Journal of Alloys and Compounds 553 (2013) 19–29

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Journal of Alloys and Compounds

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Photocatalytic degradation of methylene blue dye using Fe2O3/TiO2

nanoparticles prepared by sol–gel method
M.A. Ahmed a,⇑, Emad E. El-Katori b, Zarha H. Gharni b
a
Chemistry Department, Faculty of Science, Ain-Shams University, Egypt
b
Chemistry Department, Faculty of Science, King Khaled University, Saudi Arabia

a r t i c l e i n f o a b s t r a c t

Article history: The photocatalytic degradation of methylene blue dye was successfully carried under UV irradiation over
Received 2 July 2012 Fe2O3/TiO2 nanoparticles embedded various composition of Fe2O3 (0–20) wt.% synthesized by sol–gel
Received in revised form 7 October 2012 process. Structural and textural features of the mixed oxide samples were investigated by X-ray diffrac-
Accepted 10 October 2012
tion [XRD], Fourier transformer infra-red [FTIR], Energy dispersive X-ray [EDX], Field emission electron
Available online 26 October 2012
microscope [FESEM] and transmission electron microscope [TEM]. However, the optical features were
estimated using UV–Vis spectrophotometer. The results reveal that the incorporation of various Fe2O3
Keywords:
up to 7% is associated by remarkable increase in surface area, reduction of particle size, stabilization of
Nanoparticles
Sol–gel
anatase phase, shifting the photoexcitation response of the sample to visible region and exceptional deg-
Rietveld analysis radation of methylene blue dye. On the other hand, increasing Fe2O3 contents up to 20 wt.% is associated
Adsorption by anatase–rutile transformation, increasing in particle size and remarkable decrease in surface area
Photocatalytic decolorization of methylene which are prime factors in reducing the degradation process. The experimental results indicate that
blue Fe2O3/TiO2 nanoparticles having both the advantages of photodegradation–adsorption process which
considered a promising new photocatalysts that involve in the abatement of various organic pollutants.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction
The discharge of several Hazardous dyes from many textiles
industries in waste water is a main cause for serious environmen-
tal problems that concerned with human health and the aquatic
medium due to the toxicity and the carcinogenic effect of these
materials [1,2]. Several approaches are devoted to remove these
toxic dyes from water such as adsorption on high surface area sup-
ports, chemical precipitation, sedimentation, biological mem-
branes and ion-exchange processes. However, these methods are
slow, require expensive equipment and may lead to transfer of
the main pollutant into a second one that requires further removal.
Moreover, the majority of the textile dyes are photocatalytically
stable and refractory towards chemical oxidation, and these
characteristics render them resistant towards decolorization by
conventional biochemical and physicochemical methods. A suc-
cessful route for dye removal is concerned with utilizing nano
semiconductors as TiO2, ZnO, Fe2O3 and CdS that exhibit high pho-
tocatalytic reactivity in removal several organic containments
without transfer a primary pollutant into series of toxic materials.
In the recent years, nano titanium oxide is considered the most
suitable candidate photocatalyst that involved in degradation and
⇑ Corresponding author. Tel.: +20 226704076; fax: +20 224831836.
E-mail address: abdelhay71@hotmail.com (M.A. Ahmed).
removal of various toxic organic pollutants [3,4] due to the stabil-
ity of its chemical structure, biocompatibility, strong oxidizing
power, non-toxicity and low cost [5,6]. The crystalline and the tex-
tural features are considered the main causes that determine the
photocatalytic features of the samples [7–10]. The photocatalytic
process is usually initiated by incident UV radiation on the oxide
samples that leads to electron transfer from the filled valence band
to the empty conduction band. This process is accompanied by
generation of the negative electron (e) and the positive hole (h+)
pairs on the surface of the photocatalyst [11–14]. These charge car-
riers are either combine with each other or involve in mineraliza-
tion of the organic pollutants on the catalyst surface through a
series of redox reactions. Moreover, possible reactions between
the positive hole and electrons with water and O2 lead to formation
of peroxide and superoxide radicals which considered as active
species in the degradation process [11–14]. The fast recombination
of charge carriers and the short wave length excitation are consid-
ered the main electronic obstacles that limit the photocatalytic
applications and restrict its reactivity to UV region only. The incor-
poration of transition elements is a suitable way in enhancing the
optical features of the titania by causing a batho-chromic shift of
the absorption response and preventing the electron–hole recom-
bination which increases the catalyst life time for the mineraliza-
tion process [15–18]. Fe3+ ion with narrow band gap energy
(1.9 eV) is one of the promising candidates that can effectively

