported nonaqueous solvothermal
synthesis of monocrystalline magnetite particles with sizes ranging
from 12 to 25 nm.45 Huang et al. synthesized different kinds of
functionalized magnetic microspheres for different bioapplications
by hydrothermal reduction. The typical procedure is as follows:
mixture consisting of FeCl3, ethylene glycol, sodium acetate, and a
polymer, such as dextran, chitosan, or poly(acrylic acid) (PAA),
was stirred vigorously to form a clear solution, sealed in a Teflon-
lined stainless-steel autoclave, and heated to and maintained at
200 °C for 8
30 h.46 In Yin’s research group, Fe3O4 colloidal
nanocrystal clusters (CNCs), with uniform sizes ranging between
∼30 and ∼180 nm, have been successfully synthesized with
diethylene glycol solvent. These CNC structures were designed
with two-stage growth process in which primary nanocrystals
nucleate first and then aggregate uniformly into larger secondary
structures.47,48
Although a variety of iron oxide nanocrystals with different
morphologies, such as nanorods,49
53 fractal,54 pea-pod-like,55
dumbbell-like,56 cubes,57 wires,58 tubes,59 spindles,60 flakes,61
flower-shaped,27 and hollow spheres,62,63 have been successfully
synthesized, to the best of the authors’ knowledge, there are few
reports on the synthesis of porous Fe3O4 nanoparticles.52,53,64
Compared with the solid counterparts of the same size, porous
nanoparticles have their particular merits, such as high surface
area, less resistance of mass transfer in catalytic system, con-
trollable pore size, and adjustable framework.
In this Article, an effective route for the synthesizing of
monodispersed porous Fe3O4 nanospheres could be adjusted
by controlling the reaction conditions, although solvothermal
method was reported. The average diameter of the porous Fe3O4
nanospheres was ∼250 nm. In this route, ethylene glycol
solution of FeCl3 3 6H2O containing PVP and NaAc was heated
to produce porous Fe3O4 nanospheres, where ethylene glycol
acted as both solvent and reducing agent, NaAc and PVP as the
precipitation and capping agents, respectively. In general, many
reports indicate that template methods can be used to get hollow
and porous nanostructures. However, in doing so, the presynthe-
sized templates and the removal of them without destruction
of the product are required, which make the procedures
complex.65,66 Compared with that method, the one reported in
this study is more convenient. The effects of temperature, time,
as well as the concentration of FeCl3 3 6H2O, NaAc, and PVP on
the crystal phase of the product and its final structure were
investigated. On the basis of the investigation, a possible me-
chanism for the formation of porous Fe3O4 nanospheres was
suggested. The as-prepared porous Fe3O4 nanospheres show
excellent magnetic behavior at room temperature, which makes it
suitable to work as a recyclable heterogeneous catalyst because
they can be separated easily from the reaction system by an
external magnet. The degradation of xylenol orange, using H2O2
as the oxidation reagent, was chosen as a model reaction to
investigate its catalytic activity. The results indicate that the
porous Fe3O4 nanospheres synthesized in this Article exhibit
high catalytic activity for the degradation of xylenol orange by
H2O2. The porous Fe3O4 nanospheres could be separated
conveniently from the reaction system with an external magnet
field and can be used in recycling.
2. EXPERIMENTAL SECTION
2.1. Chemicals. All chemicals were analytical grade and
purchased from Sinopharm Chemical Reagents Company. The
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water used in this study was deionized by milli-Q Plus system
(Millipore, France), whose electrical resistance is 18.2 MΩ.
2.2. Syntheses of Porous Fe3O4 Nanospheres. Porous
Fe3O4 nanospheres were prepared with the solvothermal. We
added 1.5 g FeCl3 3 6H2O, 1 g PVP, and 2 g NaAc to 30 mL of
ethylene glycol. The mixture was stirred vigorously for 2 h to
ensure all materials dissolve completely. Then, the mixture was
transferred to a Teflon-lined stainless-steel autoclave and sealed
for heating at 200 °C for 8 h. The precipitated black products
were collected from the solution with an external magnet and
washed with ethanol for a few times. Finally, the black products
were dried in a vacuum at 60 °C for 24 h. The sizes of the as-
prepared porous Fe3O4 nanospheres could be controlled by
changing the concentration of FeCl3 3 6H2O, PVP, and NaAc, or
the reaction temperature.
