Journal of Photochemistry and Photobiology B: Biology 133 (2014) 9098

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Journal of Photochemistry and Photobiology B: Biology

journal homepage: www.elsevier.com/locate/jphotobiol

Visible light catalysis of rhodamine B using nanostructured

Fe2O3, TiO2 and TiO2/Fe2O3 thin lms
M.A. Mahadik a, S.S. Shinde a, V.S. Mohite a, S.S. Kumbhar a, A.V. Moholkar a, K.Y. Rajpure a, V. Ganesan b,
J. Nayak b, S.R. Barman b, C.H. Bhosale a,
a
b

Electrochemical Materials Laboratory, Department of Physics, Shivaji University, Kolhapur 416 004, MS, India
UGC-DAE Consortium for Scientic Research, University Campus, Khandwa Road, Indore 452017, Madhya Pradesh, India

a r t i c l e

i n f o

Article history:
Received 22 September 2013
Received in revised form 26 December 2013
Accepted 28 January 2014
Available online 12 February 2014
Keywords:
TiO2/Fe2O3 thin lms
Photocatalysis
Rhodamine B

a b s t r a c t
The Fe2O3, TiO2 and TiO2/Fe2O3 composite lms are deposited using spray pyrolysis method onto glass
and FTO coated substrates. The structural, morphological, optical and photocatalytic properties of
Fe2O3, TiO2 and TiO2/Fe2O3 thin lms are studied. XRD analysis conrms that lms are polycrystalline
with rhombohedral and tetragonal crystal structures for Fe2O3 and TiO2 respectively. The photocatalytic
activity was tested for the degradation of Rhrodamine B (Rh B) in aqueous medium. The rate constant
(k) was evaluated as a function of the initial concentration of species. Substantial reduction in concentrations of organic species was observed from COD and TOC analysis. Photocatalytic degradation effect is
relatively higher in case of the TiO2/Fe2O3 than TiO2 and Fe2O3 thin lm photoelectrodes in the degradation of Rh B and 98% removal efciency of Rh B is obtained after 20 min. The photocatalytic experimental
results indicate that TiO2/a-Fe2O3 photoelectrode is promising material for removing of water pollutants.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Many organic dyes are toxic, carcinogenic and are found in
industrial wastewater which causes the signicant hazard to human health and environmental pollution control [1]. It is important
to remove the organic dyes from the wastewater. Nowadays various wastewater treatment methods have been explored but among
these the advanced oxidation processes (AOPs) have proved to be
effective for the degradation of pollutants [2]. TiO2 is a commonly
used photocatalyst due to its easy availability, low price and chemical stability. The major drawback of TiO2 is that, its large band gap
(3.2 eV) which absorbs only 4% of sunlight from solar spectrum [3].
Accordingly, many efforts have been made to extend the absorbance of TiO2 to visible light by doping the transition metal and
nanocomposites [4]. Recently, the research has been focused on
degradation of organic compounds present in wastewater using
multilayered photocatalysis which are based on the generation of
highly reactive and oxidizing hydroxyl radicals [5]. One of the
alternative ways, to enhance visible light photocatalytic activity
of semiconductors is by doping it with non-metal elements [6] or
by heterojunction and composite photoelectrodes [79]. Presently,
most study focus on developing TiO2/Fe2O3 powder photocatalyst
by various methods. However, there are some drawbacks of use
Corresponding author. Tel.: +91 231 2609435; fax: +91 231 2691533.
E-mail address: chbhosale@gmail.com (C.H. Bhosale).
http://dx.doi.org/10.1016/j.jphotobiol.2014.01.017
1011-1344/ 2014 Elsevier B.V. All rights reserved.

the powder photocatalyst during the photocatalytic process [10]:

