Applied Surface Science 325 (2015) 112–116

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Applied Surface Science

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

Effect of oxygen vacancy on enhanced photocatalytic activity of

reduced ZnO nanorod arrays
Chao Wang, Di Wu, Peifang Wang, Yanhui Ao ∗ , Jun Hou, Jin Qian
Key laboratory of Integrated Regulation and Resource Development on Shallow Lakes, Ministry of Education, College of Environment, Hohai University,
Nanjing 210098, China

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

Article history: Partially reduced ZnO nanorod arrays (NRAs) were synthesized in a reducing reagent of NaBH4 . The
Received 24 July 2014 NaBH4 treatment substantially increased the density of oxygen vacancies. The obtained materials were
Received in revised form 25 October 2014 characterized by a field emission scanning electron microscopy, X-ray diffractometer, X-ray photoelec-
Accepted 2 November 2014
tron spectroscopy and UV–vis absorption spectra. The photocatalytic activity of the resulting samples
Available online 7 November 2014
was evaluated by degradation of methylene blue (MB) under UV light irradiation. The ZnO NRAs with a
partially reduced surface exhibited enhanced photocatalytic activity. The improvement was ascribed to
Keywords:
the introducing oxygen vacancies in ZnO by NaBH4 treatment. The increased surface oxygen vacancy
ZnO nanorod arrays
NaBH4
decreased the surface recombination centers, and improved the charge separation efficiency, thus
Oxygen vacancies enhances the photocatalytic activity. Furthermore, we found that moderate treatment enhanced pho-
Photocatalysis tocatalytic activity. However, with longer time of treatment, bulk oxygen vacancies appeared, which
Visible light would cause a reduced activity.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction
Zinc oxide (ZnO) has been recognized as a promising semicon-
ductor material for photocatalytic applications owing to its direct
wide bandgap (Eg ∼3.37 eV), and large exciton binding energy
(∼60 meV). In particular, 1D ZnO nanostructures such as nanowire,
nanorod, nanotube are considered to be one of the most promising
nanomaterials for their strong application potentials as compo-
nents of nano-scale electronic or optoelectronic [1,2]. Graugnard
et al. studied the properties and applications of 1D ZnO nanostruc-
ture arrays [3–5]. However, problems such as increased carrier
recombination centers and decreased incident photon to electron
conversion efficiency (IPCE), which significantly limits its photo-
electrochemical applications [6]. It is very important to improve the
morphology and electronic structure of ZnO for effective separation
and transportation of photoexcited charge carriers [7,8].
Various techniques have been employed to solve the problems.
These techniques include non-metals doping [9,10], metals doping
[11–13], surface modification via organic materials [14] and semi-
conductor coupling [15]. Apart from this, the defects of metal oxide
nanostructures are attracting an increasing interest in recent sev-
eral years [16–20]. It has been reported that the existence of defects
in a ZnO crystal leads to electrical and optical changes [21]. Accord-
ing to the published work, oxygen vacancies not only enhanced UV
light photocatalytic activity of metal oxide, but also induced visible
light-active activity [22–25]. This can be ascribed to oxygen vacancy
defects induce new donor energy levels below its conduction band
[26]. Recently, researchers have taken their attentions to the cre-
ation of oxygen vacancy to improve photocatalytic activity of ZnO
nanomaterials using different techniques [27–31]. However, these
strategies need harsh synthetic conditions or expensive facilities
which limit their practical application.
Hence, developing a simple and economical strategy to syn-
thesize a stable reduced ZnO photocatalyst with suitable localized
states is still a great challenge. To resolve these issues, we have
used a one-step method that can substantially increase the density
of oxygen vacancies by reducing ZnO nanostructures in a reduc-
ing reagent, low-cost NaBH4 is used as a reducer. The increased
surface oxygen vacancy decreases the surface recombination cen-
ters, enhances the electrical conductivity, and improves the charge
transportation.
2. Experimental