2.3. Characterization. Transmission electron microscopy
(TEM: Tecnai-12, HRTEM: Tecnai-G2 F30 S-TWIN, Philips)
and field emission scanning electron microscopy (FE-SEM;
Hitachi S-4800) were used to observe the morphologies of
the product. X-ray powder diffraction (XRD) was performed
on a D8 Advance (Super speed) X-ray diffractometer (Bruker).
Raman spectra were taken on a Renishaw InVia spectrometer at
room temperature with an argon-ion laser at an excitation
wavelength of 532 nm. The X-ray photoelectron spectroscopy
(XPS) experiments were carried out on a Thermo Escalab 250
system using Al Kα radiation (hν = 1486.6 eV). The test chamber
pressure was maintained below 2  10
9 Torr during spectral
acquisition. The Fourier transform infrared (FT-IR) spectra were
recorded with a Tensor 27 spectrometer (Bruker) using a KBr
wafer with the wavenumber ranging 4000
400 cm
1. Magnetic
properties of the products were investigated using a vibrating
sample magnetometer (VSM, EV7, ADE) with an applied field
between
8000 and 8000 Oe at room temperature. The surface
area and pore size distribution were measured by N2 adsorp-
tion
desorption technique in an automated surface area and
porosity analyzer (ASAP 2020, Micromeritics) at 77 K after the
sample was dried at 200 °C for 4 h. The Brunauer
Emmett

Teller (BET) surface area and the pore size distribution plots
were calculated by applying the linear part of the BET plot and
the Barrett
Joyner
Halenda (BJH) model, respectively.
2.4. Catalytic Activity of Porous Fe3O4 Nanospheres. To
investigate the catalytic activity of the as-prepared porous Fe3O4
nanospheres, the degradation of XO with H2O2 oxidant under
ultrasound were chosen as a test reaction model. We mixed 10 mg
porous Fe3O4 nanospheres, 20 mL of 1  10
4 M XO mother
solution, and 10 mL of 30% H2O2 aqueous solution were mixed
together. The concentration of XO at different reaction time was
determined by UV spectroscopy (Shimadazu UV-2500 spectro-
photometer). The content of total organic carbon (TOC) was
analyzed by using a multi N/C 2100 analyzer (Analytik Jena AG).
3. RESULTS AND DISCUSSION
3.1. Morphology, Structure, and Properties of Porous
Fe3O4 Nanospheres. The size and morphology of Fe3O4 nano-
spheres were characterized via TEM and FE-SEM. The TEM
images of magnetic Fe3O4 nanospheres in different magnifica-
tions are shown in Figure 1A,B. The diameter of those Fe3O4
nanospheres is ∼250 nm. A typical HRTEM image of a Fe3O4
nanosphere is depicted in Figure 1C, where the polycrystalline
nature of the product can be confirmed by electron-diffraction
pattern (see the inset). From Figure 1D, the lattice spacing
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The Journal of Physical Chemistry C ARTICLE

Figure 1. (A,B) TEM images of Fe3O4 nanospheres with different magnifications, (C) representative HRTEM image and the electron-diffraction
pattern (inset) of a Fe3O4 nanosphere, (D) HRTEM image of the boxed region of part C, and (E,F) FE-SEM images with different magnifications of
Fe3O4 nanospheres. The synthesis conditions: 1.5 g FeCl3 3 6H2O, 1 g PVP, 2 g NaAc, 30 mL ethylene glycol, 200 °C, and 8 h.

distance is calculated to be 0.29 nm, in good agreement with the
(220) spacing of the Fe3O4 structure. Figure 1E,F shows the FE-
SEM images of the nanospheres, which clearly reveal that each
magnetic microsphere consists of many magnetic grains. Un-
fortunately, the size distribution of them is very wide.
Figure 2A shows the XRD patterns of the porous Fe3O4
nanospheres. The diffraction peaks locating at 2θ = 30.1, 35.8,
43.1, 53.8, 57.3, and 63.0° can be indexed to (220), (311), (400),
(422), (511), and (440) planes of Fe3O4 in a face-centered
cubic (fcc) Fe3O4 (JCPDS card no. 19-629), respectively. The
broadened peak centered at a small angle (2θ < 30°) indicates
the presence of amorphous materials. The crystal size deter-
mined by Debye-Scherre equation from XRD is 11.8 nm,
which further confirms that the porous Fe3O4 nanospheres
were composed of the primary grains with a diameter of
ca. 12 nm.