(a) separation of powder from water is difcult; (b) the suspended
powder tends to aggregate especially at high concentrations.
Therefore, developing the TiO2/Fe2O3 photocatalyst in the form of
thin lm is of obvious practical signicance. In the TiO2/Fe2O3
charge transport is key step for increasing the photocatalytic efciency. This might be due to at band potential of Fe2O3 is 0.32 V
versus NHE and a band gap of 2.2 eV, so it can be considered to
be a sensitizer for TiO2. When the TiO2/Fe2O3 composite lm [11]
was irradiated with visible light, the electrons in the valence band
of Fe2O3 layer are excited to the conduction band, leaving holes in
the valence band. As a consequence, electrons in the valence bands
of TiO2 injected into Fe2O3 layer driven by the built-in eld in TiO2/
Fe2O3 layered thin lms. Thus charge transport between the
valence bands of Fe2O3 and TiO2 is an effective process for the photocatalytic activity, because it increases the electronhole recombination time.
These thin lms can be prepared on the glass and FTO coated
glass substrate by various deposition techniques like solgel method, chemical vapor deposition, electrodeposition and chemical
spray pyrolysis [12]. Among these methods, the spray pyrolytic
decomposition method (SPD) has many advantages as simplicity,
low cost, layered and large area depositions are possible with easily adjusting various deposition parameters to prepare homogeneous thin lms [13].

M.A. Mahadik et al. / Journal of Photochemistry and Photobiology B: Biology 133 (2014) 9098

In present work a set of Fe2O3, TiO2 and TiO2/Fe2O3 multilayered

thin lms on amorphous and FTO coated glass substrates have been
synthesized. The deposited thin lms are characterized by the PEC,
XRD, UVVis spectroscopy, scanning electron microscopy, Raman
and X-ray Photoelectron Spectroscopy techniques. The photoelectrocatalytic degradation of rhodamine B dye has been investigated
with Fe2O3, TiO2 and TiO2/Fe2O3 multilayered photocatalysts in
the presence of visible light illumination. A mechanism of photodegradation and improvement in photocatalytic activity of TiO2/
Fe2O3 is also proposed.
2. Material and methods

from backside using visible light with the active surface area of the
electrode in contact with the pollutant species. The external bias
voltage of 1.5 V was applied in order to increase the rate of reaction
using the Amel-2059 potentiostat. The 1 mM Rh B in aqueous electrolyte was used as a model organic species. The electrolyte was recirculated through the single PEC reactor with a constant ow rate
14.4 l/h using a Gilson MINIPLUS peristaltic pump, France with silicon tubing. The schematic diagram of photoelectrochemical degradation experiment is shown in Fig. 1. The specic amount of
sample was withdrawn from the reaction mixture at specic interval of time; the concentration of impurities in the solution was
determined by measuring the extinction spectra.

2.1. Materials synthesis

3. Results and discussion

The Fe2O3 and TiO2 thin lm photoelectrodes were deposited on

large area (10 cm  10 cm  0.125 cm) FTO coated glass substrates
(with sheet resistance of 1020 X cm2) by spray pyrolysis method
at optimized temperatures 400 and 470 C respectively. Similarly
the TiO2/Fe2O3 thin lms were deposited by spraying methanolic
solution of Titanyl acetylacetonate (TiAcAc) (C10H14O5Ti) (AR
grade, 99.9% pure, Merk made, Germany) on pre-deposited Fe2O3
thin lms by 0.1 M ethanolic solution of FeCl36H2O. The compressed air was used as a carrier gas at constant spray rate of
4.5 cc/min. The synthesis of the TiO2 layer has been reported elsewhere [14] and thickness of around 25 nm was chosen. All lms
are annealed at 500 C in air for 2 h after deposition.

3.1. Structural analysis

2.2. Catalyst characterization

The structural characterization of annealed thin lms was carried out, by analyzing the X-ray diffraction patterns obtained using
Bruker powder diffractometer (AXS) Analytical Instruments Pvt.
Ltd., Germany, Model :D2 Phaser (k = 1.5406 for Cu Ka). The surface morphology of the lms, grain size and distribution of grains
were examined by JEOL, Japan made scanning electron microscope
(SEM) model JSM-6360. The morphology of the deposited lms
was further examined by using atomic force microscopy (AFM,
Digital Instrument, Nanoscope III) operated at room temperature.
AFM images were collected in contact mode on a molecular imaging system using a silicon nitride cantilever. The optical absorption
study was carried out using Shimadzu UV-1800 spectrometer, Germany. Raman scattering spectrum was recorded in air at room
tempera-ture with micro Raman system from Jobin Yvon Horibra
LABRAM-HR visible within 100800 cm1. The Raman spectra
were excited using the HeNe 632 nm laser source with 600 and
1800 lines/mm gratings and CCD detector. The thickness was measured using Steller Net Inc. USA spectroscopic reectometer having
UVVis light source with CCD detector. The XPS measurements on
TiO2/Fe2O3 thin lms were performed after mounting them on a
multi-purpose sample holder [15] using Al Ka X-ray source and
Phoibos 100 analyzer from Specs GmbH, Germany. The samples
were lightly sputtered by Ar+ ions to remove the contamination
due to exposure to air. Some XPS measurements were also performed using ESCA + from Omicron Nano Technology, Germany.
The specic heat capacity and thermal conductivity was measured
by using CT meter made by Teleph. Pvt. Ltd., France.
2.3. Photoelectrocatalytic degradation
In order to study photocatalytic activity, the large area
(100 cm2) Fe2O3, TiO2 and TiO2/Fe2O3 thin lms were used as photoelectrodes in separate set of experiments. The lms are used as
photoanode and stainless steel disc as a cathode kept at a distance
of 0.1 cm facing the photoanode. The photoanode was illuminated

