Materials Chemistry and Physics 114 (2009) 217–226

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Materials Chemistry and Physics

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Preparation and photocatalytic activity of rare earth doped TiO2 nanoparticles

Václav Štengl ∗ , Snejana Bakardjieva, Nataliya Murafa
Institute of Inorganic Chemistry v.v.i. AS CR, 250 68 Řež, Czech Republic

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

Article history: A one-step, a one-pot, no post-synthesis calcination and no sol–gel synthesis was used for preparation of
Received 3 September 2007 rare earth doped visible-light sensitive titania. This method is easy transferable to industrial conditions, is
Received in revised form ecologically friendly and make it possible to production of low-cost photocatalytic pigment. The products
10 September 2008
were characterized by all common techniques (X-ray diffraction (XRD), BET and porosity, scanning electron
Accepted 13 September 2008
microscopy (SEM) and high resolution transmission electron microscopy (HRTEM), UV/VIS spectra). The
photocatalytic activity of the prepared samples was assessed by the photocatalytic decomposition of
Keywords:
Orange II dye in an aqueous slurry under irradiation of 254, 365 and 400 nm wavelength. The rare earth
Anatase
Urea
(La, Ce, Pr, Nd, Sm, Eu, Dy, Gd) for doped titania were used, the best photocatalytic properties in visible
Rare earth light have samples doped with Nd3+ ions (k = 0.0272 min−1 for UV and 0.0143 min−1 for visible light).
Homogeneous precipitation © 2008 Elsevier B.V. All rights reserved.
Photocatalytic activity

1. Introduction up to 5 mol.% was directly formed as nanometer-sized particles

Most of investigations are focused on anatase titania to photo-
degrade various organic pollutants under ultraviolet (UV) light
( < 365 nm) [1]. The band gap of anatase (3.2 eV) is not ideal
for solar applications, which limits its wide application in visible
range. The development of photo-catalysts that can be excited by
visible light ( > 400 nm) has received great attention. Many meth-
ods are attempted such as dye sensitization and transition metals
doping.
A sol–gel method to prepare thermally stable La3+ doped meso-
porous titania powders with highly crystallized walls and high
photocatalytic activity is reported [2]. Lanthanum-doped anatase
TiO2 thin films on glass prepared via a sol–gel process have been
shown to have much higher photocatalytic activity for the degra-
dation of gaseous benzene than pure anatase TiO2 thin film [3]. The
photocatalytic activity of La doped TiO2 photo-catalysts exceeds
that of pure TiO2 photo-catalyst prepared by the same method [4]
when the molar ratio of La to Ti is kept at 0.3%.
A mixed oxide consisting of TiO2 as the major phase and
CeO2−y (0 < y < 0.5) as the dopant phase was prepared via the
sol–gel reaction of Ti(i-OC3 H7 )3 in an aqueous solution of Ce(NO3 )3
[5], a series of Ce–TiO2 prepared by the sol–gel process with
ammonium cerium(IV) nitrate and tetra-n-butyl titanium is pre-
sented in paper [5–8]. Anatase-type TiO2 doped with cerium
∗ Corresponding author. Tel.: +420 2 6617 3534; fax: +420 2 2094 0257.
E-mail address: stengl@iic.cas.cz (V. Štengl).
from TiO(NO3 )2 –Ce(NO3 )2 –NH4 NO3 –citric acid complex com-
pound system by sol–gel auto-igniting synthesis process [9].
Cerium-doped mesoporous TiO2 nanoparticles with high sur-
face area and thermal stable anatase wall were synthesized
via hydrothermal process in a cetyltrimethylammonium bromide
(CTAB)–Ti(SO4 )2 –Ce(NO3 )4 –H2 O system [10]. The cerium ion (Ce4+ )
modified titania sol and nanocrystallites were prepared by chemical
coprecipitation–peptization and hydrothermal synthesis meth-
ods, respectively [11]. Pure and Ce4+ doped anatase and rutile
TiO2 were prepared by hydrothermal methods from TiCl4 and
(NH4 )2 Ce(NO3 )6 [12].
Nd3+ doped titania nanoparticles with mesostructures were
synthesized via hydrothermal process by using cetyltrimethylam-
monium bromide (CTAB) as directing and pore-forming agent [13].
The maximum photocatalytic activity corresponds to the 0.5 at.%
Nd3+ -doped anatase nanopowders with mesostructures, which is
higher than that of undoped samples. Nd3+ ion modified titania sol
was prepared by chemical coprecipitation–peptization method by
ammonium hydroxide from mixture of TiCl4 and NdCl3 in aqueous
solution [14].
High photocatalytic activity of Sm3+ -doped TiO2 nanocrystalline
under visible light has been successfully prepared by sol–gel
technique [15,16]. High-quality nanocrystalline TiO2 thin films of
anatase phase were prepared by using the atomic layer deposition
technique and implanted with Sm3+ ions [17].
A one-step solvothermal synthesis is proposed for the prepa-
ration of nanocrystalline single-phase TiO2 in the anatase form
doped with lanthanide ions Eu3+ , Er3+ and Sm3+ [18]. Rare earth