0925-8388/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2012.10.038
20 M.A. Ahmed et al. / Journal of Alloys and Compounds 553 (2013) 19–29

enhance the photocatalytic features of titania due to its half-filled
electronic configuration and the similarity of the ionic radius of
Fe3+ (0.64 A) with that of coordinated Ti4+ (0.68 A). Several authors
claim that the incorporation of Fe3+ on titania improves the photo-
catalytic features of the sample by reducing the band gap energy
by about 2 eV and extending the photoexcitation response to visi-
ble region [19–25]. Many recent works have been devoted to study
the influence of iron oxide on the physicochemical and optical fea-
tures of titania in degradation of several organic pollutants. The re-
sults obtained indicate that the existence of an appropriate amount
of iron (III) (less than 10%) shifts the photocatalytic reactivity to-
ward a more favorable direction [26–28] as doped Fe3+ replaces
Ti4+ in TiO2 lattice, forming localized bands near the bottom of con-
duction band and thereby decreasing the band gap energy. It is
well established that the conduction and valence band of titania
have potential of 0.2 to 0.65 and 2.6–3.0 eV, respectively [30],
can provide electrons for the reductions of Fe3+ and Fe2+ (Fe3+ +
e ? Fe2+ E0 = 0.771 eV and Fe2+ + 2e ? Fe0 E0 = 0.44 eV)
[29,30]. This arguments will allow the electrons generated on
TiO2 by UV irradiation to be trapped by the two half reactions of
Fe3+/Fe2+ and Fe2+/Fe0, that inhibit the electron–hole recombina-
tion. Elghniji et al. prepare Fe3+ doped titania by acid-catalyzed
sol–gel process and they indicate that Fe3+ ions can be successfully
inserted into the TiO2 crystal lattice by substituting Ti4+ which
inducing a red shift of TiO2 absorption edge toward visible region
[31]. Tada et al. prepare iron oxide modified anatase and
anatase–rutile titania by ligand exchange method and they
indicate that the existence of ferric oxide chemisorbed on titania
surface improves the photocatalytic response of the samples under
both the ultraviolet and visible light. Moreover, they indicate that
the surface iron oxide species rapidly capture the excited electrons
in the conduction band of TiO2 to suppress recombination via sur-
face oxygen vacancy levels [32,33]. In the recent year, Sun et al.
indicate that the existence of bulk-Fe3+ can trap photogenerated
electrons and transfer them to pre-adsorbed species to form active
species, whereas incorporation of Fe3+ sites on the sample surface
can trap holes. These different roles of Fe3+ increase the efficiency
of charge separation and transfer of Fe–TiO2 and extend the photo-
catalytic oxidation of pollutants under visible light irradiation [21].
Jamalluddin and Abdullah indicate that the combination of
0.4 mol.% of Fe(III)/TiO2 with ultrasonic irradiation gave the high-
est sonocatalytic activity in the removal of RB4 from the aqueous
solution. In addition, they indicate that the existence of too low
of Fe(III) loading, the generation of OH radicals could not be suffi-
ciently accelerated to consequently cause low removal of RB4.
However, if the Fe(III) content was too high, it might inhibit the
surface reaction of the TiO2 and decrease the production of OH rad-
icals [26].
Although several studies have been focused on Fe/TiO2 nano-
particles, all the previous works are not sufficient to investigate
the influence of existence of various Fe2O3 contents on the struc-
ture, texture and the morphology of TiO2 nanoparticles system pre-
pared by sol–gel method using an effective template as
octadecylamine. This new system is expected to exhibit powerful
influence on the photocatalytic degradation of several hazardous
dyes.
In the present work, we make an attempt to synthesize Fe2O3/
TiO2 nanoparticles by sol–gel method using octadecylamine tem-
plate to fabricate nanoparticle with definite shape and size. The
prepared samples are investigated using developed techniques as
FTIR, XRD, BET, FESEM and TEM to assist the role of the existence
of different composition of iron oxide on the structure, particle
size, pore texture, morphology and optical features of the samples.
Moreover, the photocatalytic performance of the samples in
degrading methylene blue dye under UV irradiation dye was esti-
mated using UV–Vis spectrophotometry.
2. Experimental
TiCl4, Fe(NO3)39H2O, ammonia solution and octadecylamine were all pur-
chased from Aldrich Company were involved in preparation of pure titania and
Fe2O3/TiO2 mixed oxide samples. An exact amount of about 6.79, 6.72, 6.5, 6.38,
6.17, 5.83 and 5.49 ml of TiCl4 solution is mixed with 0.25, 0.5, 1.25, 2.5, 3.75 and
5 g of Fe(NO3)39H2O dissolved in acetone in order to prepare mixed oxide samples
embedded 1, 2, 5, 7, 10, 15 and 20 wt.% Fe2O3/TiO2, respectively. About 10.5 g of

20 40 60
1000
TiFe20
500
0
400
300 TiFe15
200
100
0
300
-100
200
100 TiFe10
0
1000
Intensity

800
(a.u.)

600
400 TiFe7
200
0
-200
800
600
400 TiFe5
200
0
600
400
200 TiFe2
0
600
400 TiFe1
200
0
A
2500
2000
1500 R TiO2
1000
500
0
20 40 60
2θ

Fig. 1. X-ray diffraction of TiO2, TiFe1, TiFe2, TiFe5, TiFe7, TiFe10, TiFe15 and TiFe20 [A = Anatase, R = Rutile].
 M.A. Ahmed et al. / Journal of Alloys and Compounds 553 (2013) 19–29 21

Fourier-transform infrared (FT-IR) spectra were measured at room temperature

100 on an ATT Mattson series FT-IR TM spectrometer using the KBr disk technique.
Anatase(%)
Rutile(%) – Adsorption–desorption isotherms of purified N2 at 77 K were determined using
a conventional volumetric apparatus connected to a vacuum system that
allowed prior outgassing to a residual pressure of 105 Torr.
80 – The evolution of the morphology of the samples was examined by Field emis-
sion scanning electron microscopy (FESEM) images were obtained on a FESEM
JEOL 6340electron microscope equipped with an EDAX energy dispersive
X-ray analysis (EDX) to investigate the elemental composition of the system.
% of crystalline phase