91

The X-ray diffraction patterns of Fe2O3, TiO2 and TiO2/Fe2O3 multilayer photoelectrodes are shown in Fig. 2. It is seen that, all the
lms are polycrystalline in nature. The diffraction peaks of Fe2O3
agree well with the hematite phase (JCPDS cards 33-0664) with
rhombohedral crystal structure. It is seen that lms preferred orientation along (1 0 4) and (1 1 0) for Fe2O3. The peaks at 2h = 25.46 and
38.17 in the spectrum of TiO2 are easily identied as the crystal of
anatase form (JCPDS card No 71-1119). Based on Scherers equation,
the mean crystalline size of the a-Fe2O3 and TiO2 lms was 52 and
28 nm, respectively. All the diffraction peaks of the TiO2/Fe2O3 multilayered thin lms could be indexed to the hematite phase of Fe2O3
and anatase phase of TiO2, there is no considerable peaks related to
FeTi composition phases were observed in the pattern, which is in
accord with the results reported by Zhao et al. [16].
3.2. Morphological study
Figs. 3 and 4 show SEM and AFM images of Fe2O3, TiO2 and TiO2/
Fe2O3 multilayered thin lms respectively. Images show that
deposited lms are uniform and compact. The surface morphology
of TiO2/Fe2O3 lm is slightly different than pure Fe2O3 and TiO2
thin lms. It can be explained that the different morphologies of
the lms might be related to the lattice structure and defects generated during deposition governed the chemical adsorption, subsequent nucleation and growth.
3.3. UVVisible spectroscopy
The Fig. 5(a and b) shows UVVis absorption and transmittance
spectra of Fe2O3, TiO2 and TiO2/Fe2O3 thin lms respectively. For
Fe2O3 and TiO2 thin lms, absorption edge is in the range 360
300 nm and 600450 nm respectively. In TiO2/Fe2O3 the absorption edge shifts towards the higher wavelength side than pure
TiO2 indicating the red shift. The direct band gap energy is calculated using equation:

a0 hm  Eg n
hm

The band gap energy (Eg) is determined by extrapolating

straight line portion of (ahm)2 versus hm spectrum to a = 0. Where
a and hm are absorption coefcient of the lm and the incident
photon energy respectively. There are two straight line portions
are observed in the graph with intercepts at two energy values,
suggesting direct allowed transitions at these energies. The optical
energy gap energy for Fe2O3, TiO2, TiO2/Fe2O3 lms is shown in inset of Fig. 5(a). Also, estimated values of band gap energies of Fe2O3
and TiO2/Fe2O3 are listed in the Table 1. The absorption in the visible region is enhanced signicantly in TiO2/Fe2O3 lm than Fe2O3

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(214)

(116)

3.4. Raman spectroscopy

TiO2 /Fe2O3

TiO2

(214)

(116)

(024)

(113)

(110)

(104)

(200)

(101)
(021)

Intensity (a.u.)

(024)

(110)

of chargecarrier separation and extends the range of the TiO2 photoresponse from ultraviolet to visible region due to the low band
gap of 2.2 eV of Fe2O3 [21].
(113)

(104)

(021)
(101)

Fig. 1. Schematic diagram of photoelectrochemical degradation experiment.

