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Phys. Status Solidi A 210, No. 6, 1190–1194 (2013) / DOI 10.1002/pssa.201228640

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applications and materials science
Capped and coupled Fe3O4/TiO2
nanopowder systems fabricated by
sol–gel and a nonthermal method
,1 ,1 1 2
Mohammad Niyaifar* , Ahmad Hasanpour** , Hory Mohammadpour , and Jamshid Amighian
1
Department of Physics, Science and Research Branch, Islamic Azad University, Khouzestan, Iran
2
Department of Physics, Najafabad Branch, Islamic Azad University, Esfahan, Iran

Received 19 September 2012, revised 5 January 2013, accepted 1 February 2013

Published online 4 March 2013

Keywords composites, core–shell nanoparticles, magnetite, nanopowders, sol–gel synthesis, TiO2

* Corresponding author: e-mail md.niyaifar@gmail.com, Phone: þ98 935 1055293, Fax: þ98 611 4457612
** e-mail hasanpour88@gmail.com, Phone: þ98 611 4457612 296, Fax: þ98 611 4457612

In this work, Fe3O4/TiO2 core–shell and composite nano-
powders have been prepared to study their structural and
magnetic properties. First a conventional sol–gel method was
used to synthesize Fe3O4 and TiO2 nanoparticles separately.
Then, they were combined to each other in two different
geometries of core–shell and composite nanopowders. The
samples were characterized by analytical techniques including
XRD, TEM, SEM, and VSM. The results show the successful
covering of the Fe3O4 nanoparticles surfaces with TiO2 in core–
shell samples. In composite samples annealed at 400, 500,
600 8C, magnetite nanoparticles are distributed randomly in the
TiO2 matrix. The magnetic measurements show that the core–
shell sample, fabricated by a nonthermal method, has higher
saturation magnetization than composite samples. Moreover,
the values of the saturated magnetization of Fe3O4/TiO2
nanoparticles decreased with increasing calcined temperature.

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1 Introduction During the last decade, nanostruc-
tured semiconductor photocatalysis have been the subject of
great scientific and technological interest [1–3]. Compared
to various oxide semiconductor photocatalysis, TiO2 was
intensively studied due to its easy availability, nontoxicity,
strong oxidizing activity, and long-term chemical stability
[4–6]. Anatase and rutile phase are the two main crystalline
phases of TiO2. The larger bandgap and lower electron–hole
recombination probability of the anatase phase make it
more active in photocatalysis than the rutile phase [7].
However, the diamagnetic behavior of pure TiO2 is a
drawback that makes it difficult to be collected for
resumption. To overcome this problem, the mixtures of
titania and magnetite particles in two forms of capped and
coupled semiconductors have been investigated by a number
of researchers [8–15]. However, the suggested systems have
two major problems, which affect the photocatalysis
properties. The first is the heat-treatment effect. Although
the calcination up to 400 8C is an essential factor to increase
the crystallinity of TiO2 particles [16], it causes a reduction
in the magnetization due to oxidation of magnetite particles,
and the formation of Fe2TiO5 as an impurity phase [17]. The
second is the photodissolution phenomenon due to electronic
interaction between titania and iron oxides [18].
In this paper, the differences between structural and
magnetic properties of the capped and coupled Fe3O4/TiO2
systems (Fig. 1) have been studied. Furthermore, a novel
nonthermal method with minimal electronic interaction is
presented for the preparation of the Fe3O4/TiO2 capped
system as a solution of mentioned problems.
2 Experimental
2.1 Preparation of Fe3O4 nanoparticles To syn-
thesize magnetite nanoparticles, 0.2 mol Fe(NO3)3 was
dissolved in 10 ml ethylene glycol with vigorous stirring
for 2 h at 40 8C, and then the sol was heated to 80 8C and kept
at this temperature to obtain a brown gel. The gel dried at
120 8C for 24 h. The prepared xerogel was annealed at 400 8C
under vacuum.
2.2 Modification of Fe3O4 core particles The
surface modification of Fe3O4 nanoparticles was carried
out by the reaction of the nanoparticles with sodium
citrate. This material was used to stabilize the magnetite

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Phys. Status Solidi A 210, No. 6 (2013) 1191

dried at 110 8C under vacuum, so that a gray powder was

formed.