– The evolution of the nanostructure and particle size of the mixed oxide powders
60 was examined by transmission electron microscopy TEM using a JEOL 2000FX
microscope.
– Photocatalytic activity of the composites was investigated by degradation of
methylene blue under blue under high pressure mercury lamp with maximum
absorption at 254 nm. The initial concentration of MB was 1  105 mol L1.
40 The dosage of the TiO2 powders was 0.1 g for 100 ml MB solution with the
pH value of 7.0. Before switching on irradiation, MB solution was continuously
stirred in the dark for 30 min to ensure adsorption–desorption equilibrium. The
solution samples were collected from the reactor at regular intervals,
centrifuged and analyzed to determine the amounts of residual MB after
20 photo-irradiation, using UV–vis spectrophotometer.

The photocatalytic degradation rate (DC) was calculated by the following

0 the methylene blue dye solution at the irradiation time (t).
0 5 10 15 20
Fe 2O3(wt %)
Fig. 2. The proportion of the crystalline phases against various Fe2O3 contents.
octadecylamine surfactant dissolved in 100 ml ethanol is added to the above
solution then the mixture solution is subjected to vigorous stirring for 3-h. A diluted
solution of ammonia (1 M) was subsequent added drop by drop to the above solu-
tion until the pH until the turbid sol start to appear. The sol mixture was left for
48 h for aging in air until the gel particles was detected. Filtration and successive
washing with de-ionized water was repeated several times to remove both ammo-
nia and chloride ions until all chloride ions had been removed (by examining the
filtrate solution using aqueous silver nitrate solution). The gel was then dried in
an oven at 100 °C for 24 h to remove the physical adsorbed species. Finally, the sam-
ple was calcined at 600 °C for three hours to remove the organic amine, stabilize the
pore structure and induce crystallization of particles. The pure sample was denoted
as TiO2 and the samples denoted as TiFe1, TiFe2, TiFe5, TiFe7, TiFe10, TiFe15 and
TiFe20 corresponding to mixed oxide samples exhibit 1, 2, 5, 7, 10, 15 and
20 wt.% Fe2O3.
2.1. Material characterization
Fine and homogeneous powders of the different samples were back-loaded into
the sample holder of a P Analytical X’PERT MPD diffractometer using Cu (Ka1/Ka2)
radiation. The XRD patterns were recorded in a diffraction angle range from 20° to
100° with a step of 0.03° and integration time of 4 s per step. The diffraction pat-
terns have been treated with the Rietveld refinement method using the MAUD pro-
gram. The instrumental imperfections were evaluated with a sample of LaB6
calibrated against a sample of NIST SRM-640b and provided by the Gem Dugout
Company.
The phase contents of the synthesized TiO2 samples were calculated from the
integrated intensities of anatase peak (1 0 1) at 25.5° and rutile peak (1 1 0) at
27.6° as shown in the following equations:
W A ¼ 0:886IA =0:886IA þ IR
W R ¼ IR =0:886IA þ IR
WA, WR are contents of anatase and rutile phases, respectively; IA, IR are
integrated intensities of anatase (1 0 1) and rutile (1 1 0) peaks, respectively.
formula:
DC = [(Co  Ct/Co)]  100% where C0 is the initial concentration of methylene
blue solution which reached absorbency balance and Ct is the concentration of
3. Results and discussion
3.1. X-ray diffraction
Fig. 1 depicts the X-ray diffraction pattern of TiO2, TiFe1, TiFe2,
TiFe5, TiFe7, TiFe10, TiFe15 and TiFe20 samples. Several crystalline
peaks are detected for pure titania sample at 2h = 25.3°, 36.9°,
37.7°, 38.5°, 48°, 51.9°, 53.8°, 55.1°, 62.6°, 68.7° and 75° indicating
the existence of predominant anatase phase, however, small peaks
are detected at 2h = 27.4°, 39°, 41°, and 44° owing to the existence
of small proportion of rutile phase. The diffraction pattern for the
samples embedded various proportion of ferric oxide (1–7%) show
several peaks reflecting the existence of anatase phase of titania.
However, the peaks associated with titania rutile phase and iron
oxide phases are completely missed. Moreover, a remarkable
reduction in the intensity of the anatase peaks was associated with
increasing iron oxide contents suggesting that excessive Fe(III) ions
would affect the crystallinity of the particles. The samples TiFe10,
TiFe15 and TiFe20 embedded high Fe2O3 (10–20%) show several
peaks assigned only to rutile phase and the peaks associated with
iron oxide phases are completely missed. These results indicate the
dissolution of Fe2O3 in titania lattice which accelerate the anatase–
rutile transformation. It is should be emphasized that the amount
of rutile phase increases upon increasing Fe2O3 contents as repre-
sented in Fig. 2.
Titanium oxide exists mainly in four polymorphs in nature, ana-
tase (tetragonal, space group I41/amd), rutile (tetragonal, space
group P42/mnm), brookite (orthorhombic, space group Pbca), and
TiO2 (B) (monoclinic, space group C2/m). It has been documented
that anatase phase is considered the most active phase involving
in photocatalytic degradation of several harmful dyes owing to
the small particle size and high surface area of this phase. How-
ever, the rutile phase which exit upon heating the prepared

Table 1
Particle size, textural and photocatalytic parameters of Fe2O3/ TiO2 mixed oxides.

