Available online at www.sciencedirect.

com

CERAMICS
INTERNATIONAL
Ceramics International 40 (2014) 8547–8559
www.elsevier.com/locate/ceramint

Magnetic photocatalysts of cenospheres coated with Fe3O4/TiO2 core/shell

nanoparticles decorated with Ag nanopartilces
Jianchao Zhana, Hui Zhangb,n, Guoqing Zhub
a
College of Material and Textile Engineering, Jiaxing University, No. 56 South Yuexiu Road, Jiaxing, Zhejiang, China
b
School of Textile & Materials, Xi'an Polytechnic University, No. 19 South Jinhua Road, Xi'an, Shaanxi, China
Received 24 November 2013; received in revised form 12 January 2014; accepted 14 January 2014
Available online 26 January 2014

Abstract

A layer of magnetite Fe3O4 nanoparticles is first loaded onto the surfaces of cenospheres using ferric trichloride, ferrous chloride, and aqueous
ammonia by a precipitation method, and then modified with silane coupling agent KH550. The modified Fe3O4 coated cenospheres are coated
further with a film of anatase TiO2 nanoparticles under hydrothermal conditions, and finally decorated with Ag nanoparticles by electroless
deposition. The surface morphology, chemical composition, crystalline structure, magnetic properties, and optical behaviors of cenosphere before
and after treatments are determined by means of field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy
(EDX), X-ray diffractometry (XRD), vibrating sample magnetometry (VSM), and diffuse reflectance spectrum (DRS). The synthetic route for the
formation of Ag decorated Fe3O4/TiO2 core/shell coating on cenosphere surfaces is established. The photocatalytic activity of the as-prepared
cenospheres for the methylene blue degradation is measured under both ultraviolet and visible light irradiation. The results show that the Ag
decorated Fe3O4/TiO2 coated cenospheres having a saturation magnetization of 21 emu g
1 are fabricated. After decoration with Ag the
photocatalytic activity of the Fe3O4/TiO2 coated cenospheres is greatly improved under visible light irradiation because of the strong scattering
and absorption properties of Ag nanoparticles. The silicon–oxygen interlayer between Fe3O4 core and TiO2 shell can be employed to prevent
photodissolution of Fe3O4 during photocatalysis.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: Cenosphere; Magnetite Fe3O4; Anatase TiO2; Ag nanoparticle; Photocatalytic activity

1. Introduction Many studies have been carried out by coating TiO2 on different
substrates like fly ash [2], silica [3], active carbon [4], and
Titanium dioxide (TiO2), acting as an interesting semicon- zeolite [5] in recent decades. It is important to note that the
ductor material, has been extensively used as the most promis- presence of different metal or nonmetal elements has a great
ing photocatalyst because of its various merits, such as high effect on the structure and photocatalytic activity of titania-
photosensitivity, chemical stability, biological inertness, low based catalysts prepared by aging the precursor gel [6] or
cost, etc. The crystalline TiO2 has mainly three polymorphs: calcination of the SiO2@TiO2@Ni(OH)2 [7] with excellent
rutile (Eg¼ 3.0 eV), brookite (Eg¼ 2.96 eV), and anatase photocatalytic performance and high stability.
(Eg¼ 3.2 eV). Brookite and anatase are metastable forms and In order to produce a recoverable photocatalyst, the TiO2 photo-
the anatase TiO2 is the most stable phase for photocatalysis. catalyst is usually deposited onto the surface of an iron oxide
It has been proved that the TiO2 mediated photocatalysts provide a (magnetite, maghemite or ferrite) core [8–10] and/or further
simple and effective method for removing inorganic and organic modified with carbon [11], CdS [12], cetyltrimethylammonium
compounds from industrial wastewaters and polluted air [1]. [13], and carboxymethyl β-cyclodextrin [14] in comparison with
other separation techniques. As the two semiconductors connect to
n
each other, the spreading of the iron oxide and the diffusion of
Corresponding author. Tel.: þ86 29 13002929736.
foreign Fe ions into TiO2 structure as well as a decline in surface
E-mail addresses: zhan1jian2chao3@163.com (J. Zhan),
hzhangw532@163.com, hzhangw532@xpu.edu.cn (H. Zhang), area and a loss in surface might occur especially during the heat
82229126@qq.com (G. Zhu). treatment. As a result, the physicochemical properties induced by

0272-8842/$ - see front matter & 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2014.01.069
8548 J. Zhan et al. / Ceramics International 40 (2014) 8547–8559

