Applied Surface Science 258 (2012) 4328–4333

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Applied Surface Science

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

Synthesis and characterization of natural zeolite supported Cr-doped TiO2

photocatalysts
Cheng Wang a,b , Huisheng Shi a,∗ , Yan Li b
a
Key Laboratory of Advanced Civil Engineering Materials (Tongji University), Ministry of Education, 4800 Caoan Road, Shanghai 201804, China
b
Institute of Material Science and Engineering, Shijiazhuang University of Economics, 136 Huaian Road, Hebei Shijiazhuang 050031, China

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

Article history: Natural zeolite supported Cr-doped TiO2 photocatalysts were synthesized for the sake of improving the
Received 16 July 2011 recovery and photocatalytic efficiency of TiO2 . The materials were characterized by X-ray diffraction
Received in revised form (XRD), Brunauer–Emmett–Teller (BET) surface areas, Fourier transform infrared spectroscopy (FT-IR),
30 November 2011
scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse
Accepted 26 December 2011
reflection spectroscopy (UV–vis DRS) and photoluminescence (PL). The photocatalytic activity was evalu-
Available online 30 December 2011
ated by the degradation of methyl orange in aqueous solution. The results show that the Cr concentration
and the calcination temperature play important role on the microstructure and photocatalytic activity of
Keywords:
Zeolite
the samples. The 10 mol% Cr-doped TiO2 /zeolite calcined at 400 ◦ C exhibits higher photocatalytic activity
Cr than that of the other samples.
TiO2 © 2011 Elsevier B.V. All rights reserved.
Photocatalyst

1. Introduction
Titanium dioxide is the most important photocatalyst for the
degradation of organic pollutants in aqueous media [1]. However,
practical applications of TiO2 are limited because of the problems
of low recycling efficiency of TiO2 fine particles, fast recombination
rate of photogenerated electron–hole pair and a low quantum yield
in the photocatalytic reactions in aqueous solutions.
Recently, researches have been devoted in searching for the
suitable substrates to support nano TiO2 in order to improve the
recovery efficiency of TiO2 . Of various substrates, zeolites have
been the most favorable to be used in supporting TiO2 , due to
their unique structures, uniform pores and channels and excellent
absorption ability [2,3]. Previous works have mainly emphasized on
synthetic zeolites [4–10] as the substrates of TiO2 . TiO2 supported
on zeolite integrates the photocatalytic activity of TiO2 with the
adsorption properties of zeolite together, which induce a synergis-
tic effect, resulting in the enhancement of photocatalytic efficiency
[2]. However, the complex synthesizing process and high cost of
the synthetic zeolites considerably limit the practical application
of the as-prepared photocatalysts. Natural zeolites are cheaper and
more abundant as compared with synthetic zeolites [2,3]. In recent
years, natural zeolites have been used instead of synthetic zeolites
∗ Corresponding author. Tel.: +86 21 69582144.
E-mail addresses: wangchengtj@163.com (C. Wang), shs@tongji.edu.cn (H. Shi).
to supported nano TiO2 [2,3,11–14]. It shows that the natural zeo-
lites supported-TiO2 display higher photocatalytic efficiency at low
initial concentration in comparison with pure TiO2 .
It is believed that doping TiO2 with foreign ions is one of the most
promising strategies for sensitizing TiO2 to visible light and also
for forming charge traps to keep electron–hole pairs separate [15].
However, so far, there is little systematic study on the supported
ions-doped TiO2 especially natural zeolite supported ions doped-
TiO2 photocatalysts. In our previous work, we have reported the
natural zeolite supported Fe3+ -TiO2 photocatalysts. It showed that
zeolite and iron ion concentration played an important role on the
microstructure and photocatalytic activity of the samples. Zeolite
inhibited the growth of TiO2 crystallite sizes. The iron ions could
diffuse into TiO2 lattice to form the Fe O Ti bond and gave TiO2 the
capacity to absorb light at lower energy levels. The photocatalytic
activity of the samples could be enhanced as appropriate dosages of
Fe3+ were doped [14]. Recently, Cr-doped TiO2 has received much
attention because Cr ion can excellently extend the visible light
absorption and improve the photocatalytic activity of TiO2 [16–18].
In this paper, natural zeolite supported Cr-doped TiO2 pho-
tocatalysts were synthesized and the aim of this work was
to investigate the effect of ions concentration and the calci-
nation temperature on the microstructure and property of the
as-prepared photocatalysts. Based on the above goals, X-ray diffrac-
tion (XRD), Brunauer–Emmett–Teller (BET), Fourier transform
infrared spectroscopy (FT-IR), scanning electron microscopy (SEM),
X-ray photoelectron spectroscopy (XPS), ultraviolet–visible diffuse
reflection spectroscopy (UV–vis DRS) and photoluminescence (PL)

0169-4332/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2011.12.108
 C. Wang et al. / Applied Surface Science 258 (2012) 4328–4333 4329

were employed to investigate the microstructure of the photocata-

lysts. The photocatalytic activity of samples for the degradation of
methyl orange (MO) was also investigated.

