Journal of Molecular Catalysis A: Chemical 370 (2013) 3543

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Journal of Molecular Catalysis A: Chemical

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Magnetic properties and photocatalytic activity of La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and
LaFe0.9 Mn0.1 O3
Zhi-Xian Wei a, , Cai-Mei Xiao a , Wei-Wei Zeng a , Ji-Ping Liu b,c,
a
b
c

Department of Chemistry, Science Institute, North University of China, Taiyuan, Shanxi 030051, PR China
Beijing Institute of Protective Materials and Technology, Beijing 100072, PR China
School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, PR China

a r t i c l e

i n f o

Article history:
Received 28 August 2012
Received in revised form
21 December 2012
Accepted 23 December 2012
Available online 31 December 2012
Keywords:
Doped perovskire oxides
Magnetic catalyst
Visible light photocatalyst
Methyl orange (MO)

a b s t r a c t
Perovskite La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3 were synthesized and characterized by X-ray
powder diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), vibrating sample magnetometer (VSM), UVvis absorption spectra and X-ray photoelectron spectroscopy (XPS)
techniques. The magnetic properties of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3 were measured,
and they were also evaluated for their photocatalytic activity toward the degradation of methyl orange
(MO) under the sunlight irradiation. The effect of various parameters such as pH and irradiation time
on the efciency of photocatalytic degradation MO was studied. The experimental results show that
the magnetic property of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3 was caused by the double
exchange between Mn3+ and Fe3+ , Mn3+ and Mn4+ as well as the defective state in them, the Ba-doping
LaFe0.9 Mn0.1 O3 , i.e., La0.8 Ba0.2 Fe0.9 Mn0.1 O3 , has higher magnetic property than that of LaFe0.9 Mn0.1 O3
because of its higher Mn4+ content which favors the double exchange interaction between Mn4+ and
Mn3+ , and it has much higher photocatalytic activities than those of the LaFe0.9 Mn0.1 O3 due to its
higher oxygen vacancies, higher Mn4+ content and higher visible light absorption. This new bifunctional
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 is extremely effective for the MO degradation, and it was easily separated by
applied magnetic eld and can be reusable and maintain relatively high activity.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Immobilization of photocatalysts on supports such as glass
and zeolite results in decreased activities due to the low specic area and slow mass transfer. In order to take advantage of
the high activity of the suspended and dispersed semiconductor
nanophotocatalysts, the concept of magnetic photocatalysts with
separation function was raised. Magnetic composite systems such
as TiO2 /iron oxide [1], Ni/titania products [2], POM-based magnetic
photocatalysts [3], and anatase TiO2 nanoparticle coating on magnetic particles including barium ferrite [4], Fe3 O4 [5], CoFe2 O4 [6]
have been studied. The single-phase magnetic catalysts function as
both photocatalysis and separation were also started to be focused
[7]. For example, Tan developed three kinds of bismuth ferrites

Corresponding author at: Department of Chemistry, Science Institute, North

University of China, Taiyuan, Shanxi 030051, PR China. Tel.: +86 0351 3921414;
fax: +86 0351 3921414.
Corresponding author at: Beijing Institute of Protective Materials and Technology, Beijing 100072, PR China/School of Materials Science and Engineering, Beijing
Institute of Technology, Beijing 100081, PR China.
E-mail addresses: zx wei@126.com (Z.-X. Wei), liujp@bit.edu.cn (J.-P. Liu).
1381-1169/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molcata.2012.12.013

(BiFeO3 , Bi25 FeO40 , and Bi25 FeO40 BiFeO3 ) through a microwave

hydrothermal method. Wei et al. also reported the magnetic and
photocatalytic properties of the perovskite-type SrTi0.1 Fe0.9 O3
[8].
Since the visible light accounts for the largest portion (ca.
46%) in the solar spectrum, the solar light-driven photocatalysts
are desirable. Hence, development of the photocatalyst possessing of superparamagnetic property and visible-light activity (i.e.,
bifunctional photocatalyst) has become an important topic in the
photocatalysis research today. Here, the superparamagnetic property is desirable for their applications considering their dispersions
and recycling.
Perovskite oxides with the general formula ABO3 are multifunctional materials. Indeed, they can even show novel coupling
of multiple coexisting states, such as magnetism and superconductivity, or ferroelectricity and ferromagnetism [9]. Further,
substitution or doping at both A and B sites can change the composition and symmetry of the oxides and create cations or oxygen
vacancies, which have a major inuence on the band structures
and the photocatalytic behavior of these materials. Moreover, many
other properties such as adsorption [10] and magnetic properties
[11] can also be designed and prepared by substitution or doping on
both A and B sites. A-site ion substitution/doping or oxygen content

