JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGY

Volume 38, Issue 4, August 2010

Online English edition of the Chinese language journal
Cite this article as: J Fuel Chem Technol, 2010, 38(4), 502507

RESEARCH PAPER

Influence of Zn doping on the photocatalytic property

of SrTiO3
WANG Gui-yun, QIN Ya, CHENG Jie, WANG Yan-ji*
School of Chemical Engineering, Hebei University of Technology, Tianjin 300130, China

Abstract: The Zn doped SrTiO3 photocatalysts were synthesized and the photocatalytic activity of the doped samples for water
decomposition to hydrogen was measured under the irradiation of a high pressure Hg lamp (400 W). The influence of doping amount of
Zn and the calcination temperature on the photocatalytic activity were investigated. The physical properties of catalysts with and
without Zn doping were characterized using XRD, XPS, SEM and UV-visible diffuse reflectance spectra. The experimental results
show that Zn doping greatly improves the photocatalytic activity of SrTiO3. The optimum molar doping amount of Zn is about 1%, and
in this case, the suitable calcination temperature is about 950C. Under this condition, the photocatalytic property of Zn doped SrTiO3
is 2.2 times higher than that of the undoped one. The characterization results indicate that 1% Zn doping does not change the crystal
structure and crystal perfection properties of SrTiO3. However, doping element Zn is enriched on the surface of SrTiO3 sample. In
addition, the crystal size increases within a certain range of Zn doping. It can be predicted that Zn2TiO4 is generated by the incorporated
Zn reacting with the Ti-rich phase existed on the SrTiO3 surface, which leads to the decrease of the surface defect concentration of
SrTiO3, and consequently increases the photocatalytic activity of Zn doped SrTiO3.
Keywords: Zn; strontium titanate; photocatalysis; water decomposition

Demand on energy is rapidly increasing in several-fold

along with the continuous development of social economy.
There is a risk for the limited fossil fuel to be used up in the
near future; therefore to develop replaceable energy is an
urgent task before us. Hydrogen is a kind of energy with the
characteristics of clean and efficient. Solar energy is the basic
of all kinds of the energy in the earth. To transfer solar energy
to hydrogen energy is one of the best ideal ways to develop
new energy, which is the main reason for hydrogen
preparation research to be highly focused by photocatalytic
decomposition of water with semiconductor catalysts. The
process for water decomposition to hydrogen and oxygen by
photocatalytic method is as follows: electron is excited to
conduction band (CB) from valance band (VB) and at the
same time, hole is formed in VB when absorbing energy is

1240

higher than that of band-gap Eg Eg (eV) (nm)

of

semiconductor catalyst. Electron has reducing capacity and

hole has oxidation capacity. Considering from view of
thermodynamics, when the electrical potential of the CB
bottom is lower than E (H+/H2), H+ adhered on catalyst surface
can be reduced by excited electrons to release H2. If the hole

potential of the VB top is higher than E (O2/OH), OH

adhered on catalyst surface can be oxidized by holes to release
O2. In addition to the complicated photocatalytic process
mentioned above, photoexcited carrier may recombine, or
some possible reaction to corrode catalyst may occur. At the
present time, catalysts used for water decomposition that have
been reported can be divided into two parts: which can absorb
visible light and which can only absorb UV light. There is a
high absorbance rate on sun light for the former, however, due
to the narrow band-gap, the photoexcited electrons and holes
might recombine easily. Therefore in order to increase
utilization rate of photoexcited electrons, one kind of electron
donor such as CH3OH, HCOOH, Na2S, and Na2SO3 should
usually be added for photocatalytic reaction to consume
holes[13]. Adding of electron donor will limit the practical
application of corresponding catalyst system to a great extent.
Meanwhile, maximum hydrogen production rate with
developed visible light catalyst system can only reach an
extent of several mmol/h. Water can be decomposed to
hydrogen and oxygen by UV light catalyst without adding
sacrificial agent. However hydrogen production rate in lab
with the irradiation of UV light can only reach several to
several hundred mol/h[4,5]. It can be seen that too low activity

Received: 04-Dec-2009; Revised: 20-Feb-2010

* Corresponding author. E-mail: yjwang@hebut.edu.cn, Tel: +86 22 60202489, Fax: +86-22-26582427
Foundation item: supported by the National Natural Science Foundation of China (20241002) and Natural Science Foundation of Hebei (B2006000012).
Copyright 2010, Institute of Coal Chemistry, Chinese Academy of Sciences. Published by Elsevier Limited. All rights reserved.

