Advanced Materials Research Vol 626 (2013) pp 131-137 Online: 2012-12-27 (2013) Trans Tech

Publications, Switzerland doi:10.4028/www.scientific.net/AMR.626.131

Preparation and Characterization Heteroagglomeration

of Fe3O4/TiO2 Composites by
Adel Fisli1,2a, Rahmi Saridewi3, Sari Hasnah Dewi2, Jarnuzi Gunlazuardi1b 1Department of
Chemistry, Faculty of Mathematic and Science, University of Indonesia, Depok 16424,
Indonesia 2 Center for Technology of Nuclear Industry Materials, National Nuclear Energy
Agency, Kawasan Puspiptek, Serpong 15314, Indonesia 3Department of Chemistry, Faculty of
Mathematic and Science, University of Andalas, Padang, Indonesia. aadel@batan.go.id,
bjarnuzi@ui.ac.id
Keywords: Composites, Heteroagglomeration, Magnetic nanoparticles, Photocatalysis.
Abstract. Fe3O4/TiO2 composites were prepared by heteroagglomeration. The
composites of different Fe3O4to TiO2 weight ratio were prepared by mixing of prepared
Fe3O4 with TiO2 in aqueous slurry, under ultrasonic treatment. All prepared samples
were characterized by XRD, VSM, SEM/EDS, raman spectroscopy and BET. The
prepared composites contained TiO2 (anatas and rutile) and Fe3O4 crystal phases. The
magnetization hysteresis loop for Fe 3O4/TiO2 nanocomposites indicated that the hybrid
catalyst showed superparamagnetic characteristics at room temperature. Photocatalytic
performance of the prepared composites was examined by its ability to degrade
methylene blue dye in aqueous solution. The photocatalytic activity of Fe 3O4/TiO2
composites was lower than that of pure TiO sample because of the presence of non-
active photocatalytic in composite (iron oxide). Under UV irradiation, the photocatalytic
activity of Fe3O4/TiO2 (1:1) composite was relatively similar to Fe 3O4/TiO2 (1:2),
however, under sunlight irradiation, the photocatalytic activity of Fe 3O4/TiO2 (1:2)
composite was relatively increase. The Fe 3O4/TiO composite can be easily recovered
from treated water in slurry-type reactor by the application of an external magnetic field.
Introduction
Water is a fundamental resource for human and economic welfare, and modern
society depends on complex, interconnected, water infrastructure to provide reliable
safe water supplies and to remove and treat wastewater [1]. More than 6000 organic
compounds have been detected in row water sources, most of which are due to human
activities [2]. Over the last 10 years the scientific and engineering interest in the
application of semiconductor photocatalyst has grown exponentially. Among
semiconductor photocatalyst, TiO2 semiconductor is the most widely used, because of
its chemical stability, strong oxidizing power, non-toxic and low cost. TiO 2 semiconductor
photocatalyst has been used in solving various environmental problems such as water
purification [3,4], disinfection [5,6] and treatment of waste [7].
The nano-size particle of catalyst is well used because of very high surface area so
that the more availability of facilities reaction/interactions between the surface active
catalyst with the interacting media [8]. However, for a slurry reactor, the dispersed TiO 2
nanoparticles are difficult to be recovered from the treated water, which resulted in the
release of TiO2 nanoparticles into the environment. One alternative solution to the
problem is to apply nanoparticle photocatalyst which is immobilized on a permanent
magnetic carrier, which allows them to be recollected from the treated water by using an
external magnetic field, and then reused again. Immobilization of photocatalytic
nanoparticles on magnetic carrier can be done by sol-gel method [9], plasma
spraying[10], and precipitate [11]. However, these methods requires calcination step
(>400oC) to activate the catalyst, which may cause agglomeration of the photocatalyst,
a loss of the magnetic properties, and even unwanted high-temperature chemical
reaction between materials [12]. To avoid calcination step to the composite, a
heteroagglomeration method can be employed, which combines magnetic materials
with an already active TiO2 photocatalyst. Heteroagglomeration may be occurred when
two particles have oppositely charge joined in the media system [13]. It is known that
Fe3O4 and TiO2 have a different isoelectrostatics point. Based on the measurements of
zeta potential, The surface charge of Fe 3O4 changes from (+) to (-) at pH 8.5 while that
of TiO2 changes from (+) to (-) at about pH 5. At pH range above 5 and below 8, Fe 3O4
possesses positive surface charge whereas TiO 2 has negative charge so that an
attractive force would adhere two particles together [14]. In this work, we present an
approach to prepare Fe3O4/TiO2 composite which combine magnetic material with
active TiO2 photocatalyst in solution at about pH 7 and under ultrasonification. The
characterization of prepared samples was accomplished by using various techniques,
such as, powder X-ray diffraction (XRD), scanning electron microscopy/electron
dispersive spectroscopy (SEM/EDS), vibrating sample magnetometer (VSM), raman
spectroscopy and BET for surface area investigation. Their photocatalytic activity was
evaluated for degradation of methylene blue.
Experimental Procedure Preparation of TiO
2