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Z.-X. Wei et al. / Journal of Molecular Catalysis A: Chemical 370 (2013) 3543

variation [12,13] and the change in crystallite size of the sample [14]
can also change the magnetism. Therefore, perovskite-type oxides
with intrinsic visible photocatalytic activity and superparamagnetic property could be easily tunabled by many methods including
adding or doping a desirable component to the A and/or B site as
well as the change in crystallite size of the sample. However, few
efforts have been carried out on that subject until now.
In general, there are several types of pervoskite structures like
NaTaO3 , BaTiO3 , and LaCoO3 LaFeO3 , etc. All the above-mentioned
substances, the Mn ions doped LaFeO3 have magnetic property.
This is because that the superexchange interaction between Mn3+
and Mn3+ and the double exchange between Mn3+ and Mn4+
are responsible for the ferromagnetism of the LaMn(1x) Fex O(3+y)
(0.0 x 1.0) [15]. Considering that the magnetic properties can
be designed and prepared by substitution or doping on both
A and B sites, therefore, LaFe0.9 Mn0.1 O3 and the Ba-doping
LaFe0.9 Mn0.1 O3 , i.e., La0.8 Ba0.2 Fe0.9 Mn0.1 O3 were prepared in
this study in order to investigate the effect of the Ba-doping on the
photocatalytic activity and magnetic properties of the perovskitetype oxides.
It is well known that a preparation method can also play an
important role in the properties of the products including magnetic properties and photocatalytic activities. In order to research
the effect of the Ba doping on the magnetism and photocatalytic activity of LaFe0.9 Mn0.1 O3 , La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and
LaFe0.9 Mn0.1 O3 were prepared by the stearic acid solution combustion method [16] and characterized by many techniques in this
study. Here, the combustion method can easily prepare powders
with higher specic surface areas, which is helpful to their photocatalytic activity and superparamagnetic property. In addition,
methyl orange (MO) was chosen as a model pollutant to evaluate the photocatalytic activity of La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and
LaFe0.9 Mn0.1 O3 in this study.

2. Materials and methods

2.1. Material synthesis and characterization
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 was synthesized by the stearic
acid solution combustion method. The detailed process could
be described as follows: First, La(NO3 )3 6H2 O, Ba(NO3 )2 ,
Fe(NO3 )3 9H2 O and MnCl2 4H2 O at the mole rates 0.8:0.2:0.9:0.1
were added in the excess molten stearic acid in a porcelain crucible
reactor. After that, the resulting mixture was heated and stirred
continuously at 123 C for about 8 h to obtain fully homogeneous
viscous LaBaFeMnstearic acid solution. Then, the porcelain
crucible reactor was placed on a hot plate increased to 500 C
at a heating rate of 10 C/min in air. At this stage, the solution
volatilized and autoignited, with the evolution of a large volume
of gases to produce loose powder, known as as-prepared powder.
After the as-prepared powder was grinded and calcined at an
annealing temperature above 650 C for 1 h, black perovskite-type
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 powders were obtained. In addition,
LaFe0.9 Mn0.1 O3 was also synthesized by the same method. The
mole rates of La(NO3 )3 6H2 O, Fe(NO3 )3 9H2 O, MnCl2 4H2 O and
the stearic acid are 1:0.9:0.1:8.
Mean valence of Fe and Mn ions in both La0.8 Ba0.2 Fe0.9 Mn0.1 O3
and LaFe0.9 Mn0.1 O3 was determined by iodometric titration, respectively. The sample was dissolved in 6 M HCl
aqueous solution and titration of iodine formed was performed using Na2 S2 O3 aqueous solution. Oxygen content in
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 /LaFe0.9 Mn0.1 O3 was estimated from
composition and valences of cations in accordance with the charge
neutrality principle.

The crystalline phase structures of the obtained samples was

40 kV, 30 mA,
determined by X-ray diffractometer (Cu K = 1.54 A,
2 from 10 to 80 ). FT-IR spectra were registered by using a
Nexus 870 FT-IR in KBr pellets. Scanning electron microscopy
(SEM) (HITACHI, Model S-4800) was used to investigate the morphology of the obtained powders. The magnetic properties were
measured at room temperature using a vibration sample magnetometer (HH-10, Instrument Factory of Nanjing University, China).
The light absorption spectrum was recorded with U-3010 UV-Vis
spectrophotometer (Hitachi, Japan) in the range of 200800 nm.
XPS analysis was performed by a PHI Quantera SXM apparatus,
equipped with a standard Al K excitation source. The binding
energy (BE) scale has been calibrated by measuring C 1s peak
(BE = 284.8 eV) from the ubiquitous surface layer of adventitious
carbon. The amounts of La, Ba, Fe and Mn in the perovskite oxide
were measured by P-4010 inductively coupled plasma atomic
emission spectrometer.
2.2. Adsorption and photocatalytic experiments
In all experiments, 5.0 g/L perovskite oxides was added to the
MO aqueous (3080 mg/L) and stirred in dark for some time,
in order to achieve adsorptiondesorption equilibrium between
MO and the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 /LaFe0.9 Mn0.1 O3 . After that,
the suspension was irradiated with sunlight and the photocatalytic experiments were conducted in July 2011, over a continuous
15 day period. All experiments were done out of the room of
chemistry department building in an open atmosphere between
9:30 a.m. and 3.30 p.m. The sky is clear and the sunrays are very
intense in this period in the city of Taiyuan (geographical location 37 51  9  North Latitude and 112 33  00  East Longitude),
between 9:30 a.m. and 3:30 p.m. where the solar intensity uctuations were minimal, and the mean illumination of sunlight is
96,000 lux. After the photocatalysis, the powder was recovered
from the solution. The concentrations of MO solution were determined by UV-Visible spectrophotometer (Model 721, Shanghai
Precision Scientic Instrument Co. Ltd., China) at max = 464 nm
using the standard curve. Adsorption and the photocatalytic conversion (%) was calculated as follows:
 (%) =