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It is widely accepted that the XRD pattern of Fe3O4 nano-
structures is very similar to that of γ-Fe2O3.67 To confirm further
the crystal phase of our product, laser micro-raman spectra were
recorded. Figure 2B shows the Raman spectra of the as-prepared
porous Fe3O4 nanospheres and the commercial Fe3O4 powder.
In both curves, the positions of main peaks are almost identical.
No peaks at either 1430 or 1580 cm
1, typical for γ-Fe2O3,46
were observed, further confirming that there is no γ-Fe2O3 in the
as-prepared porous Fe3O4 nanospheres. XPS as in Figure 2C
E
also comes to the same conclusion. Figure 2C shows XPS of the
porous Fe3O4 nanospheres and the inset the expanded spectra of
N1s. Figure 2 D shows the high-resolution XPS spectra of Fe2p,
and Figure 2E shows the high-resolution XPS spectra of O1s. It is
clear that in the as-prepared porous Fe3O4 nanospheres, some
PVP exists as N 1s and C 1s are observed from Figure 2C. Two
distinct peaks at 712.3 and 726.2 eV appear in Figure 2D. The
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The Journal of Physical Chemistry C ARTICLE

Figure 2. (A) XRD patterns of Fe3O4, (B) Raman spectra of Fe3O4 obtained by this work (a) and commercial (b), (C) XPS of Fe3O4 and the inset is
expanded spectra of N1s, (D) high-resolution XPS spectra of Fe2p, (E) high-resolution XPS spectra of O1s, (F) magnetic hysteresis and enlarged partial
(inset) curves of Fe3O4, (G) typical BET isotherm of Fe3O4, and (H) BJH isotherm and enlarged partial (inset) curves of the Fe3O4. All Fe3O4 are
prepared under same conditions as those described in Figure 1.

former is attributed to Fe2p3/2, and the latter to Fe2p1/2. In
Figure 2E, The O1s centered at 529.9 eV belongs to O2
. The
above results confirm the formation of Fe3O4 in the system.
It is well known that the magnetic properties of the material
are related to its size, structure, and morphology. Figure 2F is the
hysteresis loop of the as-prepared porous Fe3O4 nanospheres
measured at room temperature. It can be found that the
magnetization saturation value (Ms) of the Fe3O4 nanospheres
is 79.8 emu/g, which is close to that of the bulk sample of Fe3O4,
92 emu/g,68 and the coercivity value (Hc) is 35.5 Oe, indicating
18926
that the porous Fe3O4 nanospheres display weak ferromagnet-
ism. The experimental phenomena can be explained by the fact
that many primary Fe3O4 particles assemble together to form
larger Fe3O4 nanoparticles as in Figure 1, making the porous
Fe3O4 nanospheres look like a block magnet and exhibit higher
saturation magnetization than individual primary particles. Nor-
mally, when the diameter is smaller than 20 nm, the super-
paramagnetic property of Fe3O4 can be observed.69 However,
the magnetic property of the porous Fe3O4 nanospheres con-
sisting of small Fe3O4 grains is different from that of the
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The Journal of Physical Chemistry C ARTICLE

Figure 3. TEM images of Fe3O4 prepared with different initial concentrations of FeCl3 3 6H2O: (a) 0.25, (b) 0.5, (c) 0.75, (d) 1.0, (e) 1.25, and (f) 1.5 g.
Other conditions: 0.5 g PVP, 1.0 g NaAc, 30 mL of ethylene glycol, 200 °C, and reaction time: 8 h.

Table 1. Magnetic Parameters of Fe3O4 Nanoparticles Pre-

pared at Different Amount of FeCl3 3 6H2Oa
sample a b c d e f

FeCl3 3 6H2O (g) 0.25 0.5 0.75 1.0 1.25 1.5

Ms (emu/g) 77.8 80.4 82.1 82.2 83.2 87.9
Hc (Oe) 68.3 85.6 72.3 72.3 85.6 73.0
a
Other conditions: 0.5g PVP, 1.0g NaAc, 30 mL of ethylene glycol,
200 °C, reaction time: 8 h.