the electronic interaction between iron oxide and TiO2 can be layer between Fe3O4 [45,46] or γ-Fe2O3 [47] core and TiO2
changed [15]. However, experimental results indicate that short- shell can prevent electrons from being transferred to the
ening of the duration of heat treatment can not only significantly magnetic iron oxide thus avoiding iron leaching. On the other
lower the extent of interaction between the iron oxide core and the hand, the missing silica interlayer will lead to the complete
TiO2 coating, but also limit the extent of oxidation of the iron suppression of photocatalytic activity, and thus at least a
oxide core [16]. The TiO2/Fe3O4 photocatalyst prepared by acid– minimum of about a 20 nm silica layer is suggested [48].
sol has higher catalytic activity than that prepared by homogenous Previous studies have shown that the PANI-modified [49] and I-
precipitation method due to the size difference of the particles doped TiO2 photocatalysts [50] consist of a Fe3O4 magnetic
[17]. There are various synthesis routes to prepare magnetic TiO2 core, a silica film mid-layer and TiO2 outer layer. Also, Bian
photocatalysts, such as the sol–gel process [18,19], coprecipitation et al. and Liu et al. have prepared the quaternary TiO2–CdS–
[20], hydrothermal treatment [21,22], spray pyrolysis [23], sono- Fe3O4@SiO2 [51] and AgBr–TiO2/SiO2@Fe3O4 [52] hybrid
chemical synthesis [24], and wet impregnation method [25]. For composites with strong magnetization and high photocatalystic
example, Watson et al. [26] and Akhavan et al. [27] have activity under visible light irradiation.
employed a sol–gel process to fabricate the coating of nanosized To shift the absorption threshold into the visible light
crystalline TiO2 directly onto magnetic core particles. The region, immobilization of Ag nanoparticles on TiO2 to form
enhancement of the photocatalytic activity of Fe3O4/TiO2 core– hybrid composite particles with tailored structure and surface
shell nanoparticles can be interpreted by energy level theory: the functionality has been reported to show a strong photocatalytic
energy level of Fe3 þ /Fe2 þ closes to the energy level of TiO2's activity [53–55] as well as bactericidal activity [56,57] under
conduction band, and the energy level of Fe3 þ /Fe4 þ closes to the visible light irradiation. It is evident that in the photocatalytic
energy level of TiO2's valence band; Fe3 þ dissolved from Fe3O4 process the metallic silver center can enhance the charge
nanoparticles can come into not only electron capture position but separation of the electrons and holes generated by UV or
also hole capture position, which causes the electron–hole pair visible irradiation and inhibit the recombination of photogen-
recombination of TiO2 to decrease [28]. Zhang et al. have also erated electron–hole pairs owing to its strong electron trap
synthesized the cryptomelane-type manganese oxide (K-OMS-2) ability. Meanwhile, silver particles facilitate the localized
nanowires, and then loaded with TiO2 nanoparticles by a hydro- surface plasmon resonance to amplify the absorption of visible
thermal method, and finally coated with the magnetic Fe3O4 light. It has been verified that smaller metal deposits are more
nanoparticles via a coprecipitation method. The hierarchically effective than larger deposits due to the high surface area to
magnetic K-OMS-2/TiO2/Fe3O4 heterojunction exhibits good volume ratio and the amount of silver deposition is optimized
photocatalytic activity for the degradation of humic acid under to be 0.05% [58]. The plasmon resonance absorption and band
solar light [29]. More recently, Hu et al. have prepared the gap values of the Ag/TiO2 films are determined by the atomic
magnetic double-shell Fe3O4@TiO2/Au@Pd@TiO2 microsphere ratio of Ag to Ti due to the changes in size of Ag nanoparticle
composed of a Fe3O4 core and double mesoporous TiO2 shells forming on the surface of films [59]. Furthermore, The Ag þ
with Au and Pd nanoparticles encapsulated via a multi-step ions in the Ag/AgCl/TiO2 nanocomposite can be partially
building-up method, resulting in a high catalytic activity and reduced to Ag0 species under Xenon lamp irradiation, which
stability for reduction of 4-nitrophenol [30]. show high visible light photocatalytic activity for the photo-
However, a direct contact between magnetic materials and catalytic degradation of 4-chlorophenol aqueous solution and
TiO2 photocatalyst usually gives rise to an unfavorable hetero- stability [60]. For instance, Guo et al. have developed the
junction, leading to an increase in electron–hole recombination superparamagnetic core–shell Fe3O4@SiO2 nanoparticles by
and photodissolution phenomenon [31]. To minimize the the solvothermal and sol–gel methods, and then fabricated the
adverse influence of the magnetic material on the photocatalysis Ag–AgI/Fe3O4@SiO2 [61] and Ag/AgCl@TiO2 [62] plasmo-
of TiO2, the intermediate layer between the magnetic core and nic photocatalysts via deposition–precipitation and photore-
the photoactive TiO2 shell [32–37] or modification of Fe3O4 duction methods. Lin et al. have reported preparation of F-
core with sodium citrate [38] can be introduced. It may be doped TiO2 loaded with Ag by using the sol–gel process
further processed by a hydrothermal treatment to selectively etch combined with the photoreduction method [63]. Additionally,
the silica, resulting in rattle-type particles with increased crystal- magnetite spheres are firstly synthesized via a solvothermal
linity and surface area [39], thereby the photocatalytic activity of method, and then coated with SiO2 nanoparticles by Stober
the catalyst can be improved to a considerable extent. It is found method, and finally deposited with Pt ion doped TiO2 by the
that the diameter of Fe3O4 core and the silica content have a sol–gel method [64].
positively effect on the photocatalytic activity of TiO2/SiO2/ Generally, the photocatalyst is generally precipitated on the
Fe3O4. The large Fe3O4 core diameters are supposed to provide bottom of water or dispersed in water by stirring. The increase of
less contact between TiO2 and Fe3O4 which should be positively the depth of polluted water decreases the path length of photon
reflected on photocatalytic activity of TiO2/SiO2/Fe3O4 and at entering the wastewater. A significant amount of light irradiation
the same time facilitate the separation of catalyst from aqueous can be absorbed by wastewater rather than the photocatalyst.
media [40]. In addition, the reaction rate of TiO2/SiO2/Fe3O4 Therefore, the catalytic efficiency decreases to some degree.
photocatalyst depends on the photocatalyst load, dye concentra- Cenosphere, which is primarily composed of SiO2, possesses the
tion, pH value, and transmittance inside photoreactor [41–44]. favorable characteristics of non-toxicity, high chemical stability,
It has been demonstrated that the presence of an insulating SiO2 low cost, light weight mass, good insulation, and hollow spherical
 J. Zhan et al. / Ceramics International 40 (2014) 8547–8559 8549

morphology. Because of the unique hollow structure and physical dried at 110 1C in an oven for 12 h. The Fe3O4 nanoparticles
mechanics properties, it can float on the surface of water and were coated onto cenosphere surface using a precipitation
absorb more solar light and thus might be used in the field of method. A stoichiometric amount of FeCl2  4H2O and
environmental treatment. Therefore, the magnetically and photo- FeCl3  6H2O (The concentration of Fe2 þ and Fe3 þ was
catalytically cenosphere has been interested in by some research- 0.1 mol l
1 and the molar ratio of Fe2 þ to Fe3 þ was 1:2.)
ers. Lu et al. have successively deposited Fe3O4, SiO2 and TiO2 was dissolved in 200 ml of deionized water under vigorous
nanoparticles on the surface of carboxyl-functionalized fly-ash stirring at 30 1C. The etched cenospheres were subsequently
cenospheres, which show high catalytic efficiency and excellent added into the above mixture solution. Aqueous ammonia
photochemical stability for degradation of enrofloxacin hydro- (28% mass fraction) was added dropwise and after that the
chloride residues under visible light irradiation [65]. In this study, mixture was kept vigorously stirring at 500 rpm. The pH was
the Fe3O4 coated cenospheres prepared by a coprecipitation adjusted to 9. When the color of the suspension gradually
method are modified with silane coupling agent KH550 instead turned from salmon pink to brown and suddenly to black, the
of SiO2 layer, and then loaded with a layer of anatase TiO2 by a process of dropping was sustained to maintain a pH of 9. The
hydrothermal process, and finally decorated with Ag nanoparti- process was kept with stirring to complete the reaction. After
cles by electroless deposition. The structure of the Ag decorated 2 h, the as-prepared cenospheres were successively washed
Fe3O4/TiO2 coated cenospheres is characterized by field emission with acetone, ethanol, and deionized water each for 15 min,
scanning electron microscopy (SEM), energy dispersive X-ray followed by filtration, and finally dried in a vacuum oven at
spectroscopy (EDX), X-ray diffractometry (XRD), vibrating 60 1C for 12 h.
sample magnetometry (VSM), and diffuse reflectance spectrum
(DRS). The photodegradation of methylene blue (MB) dye is
2.3. Surface modification of the Fe3O4 coated cenospheres
examined in an aqueous solution of the as-prepared cenospheres
under both UV and visible light irradiation and the activity of the
A mixture of 150 ml of anhydrous ethanol and deionized
recycled photocatalysts is studied. The effect of Ag decoration on
water was first prepared according to volume ratio of 1:1. The
the photocatalytic activity of the Fe3O4/TiO2 coated cenospheres
pH was adjusted to 5.5 by adding of acetic acid. About 1.0 g of
is also discussed.
silane coupling agent KH550 was accordingly dissolved in the
mixture solution at 40 1C under vigorous stirring. The Fe3O4
2. Experimental section coated cenospheres were then added into the above solution
under mechanical stirring. After 12 h, the as-prepared ceno-
2.1. Materials spheres were filtered by a vacuum filtration, and then dried in a
vacuum oven at 90 1C for 40 min, and finally cured at 120 1C
The white cenospheres were obtained from Shanghai FEP for 3 min. The hydrolysis of the ethoxysilane to a silanol took
International Trade Co., Ltd. The average diameter of the ceno- place followed by condensation reactions [66]. During the
sphere particles from 15 to 85 μm was about 40 mm. The average following hydrothermal process, some Si–O–Si links were
compressive strength was about 38 MPa and the average true ruptured and new silanols (Si–OH) groups were formed, so the
particle density was 0.38 g cm
3. All the analytical grade reagents loading of TiO2 could be enhanced through the Ti–OH
were used without any additional purification, including ferric bonding [67]. As illustrated in the inset (a) of Fig. 5, the film
trichloride hexahydrate (FeCl3  6H2O), ferrous chloride tetrahy- comprising a silicon–oxygen cross-linked structure was formed
drate (FeCl2  4H2O), tetrabutyl titanate (Ti(OC4H9)4), silver nitrate on the surfaces of Fe3O4-coated cenospheres, which acted as a
(AgNO3), aqueous ammonia (NH3  H2O), glucose (C6H12O6), chemically inert barrier to inhibit the oxidation of the Fe3O4
tartaric acid (H2C4H4O6), sodium hydroxide (NaOH), hydrofluoric coating.
acid (HF), acetic acid (CH3COOH), methylene blue (MB) dye,
acetone, and anhydrous ethanol. The silane coupling agent
2.4. Coating of TiO2 nanoparticles onto the modified Fe3O4
KH550 (H2N(CH2)3Si(OC2H5)3, 3-aminopropyltriethoxysilane)
coated cenospheres
was obtained from Dow Corning (Shanghai) Co., Ltd. Deionized
water was used throughout the experiment.
About 1.2 ml of tetrabutyl titanate was first dipped into
40 ml of anhydrous ethanol solution under vigorous stirring at
2.2. Coating of Fe3O4 nanoparticles onto cenospheres room temperature, followed by being added 120 ml of
deionized water. The modified Fe3O4 coated cenospheres were
About 6.0 g of cenospheres was first degreased with 150 ml then added to the above solution under stirring for 10 min. The
of 1.0 M NaOH solution under magnetic stirring at 90 1C for mixture solution containing the cenospheres was transferred to
30 min, and then washed thoroughly with deionized water at a 200 ml PTFE-lined stainless steel autoclave. A slow flow of
40 1C until the pH reached neutral, and then separated by nitrogen gas was bubbled into the mixture solution for 15 min
filtration. The degreased cenospheres were etched in 150 ml to purge oxygen. The autoclave was immediately sealed and
of 1% HF solution at 40 1C for 10 min, followed by being placed in a furnace, and then heated to 120 1C at a rate of
washed with the anhydrous ethanol solution for 10 min, and 2 1C min
1. After 3 h, the autoclave was cooled down and the
then were completely washed with deionized water, and finally as-prepared cenospheres were successively washed in acetone,
8550 J. Zhan et al. / Ceramics International 40 (2014) 8547–8559