/Fe
3

O
4

Composite. Fe
3

O
4

nanoparticles were prepared according to

Kang et.al [15], where 5.2 g FeCl
3

.6H
2

O and 2 g FeCl
2

.4H
2

O (mol ratio of Fe(III):Fe(II) = 2:1) were

dissolved in 10.3 mL of 1 N HCl and then 15 mL deionized water was added with
vigorous stirring. The mother solution was dropped into 250 mL of 1,5 M ammonium
hidroxide solution under vigorous stirring. The precipitated magnetic solid was
separated from the solution by magnetic bar, then was being washed with deionized
water until the washing water reach neutral pH (at about pH 7). Finally, magnetic solid
was dispersed into the 200 mL deionized water. On other beaker, 1.16 g, 2.32 g and
4.64 g TiO
2

was dispersed into 100 mL of 0.02 M (NH

4

)
2

SO
4

0.02 M and mixed

with the magnetic material suspension. The suspension was sonicated for 30 minute at
room temperature with Sonics Vibracell model at VCX 750, 750watts power, frequency
20kHz, Sonics &Materials INC and centrifuged at 4000 rpm. The obtained solid was
dried in oven for overnight at temperature of 100oC. Three variabels of the composite
was obtained in weight ratio of Fe
3

O
4

/TiO
2

,
namely: Fe
3
O
4

/TiO
2

(1:0.5); Fe
3

O
4

/TiO
2

(1:1) and Fe
3

O
4

/TiO
2

(1:2), and ready for further

experiments. Characterization. XRD patterns of the sample were obtained by X-ray
Diffractometer XD-610 Phillips Cu-K (a = 0.154 nm), SEM images were taken using
JEOL JSM 6510 LA. The percentage of Ti and Fe in composite was calculated from
energy dispersive spectra (EDS) measurements recorder on SEM JEOL JSM 6510 LA
operating 20 kV. The magnetic properties of the sample were measured at room
temperature using a vibrating sample magnetometer (VSM) Oxford type 1.2 T. The
raman spectra were excited by 785 nm radiation with laser power of 1 mW using
Raman Spectrometer Bruker serial Number 254. BET was calculated from Nova 1000e
series Quantachrome Instruments. Evaluation of the Photocatalytic Activity. The
photocatalytic activity of the synthesized materials were evaluated for the degradation of
methylene blue solution in water. Approximately 200 mg of tested materials was
dispersed into 250 mL of 1x10
-5

M methylene blue. The suspension

was shaked under UV lamp (2 x 18 Watts) having main radiation at 254 nm, at room
temperature. Parallel experiments were also conducted under direct sunlight. The
treated water were periodically sampled at 1 hour interval. The concentration of
methylene blue in treated water was determined by UV/Vis Spectrophotometer Lamda
25 at wavelenght of 663 nm.
Results and Discussion
Fig. 1 shows the diffraction patterns of prepared Fe
3