WANG Gui-yun et al. / Journal of Fuel Chemistry and Technology, 2010, 38(4): 502507

for catalyst is the bottleneck to limit further development of

the technology. In order to improve the photocatalytic
hydrogen production rate, people have chosen many kinds of
ways to change the performance of catalyst. Doping of
semiconductor catalyst is the most commonly used modifying
method. Effective doping can improve catalyst activity by
expanding inductive range of catalyst by irradiation light[6,7],
promoting production and separation of photon-generated
carrier[8], increasing concentration of photon-generated carrier,
and improving surface structure and performance of
catalyst[10,11]. As crystal particles with photocatalysis function,
adding of other components may at the same time affect
photocatalytic activity by improving crystallinity of catalyst. It
is found by the authors of this paper in the previous research
on SrTiO3 that crystalline perfection has a great effect on the
activity[12], which means crystal defect may offer
recombination center for photoexcited carrier and obviously
reduce the photocatalytic activity of catalyst. In order to
further improve the photocatalytic activity of SrTiO3, doping
modification has been carried out on SrTiO3, and this paper is
focused on corresponding research results.

for rapid scanning. Element composition on catalyst surface

was tested with PHI-1600 type XPS produced by American PE
company. Mg K was excitation source and the bonding
energy was calibrated by pollution C (1s) electron bonding
energy of 284.8 eV. The XRD patterns were recorded with a
Rigaku D/max 2500 V powder X-ray diffractometer using Cu
K radiation.

1.1

Experimental
Preparation of catalysts

10 g of tetrabutyl titanate was diluted in 100 mL ethanol and

then 100 mL water was added dropwise slowly into the
solution with stirring and heating. After complete hydrolysis,
the filtered cake was mixed with pre-dissolved and
stoichiometric strontium nitrate, certain amount of zinc nitrate
and water solution of mineralizer potassium hydrate before
drying. Doping methods of other mixed elements were in the
same way and the raw materials were all nitrate of
corresponding elements. According to the literature[12], adding
amount of mineralizer potassium hydrate is 2.0% (w%, relative
to theoretical yield of SrTiO3 ). The precursor powder was
calcinated at a certain temperature for 6 h, then ground,
washed with deionized water, dried, and screened to obtain
particles with particle size less than 38 m for activity test.
Previous research indicated that CoO was an effective assistant
catalyst for SrTiO3, and 0.2% of CoO (w%) was loaded on the
catalyst surface to prepare CoO/SrTiO3 photocatalyst using the
adopting method as literature[12].
1.2

Characterization of catalysts

Crystallite sizes and shapes were observed using scanning

electron microscopy (SEM) (Philips XL30, Holland). UV-vis
absorption spectra of catalysts were obtained using a
UV-visible spectrophotometer (UV-2401PC, Shimadzu Co.,
Kyoto, Japan), with step length of 2 mm and slit-width of 5 nm

1.3

Photocatalytic experiment

The photocatalytic reaction was carried out in an air free

closed gas circulation system with a reactor (1000 mL) made
of quartz. The catalyst powder (0.1 g) was dispersed in
deionized water (800 mL) containing Na2CO3 using a
magnetic stirring. The dispersed mixture was irradiated
externally under Ar atmosphere by a high pressure Hg lamp
(400 W). Argon was introduced into the system after the
reaction to make the gases well-mixed. The gaseous products
were measured using gas chromatography (MS-5A column, Ar
carrier, thermal conductivity detector) through a gas sampler
(ca.2 mL) which was directly connected to the reaction system.