Sample TiO2 TiFe1 TiFe2 TiFe5 TiFe7 TiFe10 TiFe15 TiFe20

Crystallite Size (nm) 48 33 19 13 7 41 51 59
Surface area (m2/g) 68 84 108 130 182 131 109 88
Pore volume (cm3/g) 0.061 0.078 0.104 0.119 0.18 0.11 0.09 0.068
Pore diameter (nm) 3.5 3.7 3.8 3.7 4.03 3.3 3.3 3.1
First order constant (min1) 0.0134 0.0175 0.0233 0.028 0.042 0.0096 0.0081 0.0064
22 M.A. Ahmed et al. / Journal of Alloys and Compounds 553 (2013) 19–29
hydroxide at higher temperature (600–1000 °C) show a little pho-
tocatalytic degradation behavior. It is interesting to mention that
the commercial titania Degussa P25 that exhibit 80% anatase and
20% rutile phase show exceptional photocatalytic degradation of
various organic pollutants which reveling that the existence of
small amount of rutile phase is favorable to prevent the recombi-
nation of the charge carriers. The anatase and the brookite form
are the metastable phases exist upon heating titanium hydroxide
in temperature range (400–600 °C), further annealing of the sam-
ples to 800 °C lead to formation of the stable rutile form [34,35].
Fan et al. indicate that doping titania with lower Fe2O3 contents
(0.1–1) is associated with formation of only anatase phase without
remarkable influence on crystallite size [36]. Tu et al. observe a red
shift in absorption in the visible region and exceptional photocat-
alytic degradation of methylene blue for iron doped titania nano-
tubes embedded 5.9 wt.% Fe2O3 prepared by the template-based
liquid phase deposition method [37]. Zhu et al. indicate that the
incorporation of small amount of Fe2O3 in the titania lattice was
attributed to the similarities of ionic radii of both [Ti]4+ and
[Fe]3+ which is considered a prime factor in increasing the photo-
catalytic reactivity of the samples for oxidation of acetone [38].
Zhao et al. observe a pronounced stabilization of titania anatase
phase upon loading the sample with various composition of iron
oxide (1, 3, 5 and 8 wt.%) which attributed to either dispersion of
amorphous iron oxide between titania granules or due to dissolu-
tion of Fe3+ in titania crystal lattice [39].
The results revealed that the existence of various Fe2O3 con-
tents plays a vital role in controlling the particle growth and the
nature of crystalline phases. The existence of small amount of ferric
oxide (1–7%) is sufficient to stabilize the anatase phase and hinder
its transformation to a more stable rutile phase. The lack of Fe2O3
diffraction peaks can be explained due to either dissolution of Fe3+
in titania lattice or dispersion of Fe2O3 between titania particles as
amorphous layers. Further, addition of ferric oxide (10–20 wt.%)
accelerates the anatase–rutile transformation as indicated in
Fig. 2. which attributed to increasing the amount of Fe3+ ion placed
in substitutional position in titania crystal structure. Similar results
for rapid transformation of anatase–rutile upon increasing iron
oxide content are observed in the work of Tu et al. [37].
Rietveld quantitative analysis [40] is used to determine crystal-
lite size, amount of phases, lattice parameters and mechanical
properties of the composite samples (Table 1). The precise analysis
of Rietveld method indicates that part of Fe2O3 occupies substitu-
tional position in titanium oxide lattice forming Fe2O3–TiO2 solid
solution. This solid solution can be exists as the ionic radii of
Fe3+ (0.64 A) is nearly or little lower than Ti4+ radii (0.68 A) that
reflecting the facility of introduction of iron ion substitutional
position in titanium oxide crystal lattice [22,38,41]. It is more
convenient that the part of ferric oxide in the samples occupy sub-
stitutional position in titania crystal lattice and other part segre-
gate as amorphous layers exist between titanium oxide particles
hindering their growth for samples exhibit (1–7 wt.%) Fe2O3.
However, increasing in Fe2O3 content is associated by increasing
in the amount of Fe3+ occupying substitutional position in titania
crystal lattice which is essential cause for rapid anatase–rutile
transformation.
The particle sizes estimated for all samples are in nano dimen-
sions and vary between 7–59 nm (Table 1) influencing by Fe2O3
content reflecting its essential role in controlling titania particle
size. It is should be emphasized that a remarkable reduction in par-
ticle size to 7 nm is detected upon increasing Fe2O3 to 7 wt.% con-
tent followed by increasing in particle size upon increasing Fe2O3
to 20 wt.%. The variation in particle size can be related to the nat-
ure of crystalline phases exist in the mixed oxide samples. A pro-
nounced reduction in particle size is recorded for samples TiFe1,