O
4

, TiO
2

and Fe
3

O
4

/TiO
2

composite.
The peaks of Fe
3

O
4

was clearly observed in difractograms which similar to the standard

diffraction pattern of magnetite (JCPDS file no. 03-0863). The crystallite size of Fe
3

O
4

was 12.7 nm,

which was estimated acording to Scherrer equation, applied to the (311) plane. The
XRD measurement result of TiO
2

being used (Aldrich) revealed the occurrence of anatase phase (JCPDF File no. 21-
Advanced Materials Research Vol. 626 133
1272) and rutil phase (JCPDF file no. 21- 1276), this is agree with the composition given
by the manufacturer. The peaks of Fe
3
A
A

O
4

, TiO
2

anatase and rutil in Fe

3

O
4

/TiO
2 composite was still clearly observed. It is
indicated that there were no phase change of TiO
2
TiO2 Aldrich Fe3O4/TiO2 (1:2)
R
Fe3O4/TiO2 (1 : 1) Fe3O4/TiO2 (1 : 0,5) Fe3O4

Fig. 1. The XRD pattern of prepared Fe

3

and iron oxide in the composite, therefore more fraction of TiO

2

in composite there was more clearly observed the

peak intensity of TiO
2
R
R

in the diffractogram.
The magnetic properties of prepared Fe
3
A
A
A
A
R
R
R
A

O
4

and Fe
3

O
4

/TiO
2

composite were measured at room temperature as illustrated in

Fig. 2. The values of saturation magnetization (Ms), remanent magnetization (Mr) and
coercivity (Hc) are shown in Table 1. The observed value of saturation magnetization for
the prepared magnetic iron oxide was found 43,4 emu/g. Magnetic properties depend
on the amount of magnetic phase fraction in the materials. The decrease in the
saturation magnetization in composite is due to the lower content of magnetic iron oxide
in materials and the presence of non-magnetic (TiO
2
10 20 30 40 50 60 70 80 2

O
4

, Fe
3

O
4

/TiO
2

composite and TiO

2.

( A = anatase, R = rutil).
-50

). Superparamagnetic behavior of material can be seen from the low value of

remanent and coercivity magnetization. The coercivity value is calculated according to
(H
Cave
50
Fe3O4
40 Fe3O4/TiO2 (1:0,5)
Fe3O4/TiO2 (1 : 1)
Fe3O4/TiO2 (1 : 2)
-1 -0.5 0 0.5 1
Field [tesla]

Fig. 2. Magnetic hysteresis for synthesized magnetic nanoparticles and Fe

3

= (H
C,+

+ |H
C,-

|)/2 equation, where H

C,-
30

is a positive coercivity and H

C,-

is a negative coercivity [16]. The coercivity and

remanent magnetization value are close to zero, it is indicated that materials have
superparamagnetic behavior which facilitate recovering photocatalyst composite from
treated water by collection through a magnetic bar.
Fig. 3 shows the scanning electron microscopy (SEM) images of Fe
3
20
10
0
-10
-20
-30
O -40
4

, TiO
 2 and composite Fe
3

O
4

/TiO
2

. As shown in the SEM images, the particle sizes of Fe

3

O
4 and TiO
2

were less then 100 nm. While more bigger agglomeration was observed in
O
4

/TiO
2

composite (mixing of Fe
3

O
4

and TiO
2

). Energy dispersive spectra (EDS) analysis of composites.