0254-0584/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2008.09.025
218 V. Štengl et al. / Materials Chemistry and Physics 114 (2009) 217–226

Table 1
Experimental conditions, crystallite size, cell parameters a and b, surfaces areas and porosity of prepared samples.

Sample Dopants (g) EDX Particle size Cell parameter a Cell parameter c BET Pore radius Pore volume
(wt.%) (nm) (m2 g−1 ) (nm) (cm3 g−1 )

Ti 0 – 4.2 3.7860 9.5148 200.4 17.344 0.190

TiNd 1 3.15 Nd2 O3 5.20 5.3 3.7920 9.5168 184.5 1.7 0.198
TiNd 2 6.31 Nd2 O3 8.72 5.6 3.7981 9.5133 256.6 1.7 0.369
TiNd 3 9.45 Nd2 O3 14.98 4.9 3.8018 9.5101 224.7 1.8 0.268
TiNd 4 11.00 Nd2 O3 15.42 4.8 3.8041 9.4828 165.5 1.7 0.299
TiNd 5 12.60 Nd2 O3 16.27 4.7 3.8099 9.4899 150.0 1.7 0.153

TiCe3 1 0.25 Ce2 (SO4 )3 0.23 5.0 3.7944 9.4982 189.1 1.8 0.185
TiCe3 2 0.50 Ce2 (SO4 )3 0.52 4.9 3.7944 9.4944 227.9 1.7 0.247
TiCe3 3 1.50 Ce2 (SO4 )3 1.47 4.7 3.8031 9.5241 217.3 1.7 0.279
TiCe3 4 3.00 Ce2 (SO4 )3 3.07 4.5 3.8037 9.5045 196.5 1.7 0.187
TiCe3 5 6.00 Ce2 (SO4 )3 5.81 4.4 3.8083 9.5126 237.5 1.5 0.235

TiCe4 1 0.25 Ce(SO4 )2 0.28 4.8 3.7959 9.5004 209.4 1.8 0.204
TiCe4 2 0.50 Ce(SO4 )2 0.52 4.7 3.7977 9.5095 246.3 1.7 0.249
TiCe4 3 1.50 Ce(SO4 )2 1.64 4.7 3.7988 9.5027 228.7 1.8 0.229
TiCe4 4 3.00 Ce(SO4 )2 3.12 4.6 3.8023 9.5101 230.7 1.8 0.232
TiCe4 5 6.00 Ce(SO4 )2 5.93 3.8 3.8054 9.5089 279.5 1.7 0.277

TiPr 1 1.50 Pr(NO3 )3 1.48 5.3 3.7971 9.5052 219.4 1.8 0.228
TiPr 2 3.00 Pr(NO3 )3 3.54 4.6 3.7991 9.5023 126.6 1.7 0.124
TiPr 3 6.00 Pr(NO3 )3 6.44 4.3 3.8002 9.4981 253.9 1.8 0.258

TiSm 1 3.00 Sm(NO3 )3 2.87 4.2 3.7853 9.5182 28.4 1.9 0.030
TiSm 2 6.00 Sm(NO3 )3 4.97 3.0 3.7854 9.5060 245.1 1.8 0.239