Results and discussion

Doping modification research had been carried out on

SrTiO3 by firstly selecting part of transition metals in the first
long period, with 1 mol% of adding amount of Ti for doping
elements. Calcination temperature for precursor was 1000C
and activity test was carried out after loding 0.2% of CoO (w%)
on the prepared SrTiO3. The results indicate that photocatalytic
activity of SrTiO3 is obviously reduced by doping of Mn, Fe,
Co, and Ni, slightly reduced by adding Cr and Cu, and
obviously increased by doping Zn. Thus, further investigation
on the photocatalytic activities of Zn-doped samples were
carried out.
2.1

Photocatalytic performance of Zn-doped SrTiO3

Photocatalytic activities of CoO/SrTiO3 with different

doping amount of Zn are shown in Table 1.
Table 1 Influence of Zn doping amount on the photocatalytic
activity of CoO/ SrTiO3
(loading amount of CoO, 0.2% (w%))
Amount of doping
wmol/%
0
0.5
0.6
0.8
1
1.4
1.5

Rate of gas evolution / molh1

O2
H2
105
38
177
70
259
141
272
146
285
140
239
118
162
57

WANG Gui-yun et al. / Journal of Fuel Chemistry and Technology, 2010, 38(4): 502507
Table 2 Influence of calcination temperature on the photocatalytic
activity of Zn-doped SrTiO3
(loading amount of CoO, 0.2% (w%))
Calcination temperature
t /C

Rate of H2 evolution /molh1

1% Zn-doped

undoped

SrTiO3

SrTiO3

900

254

85

950

315

119

1000

285

105

1050

269

139

1100

239

132

The results indicate that there is an obvious improvement of

photocatalytic activity of SrTiO3 when the molar doping
amount of Zn is within 0.5% to 1.5%, and the optimum doping
amount is 1%.
Calcination temperature is one of the main factors that affect
the performance of oxide catalyst. Photocatalytic activities of
prepared SrTiO3 with 1% Zn doping (mol%) and without Zn
doping at different precursor calcination temperatures are
shown in Table 2, with the CoO loading amount of 0.2%(w%).
The suitable calcination temperature for 1% Zn-doped (mol%)
catalyst is about 950C, which is 100C lower than that of
sample without Zn doped. The activities of catalysts with
Zn-doped are higher than those of without Zn doped in the
tested scope. When the samples are prepared at the optimum
calcination temperatures respectively, it can be seen that the
activity of sample with Zn doped is 2.2 times higher than that
of sample without Zn added, which means it increased by
120%.
2.2

Characterization results of Zn doped SrTiO3

XRD and UV-vis diffuse reflection analysis are respectively

carried out on the SrTiO3 samples calcinated at 1000C with

Fig. 1 XRD patterns of Zn-doped SrTiO3

a: without doping; b: doped with 1.0% Zn

1% Zn doped (mol%) and without Zn added, which are shown

in Fig. 1 and Fig. 2. XRD analysis results in Fig. 1 show that
there is no impurity peak for the Zn doped SrTiO3 sample, and
there is no obvious difference in position of diffraction peak
and relative strength for with and without Zn doped samples,
which indicates that Zn ion does not enter the crystalline
lattice of SrTiO3. Zn is scattered on the surface of SrTiO3
particles in a form of certain oxide. Fig. 2 indicates that the
intrinsic transition existing in the 1% Zn added (mol%) sample
is similar to that of without Zn added, and the band gap widths
calculated with absorption curve of both are about 3.2 eV. The
main difference between the two samples is that there is a few
impurity peaks for Zn-added sample in 300-350 nm, which
may be caused by UV absorption of Zn-containing substance.
SEM analysis results of SrTiO3 samples calcinated at
1000C with 1% Zn doped (mol%) and without Zn added are
given in Fig. 3. It can be seen that the particle size of Zn doped
SrTiO3 particles is obviously bigger than that of without Zn
added, however there is no obvious change for morphology of
crystal particles.
Comparing SEM analytical results of samples with different
Zn doping amount of 0.0%, 0.5%, 1.0%, and 1.5%, the particle
sizes are 0.8 m, 1.7 m, 2.1 m, and 2.0 m, respectively. It
can be seen that the particle size of SrTiO3 increases with the
doping amount in a certain range.
XPS analysis on 1% Zn doped (mol%) SrTiO3 sample
shows that the element contents are C (61.8%), O (28.7%), Sr
(4.2%), Ti (4.4%), Zn (0.7%), K (0.2%). The Zn/Ti mol ratio
is 1:6.3, which is obviously higher than the batch charging
ratio of 1:100. XPS is a surface analysis technology and it can
only detect atoms within 4 nm of surface[13]. Thus, after SrTiO3
catalyst has been doped with Zn and calcinated, the Zn content
on the surface or the adjacent surface of SrTiO3 is much higher
than that in the bulk phase.