2.6 Characterization X-ray diffraction patterns of

Figure 1 Schematic of (a) Fe3O4/TiO2 capped system where the
magnetite is totally surrounded with the titanium dioxide and
(b) Fe3O4/TiO2 coupled system where the magnetite phase is found
to be doped in the titanium dioxide matrix.
nanoparticles before coating with TiO2. The effect of the
citrate is to make surface possess a negative charge, so that
aggregation of magnetite nanoparticles is prevented by a
repulsive electrostatic force. The typical procedures are: 4 g
Fe3O4 nanoparticles with 200 ml sodium citrate 0.5 M were
mixed together in a flask. The mixture was kept under
ultrasonic agitation for 30 min to reduce the aggregation of
modified nanoparticles, and then stirred for 12 h at a
temperature of 60 8C under Ar protection. The precipitate
was collected by magnetic-field separation and was washed
with acetone several times.
2.3 Preparation of TiO2 nanoparticles In the
present study, the TiO2 nanoparticles were prepared via a
sol–gel method. Tetrabutyl ortho titanate (Merck, 99.99%,
TBOT) was used to prepare transparent TiO2 sol at room
temperature as follows: First, the TBOT was dissolved for
half an hour to get a precursor solution. A mixture of distilled
water, glacial acetic acid, and ethanol was then dropped into
the precursor solution at a speed of one drop per second under
vigorous stirring. After that, the solution was continuously
stirred for 1 h to achieve a transparent yellow TiO2 sol. The
prepared sol was slowly dropped into the sonicated
magnetite nanoparticles. Finally, the generated mixture
was dried and calcined at 400, 500, and 600 8C.
the samples were obtained on a Seifert ID3003 diffract-
ometer working in the Bragg–Brentano configuration with
Cu Ka radiation; the surface morphology and the status of
the coating of the samples were investigated on a Philips
CM120 transmission electron microscope (TEM), and a
Philips XL30 scanning electron microscope (SEM); the
magnetic properties were tested at room temperature via a
vibrating sample magnetometer (VSM).
3 Results and discussion Figure 2 shows the XRD
patterns of TiO2 nanopowders calcined at different tempera-
tures ranging between 300 and 850 8C.
The XRD patterns of anatase have a main peak at
2u ¼ 25.28 corresponding to the (101) plane (JCPDS 21-
1272) while the main peaks of rutile phase (JCPDS 21-1272)
is at 2u ¼ 27.48 (110). No diffraction peaks in the XRD
pattern of 300 8C were detected (Fig. 2a), indicating the
amorphous nature of the sample [19]. The anatase phase
transformation starts from 600 8C to pure rutile at 850 8C,
as reported previously [20, 21]. Figure 3 shows the
phase compositions calculated by Klug formula (Eqs. (1)
and (2)).
  
1
IR
fA ¼ 1 þ 1:26 ; (1)
IA

2.4 Preparation of Fe3O4/TiO2 nanocomposite

First, the Fe3O4 nanoparticles of Section 2.1 were sonicated
in ethanol. Then, tetra butyl ortho titanate was dissolved in
ethanol and stirred for half an hour to get a precursor solution.
A mixture of distilled water, glacial acetic acid, and ethanol
was then dropped into the precursor solution at a speed of
one drop per second under vigorous stirring. After that,
the solution was continuously stirred for 1 h to achieve a
transparent yellow TiO2 sol. The sol was dried at 100 8C
for 2 h and then the obtained gel was heat treated at 400 8C
for 2 h.

2.5 Preparation of Fe 3 O 4 /TiO 2 core–shell

nanoparticles To prepare the Fe3O4/TiO2 core–shell
nanostructure, the modified magnetic core particles of
Section 2.2 were initially dispersed in 100 ml deionized
water and kept under ultrasonic agitation for 30 min to
obtain a stable ferrofluid. This was followed by the addition Figure 2 X-ray diffraction patterns of TiO2 nanoparticles calcined
of TiO2 nanoparticles. The molar ratio of Fe3O4 to TiO2 at (a) 300 8C, (b) 400 8C, (c) 450 8C, (d) 500 8C, (e) 600 8C, (f) 7008C,
was kept to 1/10. The mixture was then stirred for 30 min and (g) 800 8C, and (h) 850 8C.