C0 Ct
100
C0

where C0 and Ct (mg/L) are the concentrations of MO solution before

and after the photocatalytic degradation, respectively.
The mineralization of MO was measured by the decrease of
chemical oxygen demand (COD) of the MO solution. COD was measured according to the standard dichromate titration method. The
mineralization efciency of MO was estimated by the following
expression.
Mineralization of MO (%) =

 1 COD 
t

COD0

100

where COD0 is the COD concentration after 5 min

adsorptiondesorption equilibrium, and CODt is the COD
concentration at certain reaction time t, respectively.
3. Results and discussion
3.1. XRD analysis
In this study, the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 was obtained by calcining the as-prepared powder, as shown in Fig. 1. It can be seen
that, when calcined at 650 C, the perovskite oxide is formed and
the major impurity in La0.8 Ba0.2 Fe0.9 Mn0.1 O3 is little La2 O2 CO3
and BaO. Here, the carbonation of La3+ would easily occur if the
oxidation decomposition was performed in the CO2 -containing

Z.-X. Wei et al. / Journal of Molecular Catalysis A: Chemical 370 (2013) 3543

37

Table 1
Effect of calcination temperature of LaFe0.9 Mn0.1 O3 on photocatalytic activity.
Sample

Temperature
( C)

Irradiation
time (min)

 (%)

LaFe0.9 Mn0.1 O3

650
700
750

120
120
120

92.7
88.3
81.4

La0.8 Ba0.2 Fe0.9 Mn0.1 O3

650
700
750

20
20
20

30.5
40.8
12.2

3.2. Effect of calcination temperature of La0.8 Ba0.2 Fe0.9 Mn0.1 O3

and LaFe0.9 Mn0.1 O3 on photocatalytic activity

Fig. 1. XRD patterns of La0.8 Ba0.2 Fe0.9 Mn0.1 O3 powder calcined at 650 C for 1 h
(a), 700 C for 1 h (b) and 800 C for 1 h (c).

gas-phase [17] (CO2 comes from the oxidation decomposition of

stearic acid or stearates). The minor peak of BaO is very low intensities (less than 1%), and this certies that the secondary phase has
negligible inuence on the overall magnetic and catalytic properties. With a rise in the heating temperature, the intensities
of the characteristic peaks of ABO3 increase, the La2 O2 CO3 peak
decrease and the BaO (PDF # 30-0143) peak gradually disappear.
The perovskite-type La0.8 Ba0.2 Fe0.9 Mn0.1 O3 calcained at 800 C
exhibits orthorhombic symmetry, with the space group of Pbnm.
In addition, the LaFe0.9 Mn0.1 O3 was obtained by calcining the
as-prepared powder. A clear transition from amorphous state to
crystalline state could be noticed in Fig. 2. The broad and poorly
dened peaks in Fig. 2a correspond to La2 O2 CO3 (PDF # 74-1144)
and MnO2 (PDF # 04-0378) and LaOCl (PDF # 64-7261). So, the
as-prepared powder obtained by the combustion is a mixture of
La2 O2 CO3 , MnO2 , LaOCl and signicant amounts of amorphous
powders. With a rise in the heating temperature, the intensities of
the characteristic peaks of ABO3 increase, and the MnO2 and LaOCl
peaks are disappeared. The major impurity in LaFe0.9 Mn0.1 O3 is
little La2 O2 CO3 after heating to 650 C (Fig. 2b). By 700 C for 1 h,
La2 O2 CO3 also disappeared. The perovskite-type LaFe0.9 Mn0.1 O3
exhibits cubic symmetry, with the space group of Pm3m.

Fig. 2. XRD patterns of LaFe0.9 Mn0.1 O3 : as-prepared powder (a), powder calcined
at 650 C for 1 h (b) and powder calcined at 700 C for 1 h (c).

