Applied Surface Science 255 (2008) 2478–2484

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Applied Surface Science

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Preparation, characterization and activity evaluation of p–n junction

photocatalyst p-ZnO/n-TiO2
Chen Shifu*, Zhao Wei, Liu Wei, Zhang Sujuan
Department of Chemistry, Huaibei Coal Normal College, Dongshan Road 100, Anhui, Huaibei 235000, People’s Republic of China

A R T I C L E I N F O A B S T R A C T

Article history: In this paper, p-type ZnO powder was prepared by decomposition of zinc nitrate at 350 8C for 1 h. p–n
Received 10 April 2008 junction photocatalyst p-ZnO/TiO2 was prepared by ball milling of TiO2 in H2O solution doped with p-
Received in revised form 9 July 2008 ZnO. The p–n junction photocatalyst p-ZnO/TiO2 was characterized by UV–vis diffuse reflection
Accepted 21 July 2008
spectrum, scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and the fluorescence
Available online 31 July 2008
emission spectra. The photocatalytic activity of the photocatalyst was evaluated by photocatalytic
reduction of Cr2O72 and photocatalytic oxidation of methyl orange (MO). The results showed that the
Keywords:
photocatalytic activity of the p–n junction p-ZnO/TiO2 is much higher than that of TiO2 on the
p-ZnO/TiO2
p–n junction
photocatalytic reduction of Cr2O72. However, the photocatalytic activity of the photocatalyst is much
Photocatalyst lower than that of TiO2 on the photocatalytic oxidation of methyl orange. Namely, the p–n junction
Activity photocatalyst p-ZnO/TiO2 has higher photocatalytic reduction activity, but lower photocatalytic
Characterization oxidation activity. When the amounts of doped p-ZnO are 0.0 and 2.0 wt.%, illumination for 20 min, the
photoreduction efficiencies are 15.7 and 42.8%, and the photooxidation efficiencies are 68.1 and 26.1%,
respectively. Effect of ball milling time on the photocatalytic activity of the photocatalyst was also
investigated. The mechanisms of influence on the photocatalytic activity were also discussed by the p–n
junction principle.
ß 2008 Elsevier B.V. All rights reserved.

1. Introduction
In recent years, the photocatalytic degradation of various kinds
of organic and inorganic pollutants using semiconductor powders
as photocatalysts has been extensively studied [1–4]. Owing to it
relatively high photocatalytic activity, biological and chemical
stability, low cost, non-toxic nature and long-term stability, TiO2
has been widely used as a photocatalyst [5,6]. However, the
photocatalytic activity of TiO2 is limited to irradiation wavelengths
in the UV region; thereby the effective utilization of solar energy is
limited to about 3–5% of the total solar spectrum. Some problems
still remain to be solved in its application, such as the fast
recombination of photogenerated electron–hole pairs. Therefore,
improving photocatalytic activity by modification has become a
hot topic among researchers in recent years [7,8]. One approach is
to dope transition metals into TiO2, and the other is to form
coupled photocatalysts [9,10]. In the past decade, there were a
number of studies related to the photocatalytic activity of TiO2 or
ZnO coupled with metal oxides, like SnO2 [11–13], WO3 [14,15],
* Corresponding author. Tel.: +86 561 3806611; fax: +86 561 3803141.
E-mail address: chshifu@hbcnc.edu.cn (S. Chen).
Fe2O3 [16] and some rare earth oxides [17], for the purpose of
improving the photocatalytic activity of TiO2 or ZnO. The results
showed that coupled semiconductor photocatalysts was a novel
approach to achieve a more efficient charge separation, an
increased lifetime of the charge carriers, and an enhanced
interfacial charge transfer to adsorbed substrates. At the same
time, their physical and optical properties are greatly modified
[14]. Recently, coupled photocatalyst ZnO/TiO2 has also been
studied extensively [18–21], the results showed that the photo-
catalytic activity of ZnO/TiO2 was higher than that of the single
one.
In this paper, nitrogen-doped ZnO (p-type) powder was
prepared by decomposition of zinc nitrate. p-Type thin films of
zinc oxide based on small substitutions of N for O were reported
[22–29]. In order to achieve p-type conducting ZnO, nitrogen is
quoted to be one of the most promising dopants [30]. Recently, Li
et al. reported that nitrogen-doped ZnO prepared by decomposing
zinc nitrate showing evidence of acceptor states from iodometric
titrations. Their titration results also indicate that the conductance
of nitrogen-doped ZnO is due to p-type conductivity [31].
As far as we know, the preparation and properties of p–n
junction photocatalyst have not been extensively investigated. It is
known that when p-type ZnO and n-type TiO2 integrate, a p–n