TiGd 1 3.00 GdAC 3.14 4.7 3.7937 9.5226 209.9 1.7 0.200
TiGd 2 6.00 GdAC 5.23 4.6 3.7964 9.5049 237.4 1.8 0.243

TiEu 1 6.00 Eu2 O3 10.81 4.3 3.7893 9.5004 203.7 1.7 0.238
TiEu 2 10.00 Eu2 O3 15.23 3.8 3.7854 9.5003 27.9 1.7 0.027

TiDy 1 3.10 Dy2 O3 6.28 4.4 3.7912 9.4947 187.1 1.8 0.178
TiDy 2 7.00 Dy2 O3 13.28 3.9 3.7929 9.4943 223.6 1.7 0.259

TiLa 1 1.00 La(NO3 )3 1.54 4.6 3.7906 9.5068 22.1 1.7 0.023
TiLa 2 6.00 La(NO3 )3 14.91 4.8 3.7963 9.5203 204.5 1.7 0.262
TiLa 3 12.00 La(NO3 )3 19.14 5.0 3.7972 9.5136 170.9 1.7 0.170

ions (Sm3+ , Nd3+ , Pr3+ ) doped TiO2 (RE3+ –TiO2 ) catalysts were pre- Orange II dye was selected as a model reactant for photodegrada-
pared by the sol–gel method [19]. In paper [20] 3.0 mol.% lanthanide tion.
europium ion modified TiO2 sol (Eu3+ –TiO2 ) was fabricated by
chemical coprecipitation–peptization method with TiCl4 as pre- 2. Experimental