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1192 M. Niyaifar et al.: Capped and coupled Fe3O4/TiO2 nanopowder systems

Figure 3 Histograms of weight percentage variation of anatase

and rutile phase of TiO2 nanopowders as a function of calcination
temperature.

  
1
IA
fR ¼ 1 þ 0:88 ; (2)
IR

where fA and fR are the weight fractions of anatase and rutile

in the mixture, IA and IR represent, respectively, the
intensities of anatase (101) and rutile (110) peaks [22, 23].
The weight percentages of TiO2 nanopowder components
are given in Table 1. For bulk TiO2 the phase transformation
begins at a temperature higher than 800 8C [24]. Further-
more, it is well known that because of the higher surface
energy of rutile compared to anatase, phase transformation
from rutile to anatase is impossible for the bulk. But at
nanodimensions, a phase transformation from rutile to
anatase is possible [25, 26].
Figure 4a shows the powder X-ray diffraction pattern of
the Fe3O4 nanoparticles. The peak positions and their
relative intensities can be well indexed to the inverse cubic
spinel structure of Fe3O4 (JCPDS 19-0629) [27]. The mean
crystalline size of the Fe3O4 nanoparticles is estimated to be
11 nm by measuring the peak widths of the X-ray diffraction
lines according to Scherrer’s formula [28].
Figure 4d–f show XRD pattern of the synthesized
Fe3O4/TiO2 coupled system calcined at 400, 500, and
600 8C, respectively. The patterns show diffraction peaks
relating to (101), (200), (105), (211), and (204 planes of
anatase phase also. The peaks indexed by Miller indices
Table 1 Weight percentages of TiO2 nanopowders components
shown in Fig. 3.
calcination weight fraction (%)
temperature (8C)
anatase
400 100
450 92
500 89
600 52
700 (vacuum) 21
800 2 98
850 0 100
Figure 4 X-ray diffraction patterns of (a) Fe3O4 nanoparticles and
(b) TiO2 nanoparticles calcined at 500 8C, (c) Fe3O4/TiO2 capped
system, and Fe3O4/TiO2 coupled system calcined at (d) 400 8C,
(e) 500 8C, and (f) 600 8C.
(220), (311) and (422) were observed in case of magnetite
phase. Moreover, the composite pattern indicated the
presence of hematite phase for the sample calcined at
600 8C (Fig. 4f). As reported previously, it is well known
that Fe3O4 nanoparticles can be oxidized to maghmaite
(g-Fe2O3), which can be transformed into hematite
(a-Fe2O3) when the heat-treatment temperature is over
400 8C [29]. Due to the nonthermal process of capped
system preparation, no other diffraction peaks correspond-
ing to other iron oxide can be observed in Fig. 4c (Fe3O4-
core/TiO2-sell), except those of magnetite and anatase.
TiO2 nanoparticles were well formed before that be
coated on Fe3O4 cores in capped structure. Thus, anatase
phase is more crystallized in capped system than that of
coupled one.
Figure 5 illustrates the TEM observations of the samples.
The Fe3O4 nanoparticles (Fig. 5a) exhibit a spherical shape
owing to the nucleation rate per unit area being isotropic at
the interface between the Fe3O4 magnetic nanoparticles.
Also, the magnetic nanoparticles have sizes between 20 and
rutile 40 nm, which is in good agreement with the results of XRD
measurements. Figure 5b shows the formation of well-
0 defined core–shell structure. The average thickness of the
8 TiO2 shell was estimated to be 5 nm and the diameter of
11 Fe3O4/TiO2 particles is about 15 nm on average. Further-
48 more, Fig. 5b and c reveal that the samples are composed of
79
dark particles, which are embedded in a light gray region.
The dark region corresponds to the Fe3O4 nanoparticle that is
due to its greater absorbed electron capability than TiO2 of

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Phys. Status Solidi A 210, No. 6 (2013) 1193

Figure 6 Magnetic hysteresis loops of (a) Fe3O4 nanoparticles,

(b) Fe3O4/TiO2 capped system, and (c) Fe3O4/TiO2 coupled geo-
metry calcined at 400, 500, and 600 8C.

by considering the diamagnetic TiO2 content (Fig. 6c and b).