0169-4332/$ – see front matter ß 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2008.07.115
 S. Chen et al. / Applied Surface Science 255 (2008) 2478–2484
junction will be formed between p-ZnO and n-TiO2. Theoretically,
when p-type semiconductor ZnO and n-type semiconductor TiO2
form p–n junction, the inner electric field will be formed in the
interface. At the equilibrium, the inner electric field makes p-type
semiconductor ZnO region have the negative charge, while TiO2
region have the positive charge. Under near UV illumination,
electron–hole pairs may be created, and the photogenerated
electron–hole pairs are separated by the inner electric field. The
holes flow into the negative field while the electrons move to the
positive field. As a result, the photogenerated electrons and holes
are separated efficiently, and the photocatalytic activity is
enhanced.
In the study, the p–n junction photocatalyst p-ZnO/TiO2 was
prepared by ball milling of TiO2 in H2O solution doped with p-ZnO.
The photocatalyst was characterized by UV–vis diffuse reflection
spectrum, scanning electron microscopy (SEM), X-ray powder
diffraction (XRD) and the fluorescence emission spectra. The
photocatalytic activity of the photocatalyst was evaluated by
photocatalytic reduction of Cr2O72 and photocatalytic oxidation
of methyl orange (MO). Effect of ball milling time on the
photocatalytic activity of the photocatalyst was discussed and
the possible mechanisms of p–n junction formation and separation
of photoexcited electron and hole were also investigated.
2. Experimental
2.1. Materials
The TiO2 (100% anatase, with crystallite size of about 40 nm, the
BET surface area is about 30 m2/g), zinc nitrate [Zn(NO3)26H2O]
(purity 99.9%), ethyl alcohol, potassium dichromate (K2Cr2O7),
methyl orange, and other chemicals used in the experiments were
of analytically pure grade. They were purchased from Shanghai and
other China chemical reagent Ltd. without further purification.
Deionized water was used throughout this study.
2.2. Preparation p-ZnO powder
Zinc nitrate [Zn(NO3)26H2O] was heated at a heating rate of
10 8C/min in air to prepare nitrogen-doped ZnO (p-type) [31].
Nitrate first melts at 36 8C, then dehydrates just above 100 8C with
complete nitrate decomposition by about 300 8C. The sample was
heated at least 350 8C for 1 h to insure complete nitrate
decomposition, as confirmed by X-ray diffraction. Zinc oxide
powders were vivid and darkish yellow in color under the
preparation condition. The XPS spectra of the sample shows that
there is nitrogen signal in the sample, the amount of nitrogen is
about 1.0 at.%. At the same time, the result also shows that p-type
conductivity of the sample is not converted during ball milling,
since there is nitrogen signal in the sample after ball milling. The
XPS spectra of the sample will be further elucidated in our future
work. The samples prepared in the condition are p-type
conductivity, which has been proved by iodometric titrations [31].
2.3. Preparation of p–n junction photocatalyst p-ZnO/TiO2
The preparation of p-ZnO/TiO2 photocatalyst was carried out in
a QM-1F ball miller (made in Nanjing University). The procedures
are as follows: TiO2 powder and agate balls were mixed in the agate
ball milling tank in a ratio of 1:10, and then a certain amount of p-
ZnO (0–20 wt.%) and H2O were added. After milling for a certain
time (0–24 h) at a speed of 700 revolutions per minute (rpm), the
wet powder was dried at a temperature of 110 8C in air. The final
samples were used for the determination of photocatalytic activity
and characterization.
2479
2.4. Photoreactor and procedure
Experiments were carried out in a photoreaction apparatus. The
schematic diagram is shown in Fig. 1. The apparatus consists of two
parts. The first part is an annular quartz tube. A 375 W medium
pressure mercury lamp (Institute of Electric Light Source, Beijing)
with a maximum emission at about 365 nm is laid in the empty
chamber of the annular quartz tube, and running water passes
through an inner thimble of the annular tube. Owing to continuous
cooling, the temperature of the reaction solution is maintained at
approximately 30 8C. The second part is an unsealed beaker of a
diameter 12 cm. At the start of the experiment, the reaction
solution (volume, 300 cm3) containing reactants and photocatalyst
was put in the unsealed beakers, and a magneton was used to stir
the reaction solution. The distance between the light source and
the surface of the reaction solution is 11 cm. The UV irradiation
intensity of the reaction solution surface is about 18,300 mW/cm2.
In the experiment, the initial pH of the reaction solution was about
5.0. The amount of photocatalyst used was 2.0 g/L, the initial
concentrations of Cr2O72 and methyl orange are 2.9  104 and
1.0  104 mol/L, respectively. The illumination time of each
experiment was 20 min. In order to disperse the photocatalyst
powder, the suspensions were ultrasonically vibrated for 20 min
prior to irradiation. After illumination, the samples (volume of
each is 5 cm3) were taken from the reaction suspension,
centrifuged at 7000 rpm for 10 min and filtered through a
0.2 mm Millipore filter to remove the particles. The filtrate was
then analyzed. In order to determine the reproducibility of the
results, at least duplicated runs were carried out for each condition
for averaging the results. The blank test was also carried out by
irradiating MO or Cr2O72 homogeneous solution without photo-
catalyst for checking the photo-induced self-sensitized photode-
gradation.
2.5. Characterization
UV–vis diffuse reflectance spectroscopy measurements were