Fig. 2 UV-vis diffuse reflection absorptive spectra of

Zn-doped SrTiO3
a: without doping; b: doped with 1.0% Zn

WANG Gui-yun et al. / Journal of Fuel Chemistry and Technology, 2010, 38(4): 502507

Fig. 3 SEM photos of Zn-doped SrTiO3

(a): without doping; (b): doped with 1.0 % Zn

2.3

Result analysis
2+

crystal structure of SrTiO3.

1/ 2O 2 + TiO 2 U TiTi + 3OO + VSr" + 2h..

4+

Radius of Zn is about 0.74 nm, bigger than that of Ti ,

0.68 nm and smaller than that of Sr2+, 1.13 nm. If the
substitutional doping occurred in the bulk phase of SrTiO3, its
lattice constant would change and diffraction peak position of
XRD would shift, or there would be a crystalline lattice
deformation of the doped sample with increased deficiency.
Therefore there will be an obvious affect on morphology of
SrTiO3 particles with 1% (mol%) doping amount. However,
the analytical results indicate that there is no obvious change
for crystalline structure, morphology characteristics,
absorption performance on UV light of doped sample, from
which it can be seen that there is low possibility for the
substitutional doping. It is also found in doping modification
research on TiO2 photocatalyst by Wang et al that it is not easy
for substitution of Zn2+ for Ti4+[14] . Combining the analysis
result of XPS, it can be inferred that added Zn can not enter
the inside of crystal lattice and Zn is segregated on SrTiO3
surface in a form of ZnO or titanium zinc composite oxide.
The raw materials for preparation of SrTiO3 are Sr(NO3)2
and tetrabutyl titanate which have certain absorbency for both
of them. Therefore it is a little difficult to accurate weight the
batch charging strictly according to stoichiometry. Even
though the suitable batch charging ratio was determined for
each batch of raw materials, there was a little difference
between element atom ratio and stoichiometric proportion of
Sr and Ti. For the formation energy of VTi'''' is very high, it is
difficult to obtain SrTiO3 with Ti ion vacancy[15]. When there
is an excessive amount of Sr, it will precipitate in form of SrO
or SrCO3 (formed during the roasting of raw catalyst materials
in air). When SrTiO3 is covered by SrO and SrCO3, the
photocatalytic activity is reduced because SrO and SrCO3 are
both insulation ionic crystal. When Ti is a little excessive,
Ti-rich phase can be formed under circumstances to keep

(1)

The following reaction may be occurred in Ti-rich phase:

VSr'' + h. U VSr'

(2)

VSr' + h. U VSr

(3)