anhydrous ethanol, and distilled water for 10 min respectively, 662 nm was measured by using a VIS-7220N spectrophot-
and finally dried in vacuum at 80 1C for 2 h. ometer (Beijing Rayleigh Analytical Instrument Corp.) at set
intervals. The degradation rate D (%) was calculated with the
2.5. Electroless deposition of Ag nanoparticles onto the following formula: D ¼ (1
At/A0)  100, where A0 is the
Fe3O4/TiO2 coated cenospheres initial absorbance of the MB solution which reaches absorption
equilibrium, and At is the absorbance of the MB solution at
The Fe3O4/TiO2 coated cenospheres were deposited with Ag time t. Prior to irradiation, the mixture solution was magne-
nanoparticles at 20 1C for 30 s based on the optimized tically stirred in the dark for 2 h to obtain the adsorption–
electroless silver plating process without surface sensitization desorption equilibrium of MB onto cenospheres. The transmis-
and activation steps. The loadage of the Fe3O4/TiO2 coated sion spectrum of MB solution in the range of 200–800 nm was
cenospheres was 5 g l
1. The electroless silver plating solution also measured using the same spectrophotometer. The cyclic
was composed of 0.03 mol l
1 silver nitrate, 0.008 mol l
1 photocatalytic performance of the as-prepared cenospheres for
aqueous ammonia, 0.1 mol l
1 sodium hydroxide, 0.005 mol l
1 MB degradation was carried out according to the above
glucose, 0.0006 mol l
1 tartaric acid, and 0.18 mol l
1 anhy- procedure. The cenosphere samples were used repeatedly,
drous ethanol. After the reaction was completed, the as-obtained while the MB solution was replaced with fresh solution.
cenospheres were rinsed with deionized water at room tempera-
ture thrice, and lastly dried at 80 1C for 2 h. 3. Results and discussion

2.6. Characterization and measurements 3.1. FESEM observation

The surface morphology of cenosphere before and after The FESEM images of cenospheres before and after
treatments was observed by using a field emission scanning treatments are shown in Fig. 1. It can be seen that the surface
electron microscope (FESEM, JEOL JSM-6700) equipped of the untreated cenosphere is very smooth and clean (Fig. 1a).
with an Oxford INCA Energy 400 energy-dispersive X-ray After treatment with HF solution, many small pits uniformly
spectrometer. X-ray energy dispersive spectroscope (EDX) form on the surface of cenosphere due to the chemical etching
was used to analyze the chemical composition of cenosphere (Fig. 1b). When the etched cenosphere is treated with
prepared at different stages. FeCl2  4H2O, FeCl3  6H2O, and aqueous ammonia, the surface
The X-ray diffraction (XRD) pattern of cenosphere before of cenosphere is completely coated with a layer of compact
and after treatments was obtained by using Cu Kα1 radiation deposition (Fig. 1c). The high-magnification SEM indicates
(λ¼ 0.154056 nm), with a 7000S diffractometer at 40 kV and that the deposition is composed of nano-scaled particles of
40 mA with an angle of 2θ from 201 to 801 at a scan speed of particle size distributions in the sub 100 nm region (Fig. 1d).
8 deg min
1. There is no significant morphological change for the modified
The static magnetic property of the as-prepared cenosphere Fe3O4 coated cenosphere. After hydrothermal treatment with
was measured by using a vibrating sample magnetometer tetrabutyl titanate, the surface of the as-prepared cenosphere
(VSM, Quantum Design Corp.) at a temperature of 300 K. becomes relatively rough. A number of laminar substances
The sample placed at the holder was caused to vibrate adhere onto the coating (Fig. 1e). From the high-magnification
vertically at a frequency of 40 Hz and amplitude of 2 mm. SEM image, the substances are constituted of well-crystallized
The optical property of cenosphere before and after treat- nanoparticles with the average size of less than 100 nm
ments was determined by using diffuse reflectance spectro- (Fig. 1f). After electroless silver deposition, some large grains
scopy (DRS). The spectrophotometer (U-3010 UV–VIS–NIR) in micrometer scale are dispersed on the surface of the as-
was equipped with an integrating sphere (∅150 mm) and obtained cenosphere (Fig. 1g), indicating the increase of the
barium sulfate (BaSO4) was used as the reference. The specific surface area. It is anticipated that the light absorption
spectrum was recorded at an ambient temperature in the of the finally as-obtained cenospheres can be enhanced owing
200–800 nm range at a scanning speed of 1200 nm min
1. to the enhanced light scattering. As illustrated in the high-
The photocatalytic degradation of the MB dye in an aqueous magnification SEM, those grains are comprised of nano-scaled
solution under both UV and visible light irradiation was clusters of less than 100 nm in diameter (Fig. 1h).
performed by using the as-prepared cenospheres. About
0.025 g of cenosphere samples was added into 40 ml of a 3.2. EDX analysis
10 mg l
1 MB solution. For UV light irradiation, two Philips
UV lamps (30 W, main wavelength 254 nm) were hung above The chemical compositions of cenospheres before and after
the solution at a distance of 10 cm. The intensity of UV light treatments are characterized by EDX survey spectra, as
was determined to be 3.2 mW cm
2 by a TM-213 UV depicted in Fig. 2. The corresponding results are listed in
illumination meter. To simulate the visible light irradiation, Table 1. The compositions of the untreated cenosphere [Fig. 2
the MB solution was covered with a 400 nm cut-off UV filter, (a)] by mass percent are O 48.93%, Si 42.02%, and Ca 9.05%.
and exposed to sunlight. The intensity of visible light was The corresponding atomic percents are O 63.78%, Si 31.20%,
measured to be 8.1  104 lx by a TES 1332A digital light and Ca 5.02%. It implies that the cenosphere is mainly
intensity meter. The absorbance of the MB solution at λmax composed of SiO2 and CaO, while other oxides of trace
 J. Zhan et al. / Ceramics International 40 (2014) 8547–8559 8551