carried out using a Hitachi UV-365 spectrophotometer equipped
with an integrating sphere attachment. The analysis range was
from 300 to 650 nm, and BaSO4 was used as a reflectance standard.
In order to determine the crystal phase composition and the
crystallite size of the photocatalysts, X-ray diffraction measure-
ment was carried out at room temperature using a DX-2000 X-ray
powder diffractometer with Cu Ka radiation and a scanning speed
of 38/min. The accelerating voltage and emission current were
Fig. 1. Schematic diagram of photoreaction apparatus (1) lamp, (2) water-cooling
inlet, (3) water-cooling outlet, (4) reaction solution, (5) stiring rod, (6) magnetic
agitator, and (7) light.
2480 S. Chen et al. / Applied Surface Science 255 (2008) 2478–2484
40 kV and 30 mA, respectively. The crystallite size was calculated
by X-ray line broadening analysis using the Scherer equation.
Fluorescence emission spectra were recorded on a JASCO FP-
6500 type fluorescence spectrophotometer over a wavelength
range of 200–730 nm.
The specific surface area was determined by N2 adsorption (the
BET method) at 150 8C using a Quantachrome NOVA 2000e
adsorption instrument.
The microcrystalline structure and surface characteristics of the
photocatalysts was also investigated by using (X-650 Japan)
scanning electron microscopy.
2.6. Analysis
The concentration of Cr2O72 in solution was determined by
spectrophotometer using diphenylcarbazide reagent as a devel-
oper. The concentration of methyl orange in solution was
determined by spectrophotometer.
The photoreduction efficiency of Cr2O72 and the photoxidation
efficiency of methyl orange were calculated from the following
expression:
C  Ct
h¼ 0  100%
C0
where h is the photocatalytic efficiency; C0 is the initial
concentration of reactant; Ct is the concentration of reactant after
illumination time t.
3. Results and discussion
3.1. Effect of amount of doped p-ZnO on the photocatalytic activity
The blank test shows that photo-induced self-sensitized
photodegradation has little influence on the results of experiment.
Fig. 2 shows the effects of amount of doped p-ZnO on the
photocatalytic reduction of Cr2O72 and photocatalytic oxidation
of methyl orange. The fixed ball milling time for each sample was
3 h, and fixed illumination time for each experiment was 20 min. It
can be seen that, for the photocatalytic reduction of Cr2O72, the
photoreduction activity of p-ZnO/TiO2 increases remarkably with
the increase in the amount of doped p-ZnO up to 2.0 wt.%. The
optimum amount of doped p-ZnO is 2.0 wt.%. When the amount of
doped is higher than optimal amount, the photoreduction activity
Fig. 2. Effects of amounts of doped p-ZnO on the photocatalytic reduction of Cr2O72
and photocatalytic oxidation of methyl orange (MO). (&) Methyl orange (MO); (*)
Cr2O72.
of the p-ZnO/TiO2 photocatalyst decreases gradually as the amount
of doped p-ZnO increases. The results also show that without p-
ZnO present, namely, the pure TiO2 powder photocatalyst, its
photoreduction activity is lowest, and the photoreduction
efficiency is 15.7%. When the amount of doped p-ZnO is
2.0 wt.%, the photoreduction activity of p-ZnO/TiO2 is at its peak,
and the photoreduction efficiency is 42.8%. It is clear that the
photoreduction activity of p-ZnO/TiO2 is higher than that of pure
TiO2 photocatalyst. It is proposed that, when the amount of p-ZnO
is lower than its optimum amount of doping, with the increase of
the amount of p-ZnO, it can increase trapping sites of carriers,
which prolongs the lifetime of carriers, thereby improving the
photocatalytic activity. The other important reason is that the TiO2
doped with suitable amount of p-ZnO, both p-ZnO and TiO2 can
form the p–n junction photocatalyst by ball milling, therefore, the
photoreduction activity increases [32]. But when the amount of p-
ZnO is higher than its optimum amount of doping, the high
concentration dopant ions act as recombination centers of
electrons and holes, decrease the thickness of the space-charge
layer on the TiO2 particle surface, and reduce the photon
absorption [33].
However, under the same condition, for the photocatalytic
oxidation of methyl orange, the photooxidation activity of p-ZnO/
TiO2 decreases rapidly with the increase in the amounts of doped
p-ZnO. For the pure TiO2 powder photocatalyst, its photooxidation
activity is at its peak, the photooxidation efficiency of TiO2 is 68.1%.
When the amounts of doped p-ZnO are 0.5 and 1.0 wt.%, the
photooxidation efficiencies are 44.7 and 33.3%, respectively.
It is known that the photocatalytic activity of TiO2 mainly
depends on whether the electron–hole pairs can be separated
effectively [6,34,35]. On the TiO2 surface, the photoexcited
electrons and holes can change in various ways. Among them,
the two competitive processes, i.e., capture and recombination, are
the most important ones. Photocatalytic reaction is effective only
when the photoexcited electrons-holes can be captured. If there
are no appropriate capturers of electrons or holes, they will
recombine with each other and give off heat inside or on the
surface of semiconductor. It is known from the mechanism of
separation of electrons and holes that, in order to increase the
photocatalytic activity of TiO2, two important ways should be
considered. One is to increase the separation efficiency of the
photoexcited electron–hole pairs, and the other is to increase the
amount of the photoexcited activity species [32]. It is known that
TiO2 is n-type semiconductor, when doping p-ZnO into TiO2
granule, a number of micro p–n junction p-ZnO/TiO2 photocata-