Fe
3

O
4

/TiO
2

composite are shown in Fig. 4. The EDS spectrum for Fe

3

O
4

/TiO
 2
composite shows elemental peaks which confirm the presence of titanium and iron in
the composite. As is expected, the higher fraction of TiO
2

in the composites the higher peak

intensity of Ti (respect to Fe peak) observed.
134 Advanced Materials Engineering and Technology
Tabel 1. Saturation magnetization (Ms), coercivity, remanent magnetization (Mr) and
BET of prepared magnetic materials.
Fig. 3. Scanning electron microscopy (SEM) images of Fe
3

/TiO
2 (1 : 2) Saturation magnetization [emu/gr]
43.4 27.8 21.5 15.4
Coercivity [Oe] 61.5 68.3 73.1 70.6 Remanent magnetization [emu/gr]
8.03 5.96 4.90 3.36
BET [m2/g] NA 91.35 63.45 56.54
Fe
3

O
4

/TiO
2

(1 : 0.5)
0.5 m

Fe
3

O
4

/TiO
2

(1 : 1)
0.5 m

Fe
3

O
4

/TiO
2

(1 : 2)
O
4

, TiO
2

and Fe
3

O
4

/TiO
2

.
Fe
3

O
4

TiO
2

Fe
3

O
4

/TiO
2

Fe
3
0.5 m
0.5 m
0.5 m

O
4

O Fe
3
4

/TiO
2 (1 : 0.5)
Fig. 4. Energy dispersive spectra (EDS) spectra of Fe
3

O
4

/TiO
2

composites.
O Fe
3
4

/TiO
2 (1 : 1)
FeKa TiKa
TiKa
FeKa
TiKa
FeKa
Fe
3

O
4
Advanced Materials Research Vol. 626 135
According to literature raman spectrum of TiO
2 frequencies anatase has peaks at the
of 143 cm
-1

(Eg), 196 cm
-1 (E
g
TiO2 Fe3O4/TiO2 (1 : 2) Fe3O4/TiO2 (1 : 1) Fe3O4/TiO2 (1 : 0.5) Iron Oxide

), cm the -1
frequencies (E
396 g
) cm-1 [17] and (B of 1g
145 TiO ), 514 cm-1 2
cm- 1 (A
1g

), 637
(E
g

), dan 612 cm
-1

(B
1g

) rutile has peaks at

(A
1g

), 447 cm-1 [18]. In this study (Fig. 5), the TiO

2

being used (Aldrich), shows all peaks mentioned above, which

clearly indicate the occurrence of both anatase and rutil phase, in agreement with XRD
data and in accordance with the composition given by the manufacturer. After TiO
2

was combined with iron oxide, the peak spectrum from anatase and rutil
phase was found weaker with the decrease of TiO
2

fraction in composite. While, the spectrum of the iron oxide showed peaks at
cm-1 frequencies of at 229 cm
-1

(A
1g

), 249
cm
-1

(E (A g
1g ), ), 295 615 cm-1 cm
-1 (E

(E g
), g
414 ) cm-1 (e
g

), 500 which indicated the occurrence of hematite phase. The use of a strongly focused
laser during raman spectroscopy measurement can causes a temperature increasing of
several hundreds degrees, resulting in a change of magnetite into hematite [19], may
responsible for this observation.
Photocatalytic activity of the prepared samples was evaluated by measuring the
degradation rate of methylene blue under UV and sunlight irradiation. Fig. 6 shows the
results of methylene blue degradation with irradiation time under UV irradiation in the
presence of different samples. On curve of non-catalyst, methylene blue was eliminated
slightly through photolysis process under UV irradiation. While Fe
3
0 200 400 600 800 1000
Wavenumber [cm-1]

Fig. 5. Raman spectra of prepared samples.

