Materials Letters 60 (2006) 129 132

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Synthesis and characterization of chromium doped SrTiO3 photocatalyst

Chia-Hao Chang, Yun-Hwei Shen *
Department of Resources Engineering, National Cheng Kung University, Tainan, Taiwan, R.O.C.
Received 24 September 2004; accepted 3 August 2005
Available online 31 August 2005

Abstract
SrTiO3 and chromium doped SrTiO3 (SrTi(1 x)Crx O3) photocatalysts were synthesized by the polymeric precursor method using citric
acid and ethylene glycol. Single phase SrTiO3 and SrTi(1 x)Crx O3 nano-size powder were produced at 450 -C. A new band gap in the visible
light range was formed by chromium doping in SrTiO3. The absorption of visible light is of practical importance for the application of SrTiO3
as a photocatalyst.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Photocatalyst; Polymeric precursor method; Chromium doping

1. Introduction
Strontium titanate (SrTiO3) has been known to possess
photocatalytic activity [1,2]. Since SrTiO3 is a wide-gap
semiconductor (3.2 eV), UV-light (k < 387 nm) is necessary
to generate electron/hole pairs by photo-excitation. From the
viewpoint of practical applications, however, utilization of
visible light is desirable. To develop active photocatalysts
under visible light, transition metal ions have been doped
into TiO2 to red-shift the absorption edge [3,4]. It has been
reported that doping with transition metal ions, such as
chromium, is an efficient means to improve photocatalytic
activity in the visible region [5,6]. It is expected that the
photoactivity of a semiconductor increases with the decrease
of particle size because the diffusion distance to the surface
of photo-induced holes and electrons decrease. Consequently, the holes and electrons can be effectively captured
by the electrolyte in solution [7].
In the synthesis of multicomponent oxide powders such
as SrTiO3, chemical solution methods offer several
advantages such as high-purity, homogeneity and precise
composition relative to the conventional solid-state method

* Corresponding author.
E-mail address: yhshen@mail.ncku.edu.tw (Y.-H. Shen).
0167-577X/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2005.08.005

which usually results in low surface area due to the hightemperature heat-treatment [8,9]. The Pechini method [10]
is an attractive synthesis technique for the preparation of
highly dispersed mixed oxide powders. The method
involves the ability of certain weak hydroxycarboxylic
acids (citric acid is preferred) to form polybasic acid
chelates with various metal ions. These chelates can
undergo polyesterification when heated in a polyhydroxyl
alcohol to form a polymeric glass which has cations
uniformly distributed throughout.
The aim of this paper is to demonstrate the lowtemperature synthesis of ultrafine SrTiO3 and chromium
doped SrTiO3 (SrTi(1 x)Crx O3) photocatalysts.

2. Experimentals
2.1. Synthesis
Strontium chlorite (SrCl2), butyl titanate (Ti(CH3
(CH2)3O)), citric acid (C3H3(OH)(COOH)3), and ethylene
glycol (HOCH2CH2OH) were employed as the starting
ingredients. All chemicals were reagent grade and used as
received. Butyl titanate was added into ethylene glycol
followed by the addition of citric acid while the solution was
heated at 60 -C with continuous stirring. SrCl2 were added

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C.-H. Chang, Y.-H. Shen / Materials Letters 60 (2006) 129 132

10 mole
Ethylene glycol

(1-X) mole Ti(O-iPr)4

4 mole Citric acid

` ` `

X=0 2 4 8 %mole of
CrCl2

1 mole SrCl2

Mixing and stirring at 80 C for 30 min

Yellow transparent gel
20nm

Calcine @ 450 C for 24h

Fig. 3. TEM micrograph of SrTiO3 powders obtained after calcining the gel
precursor in air at 450 -C for 24 h.

Powder
Fig. 1. Schematic of the synthesis process used in this study.