TiFe2, TiFe5 and TiFe7 that exhibit predominant anatase phase.
However, large particle size is detected for samples TiFe10, TiFe15
and TiFe20 that exhibit predominant rutile phase.
3.2. Surface characterization
The surface parameters indicated in Table 1 represent a drastic
increase in surface area, pore volume and average pore radius for
the samples embedded small content of Fe2O3 up to 7%. Further
addition of Ferric oxide is associated by decrease in surface param-
eter which can be attributed to blocking of the porous system with
iron oxide particles and contribution of Fe2O3 to the total area of
the samples.
These results are confirmed from X-ray and TEM measurements
in which large reduction in grain size is detected for the mixed
oxide samples. The textural measurements realize the influence
of ferric oxide in increasing the surface area of the oxide samples.
3.3. FTIR measurements
Fig. 3 depicts FTIR spectrum of TiO2, TiFe1, TiFe2, TiFe5, TiFe7,
TiFe10, TiFe15 and TiFe20 samples. The spectrum displays two
characteristics broad band centered at 3480 and 1620 cm1 which
are referring to the stretching and bending modes of vibrations of
physical adsorbed water and hydroxyl group exist on the oxide
surfaces [42,43]. These bands are very essential for photocatalytic
degradation process since they can react with photoexcited holes
exist on the catalyst surface and form hydroxyl radicals that in-
crease the oxidizing power of the samples. A remarkable broad
band centered at 640 cm1 is detected which are associated with
the stretching mode of vibrations of bridged Ti–O bonds is ob-
served for pure titanium oxide [41]. It is should be emphasizing
to notice two bands at 1400 and 1050 cm1 which assigned to
Ti–O–Fe bond. The band located at 1200 cm1 is detected
Ti–O–Ti bending mode [22]. A small shoulder band at 470 cm1
TiFe20
TiFe15
TiFe10
TiFe7
TiFe5
Transmittance
(a.u.)
TiFe2
TiFe1
TiO
2
0 500 1000 1500 2000 2500 3000 3500
-1
Wave number (cm )
Fig. 3. FTIR of TiO2, TiFe1, TiFe2, TiFe5, TiFe7, TiFe10, TiFe15 and TiFe20.
 M.A. Ahmed et al. / Journal of Alloys and Compounds 553 (2013) 19–29
Fig. 4. FESEM of TiO2, TiFe1, TiFe2, TiFe5, TiFe7, TiFe10, TiFe15 and TiFe20.
attributed for Fe–O bond is detected in all samples indicating the
existence of crystalline ferric oxide. The sample contain different
proportion of ferric oxide exhibit some small bands at 1050 cm1
which are attributed to ferric oxide [44]. The lack of C–H and
N–H bands reflected the complete decomposition of template
agent during the progress of calcination.
3.4. Field emission electron microscope
Fig. 4 depicts FESEM images of pure titania and Fe2O3/TiO2 sam-
ples. The micrograph of pure titania indicates the existence of large
number of spherical particles aggregations that dispersed homog-
enously through the matrix of the oxide. On careful examining
Fig. 4, one can notice that the morphology of the samples is very
sensitive to the Fe2O3 content in each sample. The existence of var-
ious ferric oxide contents deforms the degree of homogeneity of
the system and large number of particles with various shapes is de-
tected. The micrograph of the samples contain 1–7 wt.% Fe2O3 indi-
cates the existence of small spherical particles similar to those
observed for parent titania, in addition to various irregular particle
agglomeration that results from the incorporation of Fe2O3 into
titania structure. However, the images for the sample TiFe10,
TiF15 and TiFe20 indicate the formation of irregular large particles
23
aggregation which results from phase transformation of small ana-
tase to large rutile crystallites. These results indicate that the
amount of Fe2O3 (10–20) wt.% is sufficient to induce the anatase–
rutile transformation and increasing the particle growth as con-
firmed from XRD analysis.
3.5. EDX analysis
The EDX analysis is performed and represented in Fig. 5 to
investigate the elemental composition of Fe2O3/TiO2 nanoparticles.
The EDX spectrum exhibits various intense peaks which are asso-
ciated with Ti, O and Fe atoms. The composition of elements in
the mixed oxide samples is in agreement with those proposed in
the preparation progress.
3.6. Transmission electron microscope
Fig. 6 illustrates the TEM images of the oxide samples embedded
various ferric oxide content in which large number of fine nanopar-
ticles of various sizes ranging (6–51) nm are detected. The precise
analysis of TEM image indicates the existence of nanorods for sam-
ples TiO2 and TiFe1. However, other samples embedded high con-
tent of Fe2O3 contains particles of between rods and sphere
24 M.A. Ahmed et al. / Journal of Alloys and Compounds 553 (2013) 19–29