Fe2O3
20

30

40

50

60

70

80

2 (Degree)
Fig. 2. X-ray diffraction patterns of Fe2O3, TiO2 and TiO2/Fe2O3 photoelectrodes
deposited on glass substrates.

and TiO2 thin lms. This indicates TiO2/Fe2O3 lm has smaller band
gap energy than that of pure TiO2. The signicant red-shift with
lower band energy of TiO2/Fe2O3 lm comparing with the TiO2 lm
may be due to the difference in the surface states [17]. Fig. 5(b)
shows all spectra have well-known transmission trends for aFe2O3 [18], TiO2 [19] and TiO2/ Fe2O3 independent from the lm
thickness of lms. The emission signal originates from the charge
transfer transition iron ions create slightly different than pure
Fe2O3. This is due to Fe3+ have half-lled electronic conguration
and can act as a trapping site for temporary photo-generated electron or hole and inhibits the recombination which enhances their
lifetime. It was found that the highly transparent TiO2 coatings
did not affect the optical characteristics and behaviors of the
TiO2/a-Fe2O3 lms [20]. The enhanced ability to absorb visiblelight of this type of TiO2/Fe2O3 makes them promising photovoltaic
devices. The enhanced photoelectrochemical behavior can be
attributed to the modied Fe2O3 which increases the probability

The structure and local symmetry of lms is studied with the

Raman spectroscopy. The Raman spectra of TiO2, Fe2O3 and TiO2/
Fe2O3 lms are taken at room temperature in the range of 100
800 cm1 as shown in Fig. 6. The spectrum of the thin lm obtained
does not show signal from the substrate. Thus Raman spectra obtained were not interfered by the glass substrate. Raman spectra
of TiO2 thin lm show four peaks at 142, 197, 397, 517 and
635 cm1 respectively which are due to symmetric vibration
modes (A1g + 2B1g + 3Eg) of tetragonal anatase phase of TiO2. These
peaks are identied at 142 (Eg), 197 (Eg), 394 (B1g), 515 (B1g) and
639 cm1 (Eg) [22] and are shown in table 2. The differences with
data reported in the literature are reasonable due to the structural
distortions into the thin lm or by intra- grain defects in samples
[23]. The Raman peaks are observed at 226, 245, 293, 298, 412,
500, and 612 cm1 for Fe2O3 thin lm which correspond to hematite phase [24]. The peak corresponds to 226 (A1g), 245 (Eg), 293
(Eg), 298 (Eg), 412 (Eg), 500 (A1g) and 612 cm1 (Eg) which are due
to the TO modes shown into the brackets. The signicant difference
between the Raman spectra of Fe2O3 and TiO2/Fe2O3 lms is the
presence of a gradual enhancement in the peak intensity relative
to the Fe2O3 lm along with relatively strong peak at 660 cm1.
This peak has been attributed to either of magnetite/maghemite
[25] or disorder. In case of TiO2/Fe2O3 lms, Raman peak intensity
is higher than Fe2O3 lms, might be due to formation of smaller
grains size at the surface of TiO2/Fe2O3 lm and also net structural
disorder as shown from AFM images.
3.5. X-ray photoelectron spectroscopy
X-ray photoelectron spectroscopy (XPS) is performed to study
the structural and chemical state of the elements present in thin
lms. Figs. 7(a) and 8(a) shows the survey scan of Fe2O3 and
TiO2/Fe2O3 thin lms deposited on glass substrates. Figs. 7(cd)
and 8(b) indicates the core level XPS spectra of typical Fe2O3 and

M.A. Mahadik et al. / Journal of Photochemistry and Photobiology B: Biology 133 (2014) 9098

Fig. 3. SEM images of (a) Fe2O3, (b) TiO2 and (c) TiO2/Fe2O3 multi-layered thin lms.

Fig. 4. AFM images of (a) Fe2O3, (b) TiO2 and (c) TiO2/Fe2O3 multi-layered thin lms.

