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Synthesis and characterization of Fe-doped TiO2 photocatalyst by the sol–gel method

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2010 Adv. Nat. Sci: Nanosci. Nanotechnol. 1 015008

(http://iopscience.iop.org/2043-6262/1/1/015008)

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IOP PUBLISHING ADVANCES IN NATURAL SCIENCES: NANOSCIENCE AND NANOTECHNOLOGY
Adv. Nat. Sci.: Nanosci. Nanotechnol. 1 (2010) 015008 (5pp) doi:10.1088/2043-6254/1/1/015008

Synthesis and characterization of

Fe-doped TiO2 photocatalyst by the
sol–gel method
Cam Loc Luu1 , Quoc Tuan Nguyen2 and Si Thoang Ho1
1
Institute of Chemical Technology, Vietnam Academy of Science and Technology, 01 Mac Dinh Chi,
Ho Chi Minh City, Vietnam
2
University of Da Lat, 01 Phu Dong Thien Vuong, Da Lat, Lam Dong, Vietnam
E-mail: lcloc@vast-hcm.ac.vn

Received 6 February 2010

Accepted for publication 17 April 2010
Published 1 June 2010
Online at stacks.iop.org/ANSN/1/015008

Abstract
Thin layers of pure TiO2 and TiO2 doped by different amounts of Fe2 O3 have been prepared
by the sol–gel method with tetraisopropyl orthotitanate and Fe(NO3 )3 . Physico-chemical
properties of catalysts were characterized by BET Adsorption, x-ray Diffraction (XRD),
FE-SEM, as well as Raman and UV-Vis spectroscopy. The photocatalytic activity of the
obtained materials was investigated in the reaction of complete oxidation of p-xylene in gas
phase under the radiation of UV (λ = 365 nm) and LED (λ = 470 nm) lamps. It has been
found that the particle size of all samples was distributed in the range 20–30 nm. The content
of the rutile phase in Fe-doped TiO2 samples varied in the range 6.8 to 41.8% depending on
the Fe content. Iron oxide doped into TiO2 enables the photon absorbing zone of TiO2 to
extend from UV towards visible waves as well as to reduce its band gap energy from 3.2 to
2.67 eV. Photocatalytic activities of the TiO2 samples modified by Fe3+ have been found to be
higher than those of pure TiO2 by about 2.5 times.

Keywords: Fe-doped TiO2 , photooxidation, p-xylene

Classification numbers: 5.00, 5.07

1. Introduction their physico-chemical properties and to test their photo-

catalytic activity in degradation (complete oxidation) of
As a conventional photocatalyst, TiO2 is applied in many p-xylene.
processes of pollutant treatment in waste water, as well
as in air [1, 2]. Doping TiO2 with transition metals such 2. Experiment
as Fe, V and Cu makes it active higher in photocatalytic
conversions [3]–[6]. This is explained by the ability of the The Fe-doped TiO2 catalysts were prepared by the sol–gel
modified titania samples to reduce the band gap energy value method as below: Dissolve 3 ml of tetraisopropyl orthotitanate
and the recombination rate of the pair electron-photoinduced (TTIP) in 50 ml of mixture HNO3 -ethanol (pH = 3). The
hole under sunlight radiation compared to that in the case of obtained solution must be clear and transparent. Make the
pure TiO2 [7, 8]. It has been indicated that the movement sol by adding Fe(NO3 )3 solution over 90 min. The content of
of λ towards the red light area decreased in the following Fe (Fe2 O3 /TiO2 ) was adjusted to be 0.025, 0.05, 0.10, 0.50,
order: V > Cr > Mn > Fe > Ni [9]. It has also been noticed 1.00 and 2.00 mol.% to obtain catalyst samples symbolized
that this movement increases slightly with the content of as 025FeTi, 050FeTi, 100FeTi, 500FeTi, 1000FeTi and
metals Mn, V, Fe and Cr in the modified samples [9, 10]. The 2000FeTi, respectively. The sol was kept at room temperature
purpose of this study is to use the sol–gel method [11, 12] until the complete hydrolysis of TTIP and gel has been formed
for the synthesis of Fe-doped TiO2 catalysts, to characterize (24 h). The obtained precipitates were filtered and washed

2043-6254/10/015008+05$30.00 1 © 2010 Vietnam Academy of Science & Technology

Adv. Nat. Sci.: Nanosci. Nanotechnol. 1 (2010) 015008 C L Luu et al

Figure 1. XRD spectra of the Fe doped-TiO2 samples with different Fe2 O3 content.