Fig. 5. EDX spectrum of TiO2, TiFe1, TiFe2, TiFe5, TiFe10 and TiFe20.

shapes. These particles arranged in several clusters embedded var-
ious mesopores of different dimensions. On careful examining the
TEM images, one can observe a progressive reduction of particle
size upon increasing in iron oxide content up to 7 wt.%. It is should
be emphasized that the existence of iron oxide control not only the
crystallite size but also the particles shape. The data obtained from
the TEM are in excellent agreement with those calculated based on
the XRD data.
3.7. Optical properties
Fig. 7 displays the UV–Vis absorption spectrum of pure TiO2 and
the samples embedded various Fe2O3 contents. The spectrum of
titania shows a definite absorption band edge in the UV region at
350–400 nm which is attributed to photoexcitation from valence
band to conduction band. It is interesting to notice that the sam-
ples embedded various iron oxide contents can significant exhibit
 M.A. Ahmed et al. / Journal of Alloys and Compounds 553 (2013) 19–29
Fig. 6. TEM of TiO2, TiFe1, TiFe2, TiFe5, TiFe7, TiFe10, TiFe15 and TiFe20.
red shift to higher wave length, this shift increases with increasing
Fe2O3 contents reveling the role of iron oxide in extending the sam-
ple absorption to visible region. On careful examining Fig. 7, one
can notice the disappearance of Fe2O3 bands which is usually exist
around 500 nm reveling that the majority of ferric oxide is incorpo-
rated in titania lattice.
The energy gap (Eg) which is the difference between filled
valence band and empty conduction band is considered one of
the important parameters that investigate the region of sample
absorption.
The energy gap (Eg) is calculated from the equation
ðahcÞ2 ¼ Aðhc  Eg Þn
where a is the absorption coefficient, A is a constant. n = 2 for direct
transition and n = 1/2 for indirect transition. An extrapolation of the
linear region of a plot of (ahc)2 versus (h) gives the value of the
optical energy gap (Eg) as represented in Fig. 8. The values of Eg,
estimated for the samples by extrapolating the linear portion of
the curve to (ahc)2 = 0, are 3.36, 3.32, 3.29, 3.26, 3.21, 3.17, 3.12
and 3.08 eV for the pure titanium oxide and the samples embedded
1, 2, 5, 7, 10, 15 and 20% Fe2O3, respectively.The general relationship
25
between the band gap energy Eg (eV) of a titanium oxide and its
wavelength k (nm), is given by the following equation
k ¼ 1240=Eg
From the above equation, it follows that the wider the band gap
Eg (eV), the lower the wavelength of absorption k (nm) will be de-
tected. The band gap energy results indicates that the incorpora-
tion of titania with various proportion of ferric oxide cause a
remarkable reduction in band gap energy that induced a red shift
of the sample photoexcitation response to visible region. It is gen-
erally accepted that most of transition metal energy levels exist be-
tween valence and conduction band of titania. Therefore, a possible
electronic transition from Fe3+ energy level to titania conduction
band is considered a main reason for reducing the band gap energy
and shifting the absorption response to visible region [Scheme 1].
Moreover, from XRD analysis, the results indicate the rapid trans-
formation of anatase–rutile form for the samples embedded
10–20 wt.% Fe2O3 and the sample exhibits 20 wt.% Fe2O3 is
completely exists in rutile form. This crystalline transformation
can be considered another reason for shifting band absorption to
visible region, since the rutile form exhibits low band gap energy
26 M.A. Ahmed et al. / Journal of Alloys and Compounds 553 (2013) 19–29

5.5

5.0 TiO2
TiFe1 1
4.5 Initial dye
TiFe2 concentration
4.0 Under dark condition
TiFe5
After exposure to UV
3.5 TiFe7 10 min
Absorbance

3.0 TiFe10 20 min

(a.u.)

TiFe15

Absorbance
30 min
2.5 TiFe20 40 min

(a.u.)
50 min
2.0
60 min

1.5

1.0

0.5

0.0

300 400 500 600 700

Wave length (nm) 0
500 600 700 800
Fig. 7. UV–visible spectra of TiO2, TiFe1, TiFe2, TiFe5, TiFe7, TiFe10, TiFe15 and
TiFe20. Wave number (nm)
Fig. 9. Photodegradation of methylene blue dye over TiFe7.

TiO 2
100
1500 TiFe1
TiFe2 90
TiFe5
TiFe7 80
TiFe10
1000 70
TiFe15
(αhγ)2

TiFe20
Degradation rate

60
(%)

50
500
40
TiO2

30 TiFe1
TiFe2
TiFe5
0 20 TiFe7
2 3 4 TiFe10

(hγ) 10 TiFe15
TiFe20

Fig. 8. The relation between hc (eV) versus (ahc)2 for TiO2, TiFe1, TiFe2, TiFe5,
TiFe7, TiFe10, TiFe15 and TiFe20.
compared with the anatase phase. The optical experimental results
indicate that the incorporation of various iron oxide contents can
induce active photocatalyst in the visible region that can generate
large number of positive holes and negative electrons that are
responsible for degradation process.
3.8. Photocatalytic degradation of methylene blue dye
Methylene blue is one of the Hazardous organic dyes which
exist in the wastewater and cause serious environmental problems
[45]. We use this dye as model sample to evaluate the photocata-
lytic activity of the pure and mixed oxide samples. The photocata-
lytic experiments were carried on the catalyst samples with
definite dye concentration (1  105 mol/l) in attempts to compare
0
0 10 20 30 40 50 60 70
Time (min)
Fig. 10. The variation of photocatalytic degradation (%) of methylene blue dye over
TiO2, TiFe1, TiFe2, TiFe5, TiFe7, TiFe10, TiFe15 and TiFe20 samples with time of
irradiation (min).
the efficiency of the various catalysts and select the most active
sample. The concentration of methylene blue dye is estimated
using the linear part of the absorbance-concentration curve (Beer’s
Law). Fig. 9 depicts the absorption spectra of the sample TiFe7 that
considered the most active photocatalyst in the degradation
process. The high adsorption capacity of the sample can be inferred
from the large amount of dye removal (30%) under the dark
conditions before exposure to UV irradiation. Fig. 10 displays the
variation of the photocatalytic activity of the samples embedded
 M.A. Ahmed et al. / Journal of Alloys and Compounds 553 (2013) 19–29 27