Fig. 1. FESEM images of cenospheres before and after treatments: (a) untreated 1000  ; (b) etched 1000  ; (c) 1000  and (d) 30,000  Fe3O4 coated;
(e) 1000  and (f) 30,000  Fe3O4/TiO2 coated; (g) 1000  and (h) 30,000  Ag decorated Fe3O4/TiO2 coated.

elements such as Al, K and Na are absent. When the are O 66.09%, Si 12.85%, Ca 1.67%, and Fe 19.39%. After
cenosphere is deposited with Fe3O4 nanoparticles [Fig. 2(b)], treatment with tetrabutyl titanate [Fig. 2(c)], the compositions
the compositions by mass percent are O 41.56%, Si 14.20%, by mass percent are O 44.56%, Si 21.03%, Ca 4.38%, Fe
Ca 2.64%, and Fe 41.60%. The corresponding atomic percents 24.75%, and Ti 5.28%. The corresponding atomic percents are
8552 J. Zhan et al. / Ceramics International 40 (2014) 8547–8559

Fig. 2. EDX survey spectra of cenospheres before and after treatments: (a) untreated; (b) Fe3O4 coated; (c) Fe3O4/TiO2 coated; and (d) Ag decorated Fe3O4/TiO2
coated.

Fig. 3. Cross-sectional FESEM image (a) and line scanning curves (b) of elements in the Ag decorated Fe3O4/TiO2 coated cenosphere.

O 66.36%, Si 17.85%, Ca 2.61%, Fe 10.56%, and Ti 2.63%. element of Ag is especially focused on the top of the coating
After deposition with Ag [Fig. 2(d)], the compositions by mass (far away from cenosphere).
percent are O 45.21%, Si 15.99%, Ca 1.75%, Fe 19.17%, Ti
12.50%, and Ag 5.38%. The corresponding atomic percents 3.3. XRD analysis
are O 63.75%, Si 21.58%, Ca 0.92%, Fe 7.21%, Ti 5.48%, and
Ag 1.06%. The cross-sectional FESEM image and line The XRD patterns of cenospheres before and after treat-
scanning curves of elements in the finally as-obtained ceno- ments are compared in Fig. 4. It is clear that there is no typical
sphere are shown in Fig. 3. It is evident that the coating of as- diffraction peak in the XRD pattern of the untreated ceno-
obtained cenosphere contains Fe, Ti, and Ag elements. The sphere. After Fe3O4 deposition, a series of diffraction peaks at
element of Fe is mainly distributed in the bottom of the coating around 2θ of 301, 361, 431, 541, 571, 631 and 751 are observed,
(close to cenosphere), and the element of Ti is primarily which correspond with the data list in JCPDS card no. 19-0629.
localized in the middle and top of the coating, while the These diffraction peaks are related to the {220}, {311}, {400},
 J. Zhan et al. / Ceramics International 40 (2014) 8547–8559 8553

{422}, {511}, {440} and {533} planes of magnetite Fe3O4, the data list in JCPDS card no. 21-1272, which are assigned to
which has a cubic inverse spinel structure [19]. In addition, the the {101}, {004}, {200}, {105}, and {204} planes of TiO2 with
characteristic diffraction peaks of ammonia at 2θ¼ 321 and 461 anatase tetragonal structure [27]. After electroless silver plating,
are identified (JCPDS card no. 50-1373). After TiO2 deposition, several characteristic peaks are found at 2θ of 381, 441, 651 and
a series of characteristic peaks at about 2θ of 251, 381, 481, 541, 771, which are ascribed to the {111}, {200}, {220} and {311}
and 631are noticed. These diffraction peaks are consistent with planes of face-centered cubic Ag phase (JCPDS card no. 65-
2871) [60]. Therefore, combined with the FESEM observation
and EDX analysis, two-layer coating of Fe3O4/TiO2 decorated
with Ag nanoparticles is coated onto the surface of cenosphere.
The processing route for the preparation of Ag decorated Fe3O4/
TiO2 coated cenospheres is presented in Fig. 5.

3.4. VSM analysis

The hysteresis loops of the as-prepared cenospheres at room

temperature (300 K) are represented in Fig. 6. The testing
results indicate that the magnetization of the as-prepared
cenosphere increases with the increase of the magnetic
field at first, and then levels off at a magnetic field of
7 10,000.0 Oe for all samples. The coercive force and remnant
Fig. 4. XRD patterns of cenospheres before and after treatments. magnetizations for all samples are equal to zero, which has the

Fig. 5. The processing route for the preparation of Ag decorated Fe3O4/TiO2 coated cenosphere. Steps: (1) etching; (2) coating of Fe3O4 nanoparticles;
(3) modification with silane coupling agent KH550; (4) coating of TiO2 nanoparticles; and (5) decoration with Ag nanoparticles. Notes: (a) formation of silicon
oxide film on cenosphere; photocatalytic mechanism for the Ag decorated Fe3O4/TiO2 coated cenosphere under (b) UV and (c) visible light irradiation.
8554 J. Zhan et al. / Ceramics International 40 (2014) 8547–8559

Table 1
The chemical compositions of cenospheres before and after treatments.

Elements Weight percent (%) Atom percent (%)

Untreated Fe3O4 Fe3O4/TiO2 Ag decorated Untreated Fe3O4 Fe3O4/TiO2 Ag decorated

coated coated Fe3O4/TiO2 coated coated coated Fe3O4/TiO2 coated

OK 48.93 41.56 44.56 45.21 63.78 66.09 66.36 63.75

SiK 42.02 14.2 21.03 15.99 31.2 12.85 17.85 21.58
CaK 9.05 2.64 4.38 1.75 5.02 1.67 2.61 0.92
FeK – 41.6 24.75 19.17 – 19.39 10.56 7.21
TiK – – 5.28 12.5 – – 2.63 5.48
AgL – – – 5.38 – – – 1.06

superparamagnetism behaviors at ambient temperature. It is

well known that as the magnetic particle sizes continue to
decrease below the single domain value, these particles exhibit
paramagnetic or superparamagnetic properties [68]. The as-
prepared cenosphere shows the high saturation magnetizations
in the presence of a magnetic field. As soon as the magnetic
field is switched off, the magnetization disappear immediately
[29]. It is obvious that the magnetization of the as-prepared
cenospheres decreases with the decreasing of the magnetite
content in unit weight samples. When the Fe3O4-coated
cenosphere is deposited with a film of TiO2 nanoparticles,
the saturation magnetization is reduced from 36 to 31 emu g
1.
Fig. 6. Hysteresis loops of as-prepared cenospheres at room temperature.
After electroless silver deposition, it further decreases to 21
emu g
1. As shown in the inset of Fig. 6, the Ag decorated
Fe3O4/TiO2 coated cenospheres can be attracted by a magnet.
After removing the magnetic field, they disperse in the solution
with a slight shake and immediately float on water surface.