2. Experimental

2.1. Photocatalyst preparation

Natural zeolite (clinoptilolite) powders were mixed with doubly

distilled water and heated up to 70 ◦ C. Subsequently, TiCl4 solu-
tion (the theoretical proportion of TiO2 in the photocatalyst was
30 wt.%) and CrCl3 solution (the nominal ratios of Cr3+ to TiO2 were
1.0 to 12.0 mol%, respectively) were added drop wise into the above
mortar and the pH of the dispersion was adjusted to about 2.0. The
system was vigorously stirred at 70 ◦ C for 4 h. After aging for 12 h,
the products were repeatedly washed with doubly distilled water
and then dried at 80 ◦ C for 2 h. The above samples were finally cal-
cined at 200–600 ◦ C for 2 h in a muffle furnace to obtain the natural
zeolite Cr-doped TiO2 photocatalysts.
Fig. 1. XRD patterns of zeolite and TiO2 /zeolite doped with different dosage of Cr
ions.
2.2. Characterization

The crystal structure of the samples were characterized by pow-
der XRD (D/max 2550VB3+/PC, Rigaku International Corporation,
Japan) under the following conditions: graphite monochromatic
copper radiation (Cu K␣ ,  = 0.15418 nm); 40 kV as accelerating
voltage; 40 mA as emission current; and the 2 range of 3◦ –70◦ at a
scan rate of 4◦ /min. The nitrogen adsorption–desorption isotherms
were determined using a Micromeritcs Tristar 3000 nitrogen
adsorption apparatus. To calculate the specific surface area the BET
equation was applied on the adsorption branch of the isotherms
whereas the pore size was calculated from the desorption branch
using the Barret–Joyner–Halenda (BJH) model. The pretreatment
(degassing) of the samples took place under vacuum (10−2 Torr)
at 150 ◦ C. FT-IR spectra were recorded by a spectrometer (Nexus,
Thermo Nicolet Corporation, America) using KBr pellets at room
temperature in the region of 400–4000 cm−1 . The morphology of
the photocatalyst was examined by field-emission scanning elec-
tron microscope (FESEM) (Quanta 200 FEG, FEI Company, America).
XPS were recorded under ultrahigh vacuum (<10−6 Pa) at a pass
energy of 93.90 eV on a PerkinElmer PHI 5000C ESCA system
equipped with a dual X-ray source by using a Mg KR (1253.6 eV)
anode and a hemispherical energy analyzer. All binding energies
were calibrated with contaminant carbon (C 1s = 284.6 eV) as a
reference. UV–vis DRS of the samples were obtained for the dry-
pressed disk samples using a UV–vis spectrophotometer with an
integrating sphere (UV-3010, HITA-CHI, Japan). The PL spectra of
the samples were recorded with RF-540 spectrofluorophotometer
(RF-540, Shimadzu Instruments, Japan), using the 280 nm excita-
tion line of a Xe lamp.
the decoloration rate of the solution; A0 means the absorbency of
the original solution; At means the absorbency of the MO solution
after treated for t hours.
3. Results and discussion
3.1. XRD analysis
Fig. 1 shows the XRD patterns of zeolite and TiO2 /zeolite doped
with different dosage of chromium ions. The peaks at 2 = 25.4◦ ,
37.5◦ , 48.2◦ , 54.0◦ , 55.0◦ , 62.7◦ ascribed to that of anatase TiO2 are
observed. No correspondent peaks to chromium oxides phases are
identified, even at the highest Cr concentration. It can be possibly
inferred that: (i) the concentration of Cr-doping is so low that it
cannot be detected by XRD; (ii) Cr ions can be incorporated into
the TiO2 lattice via displacing Ti4+ sites due to the close ionic radius
of Ti4+ (0.68 Å) and Cr3+ (0.64 Å), forming a chromium–titanium
solid solution [18,19].
Fig. 2 shows the XRD patterns of 10%Cr/TiO2 /zeolite calcined at
200–600 ◦ C. With the ascent in calcination temperature, the peak
intensity of anatase phase increases significantly, indicating the
improvement in crystallization of anatase phase. Simultaneously,
the width of the (1 0 1) peak becomes narrower, suggesting the