In this study, MO cannot be degraded by sunlight photolysis in

the absence of photocatalyst [8]. The effect of the calcination temperature of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3 on
the degradation of MO was investigated from 650 C to 750 C, at a
concentration of 30 mg/L of MO and 5.0 g/L catalyst concentration
(pH: not adjusted). The results show that methyl orange degradation rate on La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3 under
the sunlight reaches the maximum value at 700 C and 650 C,
respectively (see Table 1). This indicates that the calcination temperature strongly affects the photocatalytic activity, in agreement
with the previous results [18].
As
mentioned
above,
the
major
impurity
in
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 calcined at 700 C and LaFe0.9 Mn0.1 O3
calcined at 650 C are La2 O2 CO3 . Can it have any intrinsic effect on
the magnetic or catalytic properties? So, the photocatalytic activity
of the La2 O2 CO3 prepared by the stearic acid solution combustion
[16] was tested according to the same experimental method
described in Section 2.2 (5.0 g/L La2 O2 CO3 ). The experimental
results show that, the La2 O2 CO3 has no catalytic performance.
In addition, La3+ , O2 and C4+ are non-magnetic ions, and hence
the magnetic interactions between them are absent. Therefore,
one can conclude that the La2 O2 CO3 has not any effect on the
magnetic or catalytic properties of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3
and LaFe0.9 Mn0.1 O3 .
The other impurity in La0.8 Ba0.2 Fe0.9 Mn0.1 O3 calcined at
700 C is BaO. So, the photocatalytic activity of the BaO prepared by
the stearic acid solution combustion [16] was also tested according
to the same experimental method. The experimental results show
that the BaO also has no catalytic performance. In addition, O2
and Ba are non-magnetic ions, and hence the magnetic interactions
between them are absent. Therefore, the BaO has no effect on the
magnetic and catalytic properties of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3
calcined at 700 C.
In addition, the amounts of metals in La0.8 Ba0.2 Fe0.9 Mn0.1 O3
are determined by inductively coupled plasma atomic emission
spectroscopy, and the values of the mass percent La, Ba, Fe, Mn
present a good balance between the theoretical and experimental
values. Those results are shown in Table 2.
In the following experiments, the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 calcined at 700 C and the LaFe0.9 Mn0.1 O3 calcined at 650 C were
further characterized. Moreover, their magnetic and photocatalytic
properties were further investigated.
Fig. 3 shows SEM images of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and
LaFe0.9 Mn0.1 O3 . It could be seen that the La0.8 Ba0.2 Fe0.9 Mn0.1 O3
and LaFe0.9 Mn0.1 O3 are almost-spherical nano-agglomerates,
leading to a rough surface and the presence of pore structure. Here,
the rough and porous surface of the powders could enhance the surface areas. Moreover the porous structure is believed to facilitate
the transportation of reactant molecules. Therefore, the powders
have a porous structure with a rough surface which is suitable for
catalytic applications [19].

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Z.-X. Wei et al. / Journal of Molecular Catalysis A: Chemical 370 (2013) 3543

Table 2
Inductively coupled plasma atomic emission spectroscopy analyses.
Perovskite oxide

Theoretical (%)

La0.8 Ba0.2 Fe0.9 Mn0.1 O3

Real (%)

La

Ba

Fe

Mn

La

Ba

Fe

Mn

46.7

11.5

21.1

2.3

40.6

10.9

18.2

2.2

Fig. 3. SEM micrograph of La0.8 Ba0.2 Fe0.9 Mn0.1 O3- calcined at 700 C for 1 h. (30,000) (a) and LaFe0.9 Mn0.1 O3- calcined at 650 C for 1 h (100,000) (b).
Table 3
Magnetic data of La0.8 Ba0.2 Fe0.9 Mn0.1 O3 obtained by calcining as-prepared powder
at different temperature for 1 h.
Temperatures ( C)

Hc (Oe)

Mr (emu/g)

Ms (emu/g)

650
700
800

56.86
20.93
89.69

10.24
4.36
4.30

41.94
19.31
10.99

3.3. Magnetic properties

The magnetic properties of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 calcined at different temperatures are investigated in air ambience,
as shown in Fig. 4. The magnetic parameters such as saturation
magnetization Ms, coercivity Hc and remanent magnetization Mr
were given in Table 3. One can see that the La0.8 Ba0.2 Fe0.9 Mn0.1 O3
calcined at different temperatures all exhibit room-temperature
ferromagnetism and have lower coercivities and remanences. The
saturated magnetization (Ms) increases as annealing temperature decreases, and attains the peak value (Ms = 41.94 emu/g) at
650 C. The response of the powder calcined at 700 C to a magnet (50 mm 50 mm 10 mm, surface eld of 3000 G) is shown
in Fig. 4d.
The magnetic hysteresis loops measured in air ambience for the
LaFe0.9 Mn0.1 O3 obtained by calcining the as-prepared powder in
the range of 600750 C are shown in Fig. 5. The magnetic parameters were given in Table 4. It can be seen that the LaFe0.9 Mn0.1 O3
calcined at different temperatures also exhibit room-temperature
ferromagnetism and have lower coercivities and remanences. The
saturated magnetization (Ms) increases as annealing temperature
decreases, and attains the peak value (Ms = 13.52 emu/g) at 600 C.

Table 4
Magnetic data of LaFe0.9 Mn0.1 O3 obtained by calcining as-prepared powder at
different temperature for 1 h.
Temperature ( C)

Hc (Oe)

Mr (emu/g)

Ms (emu/g)