3.5. DRS analysis

The diffuse reflectance spectra of cenospheres before and

after treatments in the range of 200–800 nm are displayed in
Fig. 7. The Fe3O4 coated cenosphere can almost completely
absorb both UV and visible light irradiation because of the
narrower band gap of Fe3O4 (0.1 eV), which leads to an
increase in the incidence of electron–hole recombination [2].
After deposition of TiO2, a strong absorption capability of the
Fe3O4/TiO2 coated cenosphere is not only maintained in UV
Fig. 7. Diffuse reflectance spectra of cenospheres before and after treatments.
region but also in visible region. Compared with the untreated
cenospheres, the average reflectances of the Fe3O4/TiO2 coated
cenospheres decrease about 32% in UV region and 80% in 1.32 eV for the Fe3O4/TiO2 coated cenosphere and 1.26 eV
visible region. This is attributed to the synergistic effects of the for the Ag decorated Fe3O4/TiO2 coated cenosphere respec-
band gap transition of TiO2 nanoparticles and the absorption of tively, far smaller than the theoretical value of anatase titania
Fe3O4 basement [47]. The absorption ability of the Fe3O4/TiO2 (3.2 eV) [28]. Those values are influenced by the Fe3O4
coated cenosphere to visible light is slightly enhanced after basement to a great degree.
decoration with Ag nanoparticles, which is ascribed to the
surface plasmon resonance effect of Ag nanoparticles induced
by visible light [62,63]. The average reflectance in visible 3.6. Photocatalysis
region increases about 4.2% with respect to the undecorated
one. Furthermore, the relationship between (αhν)1/2 and the The transmission spectra of MB solution exposed to UV
incident photon energy (hν) is plotted in the inset of Fig. 7, light irradiation at different times are exhibited in Fig. 8. It is
where α is the absorption coefficient [9]. The calculated band seen that the transmission spectra of MB solution vary with the
gaps optically obtained in such a way are approximately irradiation time for all samples. The characteristic absorption
 J. Zhan et al. / Ceramics International 40 (2014) 8547–8559 8555

Fig. 8. Transmission spectra of MB solution exposed to UV irradiation at different times: (a) without cenospheres; (b) Fe3O4 coated; (c) Fe3O4/TiO2 coated; and
(d) Ag decorated Fe3O4/TiO2 coated.

peaks at 250 nm, 292 nm, and 662 nm gradually diminish with Ag occurs. As a result, the life time of excited hole and
the increase of irradiation time. It has been confirmed that the electron pair is prolonged [55]. However, this kind of
hydroxyl radicals and superoxide radical anions (oxidizing phenomenon may result from the unfavorable charge transfer
species) attack the organic pollutants leading to the complete process to adsorbed substance during light illumination where
mineralization of organic molecules [69]. If there are any excess accumulation of electron and hole undergoes recombi-
heteroatoms like S, N and Cl present in the original organic nation immediately without taking part in the photocatalytic
pollutant, the minerals will be generated. However, the reaction. Therefore, the electron–hole pair formation and
removal of total organic compound usually takes longer time separation process is a key factor in photocatalytic reaction
after the disappearance of the substrate color [70]. The changes [23], which is mainly determined by the electron transfer from
of absorption peaks of the Fe3O4/TiO2 coated and Ag TiO2 to Ag and the thickness of TiO2 film [57]. In addition, the
decorated Fe3O4/TiO2 coated cenospheres are more significant photocatalytic activity of Fe3O4/TiO2 core/shell coating makes
compared with those of the Fe3O4 coated cenospheres and MB a contribution to the degradation of MB dye, which is
solution without cenospheres. Moreover, the photocatalytic determined by the synergic effects of hydrophilicity (hydroxyl
activity of the Fe3O4/TiO2 coated cenosphere behaves better groups), surface area, and light transmittance [29,40].
than that of the Ag decorated Fe3O4/TiO2 coated one. It has Although the membrane of silicon–oxygen structure can
been demonstrated that the decrease in the photocatalytic prevent photo-dissolution between Fe3O4 and TiO2 during
efficiency of the Ag decorated TiO2 under UV irradiation is photocatalytic process [36,72], a trace of Fe ions might
not only due to the trapping effect, but also due to the change penetrate through the intermediate layer. The presence of Fe
of the reaction site density [53,55]. Because the Ag particles ions in aqueous solution can accelerate the MB degradation by
loaded on the TiO2 particles are relatively negatively charged, a Fenton-like reaction mechanism [27,73].
the photoholes in the interfacial region of the TiO2 film may be The photocatalytic activities of the Fe3O4/TiO2 coated and
trapped by the negatively charged Ag particles before they Ag decorated Fe3O4/TiO2 coated cenospheres are further
react with water and organics. At the same time, the coverage compared under visible light irradiation, as shown in Fig. 9.
of Ag on TiO2 surface increases with the increase of the Ag þ There has been a little change for the transmission spectra of
concentration, thus the density of reaction sites for absorption MB solution without samples (not given), which is ascribed to
of UV light, producing photohole and photoelectrons at the dye self-photosensitized degradation process [74]. The
surface of the resulting film can be reduced to some extent absorption peak of the Ag decorated Fe3O4/TiO2 coated
[71]. Besides the electron transfers from the valence band to cenosphere changes much faster than that of the Fe3O4/TiO2
the conduction band of TiO2, the electron transfer from TiO2 to coated one, indicating that the Ag nanoparticles can enhance
8556 J. Zhan et al. / Ceramics International 40 (2014) 8547–8559

Fig. 9. Transmission spectra of MB solution exposed to visible light irradiation at different times: (a) Fe3O4/TiO2 coated and (b) Ag decorated Fe3O4/TiO2 coated.

the photocatalytic activity of TiO2. It is due to the fact that a [23]. According to the above equation, the larger the k value
charge density oscillation occurs at the Ag–Fe3O4 interface, the better the photocatalytic activity of the sample. The
and the plasmon wavelength depends on the chemical compo- apparent rate constants of the Fe3O4/TiO2 coated cenosphere
sition, size, and shape of the nanoparticles in the composite. are 0.09 min
1 (squared correlation coefficients, R2 ¼ 0.96)
The reduction of the Ag particle sizes causes greater loss of for UV irradiation and 0.24 h
1 (R2 ¼ 0.98) for visible light
energy by metallic electrons due to surface scattering and leads irradiation. The apparent rate constants of the Ag decorated
to changes in form and intensity of the plasmon absorption Fe3O4/TiO2 coated cenosphere are 0.04 min
1 (R2 ¼ 0.95) and
band [59]. The results agree well with the previous study [52]. 1.30 h
1 (R2 ¼ 0.97) under UV and visible light irradiation,
Under visible light irradiation, the surface plasmon resonance respectively.
of Ag species, which is excited by visible light to create The reusability of the as-prepared photocatalytic ceno-
electron–hole pairs, plays an important role in the degradation spheres is also investigated. As can be seen from Fig. 11,
of MB [61]. The photoexcited electrons at the Ag decorated the degradation rates of MB dye irradiated with UV light after
Fe3O4/TiO2 coating inject into the TiO2 conduction band [60]. 2 h and with visible light after 6 h decrease slightly with the
The Ag decorated Fe3O4/TiO2 coated cenosphere can offer a increase of the experimental cycles. As the experimental cycle
larger surface area, which may be benefit to the high increases, the amount of organic intermediates adsorbed on the
photocatalytic performance because of its enhanced adsorption surface of the as-prepared cenosphere increases. The active
of photons and dye molecules [75]. Moreover, the dye sites on catalyst surface thus decrease due to the increased
molecule can be excited by visible light to appropriated excited retardation effect, which result in the decrease of competitive
states. The energy transfer is generated not only from the adsorption of OH
species and a lower formation rate of OHd
excited dye to ground state oxygen, but also from an excited radical [76]. Consequently, the degradation rates of MB dye
state of dyes to the conduction band of photocatalyst, resulting decreases as the degradation cycle increases. After eight
in the photooxidiation of dye [32]. The photocatalytic mechan- cycles, the degradation rates are about 87% for the Fe3O4/
isms are proposed in insets (b) for UV light and (c) for visible TiO2 coated cenospheres and 80% for the Ag decorated Fe3O4/
light of Fig. 5, respectively. TiO2 coated cenospheres under UV irradiation, respectively.
The dependences of degradation rates with irradiation time But for the visible light irradiation, the degradation rates are
under UV and visible light irradiation are revealed in Fig. 10. 83% and 67% for the Ag decorated Fe3O4/TiO2 coated and
It is apparent that the degradation rates increase with the Fe3O4/TiO2 coated cenospheres, respectively. It implies that
increase of irradiation time for all samples. After 2 h of UV the coating of Fe3O4/TiO2 or Ag decorated Fe3O4/TiO2 firmly
irradiation, the degradation rates reach 98% for the Fe3O4/TiO2 adhere on the cenosphere surface, not to be easily exfoliated
coated cenosphere and 90% for the Ag decorated Fe3O4/TiO2 from the cenosphere.
coated cenosphere respectively, larger than 84% for the Fe3O4
coated cenosphere. Under visible light irradiation for 6 h, the 4. Conclusions
Ag decorated Fe3O4/TiO2 coated cenosphere has a higher
degradation rate of above 97%, where it is about 73% for the Magnetite Fe3O4 nanoparticles are first coated on the surface
Fe3O4/TiO2 coated cenosphere. Because UV rays have higher of cenosphere using FeCl2  4H2O, FeCl3  6H2O, and aqueous
photo energies than visible light, the efficiency of MB ammonia by a precipitation method, followed by being
degradation under UV irradiation is obviously greater than modified with silane coupling agent KH550, and then coated
that under visible light irradiation. The photodegradation with a layer of anatase TiO2 nanoparticles under hydrothermal
of MB follows the Langmuir–Hinshelwood kinetic equation: conditions, and lastly decorated with Ag nanopartilces by
ln(C0/C)¼ kt (where C0 is the initial concentration of dyes electroless silver deposition. The FESEM, EDX, and XRD
aqueous solution, C is the concentration of dyes measured at results show that the Ag decorated Fe3O4/TiO2 core/shell
the time t and k is the apparent photodegradation rate constant) structure is firmly coated on cenosphere surface. The VSM
 J. Zhan et al. / Ceramics International 40 (2014) 8547–8559 8557