lysts will be formed. At the equilibrium, the inner electric field
formed which made p-ZnO region have the negative charge while
TiO2 region have the positive charge. Under near UV illumination,
electron–hole pairs may be generated, with the effect of the inner
electric field, the holes flow into the negative field while the
electrons move to the positive field. Thus, the photogenerated
electron–hole pairs will be separated effectively by the p–n
junction formed in the p-ZnO/TiO2. Furthermore, according to the
band edge position, as the conduction band of TiO2 is lower than
that of p-ZnO, the former can act as a sink for the photogenerated
electrons. The photogenerated electrons of the p-ZnO conduction
band will be transferred to the conduction band of TiO2, while the
photogenerated electrons of TiO2 will remain in the conduction
band of TiO2. Since the holes move in the opposite direction from
the electrons, the photogenerated holes of the TiO2 valence band
will be transferred to the valence band of p-ZnO, which makes
charge separation more efficient. Thus, the enhancement of
photocatalytic performance of the p-ZnO/TiO2 is attributed to
inner electric field assisted charge transfer at the junction
interfaces between the semiconductors with matching band
 S. Chen et al. / Applied Surface Science 255 (2008) 2478–2484
potentials, which consequently favors an effective photoexcited
electron–hole separation in the two semiconductors [36,37].
At the same time, it was reported that ZnO could trap the hole
by the following reaction [38]:
þ
ZnO þ 2h ! Zn2þ þ 12O2
Therefore, there were enrichment electrons in the interface to
react with Cr2O72 adsorbed on the photocatalyst surface, so the p–
n junction photocatalyst p-ZnO/TiO2 has higher photocatalytic
reduction activity than that of TiO2, but lower the photooxidation
activity. According to the above observations, the p–n junction
formation model and the schematic diagram of electron–hole
separation process are illustrated in Fig. 3.
3.2. Effect of ball milling time on the photocatalytic activity
The effect of ball milling time on the photocatalytic activity of
p-ZnO (2.0 wt.%)/TiO2 photocatalyst is shown in Fig. 4. It can be
seen that the ball milling time influences the photocatalytic
activity strongly. Without ball milling, the photoreduction
efficiency is 15.1%, and the photooxidation efficiency is 60.2%.
The photoreduction efficiency of Cr2O72 increases gradually with
the increase in ball milling time up to 12 h. When the ball milling
time is 3, 6, 12 and 24 h, the photoreduction efficiency is 42.8, 45.1,
54.4 and 50.3%, respectively. For the photocatalytic oxidation of
methyl orange, the photooxidation efficiency decreases rapidly
with the increase in the ball milling time. When the ball milling
time is 3 h, the photooxidation efficiency is the lowest, and it is
26.1%. However, when ball milled is longer than 3 h, the
photooxidation efficiency increases gradually with the increase
Fig. 3. p–n Junction formation model and the schematic diagram of electron–hole
separation process.
2481
Fig. 4. Effects of ball milling time on the photocatalytic reduction of Cr2O72 and
photocatalytic oxidation of methyl orange (MO). (&) Methyl orange (MO); (*)
Cr2O72.
in ball milling time up to 12 h. When the ball milling time is 12 h,
the photooxidation efficiency of methyl orange is 35.1%, when the
ball milling time is longer than 12 h, the photooxidation efficiency
decreases gradually.
The reason is that without ball milling, TiO2 and p-ZnO only
play their own photocatalytic role, and the p–n junction
photocatalysts are not formed; but after ball milling, TiO2 and
p-ZnO can form p–n junction photocatalyst, and result in the
photoreduction activity increasing and the photooxidation activity
rapidly decreasing. Another reason is that with the increase in the
ball milling time, the specific surface area of the photocatalyst
increases. Correspondingly, the number of active sites per unit
weight of photocatalyst also increases. The assumptions are
verified by the results of specific surface area in the behind part
of the study. But when the ball milling time is longer than the
optimum time, it is proposed that with the increase in the ball
milling time, the fresh surface formed by high-energy ball milling
possess high surface energy and prefer to agglomerate [15,39]. The
assumption is proved by the results of SEM.
3.3. The stability of p-ZnO/TiO2 photocatalyst
In order to determine the stability of p-ZnO/TiO2 photocatalyst
during the photocatalytic reaction, the repeated experiments of p-
ZnO/TiO2 photocatalyst was investigated. The results showed that
the photocatalytic activity of p-ZnO/TiO2 photocatalyst for
photocatalytic reduction of Cr2O72 faded along with the increase
of the reusing times. This may be attributed to the loss of the active
composition p-ZnO during the photocatalytic reaction [38], and
thus resulting in the decrease of the photocatalytic activity.
3.4. Characterization of p-ZnO/TiO2 photocatalyst
3.4.1. Fluorescence emission spectra
Photocatalysts generate electrons and holes after being
activated by light, and recombination of some electrons and holes
can release energy in the form of fluorescence emission. Lower
fluorescence emission intensity implies lower electron–hole
recombination rate [40].
Using an ultraviolet light with a 260 nm wavelength as the
excitation source, the fluorescence emission spectra of TiO2 doped
with different contents of p-ZnO are shown in Fig. 5. It can be seen
that the pure TiO2 powder has emission peaks at around 414 nm
2482 S. Chen et al. / Applied Surface Science 255 (2008) 2478–2484