various molar compositions of ferric oxide determined at the 3.2

maximal absorption wavelength of methylene blue (664 nm) with 3.0
the time of irradiation. On careful examining of this figure, one can TiO2
2.8
notice a remarkable increase in the photocatalytic activity of the TiFe1
2.6
samples up to 7% followed by decrease in activity of the samples TiFe2
embedded 10, 15 and 20 mol.% that exhibit lower activity 2.4
TiFe5
compared with pure titania sample. 2.2
TiFe7
Fig. 12 indicates that the photocatalytic degradation of 2.0
methylene blue obeys the first-order decay kinetics. The photocat- TiFe10

LnCo/Co-Ct
1.8
alytic degradation rate of dyes in heterogeneous photocatalytic TiFe15
1.6
systems under UV-light illumination can followed the Langmuir– TiFe20
Hinshelwood equation [44–46] that can be illustrated as. 1.4
1.2
ln C 0 =C ¼ kKt ¼ kappt 1.0
0.8
Plotting ln (C0/C) versus t gives the apparent rate constant for
0.6
degradation of methylene blue from the slope of curve fitting line
and the intercept is equal to zero. Meanwhile, the linear relation- 0.4
ship between ln (C0/C) and t indicates that the photo-catalytic 0.2
degradation reaction also follows imply the pseudo first- order 0.0
reaction, the apparent rate constants were calculated to be 0 10 20 30 40 50 60
0.0134, 0.0175, 0.0233, 0.028, 0.042, 0.0096, 0.0081 and Time (min)
0.0064 min1 for pure TiO2, TiFe1, TiFe2, TiFe5, TiFe7, TiFe10, TiFe15
and TiFe20 catalysts, respectively. On careful examining Fig. 13 and Fig. 11. The pseudo first order kinetics of degradation of methylene blue dye over
Fig. 11. one can deduce a direct relationship between increasing a TiO2, TiFe1, TiFe2, TiFe5, TiFe7, TiFe10, TiFe15 and TiFe20 samples with time of
irradiation (min).
photocatalytic degradation of methylene blue dye with decreasing
in particle size down to 7 nm and increasing the surface area up
to 182 m2/g that is associated with increase Fe2O3 contents up to
7 wt.%. 60
The heterogeneous photocatalytic process is usually involves
partial or complete mineralization of the organic dyes by the active 50
species exist on the surface of titanium oxide. Once titanium oxide
is illuminated with UV-light energy, the electrons are excited from
40
lower valence band to higher conduction band which lead to
particle size

formation of positive hole and negative electron on the catalyst

30
(nm)

surface. The hole reacts with water or hydroxyl ions thus produc-
ing hydroxyl radicals. Electron in the conduction band (e CB ) on
the catalyst surface can reduce molecular oxygen to superoxide an- 20
ion. Hydroxyl (HO), hydrogen peroxides (HO2 ) and superoxide
(O2 ) radicals are considered the reactive species that will oxidize 10
the organic compounds adsorbed on the oxide surface [47,48].
These generated radicals, which further react with a dye or other
0
organic compound producing a whole range of intermediates 0 5 10 15 20
including radical and radical cations to achieve complete mineral- Fe2O 3 (wt%)
ization with the formation of carbon dioxide, water, and inorganic
nitrogen with nitrate ion. Fig. 12. The variation of Fe2O3 content (wt.%) with particle size (nm).
The photocatalytic activity of TiO2 in degradation process de-
pends on many factors: the adsorption of dye on catalyst surface,
band-gap energy, surface area, particle size, crystallinity, and elec-
tron–hole recombination rate [49–52]. The restriction of titania 0.04

absorbance to UV region only and the fast recombination of charge

carriers that in competition with the reactions decomposing the 0.03
Rate constant

hazardous dye are considered the main obstacles in applying tita-

(min )
-1

nia in several industrial processes. Modifying the electronic struc- 0.02

ture of titania with transition metal ions is considered an essential
key in extending the sample absorption to visible region and pre-
0.01
venting the electron–hole recombination. Fe3+ is considered one
of the promising ions in improving the optical features of the sam-
0.00
ple owing to its multivalence electronic nature. Ambrus et al. re- 0 5 10 15 20
port that incorporation of 3% iron oxide on titania improves the F e 2O 3
(w t% )
photocatalytic degradation of phenol under UV irradiation [53].
Zhao et al. indicate that loading titania with ferric oxide affect Fig. 13. Variation of Fe2O3 content with rate constant for degradation of methylene
the photocatalytic features of the samples depending on its blue dye.