Figure 4. Magnetic hysteresis curves and enlarged partial curves (inset) of
Fe3O4 prepared under the same conditions as those described in Figure 3.
individual particles. This interesting phenomenon may be related
to the interaction among the small particles, which is subject to
further study.
The surface area and porosity of Fe3O4 nanospheres were
determined by measuring the adsorption and desorption iso-
therms of N2. As is shown Figure 2G, the BET surface area of
Fe3O4 nanospheres was calculated to be 47.7 m2/g. Figure 2H
displays the distribution of the pores in Fe3O4 nanospheres. A
main peak centered at ∼4 nm. Most of the pores range from 3 to
10 nm. The result shows that Fe3O4 nanospheres are a type of
mesoporous materials. Such porous structure provides efficient
transport pathways to the interior cavities, which would enhance
the catalytic activity of catalyst.70
3.2. Mechanism for the Formation of Porous Fe3O4 Nano-
spheres. In our reaction system, the formation of Fe3O4 nano-
spheres includes nucleation, growth of nucleus to form primary
18927
crystal, and self-assembly of the primary crystals to form larger
nanoshperes. The initial concentration of precursor is a most
important factor that affects the formation of nanocrystals.
Figure 3 shows the TEM of Fe3O4 prepared under different
initial concentrations of FeCl3 under the given conditions. As is
displayed in Figure 3 A, no regular porous Fe3O4 nanosphere was
observed at low concentration of FeCl3. The concentration of
FeCl3 determines the regularity and the morphology of the
product. The higher the concentration of FeCl3, the more regular
the morphology of porous Fe3O4 nanospheres. The diameter of
Fe3O4 nanospheres increases with the concentration of FeCl3.
However, the particles are polydispersed except for those pre-
pared, whereas the initial concentration of FeCl3 is >0.0417
g 3 mL
1, where uniform, regular, and monodispered Fe3O4
nanospheres will be obtained, whose diameter of the nanopar-
ticles is ∼250 nm. The above phenomenon can be explained by
the theory of Von Weimarn rules.71 At the low concentration
of FeCl3, although the rates of both nucleation and growth are
slow, plenty of precursors can be nucleated with the help of
precipitation agent. Therefore, there is not enough FeCl3 for the
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The Journal of Physical Chemistry C
Figure 5. TEM images of Fe3O4 obtained at different temperature of (A) 200, (B) 220, (C) 230, (D) 235, (E) 240, and (F) 250 °C. Other conditions:
1.5 g FeCl3 3 6H2O, 1 g PVP, 2 g NaAc, 30 mL of ethylene glycol, and reaction time: 8 h.
self-assembly step in the system, and thus no porous Fe3O4
nanospheres are observed in Figure 3A. When the concentration
of precursors slightly increases, some of them could not be
nucleated at the initial period for the limitation of precipitation
agent. Therefore, some porous Fe3O4 nanospheres can be
obtained (Figure 3B
D). As for further increasing the precursor
concentration, the rate of nucleation will not increase. However,
the growth and self-assembly steps will take longer, so large-sized
porous Fe3O4 nanospheres can form in the system as in
Figure 3E,F. The magnetic properties of all samples were shown
in Figure 4. It is observed that all samples exhibit weak ferro-
magnetic behavior at room temperature. Their Ms values increase
with the concentration of FeCl3, which might be related to size.
In another word, the larger the size of Fe3O4 nanospheres, the
higher the value of Ms. Table 1 lists the values of the main
magnetic parameters (Ms and Hc) of the as-prepared samples.
Temperature is another important parameter in the formation.
Figure 5 shows TEM images of Fe3O4 prepared at 200, 220, 230,
235, 240, and 250 °C. Figure 5A
D displays the fact that
temperature has a strong impact on size and morphology. The
higher the temperature is, the smaller the particles are. Below
235 °C, Fe3O4 nanospheres formed of primary particles can be
obtained. However, when the temperature is >235 °C, the mor-
phologies of Fe3O4 changed significantly. From Figure 5E,F, the
shapes of Fe3O4 obtained at 240 and 250 °C are not regular, the size
was <50 nm, and the separate sphere-shaped particles and polygon-
shaped grains occur, compared with those obtained between 200
and 235 °C. As for the size, the product at 250 °C is smaller than that
at 240 °C. This reason might be that the capping agent (PVP) could
not be effectively adsorbed on the surface of Fe3O4 nanoparticles at
higher temperature, stopping the process of self-assembly.