cursor. Sol–gel derived titania xerogel films were prepared from 2.1. Preparation of rare earth doped titania samples
a Ti(OC2 H5 )4 precursor doped with Eu and fabricated on 30 mm
thick porous anodic alumina [21]. Erbium doped TiO2 nanocrystals All chemical reagents used in the present experiments were obtained from
with the structures of anatase, Er2 Ti2 O7 , and rutile was prepared commercial sources and used without further purification. Urea, TiOSO4 , Pr(NO3 )3 ,
Sm(NO3 )3 , Ce(SO4 )2 , Ce2 (SO4 )3 , Nd2 O3 , Eu2 O3 , Dy2 O3 , La2 O3 and gadolinium acetate
reaction of mixture titanium isopropoxide and Er(NO3 )3 with
were supplied by Fluka, Munich, Germany. The oxides were converted to soluble
tetramethylammonium hydroxide [22]. The photocatalytic activity sulphate salts by reaction with sulphuric acid.
of titanium dioxide catalysts and also extend the light absorption The rare earth doped nanocrystalline anatase TiO2 (see Table 1) was prepared by
towards the visible-light region, three types of the lanthanide ion- homogeneous hydrolysis of TiOSO4 aqueous solutions using urea as the precipitation
modified (Ce4+ , Nd3+ and Eu3+ ) titanium dioxide sol catalysts were agent: In a typical process, 100 g TiOSO4 was dissolved in 100 mL hot distilled water
acidified with 98% H2 SO4 . The pellucid liquid was diluted into 4 L of distilled water,
prepared by a chemical method of coprecipitation–peptization added defined amount of lanthanide (see Table 1) and mixed with 300 g of urea.
[23]. RE/TiO2 photocatalysts were prepared by the sol–gel method
using rare earth (RE = La3+ , Ce3+ , Er3+ , Pr3+ , Gd3+ , Nd3+ , Sm3+ ) metal
salts with tetranbutyl titanate [24] and titanium isopropoxide [25]
respectively, as precursor.
As it has been shown earlier [26,27] the homogeneous pre-
cipitation with urea leads to anatase nanoparticles assembled
into a rather big (1–2 ␮m) porous clusters established good pho-
tocatalytic properties. Homogenous hydrolysis with urea is very
simple preparation method, which can be easy executable in pro-
duction and such way produced low-cost photocatalytic pigment
e.g. for production of self-cleaning paintings colours. Based on
the work of our laboratory we used the modified homogeneous
hydrolysis of titania and rare earth sulphates with urea in prepara-
tion of series of photo-catalysts including La3+ , Ce3+ , Ce4+ , Nd3+ ,
Sm3+ , Pr3+ , Eu3+ , Gd3+ and Dy3+ doped TiO2 and their photo-
Fig. 1. XRD pattern of doped TiO2 sample denoted as (a) TiNd 3, (b) TiCe3 1, (c)
catalytic activity under UV and visible light were investigated; TiCe4 1, (d) TiPr 1, (e) TiSm3 1, (f) TiEu 1, (g) TiDy 1, (h) TiGd 1 and (i) TiLa 1.
 V. Štengl et al. / Materials Chemistry and Physics 114 (2009) 217–226
The mixture was heated to 100 ◦ C under stirring and kept at this temperature for
6 h until pH 7 was reached and ammonia escaped from the solution. The formed
precipitates have been washed by distilled water with decantation, filtered off and
dried at temperature 105 ◦ C in dry oven.
2.2. Characterization methods
Surface area of the samples was determined from nitrogen adsorption–
desorption isotherms at liquid nitrogen temperature using a Quantachrom
Nova2000 instrument with outgas 15 min at 120 ◦ C. The B.E.T. method was used
for surface area calculation [28], the pore size distribution (pore diameter and pore
volume of the samples) was determined by the B.J.H. method [29].
Transmission electron microscopy (TEM and HRTEM) micrographs were
obtained by using two instruments, namely Philips EM 201 at 80 kV and JEOL JEM
3010 at 300 kV (LaB6 cathode). Copper grid coated with a holey carbon support
film was used to prepare samples for the TEM observation. A powdered sample
was dispersed in ethanol and the suspension was treated in ultrasonic bath for
10 min.
Scanning electron microscopy (SEM) studies were performed using a Philips
XL30 CP microscope equipped with EDX (energy dispersive X-ray), Robinson, SE
(secondary electron) and BSE (back-scattered electron) detectors. The sample was
placed on an adhesive C slice and coated with Au–Pd alloy 10 nm thick layer.
X-ray diffraction (XRD) patterns were obtained by Siemens D5005 instru-
ment using Cu K␣ radiation (40 kV, 30 mA) and diffracted beam monochromator.
Qualitative analysis was performed with the Eva Application and the Xpert High-
Score using the JCPDS PDF-2 database [30]. The crystallite size of the samples
was calculated from the Scherrer equation [31] using the X-ray diffraction peak
at 2 = 25.4◦ (anatase); the cell parameters was calculated by PowderCell v.1.2.
programme.
Diffuse reflectance UV/VIS spectra for evaluation of photophysical properties
were recorded in the diffuse reflectance mode (R) and transformed to absorption
spectra through the Kubelka–Munk function [32]. A PerkinElmer Lambda 35 spec-
trometer equipped with a Labsphere RSA-PE-20 integration sphere with BaSO4 as a
standard was used.
Fig. 2. BHJ pore size distribution dV(r) versus pore radius titania doped with (a) Pr3+ , (b) Nd3+ , (c) Ce3+ and (d) Ce4+ .
219
Photocatalytic activity of samples was assessed from the kinetics of the pho-
tocatalytic degradation of 0.01 M Orange II dye (OII) in aqueous slurries. Kinetics
of the photocatalytic degradation of aqueous Orange II dye solution, was mea-
sured by using a self-constructed photoreactor [33,34]. The photoreactor consists
of a stainless steel cover and quartz tube with florescent lamp wavelength with
power 8 W. Germicid (254 nm) and Black light (365 nm) respectively, for UV, Bio
light (over 400 nm) for visible-light irradiation samples were used. Orange II dye
solution circulated by means of membrane pump through flow cuvette. The con-
centration of Orange II dye was determined by measuring absorbance at 480 nm
with VIS spectrofotometer ColorQuestXE.
3. Results and discussion
3.1. X-ray diffraction
The powder XRD patterns of the rare earth doped titanium oxide
prepared by homogeneous hydrolysis of titanium oxo-sulphate are
shown in Fig. 1, which can be indexed as a single phase of anatase
(PDF 21-1272). No other polymorph of titania are observed and no
rare earth peaks are found in the XRD patterns.
The broadening of diffraction peaks indicates small size of
nanocrystals. The average size t of crystallites was calculated from
the peak half-width B, using the Sherrer equation [31],
k
t= (1)
B cos 
where k is a shape factor of the particle (it is 1 if the spherical shape
is assumed),  and  are the wavelength and the incident angle of
the X-rays, respectively. The peak width was measured at half of the
maximum intensity. The crystallite size was calculated from diffrac-
220 V. Štengl et al. / Materials Chemistry and Physics 114 (2009) 217–226