120
Non-catalist Fe3O4
100
Fe3O4/TiO2 (1:0.5) Fe3O4/TiO2 (1:1) Fe3O4/TiO2 (1:2) TiO2
80
60
40
20
0
0 1 2 3 4 5 6 7 Time [hour]

Fig. 6. Degradation of methylene blue with different photocatalysts under UV irradiation

O
4 play roles for adsorption of methylene blue [20],
may also responsible for this slight decrease of methylene blue concentration. TiO
2

is regarded as the only material that has high photocatalytic degradation activity of
methylene blue, within the first 1 hour of UV irradiation about 12.2 % of methylene blue
remained and by the end of the processes (6 hours) less than 5.6% of methylene blue
remained. The photocatalytic activity of Fe
3

O
4

/TiO
2
composite was found lower than that of pure TiO
2

due to the presence of non-active

photocatalytic in composite (iron oxide), the strong light absorption by iron oxide [21]
and photodissolution [22]. The photodissolution may be occurred due to electronic
interaction between the two semiconductor, which cause transfer of charge carriers
across junction when two or more semiconductor are in contact [22]. The
photogenerated charge carriers in the excite TiO
2

ca
n be transferred into Fe
3

O
4

phase because of its lower lying conduction band and upper lying valence
band [23]. To improve the catalytic activity of the Fe
3

O
4

/TiO
2

composite, for the future work, it is suggested to make barrier

of SiO
2

between Fe
3

O
4

and TiO
2 materials to prevent photodissolution.
Among composites, photocatalytic activity of Fe
3

O
4

/TiO
2

(1:0.5) was the lowest one because of less active materials

present in the composites. Photocatalytic activity of Fe
3

O
4

/TiO
2 (1:1) was almost same with Fe
3

O
4

/TiO
2 (1:2), although the fraction of TiO
2
 in Fe
3

O
4

/TiO
2

(1:2) was two times more than Fe

3

O
4

/TiO
2

(1:1). The diffrence in surface area, in which the surface area of Fe

3

O
4

/TiO
2

(1:1) was higher than that of

Fig. 7. Degradation of methylene blue with different
Fe
3

O
4

/TiO
2 (1:2) photocatalysts
under sunlight irradiation.
(Tabel 1), may be responsible for this observation.
Fig. 7 shows the results of methylene blue degradation with irradiation time under
sunlight in the presence of different photocatalyst materials. Photocatalytic activity of
prepared sample under sunlight irradiation was higher than under UV irradiation
because the light intensity of sunlight was higher than that of UV being used in these
experiments. Intensity of light was proportional to the rate of reaction that confirms the
photo-induced nature of the activation of the catalytic process, with the participating of
photo-induced electrical charges (electrons and holes) to the reaction mechanism [24].
Summary
Fe
3

O
4

/TiO
2

composites were successfully prepared by heteroagglomeration during

mixing of Fe
3

O
4

and active TiO

2

and the aid of ultrasonication. This composite showed only a fair

photocatalytic activity, but can be easily recovered from the treated water by simply
assistance of external magnetic bar. All of the prepared Fe
3

O
4

/TiO
2

composites showed photocatalytic

activity for degradation of methylene blue under UV and sunlight irradiation, but its rate
of photocatalytic degradation was lower than that of pure TiO
2