Fig. 6. XRD patterns of photocatalysts (a) TiO2, (b) p-ZnO, (c) p-ZnO (20 wt.%)/TiO2,
Fig. 5. Fluorescence emission spectra of different samples (1) TiO2, (2) p-ZnO (d) p-ZnO (10 wt.%)/TiO2, (e) p-ZnO (5.0 wt.%)/TiO2 and (f) p-ZnO (1.0 wt.%)/TiO2.
(5.0 wt.%)/TiO2, (3) p-ZnO (2.0 wt.%)/TiO2 and (4) p-ZnO.

(3.0 eV) and 468 nm (2.6 eV), showing indirect band gap char-
acteristics [14]. It is clear that the relative intensity of the emission
spectra of p-ZnO is the lowest, illustrating a low recombination
rate of electrons and holes. TiO2 has the greatest relative intensity
of emission spectra, which means that electrons and holes of TiO2
are easy to recombine. The relative intensity of both the p-ZnO
(2.0 wt.%)/TiO2 and p-ZnO (5.0 wt.%)/TiO2 is lower than that of
TiO2, it is clear that doping TiO2 with p-ZnO is helpful to inhibit the
recombination of electrons and holes and improve the photo-
catalytic activity.
The p-ZnO content can influence the thickness of the superficial
space-charge layer of TiO2. Only when the space-charge layer
thickness approximates the penetration depth of light into the
solid, can the electron–hole pairs be effectively separated [40].
When the doped p-ZnO content is 2.0 wt.%, the relative intensity of
emission spectra is lower than that of the 5.0 wt.% doping quantity
of p-ZnO, which shows that 2.0 wt.% doping quantity of p-ZnO can
effectively restrain the recombination of electrons and holes.
When the p-ZnO content is too small, the high recombination rate
of electron–hole pairs is due to the absence of adequate traps.
When the doping quantity is considerably high, the absorption of
light and generation of electrons–holes are decreased. These
analyses coincide with the photocatalytic reduction activity of the
photocatalysts with UV illumination.
possibly indicates that this shift is due to Zn2+ substitutes for Ti4+
site of the TiO2 crystal lattice [42]. The crystallite size obtained
from the (1 0 1) peak of the TiO2 is about 40 nm, when the amounts
of doped p-ZnO are 1.0, 5.0, 10 and 20 wt.%.
3.4.3. UV–vis analysis
Fig. 7 shows UV–vis diffuse reflection spectra of TiO2, p-ZnO
powder and p-ZnO (5.0 wt.%)/TiO2 photocatalyst. The samples
were ball milled for 12 h.
It is known that the band gap of n-ZnO is 3.2 eV, it can be excited
by photons with wavelengths below 387 nm. From the Fig. 7, it can
be seen that, the curve of p-ZnO powder has a clear absorption in
the visible range, beside the absorption edge near 380 nm. It is
proposed that the absorption in the visible range can be attributed
to the nitrogen doping. Li and Haneda [43] assigned the mentioned
absorption to the nitrogen atoms doped into the oxygen sites of the
ZnO crystal lattice. The decrease of the energy-gap accounts for the
difference in the energy levels of the oxygen and nitrogen 2p orbits
E2p(O) = 14.8 eV and E2p(N) = 13.4 eV [44,45]. It is proposed
that because the doped-nitrogen content of the p-ZnO samples is
too low, the band gap of ZnO is not changed probably. Hence, it is
believed that an electronic impurity level (EIL) is newly formed by