Fig. 3. SEM images of sample denoted as (a) TiNd 1, (b) TiSm 1, (c) TiCe3 1, (d) TiCe4 1, (e) TiDy 1, (f) TiEu 1, (g) TiPr 1 and (h) TiLa 1.

tion plane (1 0 1) of anatase and doped samples slightly decrease
with nominal content of rare earth (RE) increasing as compared
with undoped TiO2 . The decrease in particle size can be attributed
to the presence of RE–O–Ti in the doped samples, which inhibits
the growth of crystal grains (see Table 1). The unit cell parame-
ters a and c increases with the content of rare earth and this fact
indicated possibility incorporation of rare earth ions to lattice of
anatase.
3.2. Surface area and porosity (BET and BJH)
BET surface area of rare earth titania depend on the amount
of doped oxides, the largest surface area (256.6 m2 g−1 ) has sam-
ple denoted as Ti Nd1 (see Table 1). In terms of shape, adsorption
isotherms of all prepared samples may be classified as type I with
hysteresis loop, which can be classified as type A [35]. Type A hys-
teresis is due to principally to cylindrical pores open at both ends
 V. Štengl et al. / Materials Chemistry and Physics 114 (2009) 217–226 221

Fig. 4. HRTEM micrographs of Nd3+ , Pr3+ , Ce3+ and Ce4+ doped titania, magnification 1 000 000 denoted as (a) TiNd 3, (b) TiPr 3, (c) TiCe3 5 and (d) TiCe4 5.

and the microporosity of pore size distribution is about pore diam-

eter ∼6 nm. Results from desorption BJH pore volume distribution
and pore area distribution confirmed microporous structure of pre-
pared undoped titania and titania doped with Ce4+ , Sm2+ , Eu3+ and
La3+ , respectively. The titania doped with Ce3+ , Pr3+ , Gd3+ and Dy3+ ,
respectively, embodied small growth of pores (∼3 nm) and titania
doped with Nd3+ and Ce4+ respectively, have small content of meso-
pores (about 5 nm). The BJH method desorption of dV(r) versus pore
radius for titania doped with Nd3+ , Ce3+ , Ce4+ and Pr3+ , respec-
tively, are presented in Fig. 2. Pore radius is in interval 0.15–0.19 nm
and pore volume is in interval 0.12–0.36 cm3 g−1 for all prepared
samples. The samples with content of mesopores have higher pho-
tocatalytic activity then microporous samples.

3.3. Scanning electron microscopy (SEM) and high resolution

transmission electron microscopy (HRTEM)