2.3. Photocatalytic activity tests

The photocatalytic activity of the samples was evaluated by the

degradation of MO in an aqueous solution. The photocatalytic reac-
tor system consisted of a 40 W UV lamp centered at 253.7 nm (the
integrated UV intensity was about 6.7 mW/cm2 , which is about
10 cm above the dishes) and a magnetic stirrer for obtaining dis-
persion. In a typical test for MO degradation, the photocatalysts
(0.2 g) were suspended in 100 mL MO solution (10 mg/L) and then
treated under UV light for different times. The decoloration rate
of the MO solution was monitored every regular time intervals by
measuring the maximum absorbance of MO (464 nm), using 722S
spectrometer (722S, Shanghai Precision & Scientific Instrument Co.,
Ltd., China). The decoloration rate of the MO solution was calcu-
lated. The calculational formula is: P = (A0 − At )/A0 × 100%. P means Fig. 2. XRD patterns of 10%Cr/TiO2 /zeolite calcined at 200–600 ◦ C.
4330 C. Wang et al. / Applied Surface Science 258 (2012) 4328–4333
Table 1
Average pore diameter (APD) and specific surface area (SSA) of the raw zeolite,
10%Cr/TiO2 /zeolite calcined at 200–600 ◦ C.
Samples APD (nm)
Raw zeolite 8.7
Cr/TiO2 /zeolite 200 ◦ C 3.1
Cr/TiO2 /zeolite 300 ◦ C 3.5
Cr/TiO2 /zeolite 400 ◦ C 4.1
Cr/TiO2 /zeolite 500 ◦ C 4.9
Cr/TiO2 /zeolite 600 ◦ C 6.7
growth of anatase crystallites. When the calcination temperature
increases to 600 ◦ C, few minor but discernible peaks correspond-
ing to rutile phase are detected. In addition, it can be seen that the
(1 0 1) peak of anatase gradually shifts to the lower angle with the
increase in calcination temperature. This result indicates that Cr
ions have entered the crystal structure and consequently induce
distortion to crystal lattice [20,21]. Simultaneously, the binding
force of Cr O Ti enhances and the crystallite defect increases with
the increase in calcination temperature [21].
3.2. BET analysis
Table 1 shows the average pore diameter and specific sur-
face area of the raw zeolite and 10%Cr/TiO2 /zeolite calcined at
200–600 ◦ C. As can be seen in Table 1, all the Cr doped samples
have smaller average pore diameter and larger specific surface area
than that of raw zeolite. This can be attributed to the supporting of
TiO2 nanoparticles on/in the surface/pores of zeolite. The nanopar-
ticles block the pores of the zeolite and decrease the average pore
diameter of the samples. The high specific surface area of TiO2
nanoparticles on/in the surface/pores of zeolite can increase the
specific surface area of the samples. The specific surface area of the
Cr doped samples decreases with the increase in calcination tem-
perature and this can be attributed to the growth of TiO2 particles.
However, with the ascent in calcination temperature, the average
pore diameter of the Cr doped samples increases. This is proba-
bly because the organics or impurity components contained in the
pores of raw zeolite decompose under high calcination tempera-
ture, and thus the average pore diameter of the samples increases
with the increase in calcination temperature.
Fig. 3. FT-IR spectra of zeolite, TiO2 /zeolite and 10%Cr/TiO2 /zeolite.
3.3. FT-IR analysis
Fig. 3 shows the FT-IR spectra of zeolite, TiO2 /zeolite and
SSA (m2 /g) 10%Cr/TiO2 /zeolite in the range of 400–4000 cm−1 . The board peak
56 around 3437 cm−1 and 1637 cm−1 can be assigned to the O H
205 stretching and bending vibration of adsorbed water, respectively.
181 As shown in the spectrum of zeolite, the peak at 1049 cm−1 cor-
187
responds to the Si O Si stretching vibration. The weak peaks
152
92 between 800–400 cm−1 correspond to Si O Si bending vibra-
tion. In contrast to the FT-IR spectra of zeolite, the spectra
of TiO2 /zeolite and Cr/TiO2 /zeolite obviously change. The board
peak appears between 800–400 cm−1 owing to the superpo-
sition of Ti O and Si O bond. The Si O Si peaks belong to
zeolite, TiO2 /zeolite and 10%Cr/TiO2 /zeolite locate at 1049 cm−1 ,
1059 cm−1 and 1071 cm−1 , respectively. This may be due to the
interrelationship of TiO2 –zeolite, Cr–TiO2 –zeolite, respectively.
3.4. SEM analysis
Fig. 4 shows the SEM images of zeolite and 10%Cr/TiO2 /zeolite.
From the SEM images it is evident that the originally smooth zeo-
lite matrix (Fig. 4a) is covered with TiO2 particles (Fig. 4b) and the
TiO2 particles are either as nanoparticles or clusters attaching to
the zeolite surface.
3.5. XPS analysis
Fig. 5 shows XPS whole scanning spectrum (a); Ti 2p (b); O 1s
(c); and Cr 2p3/2 (d) of TiO2 /zeolite and 10%Cr/TiO2 /zeolite, respec-
tively. From Fig. 5a, it can be seen that peaks of Ti, O, C, Si exist in
XPS spectra of the above two samples. A weak peak of Cr appears
in the XPS spectrum of ion-doped sample. The two strong peaks in
Fig. 5b correspond to Ti4+ 2p1/2 and Ti4+ 2p3/2 , respectively, which
is consistent with the values of Ti4+ in the TiO2 lattices [16,17]. It
can be seen that the Ti 2p1/2 and Ti 2p3/2 binding energies of the
Cr/TiO2 /zeolite (466.0 eV and 460.2 eV) shift to higher energies as
compared with that of TiO2 /zeolite (465.6 eV and 460.0 eV). It infers
that the doped Cr ions may diffuse into TiO2 lattices to form the
Cr O Ti bond. In order to achieve the charge balance in the TiO2
lattice, a trace of titanium ions may transform to higher valent by
releasing the plethoric electrons, which leads to the XPS peaks shift
in the Cr/TiO2 /zeolite [17]. The O 1s spectra of Cr/TiO2 /zeolite and
TiO2 /zeolite are shown in Fig. 5c. It is noted that O 1s spectrum
of Cr/TiO2 /zeolite obviously shifts from 532.9 eV to 534.1 eV com-
pared with that of TiO2 /zeolite. The results can be ascribed to an
increase in the ionic state of the oxygen bond causing the binding
energies of all electronic states of oxygen to shift [22]. The peaks of
XPS spectra of Cr 2p3/2 (Fig. 5d) at 577.2 eV and 579.6 eV should be
assigned to Cr3+ and Cr6+ , respectively [18]. The integral area under
Cr3+ and Cr6+ peaks reveals that Cr6+ is the predominant species
(81.2 at.%).
3.6. UV–vis DRS analysis
The UV–vis DRS spectra of TiO2 /zeolite and 10%Cr/TiO2 /zeolite
and their correspondent energy band gaps (Eg ) are shown in Fig. 6. It
can be seen that the UV–vis absorbance for the Cr/TiO2 /zeolite sig-
nificantly shifts to longer wavelength (the red shift) in comparison
with that of TiO2 /zeolite. The band gap energies of TiO2 /zeolite and
Cr/TiO2 /zeolite obtained by the Kubelka–Munk theory are 2.84 eV
and 1.70 eV, respectively. The reduction in the band gap and visible
response of Cr/TiO2 /zeolite has been attributed to (i) the localized
states near the conduction or valence band of the modified TiO2 ;
(ii) the formation of color centers, which were associated with the
 C. Wang et al. / Applied Surface Science 258 (2012) 4328–4333 4331