2.1. Materials

∗ Corresponding author. Tel.: +86 25 83787330; fax: +86 25 83787330. All chemicals were of analytic reagent grade and used without
E-mail address: andyao@hhu.edu.cn (Y. Ao). further purification. All the aqueous solutions were prepared using

http://dx.doi.org/10.1016/j.apsusc.2014.11.003
0169-4332/© 2014 Elsevier B.V. All rights reserved.
 C. Wang et al. / Applied Surface Science 325 (2015) 112–116
Fig. 1. SEM images of the pristine ZnO NARs. (A) Top view and (B) cross-section view.
deionized water. Ti plates (4 cm × 3 cm × 0.1 cm) were cleaned
ultrasonically in acetone, ethanol, and deionized water for 30 min,
and dried at 60 ◦ C. Pickling was performed in a 1:3:6 (involume)
mixture of aqueous solution of HF (55 wt%), HNO3 (63 wt%) and
distilled water for 45 s.
2.2. Preparation of ZnO nanorod array films on Ti foil
ZnO NRAs were synthesized by hydrothermal growth on Ti foil
(4 cm × 3 cm) coated with a layer of ZnO nanoparticles. The pro-
cedure consists of two steps: (1) modification of Ti foil with a
thin layer of densely and uniformly dispersed ZnO nanoparticles
by spin coating. The seed layer was prepared using a mixed solu-
tion of 0.5 M zinc acetate dehydrate (Zn(CH3 COO)2 ·2H2 O) and 0.6 M
diethanolamine (C4 H11 NO2 ) in ethanol. The resulting mixture was
then agitated at 60 ◦ C for 30 min to yield a homogeneous and sta-
ble colloid solution, which served as coating solution. After 2 min
spin coating, the substrates were dried at room temperature for
120 min and then annealed at 400 ◦ C for 60 min. (2) Hydrothermal
growth of ZnO nanorods in aqueous solution. The aqueous solu-
tion used for ZnO nanorods growth process was prepared using
0.05 M zinc nitratehexahydrate (Zn(NO3 )2 ·6H2 O) and 0.05 M hex-
amethylenetetramine (C6 H12 N4 ). Those solutions were transferred
into the Teflon-lined stainless steel autoclaves with a volume of
70 mL. The Ti plates coated with ZnO seed layer were vertically
immersed into the reaction solution. Subsequently, the autoclaves
were sealed and heated to a constant temperature of 95 ◦ C for 2 h.
After taking out, the samples were cleaned ultrasonically in ethanol
and distilled water for 30 min, then dried at 90 ◦ C. Finally the sam-
ples were dipped in 0.1 M NaBH4 for 15 min, 30 min and 45 min
respectively at room temperature followed by rinsing with water
and air drying. Samples N-15, N-30, N-45 were respectively gained.
2.3. Characterization
The surface morphologies were characterized with a field emis-
sion scanning electron microscopy (SEM, Hitachi, S-4800). The
crystalline structures of as-prepared samples were deter-mined by
an X-ray diffractometer (XRD, Shimadazu, XD-3A) over the 2Â range
30–75◦ . The photoluminescence (PL) spectra in the wavelength
range 350–600 nm has been recorded using 325 nm line of Xe
laser using a fluorescence spectrophotometer (F-7000). The UV–vis
absorption spectra of the samples were measured by a UV–vis
spectrophotometer (Shimadzu, UV-3600). The surface chemical
bonding of the samples was examined by X-ray photoelectron spec-
troscopy (XPS) with Mg-K␣ radiation (ESCALB MK-II).
113
2.4. Photocatalytic activity measurement
The photocatalytic activity of the resulting samples was eval-
uated by degradation of methylene blue (MB) under UV light
irradiation. The experiments were carried out in the closed com-
partment to avoid interference from ambient light. A ZnO film
(effective area was 3 cm × 3 cm) was inserted into 100 ml MB
solution whose initial concentration was 10 mg/L. The solution
was stirred for 30 min to allow adsorption–desorption equilibrium
before light irradiation. After that, the ZnO film was illuminated
with an ultraviolet lamp (Model: MUA-165, with a peak wavelength
of 365 nm) passing through the quartz window. Then, 1 mL solution
was collected and analyzed by a UV–vis spectrophotometer (Shi-
madzu, UV-3600) at a wavelength of 665 nm at regular interval
(15 min). Photocurrent responses were recorded using an electro-
chemical station (Chenhua Instruments, CHI660D) operated in a
three-electrode configuration with the ZnO films as the working
electrode, a Pt foil as the counter electrode and a Ag/AgCl electrode
as the reference electrode. An ultraviolet lamp (Model: MUA-165,
with a peak wavelength of 365 nm) was used as the light resource.
50 mL of Na2 SO4 (0.1 M) was used as the electrolyte. The applied
potential biases were +0.3 V in the irradiation process.
3. Results and discussion
3.1. Characterization of the samples
Fig. 1 shows the morphology of ZnO NRAs grown on Ti sub-
strates. The top-view of the SEM image (Fig. 1A) illustrates that
well aligned ZnO nanorods grow uniformly in large scale. The
cross-section image of as-prepared NARs shown in Fig. 1B indi-
cates that ZnO nanorods grown on Ti substrates have an average
length of ∼800 nm and diameter of approximately 100 nm. Over-
all, the images show that ZnO NRAs of sharp tips are vertically
oriented from the Ti foil substrate. Due to the one-dimensional fea-
tures of the nanorods, directional charge transport is promoted [4].
Fig. 2 shows that the reduced ZnO NARs after NaBH4 treatment
have kept their pristine structure (including orientations, lengths,
diameters, etc.), indicating the NaBH4 treatment has not destroyed
the structure of ZnO nanorods.
Fig. 3 shows the XRD patterns of the as-prepared samples. The
samples gave similar XRD patterns indicating the nanorods in high
crystallinity. All the peaks can be indexed to the standard diffraction
pattern of hexagonal phase ZnO (JCPDS 36-1451). The much higher
intensity of the 002 diffraction peaks for the samples indicates that
excellent orientation in the c-axis direction ZnO NARs grown on
Ti foils [32,33]. Furthermore, the results indicate that the NaBH4
114 C. Wang et al. / Applied Surface Science 325 (2015) 112–116