Fig. 3 shows the electron micrographs of Nd3+ , Pr3+ , Ce3+ , Ce4+ ,

Eu3+ , Sm3+ , Gd3+ and La3+ doped anatase precipitate prepared
according to the procedure described above. As it follows from the
SEM micrographs, (see Fig. 3), the synthesized samples consisted
of spherical clusters of rather narrow size distribution 1–2 ␮m in
Fig. 5. HRTEM micrographs of pure undoped anatase.
diameter. Based on the HRTEM results (see Fig. 4), these spherical
222 V. Štengl et al. / Materials Chemistry and Physics 114 (2009) 217–226
Fig. 6. Absorbance UV/VIS spectra of titania doped with (a) Pr3+ , (b) Nd3+ , (c) Ce3+ and (d) Ce4+ .
particles consist of primary 4–5 nm anatase nanocrystals interlayed
by small fraction of amorphous material. The EDX analysis of con-
tent La, Ce, Pr, Nd, Sm, Eu, Dy and Gd is presented in Table 1.
Results obtained by high resolution transmission electron
microscopy (HRTEM) are shown in Fig. 4. The HRTEM micrographs
in Fig. 4a–d characterized the surface morphology of the samples
denoted TiNd 3, TiPr3, TiCe3 5 and TiCe4 5. It is obvious that these
samples are consist of very good crystallized areas of nanosized
titania. The interlayer spacing d = 0.35 nm of the all samples corre-
sponding to the (1 0 1) plane of anatase (Fig. 4b). As compare to pure
undoped anatase (see Fig. 5), the fringes of doped anatase lattice are
expanded and showed considerable waviness (see Fig. 4a, c and d,
marked with arrows). These dislocations were possibly attributed
to electric stress, which may originate from earth ions doping
[36–38]. Structure of the all prepared samples was resolved by
selected electron diffraction patterns (SAED) and analysed by Pro-
cessDiffraction program, only anatase phase (ICDD PDF 21-1272)
resulted.
3.4. UV/VIS spectra and band-gap energy
Fig. 6 presents UV/VIS absorption spectra of the prepared sam-
ples doped with Nd3+ , Pr3+ , Ce3+ and Ce4+ ions, respectively. The
spectra of La3+ , Ce3+ , Ce4+ , Eu3+ , Gd3+ and Sm3+ doped TiO2 show
red shift in the band-gap transition. Red shift of this type can be
attributed to the charge-transfer transition between earth ion f
electrons and the TiO2 conduction or valence band [39]. The absorp-
tion edge shift to a longer wavelength on the amount of rare earth
metal is depended.
The titania doped with Nd3+ (at 431, 474, 527, 582, 747 and
805 nm), Pr3+ (at 444, 469, 482 and 590 nm), Dy3+ (at 452, 755,
805 and 905 nm) have much absorption bands in agreement with
the visible-light absorbability. These peaks are attributed to the 4f
electron transitions of these ions [40]. Moreover, the intensity of
this absorption bands was found to increase with increasing in rare
earth content.
The method of UV/VIS diffuse reflectance spectroscopy was
employed to estimate band-gap energies of the prepared rare earth
titania. Firstly, to establish the type of band-to-band transition in
these synthesized particles, the absorption data were fitted to equa-
tions for direct band-gap transitions. The minimum wavelength
required to promote an electron depends upon the band-gap energy
Ebg of the photocatalyst and is given by
1240
Ebg = (eV), (2)

where  is the wavelength in nanometers [41,42].
Fig. 7 shows the (˛Ebg )2 versus Ebg for a indirect band-gap tran-
sition titania doped with Nd3+ , Pr3+ , Ce3+ and Ce4+ , respectively,
where ˛ is the absorption coefficient and Ebg is the photon energy.
The value of Ebg extrapolated to ˛ = 0 gives an absorption energy,
which corresponds to a band-gap energy (see Table 2). The value of
3.20 eV for sample denoted as Ti 0 is reported in the literature for
pure TiO2 anatase nanoparticles [41], the value of band-gap energy
decreases with increasing content of rare earth ions. The density
of the colour of prepared samples depends on the content of rare
earth dopants, the titania doped with Nd3+ have tone colour to blue,
Ce3+ and Ce4+ to yellow and Pr3+ to slightly green. The titania doped
with Sm3+ , Dy3+ , Eu3+ , Gd3+ and Dy3+ are slightly yellow and titania
doped with La3+ is white.
 V. Štengl et al. / Materials Chemistry and Physics 114 (2009) 217–226 223

Fig. 7. Band-gap energy of titania doped with (a) Nd3+ , (b) Pr3+ , (c) Ce3+ and (d) Ce4+ .