Fig. 10. Effect of irradiation time on the degradation rate of MB solution: (a) UV light and (b) visible light.

[2] Y.T. Yu, Preparation of nanocrystalline TiO2-coated coal fly ash and

effect of iron oxides in coal fly ash on photocatalytic activity, Powder
Technol. 146 (2004) 154–159.
[3] H.J. Kim, Y.G. Shul, H. Han, Photocatalytic properties of silica-
supported TiO2, Top. Catal. 35 (2005) 287–293.
[4] M. Asilturk, S. Sener, TiO2-activated carbon photocatalysts: preparation,
characterization and photocatalytic activities, Chem. Eng. J. 180 (2012)
354–363.
[5] T. Kamegawa, R. Kido, H. Yamahana, Design of TiO2–zeolite compo-
sites with enhanced photocatalytic performances under irradiation of UV
and visible light, Microporous Mesoporous Mater. 165 (2013) 142–147.
[6] J.C. Colmenares, M.A. Aramendia, A. Marinas, J.M. Marinas,
F.J. Urbano, Synthesis, characterization and photocatalytic activity of
different metal-doped titania systems, Appl. Catal. A–Gen. 306 (2006)
120–127.
Fig. 11. Effect of experimental cycle on the degradation rate of MB solution. [7] W. Dong, Y. Zhu, H. Huang, L. Jiang, H. Zhu, C. Li, B. Chen, Z. Shi,
G. Wang, A performance study of enhanced visible-light-driven photo-
catalysis and magnetical protein separation of multifunctional yolk–shell
results show that the Fe3O4 coated cenosphere is endowed with nanostructures, J. Mater. Chem. A 1 (2013) 10030–10036.
the superparamagnetic features. The saturation magnetization [8] Y. Li, M. Zhang, M. Guo, X. Wang, Preparation and properties of a nano
is reduced after being coated with TiO2 nanoparticles, and TiO2/Fe3O4 composite superparamagnetic photocatalyst, Rare Metals 28
(2009) 423–427.
further decreases after being decorated with Ag nanoparticles.
[9] S.A. Jadhav, R. Bongiovanni, Synthesis and organic functionalization
The Ag decorated Fe3O4/TiO2 coated cenosphere has a high approaches for magnetite (Fe3O4) nanoparticles, Adv. Mater. Lett. 3
saturation magnetization of 21 emu g
1. The DRS and photo- (2012) 356–361.
catalytic degradation of MB dye results show that the photo- [10] C. Li, L. Chen, Determination of pyrethroid pesticides in environmental
catalytic activity of the Ag decorated Fe3O4/TiO2 coated waters based on magnetic titanium dioxide nanoparticles extraction
followed by HPLC analysis, Chromatographia 76 (2013) 409–417.
cenosphere is much higher than that of the Fe3O4/TiO2 coated
[11] T.A. Gad–Allah, S. Kato, S. Satokawa, T. Kojima, Effect of carbon
one, which is ascribed to the surface plasmon resonance of Ag coating of TiO2/Fe3O4 particles on their photocatalytic activity, Int. J.
nanoparticles. The silicon-oxygen interlayer between Fe3O4 Chem. React. Eng. 6 (2008) 1–15.
core and TiO2 shell can be employed to prevent photodissolu- [12] X.L. Dong, X.Y. Mou, H.C. Ma, X.X. Zhang, X.F. Zhang, W.J. Sun,
tion of Fe3O4 during photocatalysis. The Ag decorated TiO2 C. Ma, M. Xue, Preparation of CdS–TiO2/Fe3O4 photocatalyst and its
photocatalytic properties, J. Sol–Gel. Sci. Technol. 66 (2013) 231–237.
layer can provide abundant reactive sites for photocatalysts.
[13] C. Li, L. Chen, W. Li, Magnetic titanium oxide nanoparticles for
hemimicelle extraction and HPLC determination of organophosphorus
pesticides in environmental water, Microchim. Acta 180 (2013)
Acknowledgment 1109–1116.
[14] R. Chalasani, S. Vasudevan, Cyclodextrin-functionalized Fe3O4@TiO2:
reusable, magnetic nanoparticles for photocatalytic degradation of
This work has been supported by the Scientific and endocrine-disrupting chemicals in water supplies, ACS Nano 7 (2013)
Technological Project (No. 2012R10012-09) from Department 4093–4104.
of Science and Technology of Zhejiang Province, China. [15] Y. Fan, C. Ma, W. Li, Y. Yin, Synthesis and properties of Fe3O4/SiO2/
TiO2 nanocomposites by hydrothermal synthetic method, Mater. Sci.
Semicond. Proc. 15 (2012) 582–585.
[16] D. Beydoun, R. Amal, Implications of heat treatment on the properties of
References a magnetic iron oxide/titanium dioxide photocatalyst, Mater. Sci. Eng.
B–Adv. 94 (2002) 71–81.
[1] A. Fujishima, X. Zhang, D.A. Tryk, TiO2 photocatalysis and related [17] J. Chen, Y. Qian, X. Wei, Comparison of magnetic–nanometer titanium
surface phenomena, Surf. Sci. Rep. 63 (2008) 515–582. dioxide/ferriferous oxide (TiO2/Fe3O4) composite photocatalyst prepared
8558 J. Zhan et al. / Ceramics International 40 (2014) 8547–8559