600
650
700
750

44.69
48.06
78.71
95.11

1.72
1.74
0.90
0.11

13.52
12.83
5.14
0.58

With the increasing temperature, the intensities of the characteristic peaks of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3
increase (see Figs. 1 and 2), indicating the increase in the
crystallinity and the decrease in the defects. Therefore, the ferromagnetism of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3
may be activated by defects induced after calcination, whereas
the decrease of ferromagnetism with the increase of calcination
temperature (see Figs. 4 and 5) is possibly due to a less-defective
state of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3- and LaFe0.9 Mn0.1 O3 . The
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3 particles in the
present study have probably been sintered and accompanied by
defect formation at particle/particle interfaces. These interfacial
defects generate ferromagnetism in these samples, possibly by acting as large volume magnetic polarons which couple the spins. This
is in agreement with that reported by Wongsaprom et al. [20].
It is reported that the superparamagnetic property of the
photocatalyst or the higher saturation magnetization, the lower
coercivity and remanent magnetization can largely reduce their
aggregation (especially for the superparamagnetic photocatalysts) after they were separated by applied magnetic eld from
original reaction solution, so such photocatalysts can be easily
redispersed in a solution for reuse [18,21]. Compared with the
LaFe0.9 Mn0.1 O3 , the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 has higher saturation magnetization (Ms) when they were calcined at the same
temperatures (see Tables 3 and 4). However, the coercivity and
remanent magnetization show irregular changes. Further work
is needed to achieve a thorough understanding, and this will be
of great interest to researchers in the eld of magnetic oxides.
The La0.8 Ba0.2 Fe0.9 Mn0.1 O3 with higher saturation magnetization can be easily separation from the solution. As shown in
Fig. 4d, the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 obtained by calcining the asprepared powder at 700 C can be easily attracted with a magnet
(50 mm 50 mm 10 mm, surface eld of 3000 G) owing to its
higher saturation magnetization.
In addition, compared with the LaFe0.9 Mn0.1 O3+ prepared by
solid state reaction [15], the LaFe0.9 Mn0.1 O3 has higher saturation magnetization (Ms) and the lower coercivity in this study. This
shows that a preparation method can indeed play an important role
in the properties of the products.
In order to analyze the origin of the ferromagnetism of the
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3 , XPS analysis was

Z.-X. Wei et al. / Journal of Molecular Catalysis A: Chemical 370 (2013) 3543

39

Fig. 4. Field dependence of magnetization of La0.8 Ba0.2 Fe0.9 Mn0.1 O3- calcined at different temperatures: 650 C (a), 700 C (b), 800 C (c) and response of
La0.8 Ba0.2 Fe0.9 Mn0.1 O3- calcined at 700 C to a magnet (d).

Fig. 5. Field dependence of magnetization of LaFe0.9 Mn0.1 O3 calcined at different

temperatures: 600 C (a), 650 C (b), 700 C (c) and 750 C (d).

performed. Fe 2p XP spectra of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and

LaFe0.9 Mn0.1 O3 are shown in Fig. 6. In Fig. 6a, the peak at 710.3 eV
with a distinct large and low intensity satellite peak at about
719.3 eV is characteristic of Fe3+ in perovskite oxides [22], while
the similar results have been observed in Fig. 6b. This indicates that
Fe elements of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3
are Fe3+ state.

Fig. 7 shows the Mn 2p3/2 spectra of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3
and LaFe0.9 Mn0.1 O3 . It can be seen that the Mn 2p3/2 of
them are broad and asymmetric toward the high binding energy
side. Peak intensities were evaluated by applying a peak synthesis procedure that includes three components, namely Mn2+
(640.4 eV), Mn3+ (641.3 eV), Mn4+ (642.3 eV) and a satellite for
the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 [23] and the Mn2+ (641.0 eV), Mn3+
(641.4 eV), Mn4+ (642.6 eV) for the LaFe0.9 Mn0.1 O3 , respectively. This demonstrates the presence of Mn2+ , Mn3+ and Mn4+
of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3. It should
be emphasized at this point that the deconvolution method
yields ambiguity in the recognition of the Mn2+ , Mn3+ and
Mn4+ species due to the small differences in their binding
energy values [2325]. Hence, it is difcult for one to determine the content of the Mn2+ , Mn3+ and Mn4+ species of the
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 /LaFe0.9 Mn0.1 O3 .
In conclusion, the magnetic Fe, Mn elements of the
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3 are Fe3+ , Mn2+ ,
Mn3+ and Mn4+ states. It is reported [26] that LaFe0.5 Mn0.5 O3
exist the possibility of double exchange between Mn3+ and
Fe3+ , and hence it has the ferromagnetism, and La1x Srx MnO3
(0 x 0.5) has double exchange interaction of Mn4+ and Mn3+
and hence it has the superparamagnetic behavior [27]. Therefore,
one can explain that the origin of the ferromagnetism of the
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3 is due to the double exchange interaction between Mn3+ and Fe3+ , Mn4+ and Mn3+
in them, respectively. After doping Ba for La in LaFe0.9 Mn0.1 O3 ,

Fig. 6. Fe 2p XP spectra of La0.8 Ba0.2 Fe0.9 Mn0.1 O3 (a) and LaFe0.9 Mn0.1 O3 (b).

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Z.-X. Wei et al. / Journal of Molecular Catalysis A: Chemical 370 (2013) 3543

Fig. 7. Mn 2p3/2 XP spectra of La0.8 Ba0.2 Fe0.9 Mn0.1 O3 (a) and LaFe0.9 Mn0.1 O3 (b).

Mn4+ ions are created due to charge balance, i.e., the Ba substitution induced the increase in Mn4+ content which favors the
double exchange interaction of Mn4+ and Mn3+ . Therefore, the
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 has higher magnetic property than that
of the LaFe0.9 Mn0.1 O3 .