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NaAc is widely used as the precipitation agent in the preparing
nanostructured materials of metals, alloys, and metal oxides.
Figure 6 shows Fe3O4 prepared in the mixture of 1.5 g FeCl3 3
6H2O, 1 g PVP, and 30 mL of ethylene glycol at 220 °C for 8 h
with different amount of NaAc. The results show that in the
above reaction system NaAc is necessary for the formation of
Fe3O4 particles. Moreover, in our systems, when no NaAc was
used, Fe3O4 could not be formed. When the concentration of
NaAc in the system is low, porous nanospheres with small size
could be obtained, as in Figure 6A. It is observed in Figure 6B,C
that a higher concentration of NaAc brings about larger porous
Fe3O4 nanospheres. However, too high concentration of NaAc
will lead to worse uniformity of the prepared Fe3O4 nanospheres.
The reason might be that when the concentration of NaAc is low,
the nucleation rate of Fe3O4 nanocrystals remains slow and even,
but the self-assembly step for the crystals has no limitation. The
higher concentration is a different case. It is well known that the
nucleation rate is much faster with higher concentration of
precipitation agent, which may in turn prevent part of crystals
from assembly because there is not enough space for them to
grow. As a result, the uniformity of the obtained porous Fe3O4
nanospheres was not good when the concentration of NaAc is
too high, seen in Figure 6 D.
The impact of capping agent PVP on the morphology of
Fe3O4 nanospheres was also studied. The TEM images of Fe3O4
nanospheres prepared in 1.5 g FeCl3.6H2O, 2 g NaAc, and 30 mL
of ethylene glycol at 220 °C for 8 h with different amount of PVP
were shown in Figure 7. The role of PVP was found to be very
critical. When no PVP was used, the product was particle in
morphology without identified size or structure, as is shown in
Figure 7A. When 0.5 g PVP was added, porous Fe3O4
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Figure 6. TEM images of Fe3O4 obtained at different amount of NaAc: (A) 0.5, (B) 1, (C) 1.5, and (D) 2.0 g. Other conditions: 1.5 g FeCl3 3 6H2O,
1 g PVP, 30 mL of ethylene glycol at 220 °C, and reaction time: 8 h.

Figure 7. TEM images of Fe3O4 obtained at different amount of PVP: (A) 0.00, (B) 0.5, (C) 1, (D) 1.5, and (E) 2.0 g. Other conditions: 1.5 g
FeCl3 3 6H2O, 2 g NaAc, 30 mL of ethylene glycol at 220 °C, and reaction time: 8 h.

18929 dx.doi.org/10.1021/jp200418j |J. Phys. Chem. C 2011, 115, 18923–18934

The Journal of Physical Chemistry C
nanospheres were obtained. However, the shape of the product was
not very regular, seen in Figure 7 B. With the increase in PVP, the
size of the prepared nanospheres decreased slightly, and the shape
of the product became more regular, as is shown in Figure 7B
E.
Figure 8. FTIR spectra of PVP (a) and PVP-stabilized Fe3O4 nano-
spheres (b).
Scheme 1. Model of the Interaction between Fe3O4 Nano-
crystals and PVP
Figure 9. TEM images of Fe3O4 at different reaction time: (a) 3, (b) 4, (c) 5, (d) 6, (e) 7, and (f) 8 h. Other conditions: 1.0 g FeCl3 3 6H2O, 0.5 g PVP,
2 g NaAc, and reaction temperature: 200 °C.
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ARTICLE
Therefore, interestingly, the uniformity of porous Fe3O4 nano-
spheres was the function of the amount of PVP. When the PVP is
1.5 g, the uniformity of the product was most satisfying. Therefore,
it could be believed that the surfactant PVP played a role in the
system. On one hand, when no or low-concentrated PVP was
applied, there lacked the capping effect for the effective coverage or
passivation of Fe3O4, generating particles with no identified size
and structure. On the other hand, the capping effect of PVP with
high concentration was so strong that some of the nanocrystals
were prevented from growing, leading to irregular nanospheres.