93

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M.A. Mahadik et al. / Journal of Photochemistry and Photobiology B: Biology 133 (2014) 9098

(a) 4

TiO2

TiO2/Fe2O3

Fe2O3

Eg

TiO2 /Fe2O3

6
4
2
0
2.0

2.5

3.0

3.5

Energy (h)

TA+ TO

TA+ TO

Eg

20000
B1g

E1g

A1g

TiO2

Eg
A1

100

400

500

600

700

800

Wavelength (nm)

60

Fe2O3

40

TiO2 / Fe2O3

20

400

500

600

700

300

400

500

TA+ TO

Fe2O3

600

700

Raman shift (cm -1 )

the oxides [27]. Therefore the XPS studies indicate iron in Fe3+
and oxygen in O2 chemical states; conrming the formation of
Fe2O3. The XPS results of Fe2O3 thin lms indicated that the surfaces of the lms contained Fe in Fe3+ state along with satellite
peak, conrms formation of Fe2O3 (hematite) which is in agreement with XRD results. The TiO2 layer with thickness of 25 nm
was selected for the XPS analysis in order to be sure to observe
the chemical composition of the TiO2/Fe2O3 interface. Fig. 6(d)
show peaks at 459.1 and 464.7 eV and are assigned to Ti (2p3/2)
and Ti (2p1/2) core levels. The difference between the Ti 2P core levels is 5.6 eV, indicating the normal state of Ti4+ in the anatase TiO2
[28]. The shoulder of the Ti (2p3/2) peak corresponds to a band at
459.1 eV. This band is assigned to formation of a TiOFe bond
in the interface of TiO2/Fe2O3 thin lm, which indicated the formation of TiO2/Fe2O3 [29]. Similar observation was also reported for
Fe2O3TiO2 coatings by Zhang and Lei [30].

80

TiO2

200

E1(TO)

A1

Fig. 6. Raman spectra of TiO2, Fe2O3 and TiO2/Fe2O3 thin lms.

(b) 100
Transmitance (% T)

A1 (2LA)

TiO2 / Fe2O3

30000

Eg

0
300

E1(TO)

10000

0
300

A1
A1

TiO2

Intensity (Counts/s)

Fe2O3

(h)2 , 1010 (ev cm2)

Absorbance (a.u.)

Eg

40000

10

800

Wavelength (nm)
Fig. 5. (a) The absorption spectra of the Fe2O3, TiO2 and TiO2/Fe2O3 thin lms and
inset shows plot of (ahm)2 versus hm and (b) Optical transmission spectra of the pure
Fe2O3, TiO2 and TiO2/Fe2O3 thin lms.
Table 1
Variation of Band gap energy.
Sample name

Eg1 (eV)

Eg2 (eV)

Fe2O3
TiO2
TiO2/Fe2O3

2.18
3.0
2.61

2.37

2.79

TiO2/Fe2O3 thin lms. The doublet line of Fe corresponding to 2p3/2

and 2p1/2 are observed at about 724.21 and 712.6 eV, respectively
which is due to spinorbit splitting. For Fe 2p3/2 level the binding
energy (B.E.) values depend on the oxidation state of the iron: (i)
in metallic iron (Fe 0) state the BE of Fe 2p3/2 are in the range
706.7707.4 eV, (ii) in the Fe2+ state the range is 709.3710.0 eV,
and iii) in the Fe3+ state, the range is 710.6711.6 eV. Presence of
satellite peak at BE of 715716 eV conrms FeO formation and
presence of Fe2O3 at 719.0719.8 eV [26]. The iron oxide phases
are identied by the presence of this satellite peaks. Figs. 6(b)
and 7(c) shows O 1 s core level XPS spectra of typical Fe2O3 and
TiO2/Fe2O3 thin lms. The O 1 s peak is in the binding energy range
of 528535 eV. Oxygen can take two chemical states due to O2
and O
2 having BE about 530 and 731.5 eV respectively. The O1s
peak position is observed at 530.6 and 530.8 eV for Fe2O3 and
TiO2/Fe2O3 thin lms. This component is usually due to OH from
air or non-stoichiometric surface oxygen. The presence of peak at
about 530.8 eV can be assigned to the surface O2 possessed in