3.4. The UVvis diffuse reectance spectra

UVvis
diffuse
reectance
spectra
of
the
The
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 calcined at 700 C and LaFe0.9 Mn0.1 O3
calcined at 650 C are recorded and illustrated in Fig. 8. Compared with the LaFe0.9 Mn0.1 O3 , the La0.8 Ba0.2 Fe0.9 Mn0.1 O3
has slightly higher absorption between the 400800 nm
ranges, indicating that visible light (460800 nm) absorption
of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 slightly increases by doping
Ba2+ in La site, i.e., it has higher visible light adsorption. The
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 could be excited under visible light
irradiation and could be developed a new visible light photocatalyst. In addition, it can be seen that the band gaps of
the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3 are hard
to be estimated due to the lack of sharpness in the optical
absorption.

Fig. 8. UVvis spectra of LaFe0.9 Mn0.1 O3 (a) and La0.8 Ba0.2 Fe0.9 Mn0.1 O3 (b).

3.5. Adsorptive and photocatalytic activities of

La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3 for the removal of
MO
3.5.1. Adsorptive and photocatalytic activities of
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3 for the removal of
MO
At the room temperature condition, adsorptive properties of the
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 calcined at 700 C and LaFe0.9 Mn0.1 O3
calcined at 650 C for the removal of MO were investigated
(see Fig. 9). The experimental results show that MO concentration rapidly decreases and slowly reaches an equilibrium
value with increasing adsorption time in approximately 4 min
for La0.8 Ba0.2 Fe0.9 Mn0.1 O3 , while MO reaches an equilibrium
value in approximately 30 min for LaFe0.9 Mn0.1 O3 , which
are ascribed to the adsorption of MO on the surface of the
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 /LaFe0.9 Mn0.1 O3 . A further increase of
adsorption time has a negligible effect on the MO adsorption. Equilibrium value of adsorption of MO with La0.8 Ba0.2 Fe0.9 Mn0.1 O3
and LaFe0.9 Mn0.1 O3 is 76.3% and 53.0% (Fig. 9a and b), respectively. This shows that the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 has higher MO
adsorption capacity and a higher adsorption velocity than those of
the LaFe0.9 Mn0.1 O3 .
Further, the effect of irradiation time on the photocatalytic degradation of MO was investigated at methyl
orange concentration of 30 mg/L at pH 1.0 with the
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 /LaFe0.9 Mn0.1 O3
concentration
of
5 mg/L for a sufcient period of time. The results are also
shown in Fig. 9. Fig. 9 shows that MO degradation rate rapidly
increased with increasing irradiation time in the initial stage,
and then reached an equilibrium value of 99.8% for 16 min for the
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and 98.2% for 3 h for the LaFe0.9 Mn0.1 O3 ,
respectively. The degradation velocity of MO in the presence of
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 was much faster than that in the presence of LaFe0.9 Mn0.1 O3 . Hence, the catalytic activity of the
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 was much higher than that of the
LaFe0.9 Mn0.1 O3 .
3.5.2. Kinetics of the photocatalytic degradation
At room temperature, the effect of the methyl orange concentration on degradation efciency was studied by varying the
concentration from 30 mg/L to 100 mg/L under sunlight irradiation
with a xed pH (1.0). The experimental results show that the degradation efciency decreases with an increase in concentration of MO
from 30 to 80 mg/L.

Z.-X. Wei et al. / Journal of Molecular Catalysis A: Chemical 370 (2013) 3543

41

Fig. 9. Effect of adsorption and sunlight irradiation time on the degradation of MO for La0.8 Ba0.2 Fe0.9 Mn0.1 O3 (a) and LaFe0.9 Mn0.1 O3 (b).

0.9
0.8

1/Ct

0.4

C0=80mg/L

0.7

Co= 100mg/L
Co= 75mg/L

C0=50mg/L

0.6

0.5

Co= 50mg/L

0.3

C0=30mg/L

1/Ct

0.5

0.2

0.4
0.3

0.1

0.2
0.0

0.1
5

10
15
Irradiation time (min)

30

60
Irradiation time (min)

90

120

Fig. 10. Second-order kinetic plots of photocatalytic degradation of MO at different initial concentration in the presence of La0.8 Ba0.2 Fe0.9 Mn0.1 O3 (a) and LaFe0.9 Mn0.1 O3
(b).

The experimental data was subjected to second-order-kinetics,

which in its usual form is given by
1
1
=  + kapp t
Ct
C0

(1)

In this study, the specic surface area, pore volume and average
pore diameter of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 calcined at 700 C
are 9.1 m2 /g, 0.05 cm3 /g, 22.9 nm, respectively, the corresponding value in LaFe0.9 Mn0.1 O3 calcined at 650 C are 15.8 m2 /g,

where C0 is the concentration value of MO of the

adsorptiondesorption equilibrium, Ct is the concentration at
time t and kapp is the apparent rate constant. Second-order kinetic
plots of photocatalytic degradation of MO at different initial
concentration in the presence of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and
LaFe0.9 Mn0.1 O3 are shown in Fig. 10 and Fig. 11, respectively. A
linear tting of the data between 1/Ct and irradiation time (t) to
the above equation conrmed the applicability of this model. The
apparent rate constant (kapp ) and the correlation coefcient values
are shown in Table 5 and Table 6, respectively. It is seen that the
apparent rate constants decrease with increasing concentrations
of MO.
Table 5
Kinetic parameters of second-order kinetic model for MO degradation by
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 .
Ct (mg/L)
80
50
30

Reaction kinetic equation

2

1/Ct = 0.0880 + 1.01 10 t

1/Ct = 0.0317 + 2.03 102 t
1/Ct = 0.0083 + 3.5 102 t

kapp (mol1 L min1 )

1.01 102
2.03 102
3.5 102

0.9989
0.9967
0.9986

Fig. 11. Effect of pH on degradation efciency of MO.