That is to say, defect sites containing in the Ti-rich phase

include

VSr , VSr' ,

and

VSr'' ,

in which

VSr

and

VSr'

are

electron traps, which can capture photoemission electron to

reduce the photocatalytic activity of catalyst. At the same time
Ti-rich phase has type P conduction characteristics, which will
make electron in SrTiO3 bulk phase shift to it to gain
grain-boundary barrier. When the photocatalytic reaction
happens, SrTiO3 will absorb photon and stimulate electrons
and holes. Some holes will move towards Ti-rich phase under
function of potential barrier and then pass through the Ti-rich
phase to jump to surface to oxidize water and release oxygen.
The photocatalytic activity of the catalyst with Ti-rich phase is
lower than that of without Ti-rich phase. This means that the
stoichiometric deviation of Sr to Ti ratio can reduce the
photocatalytic activity of sample. However, compared with the
condition of Sr excess, slight excess of Ti can cause a little
activity decrease of SrTiO3. Previous Sr/Ti test results indicate
that the activity decrease tendency of SrTiO3 with excess of Ti
is slow and the tendency with excess of Sr is rapid. Actually,
there is more or less Ti-rich phase on the SrTiO3 surface
during the optimization of raw materials with an aim at
improving catalyst activity. Therefore, the activity of prepared
catalyst is lower than that of ideal crystal which is strictly
composed of stoichiometry ratio.
Zn may react with Ti-rich phase of SrTiO3 to form
Zn2TiO4[16,17] at a corresponding calcination temperature. The
formed Zn2TiO4 has an inverse spinel structure, which is
greatly different from that of SrTiO3. So it is not easy to
continuously grow and cover on SrTiO3 surface and it may

WANG Gui-yun et al. / Journal of Fuel Chemistry and Technology, 2010, 38(4): 502507

segregate to two or more crystal boundaries formed by SrTiO3

crystal particles. That means the added Zn has the functions to
reduce the amount of Ti-rich phase and the defection
concentration on the surface of SrTiO3, which may be the main
reason for the activity of Zn-added SrTiO3 improved. Surface
defect is the main factor to prevent particles from further
growing. Therefore defection concentration on catalyst surface
is reduced and the catalyst particles become bigger after
doping with certain amount of Zn.
When doping amount of Zn is too low, the Ti-rich phase on
the SrTiO3 surface can not be eliminated. When adding
amount of Zn is relatively high, the excessive Ti will combine
with Zn and Sr will precipitate in a form of SrO, which will
cause the reduction of photocatalytic activity. In addition, ZnO
will be formed as well as Zn2TiO4 when doping amount is too
high, then enough amount of Zn2TiO4 and ZnO impurity phase
will cover on the SrTiO3 surface to prevent further growing of
SrTiO3, to reduce effective surface exposure of SrTiO3, to
reduce absorption rate on illumination light by SrTiO3, and
therefore rapidly reduce the photocatalytic activity of SrTiO3.
Thus, a suitable amount of Zn doping can get a maximum
photocatalytic activity and particle size of SrTiO3 is firstly
increased and then decreased along with the doping amount of
Zn.
If the calcination temperature is too low, when preparing Zn
added SrTiO3, it is not easy for guarantee the purity and
integrity of crystallization of SrTiO3 because of the low
reaction speed and the incomplete precursor reaction. However,
if the calcination temperature is too high, because of the low
sintering temperature[18] Zn2TiO4 in crystal boundary may
soften and frit to partially cover the effective surface of SrTiO3
and therefore reduce its activity. So the optimum roasting
temperature exists for the doping samples. Compared with the
sample without doping, its suitable roasting temperature is
lower. That is because the determination factor of suitable
calcination temperature for both is different. Suitable
calcination temperature for sample without doping is caused
by crystalline perfection of SrTiO3, particle growing and
sintering. Roasting temperature for SrTiO3 is a little high,
therefore its suitable calcination temperature is a little higher
than that of Zn-doped SrTiO3.

Conclusions

undoped SrTiO3 in crystalline morphology characteristics,

XRD diffraction peak position and relative strength, and the
absorption performance on Vis-UV light. However, particle
size of Zn doped catalyst is a little increased. XPS analysis
result indicates that the added Zn is enriched on the surface of
SrTiO3.
The added Zn may react with Ti-rich phase existing on the
surface of SrTiO3 to form Zn2TiO4, which reduces the possibly
existing impurities phase on SrTiO3 surface. Therefore, the
defection concentration on Zn doped SrTiO3 surface is reduced
and the photocatalytic activity is increased.

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