The Ms value of the prepared magnetite nanoparticle was
Figure 5 TEM images of the Fe3O4 nanoparticles (a), Fe3O4/TiO2 significantly lower than that of bulk magnetite (92 emu g
1).
capped (b), and Fe3O4/TiO2 coupled systems (c). This may be due to the surface spin canting of the small
magnetic nanoparticles [32]. In this case, the superexchange
interaction between Fe ions occurs through the oxygen ions,
the lighter parts, which means that the electron binding incomplete coordination at the surface and the high
ability of Fe3O4 is higher than that of nonmagnetic TiO2, and surface/volume ratio of the small particles are believed to
TiO2 releases energy under the beam bombardment of the be responsible for a surface spin disorder. These effects are
electron gun in TEM detection, so the lighter area was much more pronounced in ferrimagnetic systems, which
observed. Therefore, the cores can be identified as the darker make the total magnetization of the nanoparticles much
region compared to the shell area [30, 31]. From Fig. 5c smaller than the bulk value [33]. Moreover, the values of the
it can be observed that the magnetite nanoparticles are saturation magnetization decreased with increasing calcina-
distributed randomly in the TiO2 matrix. tion temperature in the composite Fe3O4/TiO2 nanoparticles.
Figure 6 shows the hysteresis loops of the pure Fe3O4 However, the partial transformation from magnetite to
(before coating), Fe3O4/TiO2 coupled system (calcined at hematite (a-Fe2O3) is the main cause for lowering the
400, 500, and 600 8C), and the Fe3O4/TiO2 core–shell saturation magnetization in composite samples, which was
structure under an external field (H) varying up to 8 kOe. The confirmed by the X-ray diffraction results. In contrast, the
magnetic parameters such as saturation magnetization Ms, uncalcined capped system had better magnetic properties
coercivity Hc and remanent magnetization Mr are listed in with the highest Ms of 9.8 emu g
1 compared to the
Table 2. composite sample. The coercivity of composite samples
All the composite and core–shell samples exhibit shows increases as the calcined temperature increases. This
ferrimagnetism behavior (Fig. 6a–c). The Ms value was less is due to the increase of Fe3O4 nanoparticle sizes with
than that of pure Fe3O4 in all cases, which could be explained increasing calcination temperature. The reason for these
variations can be interpreted as follows: The cause of high
coercivity in nanocomposites at 400 8C is due to diamagnetic
Table 2 Magnetic parameters of pure Fe3O4, coupled and capped TiO2 phase that prevents the rotation of magnetization in
Fe3O4/TiO2 systems.
Fe3O4 nanoparticles, which results in a coercivity of 85.57
temperature (8C) Hc (Oe) Ms (emu g
1) samples Oe. When the temperature rises to 500 and 600 8C, a new
antiferromagnetic a-Fe3O4 phase (hematite) will appear,
600 141.18 1.78 composite which again is another extra source in prevents of magnetic
500 123.07 2.05 composite moment rotations.
400 85.57 3.23 composite
– 48 9.8 core–shell
400 0 57.33 Fe3O4
4 Conclusions We report the synthesis, the charac-
terization and the comparative study on Fe3O4/TiO2

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 pss a
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1194 M. Niyaifar et al.: Capped and coupled Fe3O4/TiO2 nanopowder systems
nanopowders in to forms of core–shell and composite
structure. The sol–gel method and a nonthermal process
have been developed for the preparation of the samples. The
XRD patterns indicated the existence of both magnetite and
anatase-titania phases in both structures. In the TEM images,
a nanoscale thickness of TiO2 shell coated on the surface of
Fe3O4 particles clearly showed the formation of core–shell
structure. The magnetic properties of the samples were
studied by a VSM. All the samples exhibit ferrimagnetism
behavior, while the core–shell structure fabricated by a
nonthermal method showed the highest saturated magneti-
zation compared to those of composite samples.
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