42

Z.-X. Wei et al. / Journal of Molecular Catalysis A: Chemical 370 (2013) 3543

Table 6
Kinetic parameters of second-order kinetic model for MO degradation by
LaFe0.9 Mn0.1 O3.
Ct (mg/L)
100
75
50

Reaction kinetic equation

3

1/Ct = 0.0333 + 1.33 10 t

1/Ct = 0.0351 + 2.13 103 t
1/Ct = 0.0372 + 3.84 103 t

kapp (mol1 L min1 )

1.33 103
2.13 103
3.84 103

0.9909
0.9985
0.9975

0.08 cm3 /g and 19.8 nm, respectively. Obviously, the specic

surface area and pore volume of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3
are lower than those of the LaFe0.9 Mn0.1 O3 . That does not
help to explain the better adsorption and catalytic activities
of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 . In addition, the mean valence
of Fe and Mn and the value for oxygen vacancies () in
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 is 3.05 and 0.08, respectively, while the
corresponding value in LaFe0.9 Mn0.1 O3 is 2.94 and 0.03, respectively. These results show that La0.8 Ba0.2 Fe0.9 Mn0.1 O3 has higher
oxygen vacancies and the mean valence of Fe and Mn than those
of the LaFe0.9 Mn0.1 O3 . The oxygen vacancies can bring on the
strong absorption of OH , H2 O or molecular O2 at the surface of the
catalyst. When the electronhole pairs are generated after absorption of radiation by the catalyst, they could be trapped by these
particular species and thus can generate some active species such
as the hydroxyl radicals and adsorbed oxygen [28], resulting in
the photocatalytic degradation of MO. The La0.8 Ba0.2 Fe0.9 Mn0.1 O3
contains more oxygen vacancies and higher absorption in the visible light region than those of the LaFe0.9 Mn0.1 O3 (see Fig. 8), and
hence, the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 has higher adsorption and catalytic activity. Further, Mn element in the La0.8 Ba0.2 Fe0.9 Mn0.1 O3
and LaFe0.9 Mn0.1 O3 is Mn2+ , Mn3+ and Mn4+ state. Hence, Mn
ions with variable valance could exert signicant inuence on photocatalytic action. Due to the fact that Mn4+ is more stable than
Mn2+ and Mn3+ , Mn4+ can serve as electron trapper to separate the
electronhole pairs, while Mn3+ and Mn2+ can give electrons to the
oxygen adsorbed on the surface of the catalyst, thus prohibiting the
recombination of the electronhole pairs, hence signicantly promoting the photocatalytic activity. Further, barium doping induced
the increase in Mn4+ content in La0.8 Ba0.2 Fe0.9 Mn0.1 O3 because
that a fraction of trivalent La ions is substituted by divalent ion Ba
and the same fraction of Mn3+ is transformed to Mn4+ . Hence, this
could induce that the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 has higher photocatalytic property than that of LaFe0.9 Mn0.1 O3 .
In conclusion, the higher catalytic activity of the
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 is due to its higher oxygen vacancies, higher Mn4+ content and higher visible light absorption.
The La0.8 Ba0.2 Fe0.9 Mn0.1 O3 is the photocatalyst possessing of
magnetic property and visible-light activity, i.e., bifunctional
photocatalyst. This also indicates that the adsorption and magnetic
properties as well as photocatalytic activities of the perovskite
oxides indeed can be designed by doping elements on the La sites.
In the following experiments, the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 calcined at 700 C was used as the magnetic visible photocatalyst and
its photocatalytic properties were further investigated.

3.6. Effect of solution pH

The pH of the aqueous solution is an important controlling
parameter in photocatalytic process. The effect of pH on the photocatalytic activity of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 was tested from
1.0 to 10.5. The results are shown in Fig. 11. It can be seen that
the photocatalytic activity is largely dependent on the pH of the
solution. The degradation efciency decreases quickly with the
increase of pH, when the pH exceeds 5.0. The degradation efciency
decreases quickly. The optimum pH is 1.0.