contents [54]. The detailed reaction steps are postulated by several

authors who explain the role of the existence of low and high in the degradation process [53,55–57]. They postulate that at low
concentration of iron oxide on formation of radicals that involve Fe2O3 concentration, Fe3+ species acting as h+/e traps, that prevent
28 M.A. Ahmed et al. / Journal of Alloys and Compounds 553 (2013) 19–29
Scheme 1. Suggested electronic transition between TiO2 and Fe2O3.
electron–hole recombination and improve the optical features of
titania as represented and suggested by Zhou et al. and Huang
et al. [56,57]
Fe3þ þ e ! Fe2þ
Fe2þ þ O2 ðadsÞ ! Fe3þ þ O2
4þ 3þ
Fe2þ þ Ti ! Fe3þ þ Ti
þ
Fe3þ þ hvb ! Fe4þ
Fe4þ þ OH ! Fe3þ þ HO
The existence of high Fe2O3 concentration permits Fe3+ ions to
act as recombination centers as suggested by Zhu et al. [58]:
Fe3þ þ e ! Fe2þ
þ
Fe2þ þ hvb ! Fe3þ
It is interesting to mention that coupling Fe2O3 (Eg = 1.9 eV) with
TiO2 (Eg = 3.2 eV) UV excitation, an electron from the anatase TiO2
and Fe2O3 may be promoted from the valence band (e
cb ) to the con-
þ
duction band, leaving behind a hole in the valence band (hVB ). As the
position of conduction band of Fe2O3 is lower than that of TiO2, it
can be act as photoelectronic receiver as represented in Scheme 1.
The photogenerated electrons of the TiO2 conduction band will be
transferred to the conduction band of Fe2O3 [59]. Since the holes
move in the opposite direction from the electrons, photogenerated
holes will be exist on titania surface which improve the charge sep-
aration [21,43]. The positive holes in the valence band be react with
OH or H2O species exist on the catalyst surface, producing reactive
hydroxyl radicals. The photo-generated electrons exist on the sur-
face of Fe2O3 could be rapidly transferred to molecular oxygenO2
to form the superoxide radical anion O 2 and hydrogen peroxide
H2O2 [18,21]. Moreover, hydroxyl radical OH, can be formed
through reaction between intermediates which is responsible for
the decomposition of MB.
It is clear from our experimental results that introduction of
appropriate amount of iron oxide (1–7 wt.%) is associated with
exceptional increase in photocatalytic degradation of the dye.
Nearly complete mineralization of methylene blue is observed over
the sample embedded 7 wt.% Fe2O3 revealing the successful role of
iron oxide in improving the optical features of titania. It is should
be emphasized that the nature of crystalline phase, particle size,
surface area and optical activity are the responsible factors that
influencing the decolorization of the dye. The precise control of
preparation route and the existence of template are the main cause
for obtain high surface oxide which in turn increase the number of
attractive sites available for dye adsorption. The experimental re-
sults indicate removal of about 30% of dye under dark conditions
reveling the high reactivity of the sample surface for dye decolor-
ization through adsorption process. The optical results indicate
that the existence of Fe2O3 is associated with narrowing in band
gap energy and shifting the absorption response to the visible re-
gion which in turn a primary cause for enhancing the photocata-
lytic reactivity of the mixed oxide samples. The photocatalytic
reactivity of the sample increases with increasing in Fe2O3 due to
increasing in surface area, reduction in particle size, reduction in
band gap energy and existence of anatase phase. However, on
increasing iron oxide (10–20 wt.%), there is a remarkable decrease
in the photocatalytic activity of the sample and the samples exhibit
15 and 20 wt.% is less reactive than pure titania, despite there is
still increase in absorption response of these three samples. This
pronounced reduction in decolorization rate can be attributed to
simultaneous transformation of anatase–rutile phase which h is
catalytic inactive for degradation process. The predominant exis-
tence of rutile phase is accompanied by increase in particle size
and decreases in surface area which in turn decrease the area ex-
posed to the degradation process and lead to reduce the dye
mineralization.
4. Conclusions
High surface area Fe2O3/TiO2 nanoparticles containing various
proportion of Fe2O3 (0–20) wt.% were successfully synthesized
using sol–gel and self assembly approach for photocatalytic degra-
dation of methylene blue dye. The introduction of an appropriate
amount of Fe2O3 (1–7 wt.%) is associated with shifting the physico-
chemical and optical features of samples toward more favorable
 M.A. Ahmed et al. / Journal of Alloys and Compounds 553 (2013) 19–29
state. XRD and FTIR results indicate the absence of crystalline ferric
oxide phases reveling the dissolution in titania crystalline phases
or existence as amorphous layers. A drastic decrease in crystallite
size to 7 nm and increasing the surface area up to182 m2/g is
accompanied by introduction of Fe2O3 up to 7 wt.%. Further loading
the sample to 20% Fe2O3 accelerates the anatase–rutile transforma-
tion which leads to a pronounced reduction in surface area and
increasing the crystallite size. The samples embedded Fe2O3 (1–
7 wt.%) content exhibit higher photocatalytic activity compared
with pure titania, however the samples contain higher Fe2O3
(10–20 wt.%) content possess low activity due to the predominant
existence of rutile phase which is optically inactive. Benefiting
from the simple sol–gel preparation route and exceptional photo-
catalytic activity under UV light, the synthesized Fe2O3/TiO2 nano-
particles may be promising candidate for practical application in
the field of photocatalysis.
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