Fig. 4. The XRD patterns of SrTi(1 x)Crx O3 (x = 0, 0.02, 0.04 and 0.08)
powders after calcining the gel precursor in air at 450 -C for 24 h.
Fig. 2. The XRD patterns of the powders obtained after calcining the
SrTiO3 gel precursor in air at 450 -C for 2 24 h.

when the solution become clear. The molar ratio of citric

acid to total metal cations concentration was kept at 2, the
molar ratio of ethylene glycol to citric acid was 2.5. With the
dissolution of SrCl2, the solution became transparent. With
continued heating at 80 -C the solution became a transparent

gel with high viscosity. The viscous mass was removed

from the hot plate and then calcined at 450 -C for 2 24 h to
obtain the SrTiO3 powders. A series of SrTi(1 x)Crx O3
powders with x = 0.02, 0.04 and 0.08 were prepared in a
similar manner as that for SrTiO3 except that CrCl3 was
added together with SrCl2 into the solution to form viscous
gel mass. A schematic of the synthesis process is shown in
Fig. 1.

Table 1
Specific surface areas and particle size of samples prepared
BET area (m2/g)
Equivalent size (nm)
Crystalline size (nm)

SrTiO3 450 -C18 h

SrTiO3 450 -C24 h

SrTi(1

55.0
21.3
18.8

53.2
21.9
21.7

55.4
21.2
21.8

x)Crx O3

x = 0.02

SrTi(1
55.2
21.3
22.0

x)Crx O3

x = 0.04

SrTi(1
42.7
27.5
22.4

x)Crx O3

x = 0.08

C.-H. Chang, Y.-H. Shen / Materials Letters 60 (2006) 129 132

131

(Perkin Elmer 835). Photocatalytic activity of these powders

was evaluated from the degradation of methyleneblue
(C16H18N3S, MB). Into a 2 mg/L MB solution of 40 ml in
a 100 ml beaker, powders of 0.02 g were added and then
irradiated with a commercial 250-W tungsten halogen spot
light satisfactorily simulating solar radiation. The light
intensity at the surface of solution was 600 nW/cm2.
Photocatalytic decolorization of MB was monitored by
measuring the absorbance of MB at its maximum. Measurements were made every 1 h of illumination.

3. Results and discussion

Fig. 5. TEM micrograph of synthesized SrTi(1

x = 0.02.

x)Crx O3

powders with

2.2. Characterization
The powder obtained was characterized by means of an Xray diffractometer (XRD, Siemens D5000) using graphite
monochrometer, CuKa1 radiation with a scanning speed of
2.4- min 1 for phase identification. The mean crystallite size
of the powders was determined by the XRD-Scherrer formula
[11]. It was applied to peaks of (211) of SrTiO3. Microstructure examinations were obtained by transmission electron microscopy (TEM, JEOL AEM-3010). To determine the
agglomerate sizes of SrTiO3, specific surface area was
measured using the BET technique (Micromeretics, Gemini
2360) and equivalent spherical diameters were calculated
from the surface area. UV Vis diffuse reflectance spectrum
of samples was measured by using an UV Vis spectrometer

The XRD patterns of the powders obtained after calcining the

SrTiO3 gel precursor in air at 450 -C for 2 24 h are shown in Fig.
2 in 2h range of 20 60. The powder was primarily amorphous in
structure after 2 h heating, as shown by the broad continuum in the
XRD in Fig 2. SrTiO3 crystallized after 6 h of heat-treatment of the
gel at 450 -C. Both SrCO3 and SrTiO3 are detected in the powder
obtained after 6 18 h of heat-treatment. SrTiO3 is the only
detectable phase after 24 h heat-treatment at 450 -C. This is the
first known successful attempt to synthesize SrTiO3 at reduced
temperatures by the Pechini method.
BET specific surface area of synthesized SrTiO3 powders is
shown in Table 1 along with the equivalent spherical size
calculated from the BET surface area and the crystallite size
obtained from the Scherrer equation. The surface area of the
SrTiO3 powder obtained after calcining the gel precursor in air at
450 -C for 24 h was 53.2 m2/g. The average particle size calculated
from the specific surface area was 21.9 nm comparable to the
crystalline size of 21.7 nm, suggesting that the SrTiO3 particles are
probably single crystals. In Fig. 3, TEM micrographs are presented
for the SrTiO3 powders obtained after calcining the gel precursor in
air at 450 -C for 24 h. The sample consists of particles of 20 nm
which is consistent with the XRD and BET results.
The XRD patterns of the powders obtained after calcining the
SrTi(1 x)Crx O3 (x = 0, 0.02, 0.04 and 0.08) gel precursor in air at