3.6. Thermal conductivity measurement

Fig. 9 shows the variation of specic heat and thermal conductivity for Fe2O3, TiO2 and TiO2/Fe2O3 lms. Thermal conductivity
and specic heat values for TiO2/Fe2O3 electrodes are relatively
higher than Fe2O3and TiO2 electrode as shown in Table 3. This
might be due to the signicant change in microstructure revealed
by morphological studies. The increase in thermal conductivity is
attributed to grain boundary conduction and decrease in thermal
conductivity is due to phonon conduction behavior in these lms
[31]. The total thermal conductivity in semiconductors consists
of the lattice and the electronic contribution. However the lattice
thermal conductivity is the dominant mechanism over a wide
range of carrier concentrations in semiconductors. Heat transfer
across materials of high thermal conductivity occurs at a faster rate
than across materials of low thermal conductivity. In accordance
with the WiedemannFranz Law equation as thermal conductivity
changes, the electrical conductivity varies in same manner. Thus
higher thermal conductivity may be helpful for improvement in
photocurrent which is important during the photoelectrocatalytic
degradation.
3.7. Photocatalytic activity of TiO2 /Fe2O3 photoelectrode thin lms
The PEC properties are investigated using a conventional
two-electrode system linked with the potentiostat (AMEL 2059).
The TiO2/Fe2O3 thin lm used as working and steel (SS) as counter
electrodes. The electrolyte was 10 mM HClO4 solution. In this
experiment the actual area of the working electrode in contact

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M.A. Mahadik et al. / Journal of Photochemistry and Photobiology B: Biology 133 (2014) 9098
Table 2
Comparison of symmetry modes in Raman spectra.
Our data frequency (cm1)

a-Fe2O3

TiO2

a-Fe2O3 /TiO2

226.46
246.44
293.11
300.53

142.67
197.77

397.73

518.06

637.09

142.67

227.17
245.87
292.54
300.82

411.72
496.22
610.26

659.50

410.01

610.40

660

Symmetry of modes

Reference data

Reference data

a-Fe2O3

TiO2

B1g
Eg
A1g
Eg
B1g
A1
B1g
A1g
A1g, B1g
Eg
Eg
A1g

226
245
293
298

412

612

142
197

394

515

[2124]

660

(b) 25,000

(a)

Reference number

531.2 eV

O1s

530.8 eV

Intensity (Counts/s)

Ti 2p
Fe2P

Intensity (Counts/s)

O KLL
FeLMM
FeLMM
FeLMM

20,000

C1s

15,000
531.6 eV

10,000

5,000

532.2 eV

0
1400

1200

1000

800

600

400

200

534

532

(c) 22400

(d)

Fe 2p3/2

22200

528

526

30000

Ti 2p3/2
25000

Intensity (Counts/s)

Intensity (Counts/s)

530

Binding Energy (eV)

Binding Energy (eV)

Fe 2p1/2
22000

21800

Ti 2p1/2
20000

15000

21600
10000
21400
740

730

720

710

700

Binding Energy (eV)

480

475

470

465

460

455

450

Binding Energy (eV)

Fig. 7. XPS spectrum of TiO2/Fe2O3 thin lm (a) survey spectrum, (b) O 1 s narrow scan spectrum, (c) Fe 2p narrow scan spectrum and (d) Ti 2p narrow scan spectrum.

with the electrolyte is about 64 cm2, and is exposed with the visible light irradiance of 100 mW/cm2 (tungsten lamp). Fig. 10 shows
the characteristics of the photocurrent versus applied potential (I
V curve) for the typical TiO2/Fe2O3 thin lms under light and
chopped conditions. It can be easily seen that for applied potential,
the photocurrent increases sharply and gives 10.5 mA photocurrent at 1.5 V applied bias. However, the dark current is found to increases after 1.8 V, therefore maximum applied potential should be
1.8 V without damage to photoelectrode. The plateau obtained

above 1.5 V may be due to long lifetime of the eh+, exhibiting a

high photocatalytic activity during photoreaction. Photocatalytic
activity of Fe2O3, TiO2 and TiO2/Fe2O3 thin lms was evaluated
by the photocatalytic degradation of rhodamine B dye. Thus TiO2/
Fe2O3 photoanode is an alternative way to improve the photocatalytic efciency and to prevent destruction of Fe2O3 thin lms during the degradation experiments. When photoanode is illuminated
by photons with energy higher than the band gap energy (Eg), a
large number of electrons are promoted from valence band (VB)

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M.A. Mahadik et al. / Journal of Photochemistry and Photobiology B: Biology 133 (2014) 9098

(a)

(b) 500000

Intensity (Counts/s)