To understand the interaction between the capping agent and
Fe3O4 nanocrystals, we conducted FT-IR spectra. Figure 8
presents the spectra of pure capping agent (curve a) and the
as-prepared porous Fe3O4 nanospheres (curve b). It is noted that
the spectrum of the obtained porous Fe3O4 nanospheres is
somewhat similar to that of the pure capping agent. The
absorption peaks centered around 2900
3000 cm
1 in curve a
are attributed to C
H stretching, and the absorption peak at
1637.4 cm
1 can be assigned to the CdO stretching. The strong
absorption peak at 584.4 cm
1 in Figure 8 b corresponds to the
Fe
O vibrations. The deformation vibration absorption at
1427.2 cm
1 for C
H in PVP moved to 1425.3 cm
1 in the
porous Fe3O4 nanospheres. Meanwhile, compared with the pure
PVP, the stretching vibration of CdO in Fe3O4 moved from
1637.4 to 1625.9 cm
1. The shifts of the CdO and C
H of PVP
vibration are due to the fact that in the system this capping agent
coordinates with the Fe3O4 nanocrystals. The possible interac-
tion between the obtained Fe3O4 nanocrystals and PVP mol-
ecules can be diagrammatically shown in Scheme 1.
To understand further the mechanism for the formation of
Fe3O4 nanospheres, time-dependent experiments were carried out.
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The Journal of Physical Chemistry C
Figure 10. Magnetic hysteresis curves and enlarged partial curves
(inset) of Fe3O4 shown in Figure 9.
Table 2. Magnetic Parameters of Fe3O4 Nanoparticles Ob-
tained at Different Reaction Timea
sample a b c d e f
reaction time (h) 3 4 5 6 7 8
Ms (emu/g) 66.1 81.2 81.6 81.6 80 79.1
Hc (Oe) 47.8 64.1 72.5 39.7 67.8 50.2
a
Other conditions: 1.0 g FeCl3 3 6H2O, 0.5 g PVP, 2.0g NaAc dispersed
in 30 mL of ethylene glycol, at 200 °C.
Scheme 2. Possible Formation Mechanism of Fe3O4
Nanospheres
As shown in Figure 9A, after 3 h of reaction, Fe3O4 nanospheres
with the diameter of 150 nm are obtained. The diameter of the
sample collected at 4 h later (Figure 9B) showed the same size with
those of 3 h but with fine hierarchical nanoarchitectures. As the
reaction proceeded (Figure 9 C), the diameter of the porous
nanospheres continues to grow. The corresponding TEM images
of the Fe3O4 samples obtained at 200 °C for 6 h (Figure 9D)
showed that many nanospheres are derived from the small
nanocrystals, which is in agreement with the morphology shown
in Figure 1. Unfortunately, failure occurred to obtain the primary
Fe3O4 nanocrystals, which may be due to the quick growing of the
primary Fe3O4 nanocrystals. However, as shown in Figure 9E,F, no
further change with increase in reaction time indicated the
completion of the growth of nanocrystal. In our system, product
at 8 h presents the best morphology. The magnetic property
evolution of the products is shown in Figure 10. It is clear that
reaction time directly affects the final magnetic property of the
products. However, there is no linear relationship between the
reaction time and the magnetic property. The values of Ms and Hc
for the samples are listed in Table 2. The results reveal that all
products show weak ferromagnetic property.
According to above experimental results, an illustration of the
predicted possible formation mechanism of Fe3O4 nanospheres
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Figure 11. UV spectra of XO oxidized by H2O2 under ultrasound
measured at (a) initial time and (b) 45 min. 10 mL 1  10
4 mol/L
10 mL 30% H2O2. The photo in the inset demonstrates no obvious
degradation of XO without the catalysts. Reaction temperature: room
temperature.
Figure 12. UV spectra of XO oxidized by H2O2 under ultrasound with
Fe3O4 as catalyst measured at different reaction time. We used 10 mg
catalyst. The photo in the inset demonstrates the convenient separation
of the catalysts applying an external magnetic field. The other reaction
condition was the same as that described in Figure 11.
could be formulated in Scheme 2. First, the solid precursor
FeCl3 3 6H2O was dissolved in ethylene glycol. Second, part of
the dissolved species was reduced by the ethylene glycol. Then,
nanocrystal nucleations of Fe3O4 were formed. At last, Fe3O4
nanocrystals grew larger and assembled to porous nanospheres
by self-assembling with PVP as capping agent. Here ethylene
glycol served not only as a solvent but also as a reducing agent.72
As for anhydrous sodium acetate, it initialized the nucleation of
Fe3O4 nanocrystals.