3.4.2. XRD analysis

Fig. 6 shows the XRD patterns of photocatalysts ball milled for
3 h. TiO2 exhibits dominant anatase phase diffraction peaks. For p-
ZnO powder, a search-match database analysis confirmed that
these powders have the phase composition of wurtzite [41]. From
Fig. 6, it can be seen that when the amount of doped p-ZnO is lower
than 5.0 wt.%, the diffraction peaks of p-ZnO cannot be found in
XRD patterns. This illustrates that p-ZnO is highly dispersed in the
bulk phase of the catalyst. When the amount of p-ZnO doped is
higher than 5.0 wt.%, the diffraction peaks of p-ZnO can be found in
XRD patterns. Since no new crystal phases are found, it can be
concluded that a new solid is not formed in the ball milling process
of TiO2 and p-ZnO.
From the XRD patterns of the photocatalysts, it clearly can be
seen that the main peak (1 0 1) of TiO2 in the region 2u (24.7–26.0)
shifts either to higher 2u value. Zn2+ dopant, which has size (0.60
Å), is smaller than Ti4+ (0.68 Å) and results in shift in the peak Fig. 7. UV–vis diffuse reflection spectra (a) p-ZnO, (b) p-ZnO (5.0 wt.%)/TiO2 and (c)
position to higher 2u when compared to pure TiO2. The result TiO2.
 S. Chen et al. / Applied Surface Science 255 (2008) 2478–2484 2483