Fe2p

O1s

400000

350000

300000

C1s

1400

1200

1000

Fe 2p3/2

450000

FeLMM

Intensity (Counts/s)

O KLL

Fe 2p1/2

800

600

400

250000

200

200000
740

735

730

Binding Energy (eV)

725

720

715

710

705

700

Binding Energy (eV)

(c) 140000

-2
O

O 1s

Intensity (Counts/s)

120000

100000
O- H

80000

60000

40000
540

535

530

525

520

515

Binding Energy (eV)

Fig. 8. XPS spectrum of Fe2O3 thin lm (a) survey spectrum, (b) Fe 2p narrow scan spectrum, (c) O 1 s narrow scan spectrum.

0.014
In dark
Under illumination
With chopping illumination

1000

0.012

Thermal conductivity
Specific heat

0.010
800

Current (A)

Thermal conductivity (mW/m.K),

specific heat (KJ/m3 K)

1200

600

0.008
0.006

400
0.004
200
0.002
0
Fe2O3

TiO2/Fe2O3

TiO2

Fig. 9. Variation of thermal conductivity and Sp. heat of Fe2O3, TiO2 and TiO2/Fe2O3
thin lms.

0.000
0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

E vs. steel (V)

Fig. 10. IV plots of TiO2/Fe2O3 catalysts used in single PEC reactor module with
0.1 M NaOH electrolyte.

Table 3
Variation in specic heat and thermal conductivity for pure Fe2O3 and TiO2 lms TiO2/
Fe2O3 thin lms.
Sample name

Thermal conductivity (W/m K)

Specic heat (kJ/m3 K)

Fe2O3
TiO2
TiO2/Fe2O3

326
387
499

858
947
1131

to the conduction band (CB) of Fe2O3 and holes are generated in valence band. The built-in eld in TiO2/Fe2O3 multilayer, electrons in
the valence bands of TiO2 is driven into the valence band of Fe2O3,
while photogenerated holes moved into the valence band of TiO2 in
an opposite direction [6]. In this way the charge transport between
valence bands of Fe2O3 and TiO2 is considered as effective process
for promoting the photocatalytic activity of the TiO2/Fe2O3 thin

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(a) 0.07

(b) 50

0 min

Fe2O3

30
Fe2O3

COD
TOC

0.06
40

COD (mg/L)

0.04
0.03

20
30
15
20
10

TOC (mg/L)

Extinction

0.05

25

0.02
10

0.01
320 min

0.00
200

300

400

500

600

700

5000

10000

15000

Time (sec)

Wavelength (nm)

(c) 0.06

0
20000

0
800

TiO2

(d) 60

0 min

18
TiO2

55

0.05

COD
TOC

15

COD (mg/L)

0.04
0.03
0.02

45
12

40
35

30

TOC (mg/L)

Extinction

50

25
0.01

20
60 min

0.00
400

15
0

450

500

550

600

650

5000

700

15000

20000

Time (sec)

Wavelength (nm)

(e)

10000

40

(f)

TiO2/Fe2O3

80

0.08

COD
TOC

TiO2 /Fe2O3

35

COD (mg/L)

0.06

0.04

70

30

60

25

0.02

TOC (mg/L)

Extinction

0 min

20

50
20 min

0.00

15
460 480 500 520 540 560 580 600 620 640

Wavelength (nm)

40
0

2000

4000

6000

8000 10000 12000 14000

Time (sec)
Fig. 11. Rhodamine B (Rh B) degradation on Fe2O3, TiO2 and TiO2/Fe2O3 thin lms under visible light illumination: (a, c, e) extinction spectra with illumination time as
parameter, (b, d, f) extent of mineralization by COD and TOC.