Table 2
(Continued)
Table 2
Sample Band-gap (eV) 255 365 400
The band-gap energy Ebg and rate constant k at 254, 365 and 400 nm wavelength.
TiDy 1 3.15 0.0743 0.0551 0.0054
Sample Band-gap (eV) 255 365 400 TiDy 2 3.15 0.0583 0.0074 0.0009
TI 0 3.20 0.0353 0.0129 0.0009 TiLa 1 3.20 0.0368 0.0154 0.0009
TiNd 1 3.10 0.0393 0.0064 0.0032 TiLa 2 3.15 0.0614 0.0096 0.0022
TiNd 2 3.10 0.0489 0.0148 0.0041 TiLa 3 3.15 0.0454 0.0057 0.0082
TiNd 3 3.15 0.0694 0.0272 0.0143 P 25 3.10 0.0647 0.0471 0.0022
TiNd 4 3.15 0.0274 0.0133 0.0049
TiNd 5 3.15 0.0346 0.0113 0.0118

TiCe3 1 3.20 0.0499 0.0083 0.0043 4. Photocatalytic activity

TiCe3 2 3.15 0.0628 0.0063 0.0038
TiCe3 3 3.05 0.0590 0.0152 0.0013 When photocatalytic reaction is conducted in aqueous medium,
TiCe3 4 2.85 0.0419 0.0071 0.0070
the holes were effectively scavenged by the water and generated
TiCe3 5 2.70 0.0254 0.0145 0.0013
hydroxyl radicals OH• , which are strong and unselected oxidant
TiCe4 1 3.15 0.1054 0.0369 0.0081 species in respect of totally oxidative degradation for organic sub-
TiCe4 2 3.10 0.0976 0.0221 0.0124
TiCe4 3 2.95 0.0321 0.0113 0.0075
strates. Both holes and hydroxyl radicals have been proposed as the
TiCe4 4 2.90 0.0199 0.0019 0.0010 oxidizing species responsible for the degradation (mineralization)
TiCe4 5 2.75 0.0455 0.0049 0.0007 of the organic substrates [43].
TiPr 1 3.15 0.0434 0.0103 0.0074 TiO2 + hv → h+ + e− (3)
TiPr 2 3.15 0.0375 0.0181 0.0039
+ +
TiPr 3 3.10 0.0418 0.0131 0.0059 h + H2 O → OH• +H (4)
TiSm 1 3.15 0.0360 0.0121 0.0085 +
h + dye → products (5)
TiSm 2 3.15 0.0919 0.0295 0.0065

TiGd 1 3.15 0.0640 0.0173 0.0058 OH• + dye → products (6)

