Académique Documents
Professionnel Documents
Culture Documents
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
36
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.
C0 Ct
100
C0
1 COD
t
COD0
100
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
650
700
750
20
20
20
30.5
40.8
12.2
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).
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).
38
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 (%)
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
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. 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).
40
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 .
Fig. 8. UVvis spectra of LaFe0.9 Mn0.1 O3 (a) and La0.8 Ba0.2 Fe0.9 Mn0.1 O3 (b).
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).
(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,
1.01 102
2.03 102
3.5 102
0.9989
0.9967
0.9986
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
1.33 103
2.13 103
3.84 103
0.9909
0.9985
0.9975
in
the
presence
of
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).
References
[1] L. Zhang, W.Z. Wang, L. Zhou, M. Shang, S.M. Sun, Appl. Catal. B: Environ. 90
(2009) 458462.
[2] J.H. Jiang, Q.M. Gao, Zh Chen, J. Hu, C.D. Wu, Mater. Lett. 60 (2006) 38033808.
[3] W. Qiu, Y. Zheng, Katy A. Haralampides, J. Chem. Eng. 125 (2007) 165176.
[4] S.W. Lee, J. Drwiega, C.Y. Wu, D. Mazyck, Wolfgang M. Sigmund, Chem. Mater.
16 (2004) 11601164.
[5] D. Beydoun, R. Amal, J. Phys. Chem. B 104 (2000) 43874396.
[6] X.Y. Li, J.N. Wang, L.L. Zhang, C.J. Li, J. Mater. Sci. 47 (2012) 465472.
[7] S.Q. Liu, Environ. Chem. Lett. 10 (2012) 209216.
[8] H.X. Chen, Z.X. Wei, Y. Wang, W.W. Zeng, C.M. Xiao, Mater. Chem. Phys. 130
(2011) 13871393.
[9] H.Y. Hwang, Nat. Mater. 4 (2005) 803804.
[10] R. Hammami, H. Batis, C. Minot, Surf. Sci. 603 (2009) 30573067.
[11] L.A. Han, C.L. Chen, H.Y. Dong, J.Y. Wang, G.M. Gao, Physica B 403 (2008)
26142617.
[12] L.A. Cano, M.V. Cagnoli, S.J. Stewart, E.D. Cabanillas, E.L. Romero, S.G. Marchetti,
Hyperne Interact. 195 (2010) 275280.
[13] N. Zhang, W. Ding, W. Zhong, K. Du, K. Wang, Y. Du, Appl. Phys. A 65 (1997)
7780.
[14] K.L. Liu, S.L. Yuan, Z.M. Tian, J.H. He, P. Li, S.Y. Yin, X.F. Zheng, C.H. Wang, H.N.
Duan, S.X. Huo, J. Magn. Magn. Mater. 322 (2010) 7378.
[15] O.F. de Lima, J.A.H. Coaquira, R.L. de Almeida, L.B. de Carvalho, S.K. Malik, J. Appl.
Phys. 105 (2009) 013907, http://dx.doi.org/10.1063/1.3054323.
[16] Z.X. Wei, Y.Q. Xu, Hai-Yan Liu, C.W. Hu, J. Hazard. Mater. 165 (2009) 10561061.
[17] V.G. Milt, R. Spretz, M.A. Ulla, E.A. Lombardo, J.L. Garca Fierro, Catal. Lett. 42
(1996) 5763.
[18] X.Q. Chen, K.F. Lam, Q.J. Zhang, B.C. Pan, M. Arruebo, K.L. Yeung, J. Phys. Chem.
C 113 (2009) 98049813.
[19] F.J. Lpez-Tenllado, A. Marinas, F.J. Urbano, J.C. Colmenares, M.C.
Hidalgo, J.M. Marinas, J.M. Moreno, Appl. Catal. B: Environ. (2012),
http://dx.doi.org/10.1016/j.apcatb.2012.02.015.
[20] K. Wongsaprom, E. Swatsitang, S. Maensiri, Appl. Phys. Lett. 90 (2007),
162506.1-162506.3.
[21] Y.H. Ao, J.J. Xu, D.G. Fu, C.W. Yuan, J. Alloys Compd. 471 (2009) 3338.
[22] J.M. Giraudon, A. Elhachimi, F. Wyrwalski, S. Siffert, A. Aboukas, J.F. Lamonier,
G. Leclercq, Appl. Catal. B: Environ. 75 (2007) 157166.
[23] K. Barbara, T. Wodzimierz, Appl. Catal. A: Gen. 335 (2008) 2836.
[24] C. Morilla-Santosa, W.H. Schreiner, P.N. Lisboa-Filho, Mater. Res. 14 (2011)
217221.
[25] S. Valencia, A. Gaupp, W. Gudat, Phys. Rev. B 75 (2007), 184431.1-184431.11.
[26] K. Ueda, Y. Muraoka, H. Tabata, T. Kawai, Appl. Phys. Lett. 78 (2001) 512514.
[27] S. Daengsakul, C. Thomas, I. Thomas, C. Mongkolkachit, S. Siri, V. Amornkitbamrung, S. Maensiri, Nanoscale Res. Lett. 4 (2009) 839845.
[28] Z.X. Wei, H.Y. Liu, X.J. Zhang, Y.B. Li, Acta Armamentii (Chin) 30 (2009)
15961601.
[29] F. Shimojo, Solid State Ionics 179 (2008) 807810.