samples due to the presence of non-

active photocatalytic in composite (iron oxide).
Aknowledgement
This study is supported by State Ministry of Research and Technology (SMRT),
Republic of Indonesia under a scholarship program for AF. The authors also greatefully
acknowledge in the part financial support from DGHE, Directorate General of Higher
Education (DIKTI), Republic of Indonesia under program Hibah Kolaborasi Luar Negeri
(HKLN) for JG.
References [1] P.H. Gleick: Water Policy Vol. 8 (2006) p. 481. [2] I. Thornton, Polllutanst
in urban waste water and sewage sludge, Europ. Com. (2001).
[3] R. Andreozzi, V. Caprio, A. Insola, R. Marotta: Catal. Today Vol. 53 (1999), p. 51. [4].
C.H. Ao, S.C. Lee: Chem. Eng. Sci. Vol. 60 (2005), p. 103.
136 Advanced Materials Engineering and Technology
Advanced Materials Research Vol. 626 137
[5]. J.C. Harper, P. A. Christensen, T. A. Egerton, T.P. Curtis and J. Gunlazuardi: J. Appl.
Electrochem. Vol. 31 (2001), p. 623.
[6] S. Gelover, L. A. Gmez, K. Reyes, Ma. T. Leal: Water Research Vol. 40 ( 2006) p.
3274. [7] A. Bernabeua, R.F. Verchera, L. Santos-Juanesa, P.J. Simnb, C. Lardnb,
M.A. Martnezc, J.A. Vicentec, R. Gonzlezc, C. Llosc, A. Arquesa, A.M. Amata: Catal.
Today Vol. 161 (2011) p. 235.
[8] X. Chen and S. S. Mao: Chem. Rev. Vol. 107 (2007) p. 2891. [9] P. M. lvareza, J.
Jaramillo, F. Lpez-Pi nero, P.K. Plucinski: Appl. Catal. B: Environ. Vol.
100 (2010) p. 338. [10] Q.Yu, C. Zhou, X. Wang: J. Mol. Catal. A: Chem. Vol. 283
(2008) p. 23.
[11] Q. He, Z. Zhang, J. Xiong, Y. Xiong, H. Xiao: Optical Mater. Vol. 31 (2008) p. 380.
[12] D. Makovec, M. Sajko, A. Selisnik, M. Drofenik: Mater. Chem. Phys. Vol. 129
(2011) p. 83.
[13] M. Cerbelaud, A. Videcoq, P. Ablard, R. Ferrando: J. Coll. Inter. Sci. Vol. 332
(2009) p.
360.
[14] J. S. Choi, H.K. Young, B. H. Kwak, Q. Wang, K. S. Yang, J. S. Chung: Appl. Catal.
B:
Environ. Vol. 91 (2009) p. 210.
[15] Y.S. Kang, S. Risbud, J. F. Rabolt, and P. Stroeve: Chem. Mater. Vol. 8 (1996) p.
2209. [16] V. Belessi, D. Lambropoulou, I. Konstantinou, R. Zboril, J. Tucek, D. Jancik,
T. Albanis, D.
Petridis: Appl. Catal. B: Environ. Vol. 87 (2009) p. 181. [17] H.C. Choi, Y.M. Jung, S.B.
Kim: Vibrat. Spec. Vol. 37 (2005) p. 33.
[18]. J. D. Pasteris: the laser Raman Microprobe as a tool for the economic geology, in:
Application of microanalytical techniques to understanding mineralizing processes,
Reviews in economic geology, M.A McKibben, W.C Shanks and W.I. Ridley (Eds),
Society of Economic Geologists, Socorro, (1998) p. 233.
[19] O.N. Shebanova and P. Lazor: J. Raman Spec. Vol. 34 (2003) p. 845. [20] S. Pirillo,
V. Pedroni and E. Rueda: Quim. Nova Vol. 32 (2009) p. 1239.
[21] F. Chen, Y. Xie, J. Zhao, G. Lu: Chemosphere Vol. 44 (2001) p. 1159. [22] D.
Beydoun, R. Amal,G. Low,and S. McEvoy: J. Catal. A: Chem. Vol. 180, (2002) p. 193.
[23] Z.Li Shi, Ce Du, S. H. Yao: J. Taiwan Inst. Chem. Eng. Vol. 42, (2011) p. 652. [24]
J.M. Herrmann: Catal. Today Vol. 53 (1999) p.115.
Advanced Materials Engineering and Technology 10.4028/www.scientific.net/AMR.626
Preparation and Characterization of Fe
3

O
4

/TiO
2

Composites by Heteroagglomeration
10.4028/www.scientific.net/AMR.626.131
DOI References [3] R. Andreozzi, V. Caprio, A. Insola, R. Marotta: Catal. Today Vol. 53 (1999),
p.51. http://dx.doi.org/10.1016/S0920-5861(99)00102-9 [4] C.H. Ao, S.C. Lee: Chem. Eng. Sci.
Vol. 60 (2005), p.103. http://dx.doi.org/10.1016/j.ces.2004.01.073