Fig. 4. SEM images of zeolite (a) and 10%Cr/TiO2 /zeolite (b).

oxygen vacancies in TiO2 or to the radicals in the titanium dioxide
lattice associated with the doping ions [18].
3.7. PL analysis
Fig. 7 shows the PL spectra of TiO2 /zeolite and
10%Cr/TiO2 /zeolite. It can be found that all of the samples can
exhibit obvious PL signal centered at approximately 467 nm. These
PL signals result from the surface oxygen vacancies and defects of
TiO2 [23]. A lower PL intensity may indicate a lower recombina-
tion rate of electron–hole pairs and higher separation efficiency
[24,25]. As shown in Fig. 7, the PL intensity of Cr/TiO2 /zeolite is
lower than that of undoped TiO2 /zeolite which means that Cr
doping decreases the recombination rate of electron–hole pairs.
Generally speaking, the smaller the particle size, the larger the
oxygen vacancy and defects content, the higher the probability of
exciton occurrence, the stronger the PL signal [26]. As analyzed
in the above section, Cr doping induces distortion to the crystal
lattice and increases the defect of TiO2 , which may show stronger
PL signal. However, the Cr ions exist in the TiO2 crystal lattice as
3+ and 6+, and Cr6+ can capture the photogenerated electrons and
then maintain the charge balance. The capture effect of defect on
the photogenerated electrons is lower than that of the Cr6+ [27],
and this may result in the lower PL signal and recombination rate
of electron–hole pairs, and thus higher photocatalytic activity of
Cr doped sample.