Fig. 12. Mineralization of 10 mL 30 mg L1 MO

La0.8 Ba0.2 Fe0.9 Mn0.1 O3 under sunlight irradiation.

in

the

presence

of

During photocatalysis, adsorption occurred rst when the

La0.8 Ba0.2 Fe0.9 Mn0.1 O3 was dispersed in MO solution. In the
reaction of adsorption, the charges of adsorbent (MO) and adsorbate (La0.8 Ba0.2 Fe0.9 Mn0.1 O3 ) played an important role. The
heterocharge between the adsorbent and adsorbate is in favor
of adsorbing reaction. At acidic conditions, more protons could
be available to protonate the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 surface
according to recent studies [29], which led to positive charges
of adsorbent surface, while MO carry negative charges (SO3 ).
The negatively charged MO was adsorbed on the positively
charged La0.8 Ba0.2 Fe0.9 Mn0.1 O3 surface via electrostatic interactions. Thereby acidic condition is helpful to the degradation of MO.
3.7. Mineralization of MO
At the room temperature condition, COD removal efciencies of 30 mg L1 MO solutions by the La0.8 Ba0.2 Fe0.9 Mn0.1 O3
under sunlight irradiation are shown in Fig. 12. It can be seen
that COD removal efciencies were increasing with the increase
of reaction time, 88.2% COD removal efciency was achieved
within 100 min reaction time for the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 . This
shows that MO molecule can be effectively mineralized by the
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 under sunlight irradiation. Additionally,
the mineralization rate is slower than the degradation rate by comparing Figs. 9 and 12. This suggests that the chromophore of MO
molecular was easily destructed for the sunlight photocatalytic
degradation by the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 , and then the degradation intermediates with small molecular were further mineralized
to CO2 and H2 O.
3.8. Regeneration and reusability of La0.8 Ba0.2 Fe0.9 Mn0.1 O3
With the aim of exploring the potential reutilization of
the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 as photocatalyst for the MO
degradation, thermal regeneration tests were carried out by
calcining the exhausted La0.8 Ba0.2 Fe0.9 Mn0.1 O3 at different
temperatures. The experimental results show the regenerated
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 calcined at 700 C for 1 h has higher
photocatalytic activity for the MO degradation, the decoloration
rate of MO reaches to 93.2%. Fig. 13 shows the FT-IR spectra
of MO, the exhausted La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and the regenerated La0.8 Ba0.2 Fe0.9 Mn0.1 O3 calcined at 700 C for 1 h. A

Z.-X. Wei et al. / Journal of Molecular Catalysis A: Chemical 370 (2013) 3543

43

between Mn3+ and Fe3+ , Mn3+ and Mn4+ as well as the defective state in La0.8 Ba0.2 Fe0.9 Mn0.1 O3 /LaFe0.9 Mn0.1 O3 . Further,
the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 can be easily recycled by an external magnetic eld and redispersed in a solution for reuse for its
higher saturation magnetization, lower coercivity (Hc) and remanent magnetization (Mr). The optimal conditions were an initial
methyl orange concentration of 30 mg L1 , at pH 1.0 with the
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 concentration of 5 g L1 for 16 min sunlight irradiation with good repeated use of the catalyst. This study
could point out a potential way to develop new and more active
magnetic perovskite-type photocatalysts for the wastewater treatment.
Acknowledgements
This project was supported by Science and Technology Item in
Taiyuan Shanxi (Nos. 120247-13) and the Natural Science Fund
Council of North University of China.
Fig. 13. FT-IR spectra: MO (a), regenerated La0.8 Ba0.2 Fe0.9 Mn0.1 O3 (b) and
exhausted La0.8 Ba0.2 Fe0.9 Mn0.1 O3 (c).

comparison of Fig. 13a and b replies that all the characteristic

peaks of MO disappear or are very weak in Fig. 13b, indicating
the degradation of MO is mainly related to the photocatalytic
degradation on the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 rather than only
adsorption, and La0.8 Ba0.2 Fe0.9 Mn0.1 O3 did play a role of an
efcient photocatalyst.
In addition, the regenerated La0.8 Ba0.2 Fe0.9 Mn0.1 O3 has excellent photocatalytic activity for the degradation of MO and it can be
reconverted into better photocatalyst for reuse. After four regeneration cycles, the MO degradation was found to decrease only
approximately 6.3% (from 93.2% to 86.9%). Heat treatment might
cause photocatalyst aggregation and a decrease in specic surface
area. This could explain the loss of catalytic capacity. However
the results above still indicate that the La0.8 Ba0.2 Fe0.9 Mn0.1 O3
is reusable and maintain relatively high activity. Therefore, the
La0.8 Ba0.2 Fe0.9 Mn0.1 O3 is potentially employable in practical
applications under mild condition such as natural light and oxygen
from air.
For perovskite-type oxides ABO3 , the photocatalysis and magnetic characteristics could be easily tunabled by appropriate
substitutions or doping at the A and B site as well as the changes
in crystallite size, etc. As a result of the combined effect, one can
design and prepare perovskite-type oxides with superparamagnetic nature and visible photocatalytic activity.
4. Conclusions
The La0.8 Ba0.2 Fe0.9 Mn0.1 O3 and LaFe0.9 Mn0.1 O3 can be synthesized by stearic acid solution combustion method. They all
exhibit room-temperature ferromagnetism and have lower coercivity (Hc) and remanent magnetization (Mr). The magnetism
of the La0.8 Ba0.2 Fe0.9 Mn0.1 O3 is improved after doping Ba at
La-site, and it has much higher photocatalytic activity than
that of the LaFe0.9 Mn0.1 O3 due to its higher oxygen vacancies and higher Mn4+ content and higher visible light absorption.
Their ferromagnetism were caused by the double exchange

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