3.3. Catalytic Activity of the Porous Fe3O4 Nanospheres.
The porous Fe3O4 nanospheres could be used in catalytic
degradation of organic dyes. Chemical oxidation degradation
of XO by H2O2 was used as a model reaction to study the
catalytic property of the porous Fe3O4 nanospheres. According
to Figure 11, without the porous Fe3O4 nanospheres as a catalyst,
the absorption peak at 434 nm for XO decreased a little when
H2O2 was added under ultrasound for 45 min, which indicates
that the degradation of XO is very slow, even with excessive
H2O2. The photo in the inset of Figure 11 can further demon-
strates that no obvious degradation occurred without the cata-
lysts. As shown in Figure 12, however, when trace porous Fe3O4
dx.doi.org/10.1021/jp200418j |J. Phys. Chem. C 2011, 115, 18923–18934
The Journal of Physical Chemistry C
Figure 13. (A) EDS of Fe3O4 nanospheres recycled after catalyzing degradation of XO seven times. (B) FTIR spectra of the porous Fe3O4 nanospheres
after treating XO (a) and XO (b). (C) XPS spectra of the used porous Fe3O4 nanosphere catalyst. The inset is expanded spectra of S2p.
Table 3. Measurement of Residual Xylenol Orange under Different Systems
treat method only H2O2 only prepared Fe3O4
C/C0 0.97 0.94
TOC/TOC0 95% 93%
nanospheres were added to the solution, the intensity of absorp-
tion peak of XO at 434 nm decreased gradually and disappeared
completely after 45 min under ultrasound, which clearly shows
that the porous Fe3O4 nanospheres are an efficient catalyst for
the degradation of XO by H2O2. Furthermore, it can be clearly
demonstrated by the photography in the inset of Figure 12 that
the catalysts can be conveniently separated by applying an
external magnetic field.
To confirm that the decrease in XO in the solution is due to the
catalysis of Fe3O4 nanospheres, instead of adsorption by porous
Fe3O4 nanospheres, EDS were taken to study the surface
element of Fe3O4. According to Figure 13A, it is clear that
no sulfur element on the surface of Fe3O4 nanospheres was
observed, which shows that no XO was absorbed by Fe3O4
nanospheres. Figure 13B shows the FT-IR Fe3O4 catalysts
recovered from the catalytic system; also, the characteristic peaks
of XO could not be observed. Furthermore, XPS, a more-
sensitive surface analysis technique, was used to examine quanti-
tatively if the sulfur is present on the surface of the used porous
Fe3O4. As is seen in Figure 13C, the signal of sulfur is too weak to
be observed in the whole spectra. From the expanded spectra of
S2p (Figure 13C inset), the percentage of sulfur was determined
to be 0.16%, which indicates that the adsorption of XO on the
surface of catalyst is negligible. On the basis of the above
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prepared Fe3O4 +H2O2 commercial Fe3O4 + H2O2
0 0.90
6% 88%
discussion, it was concluded that the degradation of XO occurred
in the presence of H2O2 with the catalysis of the porous Fe3O4
nanospheres.
As a comparison, a series of experiments was carried out. The
experimental results are listed in Table 3, where the solution that
contained XO was treated by several methods, for example: (1)
only H2O2, (2) only Fe3O4 prepared in this Article, (3) H2O2 +
Fe3O4 prepared in this Article, and (4) H2O2 + commercial
Fe3O4. The decrease in XO in solution was determined by
measuring the UV spectrum and TOC of the reaction system.
It can be found from Figure S1 of the Supporting Information
that the commercial Fe3O4 shows poor catalytic performance
because the UV absorption at 434 nm decreases slightly after
ultrasound irradiation for 45 min in the presence of H2O2. As
displayed in Table 3, concentration of both XO and TOC in the
reaction system decreased near to zero while the oxidant H2O2
and the as-prepared Fe3O4 were added. However, the decrease in
XO was minimal by other methods, further confirming that the
decrease in XO in our reaction system is due to the oxidation of
XO by H2O2 with the as-prepared Fe3O4 catalyst. The very low
catalytic activity of the commercial Fe3O4 may be mainly due to
its large size, low porosity, and low surface area. Figure S2 of the
Supporting Information shows the TEM image and BET iso-
therm of the commercial Fe3O4. From Figure S2A of the
dx.doi.org/10.1021/jp200418j |J. Phys. Chem. C 2011, 115, 18923–18934
The Journal of Physical Chemistry C
Figure 14. First-order kinetic plot of XO degradation using H2O2 as
oxidizing agent under ultrasound in with Fe3O4 nanospheres as catalyst.