nitrogen introduction between the VB and CB in the ZnO band

structure, and the EIL should be close to the VB of ZnO since the
energy levels of the nitrogen 2p orbit (13.4 eV) are higher than
that of oxygen (14.8 eV)[44,45].
From Fig. 7, it is clear that the absorption wavelength range of
p–n junction photocatalyst p-ZnO/TiO2 red shifts about 20 nm,
compared with pure TiO2 photocatalyst, and its absorption
intensity also increases. Because of the absorption wavelength
range red shifts of about 20 nm and absorption intensity increases,
the formation rate of electron–hole pairs on the photocatalyst
surface also increases greatly, resulting in the photocatalyst
exhibiting higher photocatalytic activity. The similar results were
reported in Ref. [46]. The reason for the absorption wavelength
range red shifts of the p-ZnO/TiO2 could probably be attributed to
the formation of defect energy level in the particles during high
energy ball milling process.
In the process of ball milling, the crystal lattices of the TiO2 and
p-ZnO undergo severe plastic deformation, producing stresses and
strains. This creates a crystal lattice distortion, while at the same
time forming many defects inside particles. These defects have
high lattice distortion energy and surface energy. This makes the
activation energy for diffusion of elements decrease markedly, and
allows for atomic or ionic marked diffusion among elements at
room temperature. When the activity of the powder system is high
enough, during the ball milling process, the collision between balls
and grains of the powder will produce a rise in the interface
temperature, which will induce the coupling reaction mentioned
here. So, when the interfaces of the TiO2 and p-ZnO contact with
each other, the p–n junction photocatalyst p-ZnO/TiO2 can be
formed [15].

3.4.4. Surface area analysis

The mechanical activation of materials is accompanied by
disintegration and generation of fresh previously unexposed
surfaces. The size distribution and the specific surface area also
depend on the secondary processes like aggregation and agglom-
eration [47]. Fig. 8 shows the effect of the ball milling time on the
surface area of the p-ZnO (2.0 wt.%)/TiO2. From Fig. 8, it can be seen
that the surface area increases gradually with the increase in ball
milling time up to 12 h, when the ball milling time is longer than
12 h, the surface area tends to decrease, indicating the aggregation
of particles. The result was verified by the TEM results of TiO2
photocatalyst [15] and SEM results in Fig. 9.
Fig. 9. SEM images of p-ZnO (2.0 wt.%)/TiO2 photocatalyst (a) ball milling time 12 h
and (b) ball milling time 24 h.
Usually the powders with high surface area are expected to be
good photocatalytic activity [48]. When the ball milling time is
12 h, the specific surface area of p-ZnO/TiO2 photocatalyst shows
the highest value, hence photocatalytic activity is the highest,
which agrees with the results of the photocatalytic experiments.

3.4.5. SEM analysis

The SEM images of p-ZnO (2.0 wt.%)/TiO2 photocatalyst are
shown in Fig. 9. It can be seen that, the crystallites are spherical
particle, and the average diameter of p-ZnO (2.0 wt.%)/TiO2
photocatalyst is about 30–40 nm. The result is the same as that
of XRD. From the Fig. 9, it also can be seen that when the ball
milling time is 24 h, the aggregation degree of the sample is higher
than that of the sample ball milled for 12 h. It agrees with the
results of the surface area analysis and the ball milling time.
Namely, when the ball milling time is longer than the optimum
time, with the increase in the ball milling time, the fresh surfaces
formed by high-energy ball milling possess high surface energy
and prefer to agglomerate.

4. Conclusions

The p–n junction p-ZnO/TiO2 photocatalyst was prepared by

ball milling of TiO2 in H2O solution doped with p-ZnO. The
photocatalytic reduction activity of p-ZnO/TiO2 photocatalysts is
higher than that of the pure TiO2. However, the photooxidation
Fig. 8. The relation between the ball milling time and specific surface area. activity of p-ZnO/TiO2 photocatalyst is much lower than that of
2484 S. Chen et al. / Applied Surface Science 255 (2008) 2478–2484
TiO2. Namely, the p–n junction photocatalyst p-ZnO/TiO2 has
higher photocatalytic reduction activity, but lower photocatalytic
oxidation activity. For the photocatalytic reduction of Cr2O72, the
optimum amount of doped p-ZnO is 2.0 wt.%. The ball milling time
also influences the photocatalytic activity strongly. The photo-
reduction efficiency of Cr2O72 increases gradually with the
increase in ball milling time up to 12 h. As the formation of p–n
junction p-ZnO/TiO2 photocatalyst and p-type ZnO species can trap
the hole, the photogenerated electron–hole pairs are separated by
the inner electric field, and the photocatalytic reduction activity is
enhanced greatly.
Acknowledgements
This work was supported by the Natural Science Foundation of
China (No. 20673042), the Natural Science Foundation of Anhui
Province (Contract No. 070415211), the Key Project of Science and
Technology Research of Ministry of Education of China (208062)
and the Natural Science Foundation of Anhui Provincial Education
Committee (KJ2007A015).
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