TiGd 2 3.10 0.1019 0.0202 0.0073 − + 2−
dye + TiO2 → CO2 + H2 O + NO3 + NH4 + SO4 (7)
TiEu 1 3.15 0.0438 0.0069 0.0073
TiEu 2 3.05 0.0377 0.0141 0.0101 The photocatalytic activity of titania doped with rare earth ions
were determined by degradation of Orange II aqueous solutions
224 V. Štengl et al. / Materials Chemistry and Physics 114 (2009) 217–226
under UV radiation. In regions where is valid Lambert–Beer law,
the concentration is proportional to absorbance.
A = εcl
where A is absorbance, c is concentration of absorbing component, l
is length of absorbing layer and ε is molar absorbing coefficient. The
time dependences of Orange II dye decomposition can be described
by using Eq. (9) for the first kinetics reaction [44]:
d[OII]
= k(a0 − [OII])
dt
where [OII] is concentration of Orange II dye, a0 is initial concen-
tration of Orange II dye and k is rate constant. It is visible from
Fig. 8, that the first order kinetics curves (plotted as lines) fitted to
all experimental points. For comparison, the photocatalytic activity
of a commercially available photocatalyst (Degussa P25) and pure
anatase TiO2 respectively, was also tested. The calculated degrada-
tion rate constants k (min−1 ) are listed in Table 2 and example of
kinetic degradation of the sample doped with Nd3+ , Ce3+ , Ce4+ ions
denoted as TiNd 3, TiCe3 4, TiCe4 2 and P25 respectively, of Orange
II dye at 254, 365 and 400 nm wavelength are presented in Fig. 8.
From Table 2 is followed, that pure anatase (sample denoted
Ti 0) and Degussa P25, respectively, exhibits very low visible-
light photocatalytic activity for aqueous Orange II dye degradation,
because the band-gap energy of Degussa P25 is of 3.1 eV
(bg = 400 nm) [45] that possibly reflects its phase composi-
tion (80% anatase and 20% rutile), corresponding to absorption
in the near UV region; band-gap energy for anatase is 3.2 eV
(bg = 388 nm) and rutile is 3.0 eV (bg = 413 nm) [41].
Fig. 8. Photocatalytic activity at wavelengths 254, 365 and 400 nm of sample denoted as (a) TiNd 3, (b) TiCe4 3, (c) TiCe 3 and (d) P25 Degussa.
The energy of a photon is related to its wavelength and the over-
all energy input to a photocatalytic process is dependent upon the
light intensity. Therefore, the effect of both, intensity and wave-
(8) length are important. Matthews and McEvoy [46] showed that
shorter wavelength (254 nm) radiation is considerably more effec-
tive in promoting degradation than radiation centred at 350 nm
and the optimum rate occurred with a lower catalyst loading than
required at 350 nm. Hofstadler et al. [47] also showed that shorter
wavelengths resulted in higher photocatalytic degradation process
rates of 4-chlorophenol with small amounts of intermediates being
(9) formed. This is due to the fact that shorter wavelength is associ-
ated with greater photon energy. The good results of photocatalytic
activity were obtained from titania doped with Nd3+ and Ce4+ . The
transitions of 4f electrons of rare earth led to the enforcement of
the optical adsorption of catalysts and supported the separation
of photo-generated electron–hole pairs. Moreover, the red shift of
the optical adsorption edge of titania by rare earth ion doping was
helpful to the improvement of visible-light photocatalytic activity
of TiO2 . However, the transitions of 4f electrons of rare earth and
red shifts of the optical adsorption edge of titania by rare earth ion
doping and dye sensitization enhanced visible-light photocatalytic
activity of TiO2 . The optimal dosage of rare earth ions at ∼3–4 wt.%
for Orange II dye degradation under UV irradiation and at 1–2 wt.%
under visible-light irradiation in this study might be contributed
to the fact that there was an optimal dosage of rare earth ions in
TiO2 particles for the most efficient separation of photo-induced
electron–hole pairs. As the content of doping ions increases, the sur-
face barrier becomes higher, and the space charge region becomes
narrower. The electron–hole pairs within the region are efficiently
separated by the large electric field before recombination which led
 V. Štengl et al. / Materials Chemistry and Physics 114 (2009) 217–226
to the higher photocatalytic activity. However, when the content of
doping ions is excessively high, the space charge region becomes
very narrow and the penetration depth of light into TiO2 greatly
exceeds the space charge layer; therefore the recombination of the
photo-generated electron–hole pairs becomes more easy, which
led to the lower photocatalytic activity of TiO2 for Orange II dye
degradation.
5. Conclusion
Great many of papers referee about rare earth ions doped tita-
nia by sol–gel method or method in non-aqueous environment. Our
samples are prepared in aqueous solution by homogeneous hydrol-
ysis from TiOSO4 . This method is patented in Czech republic, is easy
transferred to industrial production and make it possible to man-
ufacture low-cost photocatalytic pigment. The titania doped with
Nd3+ ions is now manufactured on large scale on 1000 l reactor
for using in photocatalytic self-cleaning paints. The doping of TiO2
with rare earth ions using homogeneous hydrolysis have a con-
siderable effect on optical properties of as-prepared samples (see
UV–VIS spectra) and leads to lowers band-gap energy comparing
with another methods (see Table 2).
The overall photocatalytic activity for Orange II dye degradation
under UV or visible-light irradiation was significantly enhanced
by doping with the rare earth ions. The increase in photocatalytic
activity was due to the higher adsorption, and the 4f electron tran-
sition of rare earth ions. The highest enhancement in photoactivity
was obtained at 0.5–1 wt.% rare earth ion doping, which may be in
positive of the most efficient separation of the charge carriers. Nd3+ -
doped TiO2 (approx. 10 wt.%) shows the highest activity among all
rare earth doped samples investigated.
Acknowledgements
The work was also supported by the Academy of Sciences of
the Czech Republic (Project No. AV0Z40320502) and Czech Science
Foundation (Project No. 203/08/0335).
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