Table 1. Characteristics of the obtained catalysts (particle size d, nm; specific surface area SBET , m2 g−1 , wavenumber of absorbed light
λmax , nm; band gap energy E bg , eV).
Catalyst TiO2 025FeTi 050FeTi 100FeTi 500FeTi 1000FeTi 2000FeTi
Fe2 O3 , mol.% 0 0.025 0.05 0.10 0.50 1.00 2.00
Anatase, mol.% 93.2 75.9 58.3 58.9 81.0 80.4 81.8
Rutile, mol.% 6.8 24.1 40.8 41.1 19.0 19.6 18.2
d, nm 30.0 27.6 29.5 30.3 24.8 21.6 19.5
SBET , m 2 g −1 45.0 15.5 11.2 9.6 34.6 36.9 42.9
λmax , nm 387 425 424 423 442 449 464
E bg , eV 3.20 2.92 2.93 2.93 2.80 2.76 2.67

with ethanol and distilled water. The samples were dried at 3. Results and discussion
110 ◦ C for one hour and then calcined and crystallized at
550 ◦ C for 4 h. 3.1. Characterization of the catalysts
Characterization of the catalyst samples was carried out XRD spectra of the catalysts (figure 1) only show the
by BET adsorption (CHEMBET 3000), XRD (x-ray Dif- characteristic peaks of TiO2 in anatase (2θ = 25.3◦ ) and
fraction XD 5A. SHIMADZU), FE SEM (HITACHI S-4800), rutile (2θ = 27.5◦ ) phases without any characteristic peaks
FT-Raman (Perkin-Elmer 2000), Absorption UV-Vis (Jassco of Fe2 O3 . This result indicates that probably some Fe3+ ions
V-550) and IR-Spectroscopy (VECTOR 22 BRUKER). replaced Ti4+ ions in the crystal framework of TiO2 .
The photocatalytic activity of the samples was tested in The particle size values of the catalysts were calculated
the gas phase deep oxidation of p-xylene at 40 ◦ C and the from the Scherrer equation. Data in table 1 show that the
initial partial concentrations of reactants (Coi , mg L−1 ) and influence of iron oxide content on the ratio of anatase/rutile
total flow velocity (V, Liter h−1 ), as described below for each phases is complex. In the range 0.05 to 0.1 mol.% of Fe2 O3
series of experiments (in tables 2 and 3). the percentage of rutile phase increased from 24.1 to 41%,
The doped-TiO2 catalyst samples were made in the form but at higher values of iron oxide content the proportion of
of transparent thin film on Pyrex tube (area of 68 cm2 and the rutile to anatase phase in the studied samples decreased
weight of 5 mg). The radiation sources were a UV lamp regularly and reached the quantity of 18.2 mol.%, close to
(λ = 365 nm, power of 8 W) and 80 pieces of LED (λ in the that in commercial TiO2 Degussa P25. Also the iron oxide
range 400–510 nm, total power 19.2 W). content influences the particle size and, as a rule, the specific
The photocatalytic activity of the catalysts was evaluated surface area of the catalyst samples. Although the trend is not
by results obtained from analysis on the gas-chromatograph very clear, a general remark could be that the particle size
GC Agilent 6890 Plus, detector FID, capillary column HP-1 decreased with the content of iron oxide, while the values of
with methyl siloxane (30 m, 0.32 mm, 0.25 µm). surface area varied in the opposite direction.

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Adv. Nat. Sci.: Nanosci. Nanotechnol. 1 (2010) 015008 C L Luu et al

(a) (b) (c)

(d) (e) (f)

Figure 2. FE SEM images of Fe-doped TiO2 catalysts: (a) 025FeTi, (b) 050FeTi, (c)100FeTi, (d) 500FeTi, (e) 1000FeTi, (f) 2000FeTi.

Figure 4. UV-Vis spectra of Fe doped- TiO2 catalysts with different

Figure 3. Raman spectra of Fe doped-TiO2 catalysts with different Fe2 O3 content.
contents of Fe2 O3 .
The pure TiO2 catalyst is characterized by the value of
The FE SEM image of the sample 025FeTi catalyst
the band gap energy of anatase TiO2 (E bg = 3.20 eV). The
(figure 2) shows a uniform particle size, but in the range 0.05
UV-Vis spectra of all the Fe doped-TiO2 catalyst samples
to 1.00 mol.% of iron oxide content one can observe a mixture
(figure 4) show the shift of the λmax towards the red light
of fine particles and bulk TiO2 . In comparison, the image of
zone and this shift depends on the iron content in the lattice.
sample 2000FeTi shows very fine and uniform particles of the
Concomitantly, the increase of iron content in the lattice
TiO2 crystals.
The Raman spectra of the Fe-doped TiO2 catalysts resulted in a decrease of E bg . The 2000FeTi sample expressed
(figure 3) show peaks at 407, 522, 648 and 853 cm−1 the biggest shift, the value of λmax reaching 464 nm and the
characterizing the absorption of anatase TiO2 [13]. No value of E bg decreasing to 2.63 eV. Also one can observe that
characteristic peaks of Fe2 O3 have been observed. It is very the color of the catalyst samples changed from white to yellow
probable that the presence of Fe3+ ions in the lattice resulted with the increase of iron content in the lattice.
in the shift of absorption peaks characteristic of TiO2 to the The IR spectra (figure 5) of all Fe doped-TiO2 samples
region of higher frequencies. This is explained by the decrease show peaks characteristic of OH at the surface (3225 cm−1 ),
in particle size of the Fe-doped TiO2 samples. The specific molecular water (1621 cm−1 ), Ti-O (653–550 cm−1 ) and
features of the Raman spectra of Fe-doped TiO2 catalysts are Ti-O-Ti (495–436 cm−1 ) as in the case of pure TiO2 . But it is
the absence of the characteristic anatase peak at 144 cm−1 interesting to note the appearance of a new peak at 2200 cm−1 ,
and the appearance of the new peak at 853 cm−1 . These facts the absorption intensity of which regularly increases
confirm the idea about the penetration of Fe3+ ions into the with iron content. The order is as follows: 2000FeTi >
framework of TiO2 crystals. 1000FeTi > 500FeTi > 100FeTi > 050FeTi > 025FeTi. It is