Fig. 6. The diffuse reflection spectra of SrTiO3 and three samples of chromium doped SrTiO3 (SrTi(1

x)Crx O3).

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C.-H. Chang, Y.-H. Shen / Materials Letters 60 (2006) 129 132

1.0

MB remaining (C/C 0 )

0.9

0.8

0%
2%
4%
8%

0.7

Cr
Cr
Cr
Cr

0.6

0.5

0.4
0

Time (hr)
Fig. 7. Concentration of MB in solution against irradiation time of visible light on different samples.

450 -C for 24 h are shown in Fig. 4. When the SrTi(1 x)Crx O3 gel
precursor was heated 450 -C for 24 h, only SrTiO3 was detected.
This indicated that Cr ions have been successfully doped into
SrTiO3 phase. It is interesting to note that an intensive background
noise was observed in the 2h range of 25 30 for SrTi(1 x)Crx O3
with x = 0.8. Presumably, the over-doped Cr ions segregate into
extremely fine unknown phases when the solubility limit of
substitution solid solution was exceeded. In addition, the major
peaks corresponding to SrTiO3 shifted slightly to lower 2h angle
for x = 0.8, which indicated a subtle change in dimensions of
crystal structure due to the over-doping of Cr ions. BET specific
surface area, equivalent spherical size, and crystalline size of
synthesized SrTi(1 x)Crx O3 powders are shown in Table 1. These
results suggest that the SrTi(1 x)Crx O3 particles are also probably
single crystals. TEM micrograph of synthesized SrTi(1 x)Crx O3
powders with an average size of 20 nm is shown in Fig. 5.
Fig. 6 shows the diffuse reflection spectra of SrTiO3, and three
samples of chromium doped SrTiO3 (SrTi(1 x)Crx O3). Although
SrTiO3 powders are white, all chromium doped SrTiO3 were dark
gray in color. SrTiO3 had an absorption edge at approximately 380
nm which agrees with the value of 387 nm in the literature. The
spectra of SrTi(1 x)Crx O3 with x = 0.02 and 0.04 exhibits obvious
absorption in visible light region (red-shift). The charge-transfer
transition between Cr ion 3d electrons and conduction band may
explain the appearance of the red-shift. There is no red-shift for
SrTi(1 x)Crx O3 with x = 0.08 presumably due to a subtle change in
dimensions of crystal structure and segregation of over-doped Cr
ions and as indicated in Fig. 4.
Fig. 7 shows the degradation curves of MB dye. From Fig. 7
it can be seen that SrTi(1 x)Crx O3 with x = 0.02 and 0.04 have
higher photocatalytic activity. After 2 h of irradiation under
visible light, the MB dye solutions were degraded 45% by
SrTi(1 x)Crx O3 with x = 0.02 and 0.04. However, SrTiO3 and
SrTi(1 x)Crx O3 with x = 0.08 demonstrated less than 20% MB
degradation after 2 h. This result is consistent with the result of
diffuse reflection spectra.

4. Conclusions
Single phase SrTiO3 and SrTi(1 x)Crx O3 nano-size
powders were synthesized at 450 -C by the polymerized
complex method. The success in decreasing the synthesis
temperature can be connected with the homogeneous
atomic scale mixing of the component cations. New band
gap in the visible light range was obtained by chromium
doping in SrTiO3. The absorption of visible light is of
practical importance for the application of SrTiO3 as
photocatalyst.

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