Fig. 5. XPS whole scanning spectrum (a); Ti 2p (b); O 1s (c); and Cr 2p3/2 (d) of TiO2 /zeolite and 10%Cr/TiO2 /zeolite.
4332 C. Wang et al. / Applied Surface Science 258 (2012) 4328–4333
Fig. 6. UV–vis DRS spectra and their corresponding calculated Eg for the TiO2 /zeolite
and 10%Cr/TiO2 /zeolite.
3.8. Photocatalytic activity
Fig. 8a shows the degradation curves of MO solution catalyzed
by the photocatalysts doped with different dosage of Cr ions cal-
cined at 400 ◦ C. It can be observed that the decoloration rates
of MO solution catalyzed by the Cr-doped samples are obviously
higher than that of the undoped sample. The decoloration rate
of MO solution catalyzed by 10%Cr/TiO2 /zeolite reaches to 41.73%
after illumination for 5 h which is 17.9% higher than that of the
undoped TiO2 /zeolite. It indicates that the photocatalytic activity
of the photocatalysts can be effectively improved after doping with
chromium ions. This phenomenon can be attributed to the visible
response and lower recombination rate of electron–hole pairs of Cr
doped sample.
Fig. 8b shows the degradation curves of MO solution catalyzed
by the 10%Cr/TiO2 /zeolite calcined at 200–600 ◦ C. It can be observed
that the decoloration rate of MO solution catalyzed by the sample
calcined at 200 ◦ C reaches to 40.68% after illumination for 5 h. As
the calcination temperature increases to 300 ◦ C, the decoloration
rate rapidly reduces to 9.58%. However, as the calcination temper-
ature further increases to 400 ◦ C, the decoloration rate drastically
increases to 41.73%. The decoloration rates reduce to 35.83% and
6.69% when the calcination temperatures are 500 ◦ C and 600 ◦ C,
respectively.
Fig. 7. PL spectra of TiO2 /zeolite and 10%Cr/TiO2 /zeolite.
Fig. 8. Decoloration rate of MO solution catalyzed by photocatalysts doped with
different dosage of Cr ions (a); 10%Cr/TiO2 /zeolite calcined at 200–600 ◦ C (b).
After calcined for 200 ◦ C, the TiO2 /zeolite photocatalysts have
high specific surface area and excellent adsorption ability, and thus
exhibit excellent decoloration effect on the MO solution due to its
remarkable ability in gathering the organic molecules onto/near
the surface of TiO2 particles. The specific surface area decreases due
to the increase in calcination temperature. This result may further
lead to the decrease of the adsorption and decoloration abilities
of the photocatalysts. Simultaneously, the photocatalytic activity
of TiO2 increases as the calcination temperature increases from
200 ◦ C to 400 ◦ C. However, when the calcination temperature rises
up to 500 ◦ C, the photocatalytic activity of TiO2 decreases again. In
conclusion, the absorption and photocatalytic synergetic effect of
Cr-doped TiO2 /zeolite can lead to the above experiential results.
4. Conclusions
Natural zeolite supported Cr-doped TiO2 photocatalysts were
successfully prepared in this study. Cr ions can be incorporated
into the TiO2 lattice via displacing Ti4+ sites due to the close ionic
radius of Ti4+ and Cr3+ . The binding force of Cr O Ti enhances with
the increase in calcination temperature. Cr dopant is present as
Cr3+ (19.8 at.%) and Cr6+ (81.2 at.%) species. The band gap energy
of 10 mol%Cr/TiO2 /zeolite significantly reduces from 2.84 eV to
1.70 eV in comparison with that of the undoped TiO2 /zeolite. The
photocatalytic activities of the doped samples strongly depend
on the concentration of chromium ions and the calcination tem-
perature. The decoloration rate of MO solution catalyzed by
10%Cr/TiO2 /zeolite calcined at 400 ◦ C reaches to 41.73% after illu-
mination for 5 h which is 17.9% higher than that of the undoped
TiO2 /zeolite.
 C. Wang et al. / Applied Surface Science 258 (2012) 4328–4333
Acknowledgments
This work was financially supported by the Hebei Natural Sci-
ence Foundation, China (grant no. E2008000537), Hebei Foundation
for Development of Science and Technology, China (grant no.
07215156) and Open Research Foundation of Key Laboratory of
Advanced Civil Engineering Materials (Tongji University), Ministry
of Education, China (grant no. 2010412).
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