lm electrodes, because this result implies that the charge recombination is reduced in process of electron transport.
Fig. 11(a, c, e) shows the extinction spectra of 1 mM rhodamine B
dye taken at various intervals of time for Fe2O3, TiO2 and TiO2/Fe2O3
thin lm photoelectrodes respectively. Fig. 11(a) shows that the
extinction of RhB decreases rapidly for rst 30 min and then decreases slowly. To study the effect of the TiO2 on the photocatalytic
degradation of RhB, the TiO2/a-Fe2O3 with 25 nm thickness of TiO2
lm is was selected. These OH and O2 are key the parameters of
degradation process. The increase in thickness of TiO2 on Fe2O3 decreases photocurrent, which is might be due to increase in distance

of the electron and hole transfer from interface of lm to surface

and decrease in thickness of TiO2 layer can reduce the effective surface area of lm containing the TiOFe bond. In our case the optimal thickness of TiO2 on Fe2O3 thin lm was 25 nm which resulted
into synergetic photoactivity as compared to TiO2 and Fe2O3 thin
lms. This better photocatalytic activity of TiO2/Fe2O3 than uncoated Fe2O3 can be assign to formation of TiO2/Fe2O3 multilayer
thin lms. This fact conrms the TiO2 layer in TiO2/Fe2O3 photocatalyst is important to improve the photocatalytic performance. It is
found that only 89% of Rh B is degraded within 320 min by Fe2O3
for TiO2 degradation is 97.80% in 60 min and 98.86% of Rh B can

98

M.A. Mahadik et al. / Journal of Photochemistry and Photobiology B: Biology 133 (2014) 9098

be degraded over TiO2/Fe2O3. This shows for degradation of Rh B

Fe2O3 takes very high time compared to TiO2/Fe2O3 which may be
due to photo-corrosion effect [32]. However in TiO2/Fe2O3, the presence of TiO2 on the surface of Fe2O3 decreases the photo-corrosion
phenomenon and enhances stability of charge carriers. The plot ln
(c/co) against irradiation time for Rh B is linear suggesting photodegradation reaction follows rst order kinetics. Rate constant
found to be 6.0574  104, 0.0013 and 0.0036 s1 for Fe2O3, TiO2
and TiO2/Fe2O3 catalysts respectively. Variation in chemical oxygen
demand (COD) and total organic carbon (TOC) in course of time for
Fe2O3, TiO2 and TiO2/Fe2O3 photoelectrodes is shown in Fig. 11(b, d,
f) respectively. The values of COD and TOC decrease with increase in
reaction time. Photocatalytic performance of TiO2/Fe2O3 for degradation of rhodamine B is higher than Fe2O3, TiO2 catalysts. The electronhole pairs are efciently separated by the applied electric
eld. It is well known that the recombination of electronhole pair
in Fe2O3 is very fast which inhibits the formation of hydroxyl radicals required for the degradation of the pollutant. The TiO2/Fe2O3
multilayer helps to signicantly separates the electronhole pairs
due to increase in penetration depth of light. Therefore, the recombination of photogenerated electronhole pairs becomes prevented
in some extent in TiO2/Fe2O3 catalyst. The photostability and reusability of the Fe2O3 thin lm catalyst for the degradation of Rh B was
evaluated. The solution after the experiment was subjected to
Atomic Absorption Spectroscopy (AAS) analysis to assess the loss
of Fe ions in solutions atomic absorption spectra has performed
for detection of Fe in the Rh B solution and it is found that
0.039 lg/l, which shows 3.9% pure Fe2O3 lm is dissolved during
photoelectrocatalytic process. However Fe is not detected in AAS
when TiO2/Fe2O3 multilayer electrode was used photoelectrocatalytic process. Thus, the stability of TiO2/Fe2O3 photocatalyst was
tried ve times. It is observed that, the TiO2/Fe2O3 photoelectrode
remains intact and does not undergo any kind of corrosion.
4. Conclusions
The Fe2O3, TiO2 and TiO2/Fe2O3 multilayered thin lms are successfully deposited by spray pyrolysis method. The X-ray diffraction
analysis of the layered lms reveals that both oxides retain their
structures. The TiO2 layer on Fe2O3 thin lm resulted in a decrease
in the optical band-gap energy of pure TiO2 from 3.25 to 2.51 eV.
The TiO2/Fe2O3 lm exhibited the highest photocatalytic activity
and achieved maximum degradation efciency of about 98.86%.
The amount of mineralization of RhB was 40% within 20 min. Thus
TiO2 /Fe2O3 multilayered thin lm is a promising photocatalyst with
the potential practical application in polluted water treatment.
Acknowledgements
The authors are very much thankful to University Grants Commission, New Delhi for the nancial support through the UGC major research project No. 39-466/2010 (SR) and Dr. Vasant Sathe,
UGC-DAE Consortium for Scientic Research, Indore for providing
Raman facility.
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