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Adv. Nat. Sci.: Nanosci. Nanotechnol. 1 (2010) 015008 C L Luu et al

Figure 5. IR-spectra of Fe doped-TiO2 catalyst samples: (1) 025FeTi; (2) 050FeTi; (3) 100FeTi; (4) 500FeTi; (5) 1000FeTi and
(6) 2000FeTi.

Table 2. Photocatalytic activity of TiO2 and of the Fe doped-catalysts expressed in initial extents of p-xylene conversion (X0 ) and
o
productivity of p-xylene degradation for 60 min. (P) under UV and LED radiation at T = 40 ◦ C; V = 6 l h−1 ; Cxylen = 19 mg l−1 ;
o −1 o −1
CO2 = 300 mg l ; CH2 O = 11.5 mg l .
Catalyst TiO2 025FeTi 050FeTi 100FeTi 500FeTi 1000FeTi 2000FeTi
UVa LEDb UVa LEDb UVa LEDb UVa LEDb UVa LEDb UVa LEDb UVa LEDb
Xo, % 41.7 14.3 93.3 26.3 40.6 38.7 65.5 61.5 100.0 52.1 42.4 58.7 55.0 43.3
P, g/g 8.10 1.88 5.59 3.62 3.48 3.72 3.02 5.88 5.34 4.29 2.74 4.09 2.52 5.64
a
3 pieces of UV-lamp, λ = 365 nm (total power 24 W).
b
80 pieces of LED, λ = 470 nm (total power 19.2 W).

very probable that this peak could be assigned to Ti-O-Fe Table 3. Conversion extent of p-xylene at different times (X) and
vibration. productivity of p-xylene degradation (P) for 60 min on catalyst
2000FeTi under different radiation regimesa .
Reaction time, min Conversion of p-xylene, X %
3.2. Photocatalytic activity of the catalysts in the gas phase Ab Bc Cd
degradation of p-xylene
1 31.2 14.4 72.7
5 38.0 22.3 80.9
From the data in table 2 it follows that practically all the
30 33.1 13.8 68.4
Fe doped-TiO2 samples expressed higher initial activities 60 24.8 13.2 69.3
than that of pure TiO2 . This fact can be explained by the P, g/g catalyst 4.72 2.08 10.50
presence of Fe making the amount of active sites higher due a
T = 40 ◦ C, V = 12 l h−1 , Coxylene = 6.33 mg l−1 ,
to the formation of Fe O Ti bonds in the TiO2 crystal
COo 2 = 300 mg l−1 , CHo 2 O = 7.83 mg l−1 .
lattice, as well as the consequent formation of defects on the b
3 pieces of UV-lamp.
catalyst surface that plays the role of a trap for preventing c
80 pieces of LED.
electron-hole recombination. Also the reduction of particle d
1 piece of UV-lamp plus 80 pieces of LED.
size and the increase of surface area should make the substrate
adsorption stronger. An important effect of the modification
4. Conclusion
of TiO2 by iron oxide doping must be the reduction of its
band gap energy value. Comparing the results obtained in two Fe3+ ions doped into TiO2 have caused changes in phase
experiments under UV-lamp and LED lighting one can see composition and some properties of the catalyst such as
that under LED radiation, in contrary with the case under UV phase composition, particle size and surface area, as well as
lighting, the modified catalysts expressed much higher activity broadening the light absorption zone towards the red region
and productivity than pure TiO2 . and reducing the band gap energy of the oxide. At low
An experiment with sample 2000FeTi using a combined concentrations of iron oxide the percentage of the rutile phase
radiation source (UV + LED) has been carried out. The data in increased and the particle size decreased with Fe2 O3 . The
table 3 show the advantage of combined radiation; in this case composition and particle size of catalyst samples containing
one can observe sufficiently high values of xylene conversion 0.50 to 2.00 mol.% Fe2 O3 have been shown to be similar to
as well as productivity in its complete oxidation. those of TiO2 Degussa P25, but their photochemical properties

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Adv. Nat. Sci.: Nanosci. Nanotechnol. 1 (2010) 015008 C L Luu et al

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