by acid–sol and homogeneous precipitation methods, J. Mater. Sci. 45 [38] M. Niyaifar, A. Hasanpour, H. Mohammadpour, J. Amighian, Capped
(2010) 6018–6024. and coupled Fe3O4/TiO2 nanopowder systems fabricated by sol–gel and a
[18] T.C. Cheng, K.S. Yao, N. Yeh, C.I. Chang, H.C. Hsu, Y.T. Chien, C. nonthermal method, Phys. Status Solidi A 210 (2013) 1190–1194.
Y. Chang, Visible light activated bactericidal effect of TiO2/Fe3O4 [39] S. Linley, T. Leshuk, F.X. Gu, Synthesis of magnetic rattle-type
magnetic particles on fish pathogens, Surf. Coat. Technol. 204 (2009) nanostructures for use in water treatment, ACS Appl. Mater. Interfaces
1141–1144. 5 (2013) 2540–2548.
[19] J. Jing, J. Li, J. Feng, W. Li, W.W. Yu, Photodegradation of quinoline in [40] T.A. Gad–Allah, S. Kato, S. Satokawa, T. Kojima, Role of core diameter
water over magnetically separable Fe3O4/TiO2 composite photocatalysts, and silica content in photocatalytic activity of TiO2/SiO2/Fe3O4 compo-
Chem. Eng. J. 219 (2013) 355–360. site, Solid State Sci. 9 (2007) 737–743.
[20] J.S. Choi, H.K. Youn, B.H. Kwak, Q. Wang, K.S. Yang, J.S. Chung, [41] T.A. Gad–Allah, S. Kato, S. Satokawa, T. Kojima, Treatment of synthetic
Preparation and characterization of TiO2-masked Fe3O4 nano particles for dyes wastewater utilizing a magnetically separable photocatalyst (TiO2/
enhancing catalytic combustion of 1,2-dichlorobenzene and incineration SiO2/Fe3O4): parametric and kinetic studies, Desalination 244 (2009)
of polymer wastes, Appl. Catal. B–Environ. 91 (2009) 210–216. 1–11.
[21] M.S. Islam, Y. Kusumoto, M. Abdulla–Al–Mamun, Y. Horie, Photo- [42] H. Liu, Z. Jia, S. Ji, Y. Zheng, M. Li, H. Yang, Synthesis of TiO2/
catalytic and AC magnetic-field induced enhanced cytotoxicity of Fe3O4– SiO2@Fe3O4 magnetic microspheres and their properties of photocataly-
TiO2 core–shell nanocomposites against HeLa cells, Catal. Commun. 16 tic degradation dyestuff, Catal. Today 175 (2011) 293–298.
(2011) 39–44. [43] X. Xu, F. Ji, Z. Fan, L. He, Degradation of glyphosate in soil
[22] Q. Yuan, N. Li, W. Geng, Y. Chi, X. Li, Preparation of magnetically photocatalyzed by Fe3O4/SiO2/TiO2 under solar light, Int. J. Environ.
recoverable Fe3O4@SiO2@meso–TiO2 nanocomposites with enhanced Res. Public Health 8 (2011) 1258–1270.
photocatalytic ability, Mater. Res. Bull. 47 (2012) 2396–2402. [44] C.F. Chang, C.Y. Man, Titania-coated magnetic composites as photo-
[23] F.X. Ye, T. Tsumura, K. Nakata, A. Ohmori, Dependence of photo- catalysts for phthalate photodegradation, Ind. Eng. Chem. Res. 50 (2011)
catalytic activity on the compositions and photo-absorption of functional 11620–11627.
TiO2–Fe3O4 coatings deposited by plasma spray, Mater. Sci. Eng. [45] P.M. Alvarez, J. Jaramillo, F. Lopez–Pinero, Preparation and character-
B–Adv. 148 (2008) 154–161. ization of magnetic TiO2 nanoparticles and their utilization for the
[24] W. Jiang, X. Zhang, X. Gong, F. Yan, Z. Zhang, Sonochemical synthesis degradation of emerging pollutants in water, Appl. Catal. B–Environ.
and characterization of magnetic separable Fe3O4–TiO2 nanocomposites 100 (2010) 338–345.
and their catalytic properties, Int. J. Smart Nano Mater. 1 (2010) [46] S.C. Pang, S.Y. Kho, S.F. Chin, Fabrication of magnetite/silica/titania
278–287. core–shell nanoparticles, J. Nanomater. (2012) 1–6.
[25] J. Lu, M. Wang, C. Deng, X. Zhang, Facile synthesis of Fe3O4@meso- [47] X. Yu, S. Liu, J. Yu, Superparamagnetic γ-Fe2O3@SiO2@TiO2 compo-
porous TiO2 microspheres for selective enrichment of phosphor peptides site microspheres with superior photocatalytic properties, Appl. Catal.
for phosphoproteomics analysis, Talanta 105 (2013) 20–27. B–Environ. 104 (2011) 12–20.
[26] S. Watson, D. Beydoun, R. Amal, Synthesis of a novel magnetic [48] K. Laohhasurayotin, S. Pookboonmee, D. Viboonratanasri,
photocatalyst by direct deposition of nanosized TiO2 crystals onto a W. Kangwansupamonkon, K. Laohhasurayotin, Preparation of magnetic
magnetic core, J. Photochem. Photobiol. A 148 (2002) 303–313. photocatalyst nanoparticles–TiO2/SiO2/Mn–Zn ferrite and its photocata-
[27] O. Akhavan, R. Azimirad, Photocatalytic property of Fe2O3 nanograin lytic activity influenced by silica interlayer, Mater. Res. Bull. 47 (2012)
chains coated by TiO2 nanolayer in visible light irradiation, Appl. Catal. 1500–1507.
A–Gen. 369 (2009) 77–82. [49] X. Huang, G. Wang, M. Yang, W. Guo, H. Gao, Synthesis of polyani-
[28] Q. He, Z. Zhang, J. Xiong, Y. Xiong, H. Xiao, A novel biomaterial— line–modified Fe3O4/SiO2/TiO2 composite microspheres and their photo-
Fe3O4:TiO2 core–shell nano particle with magnetic performance and high catalytic application, Mater. Lett. 65 (2011) 2887–2890.
visible light photocatalytic activity, Opt. Mater. 31 (2008) 380–384. [50] Z.Q. He, T.M. Hong, J.M. Chen, S. Song, A magnetic TiO2 photocatalyst
[29] T. Zhang, X. Yan, D.D. Sun, Hierarchically multifunctional K–OMS doped with iodine for organic pollutant degradation, Sep. Purif. Technol.
–2/TiO2/Fe3O4 heterojunctions for the photocatalytic oxidation of humic 96 (2012) 50–57.
acid under solar light irradiation, J. Hazard. Mater. 243 (2012) 302–310. [51] X. Bian, K. Hong, L. Liu, M. Xu, Magnetically separable hybrid CdS–
[30] W. Hu, B. Liu, Q. Wang, Y. Liu, Y. Liu, P. Jing, S. Yu, L. Liu, J. Zhang, TiO2–Fe3O4 nanomaterial: enhanced photocatalystic activity under UV
A magnetic double-shell microsphere as a highly efficient reusable and visible irradiation, Appl. Surf. Sci. 280 (2013) 349–353.
catalyst for catalytic applications, Chem. Commun. 49 (2013) [52] J. Liu, S. Zuo, L. Yu, Y. Yu, B. Li, P. Chen, Visible light photodegradation
7596–7598. of methylene blue by AgBr–TiO2/SiO2@Fe3O4 magnetic photocatalysts,
[31] M. Ye, Q. Zhang, Y. Hu, J. Ge, Z. Lu, L. He, Z. Chen, Y. Yin, Particuology 11 (2013) 728–731.
Magnetically recoverable core–shell nanocomposites with enhanced [53] I.M. Arabatzis, T. Stergiopoulos, M.C. Bernard, D. Labou,
photocatalytic activity, Chem. Eur. J. 16 (2010) 6243–6250. S.G. Neophytides, P. Falaras, Silver-modified titanium dioxide thin films
[32] F. Chen, Y. Xie, J. Zhao, G. Lu, Photocatalytic degradation of dyes on a for efficient photodegradation of methyl orange, Appl. Catal. B–Environ.
magnetically separated photocatalyst under visible and UV irradiation, 42 (2003) 187–201.
Chemosphere 44 (2001) 1159–1168. [54] M.W. Xua, S.J. Bao, X.G. Zhang, Enhanced photocatalytic activity of
[33] S. Kurinobu, K. Tsurusaki, Y. Natui, M. Kimata, M. Hasegawa, magnetic TiO2 photocatalyst by silver deposition, Mater. Lett. 59 (2005)
Decomposition of pollutants in wastewater using magnetic photocatalyst 2194–2198.
particles, J. Magn. Magn. Mater. 310 (2007) e1025–e1027. [55] A.R. Malagutti, H.A.J.L. Mourao, J.R. Garbin, C. Ribeiro, Deposition of
[34] J. Xu, Y. Ao, D. Fu, C. Yuan, Low–temperature preparation of anatase TiO2 and Ag:TiO2 thin films by the polymeric precursor method and
titania–coated magnetite, J. Phys. Chem. Solids 69 (2008) 1980–1984. their application in the photodegradation of textile dyes, Appl. Catal.
[35] R. Wang, X. Wang, X. Xi, R. Hu, G. Jiang, Preparation and photo- B–Environ. 90 (2009) 205–212.
catalytic activity of magnetic Fe3O4/SiO2/TiO2 composites, Adv. Mater. [56] W.C. Lin, C.N. Chen, T.T. Tseng, M.H. Wei, J.H. Hsieh, W.J. Tseng,
Sci. Eng. (2012) 1–8. Micellar layer-by-layer synthesis of TiO2/Ag hybrid particles for bacter-
[36] J. Joo, Y. Ye, D. Kim, J. Lee, S. Jeon, Magnetically recoverable hybrid icidal and photocatalytic activities, J. Eur. Ceram. Soc. 30 (2010)
TiO2 nanocrystal clusters with enhanced photocatalytic activity, Mater. 2849–2857.
Lett. 93 (2013) 141–144. [57] B. Cui, H. Peng, H. Xia, X. Guo, H. Guo, Magnetically recoverable core–
[37] H. Liu, S. Ji, Y. Zheng, M. Li, H. Yang, Porous TiO2-coated magnetic shell nanocomposites γ-Fe2O3@SiO2@TiO2–Ag with enhanced photo-
core–shell nanocomposites: preparation and enhanced photocatalytic catalytic activity and antibacterial activity, Sep. Purif. Technol. 103
activity, Chin. J. Chem. Eng. 21 (2013) 569–576. (2013) 251–257.
 J. Zhan et al. / Ceramics International 40 (2014) 8547–8559 8559