Figure 15. Catalytic activity of Fe3O4 nanospheres in different cycling
numbers.
Supporting Information, the size of the commercial Fe3O4 can be
determined to be >1 μm, which is very large compared with that
prepared in this work. Meanwhile, the porosity of the materials is
another most important factor influencing the catalytic activity.
Figure S2B of the Supporting Information shows the N2 adsorp-
tion
desorption isotherm of the commercial Fe3O4, determining
that the BET surface area of the commercial Fe3O4 is 1.41 m2/g,
whereas the value for the prepared Fe3O4 in this study was
determined to be 47.7 m2/g (seen in Figure 2G).
The degradation kinetic of XO was investigated by adding
excess H2O2. Therefore, the degradation can be considered to be
a pseudo-first-order reaction. The concentration, ct, of XO at
different reaction time, t, could be described as follows
ct ¼ c0 expð
ktÞ
where c0 is the initial concentration of XO and k is the pseudo-
first-order rate constant. Figure 14 shows the logarithmic plot of
the concentration of XO as a function of degradation time. A
well-behaved linear straight line shows that the degradation of
XO is a pseudo-first-order reaction. The rate constant k can be
calculated from the slope of the straight line. The value of k is
0.056 min
1, which is much larger than the literature reported
0.013 min
1 using Pd/TiO2 as the catalyst.73
For practical recyclable catalysts, keeping high catalytic activity
in each cycle is necessary. The effect of recycling times of the
porous Fe3O4 nanospheres on the catalytic performance was
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repeated seven times, and the results are shown in Figure 15.
The catalytic performance of the porous Fe3O4 nanospheres
decreased slowly with the increase in cycle number. The percen-
tage degradation remained steady (>95%) in the first four cycles;
then, the degradation of XO decreased from the fifth cycle to
the seventh cycle. At the end of seven cycles, the percentage
degradation remained steady at >75% of the initial value. These
results show that the porous Fe3O4 nanospheres can be recycled
for catalyzing degradation of XO with H2O2 solution. Therefore,
the as-prepared Fe3O4 nanospheres can be used as ideal catalysts
in practical applications.
4. CONCLUSIONS
In conclusion, porous Fe3O4 nanospheres have been prepared
with solvothermal method. The products exhibit weak ferromag-
netic properties at room temperature. The quality of the product
is determined by the experimental variables, such as the con-
centration of the precursor, capping agent, and precipitation
agent as well as the reaction temperature and reaction time. The
disadvantage of the method reported here is the wide size
distribution of the product. The as-prepared porous Fe3O4
nanospheres show highly catalytic degradation ability toward
degradation of organic dyes in aqueous solution. Although the
catalytic activity decreases slightly with increasing the cycles of
tests, such nanostructured catalyst is expected to find application
in industrial applications, where separation and recycling are
crucially required in terms of cost and environmental protection.
’ ASSOCIATED CONTENT
bS Supporting Information. UV spectra of XO catalyzed by
the commercial Fe3O4; TEM image and BET isotherm of the
commercial Fe3O4. This material is available free of charge via the
Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*Tel: +86-514-87975436. Fax: +86-514-87975244. E-mail:
gwdiao@yzu.edu.cn.
’ ACKNOWLEDGMENT
We acknowledge the financial support from the National
Natural Science Foundation of China (grant no. 20973151,
20901065), the Natural Science Key Foundation of Educational
Committee of Jiangsu Province of China (grant no. 07KJA
15015), the Specialized Research Fund for the Doctoral Program
of Higher Education (SRFDP, 20093250110001), the Founda-
tion of Jiangsu Provincial Key Program of Physical Chemistry in
Yangzhou University, and the Foundation of Jiangsu Key La-
boratory of Fine Petrochemical Technology. We also acknowl-
edge the Foundation of the Educational Committee of Jiangsu
Provincial General Universities Graduate Student Scientific
Research Invention Plan.
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