[58] L.G. Devi, B. Nagaraj, K.E. Rajashekhar, Synergistic effect of Ag [67] L. Wang, H. Wang, A. Wang, M. Liu, Surface modification of a magnetic
deposition and nitrogen doping in TiO2 for the degradation of phenol SiO2 support and immobilization of a nano-TiO2 photocatalyst on it,
under solar irradiation in presence of electron acceptor, Chem. Eng. Chin. J. Catal. 30 (2009) 939–944.
J. 181–182 (2012) 259–266. [68] S. Liu, J. Zhou, L. Zhang, In situ synthesis of plate-like Fe2O3
[59] M.M. Viana, N.D.S. Mohallem, D.R. Miquita, K. Balzuweit, E. Silva– nanoparticles in porous cellulose films with obvious magnetic anisotropy,
Pinto, Preparation of amorphous and crystalline Ag/TiO2 nanocomposite Cellulose 18 (2011) 663–673.
[69] C. Quispe, J. Villasenor, G. Pecchi, P. Reyes, Catalytic ozonation of
thin films, Appl. Surf. Sci. 265 (2013) 130–136.
oxalic acid with MnO2/TiO2 and Rh/TiO2, J. Chil. Chem. Soc. 51 (2006)
[60] J. Zhou, Y. Cheng, J. Yu, Preparation and characterization of visible–
1049–1051.
light–driven plasmonic photocatalyst Ag/AgCl/TiO2 nanocomposite thin
[70] P. Sathishkumar, S. Anandan, P. Maruthamuthub, T. Swaminathan,
films, J. Photochem. Photobiol. A 223 (2011) 82–87. M. Zhou, M. Ashokkumar, Synthesis of Fe3 þ doped TiO2 photocatalysts
[61] J.F. Guo, B. Ma, A. Yin, K. Fan, W.L. Dai, Photodegradation for the visible assisted degradation of an azo dye, Colloid Surf. A 375
of rhodamine B and 4-chlorophenol using plasmonic photocatalyst of (2011) 231–236.
Ag–AgI/Fe3O4@SiO2 magnetic nanoparticle under visible light irradia- [71] J. Zheng, H. Yu, X. Li, S. Zhang, Enhanced photocatalytic activity of
tion, Appl. Catal. B–Environ. 101 (2011) 580–586. TiO2 nano-structured thin film with a silver hierarchical configuration,
[62] J.F. Guo, B. Ma, A. Yin, K. Fan, W.L. Dai, Highly stable and efficient Appl. Surf. Sci. 254 (2008) 1630–1635.
Ag/AgCl@TiO2 photocatalyst: preparation, characterization, and applica- [72] D. Beydoun, R. Amal, G. Low, S. McEvoy, Occurrence and prevention
tion in the treatment of aqueous hazardous pollutants, J. Hazard. Mater. of photodissolution at the phase junction of magnetite and titanium
211–212 (2012) 77–82. dioxide, J. Mol. Catal. A–Chem. 180 (2002) 193–200.
[63] X. Lin, F. Rong, D. Fu, C. Yuan, Enhanced photocatalytic activity of [73] M.S. Lucas, P.B. Tavares, J.A. Peres, J.L. Faria, M. Rocha, C. Pereira,
fluorine doped TiO2 by loaded with Ag for degradation of organic C. Freire, Photocatalytic degradation of reactive black 5 with TiO2-coated
magnetic nanoparticles, Catal. Today 209 (2013) 116–121.
pollutants, Powder Technol. 219 (2012) 173–178.
[74] P.Q. Li, G.H. Zhao, K.J. Zhao, J.X. Gao, T. Wu, An efficient and energy
[64] J. Cui, T. He, X. Zhang, Synthesis of Fe3O4@SiO2@Ption–TiO2 hybrid
saving approach to photocatalytic degradation of opaque high-chroma
composites with high efficient UV–visible light photoactivity, Catal.
methylene blue wastewater by electrocatalytic pre-oxidation, Dyes
Commun. 40 (2013) 66–70. Pigments 92 (2012) 923–928.
[65] Z. Lu, W. Zhou, P. Huo, Y. Luo, M. He, J. Pan, C. Li, Y. Yan, [75] M. Asilturk, F. Sayilkan, E. Arpac, Effect of Fe3 þ ion doping to TiO2 on
Performance of a novel TiO2 photocatalyst based on the magnetic floating the photocatalytic degradation of Malachite Green dye under UV and vis-
fly–ash cenospheres for the purpose of treating waste by waste, Chem. irradiation, J. Photochem. Photobiol. A 203 (2009) 64–71.
Eng. J. 225 (2013) 34–42. [76] M.L. Huang, C.F. Xu, Z.B. Wu, Y.F. Huang, J.M. Lin, J.H. Wu,
[66] B. Arkles, Silane Coupling Agents: Connecting Across Boundaries, first Photocatalytic discolorization of methyl orange solution by Pt modified
ed., Gelest, Morrisville, 2003. TiO2 loaded on natural zeolite, Dyes Pigments 77 (2008) 327–334.