Fig. 2. SEM images of the ZnO NARs after NaBH4 treatment.

002 In our case, NaBH4 treatment is an effective method to introduce

Pristine ZnO NRAs surface defect (oxygen vacancy) into ZnO NARs [34,35].
Reduced ZnO NRAs Fig. 5 shows the PL spectra of the ZnO NARs samples. Clearly,
XRD Intensity (a.u.)

in comparison to the pristine ZnO NARs, the reduced ZnO NARs

101
show two new bands at 449.5 nm, 474.8 nm. The two new bands
100 103 are ascribed to the oxygen vacancies forming at the surface of ZnO
102 110
NARs [36,37]. The proposed new surface oxygen vacancies may act
as the radiate recombination sites and increase the opportunity of
electron transition from the energy level of oxygen vacancies to the
valence band [38].

3.2. Photocatalytic properties

30 35 40 45 50 55 60 65 70 75 Fig. 6(a) shows the photodegradation plot of MB under UV light

irradiation by different samples. The photocatalytic degradation of
2 theta (degree)
MB is used as a model reaction to compare the photocatalytic activ-
ity of the as-prepared ZnO NRAs. The initial concentration of MB is
Fig. 3. XRD patterns of the ZnO NARs before and after NaBH4 treatment.
10 mg/L and the adsorption time is 30 min. With the increase of
degradation time, the residual MB concentrations decrease gradu-
ally. It can be seen that the ZnO NARs being treated for 30 min by
treatment has no significant effect on the ZnO bulk nanocrystal
NaBH4 shows the highest photocatalytic activity. The degradation
structure.
efficiency for pristine ZnO NRAs, N-15, N-45 are little difference.
Fig. 4 shows oxygen 1s XPS profiles of the ZnO NARs before and
After 15 min UV irradiation, the degradation efficiency for pristine
after NaBH4 treatment, which slightly shifted to lower energy after
ZnO, N-15, N-45 samples are 29%, 28%, 27%, however, N-30 shows
reduction process. It shows the change of surface chemical bonding
enhanced degradation efficiency about 55%. After 60 min UV, the
of ZnO nanocrystals induced by NaBH4 treatment. The shift is in line
degradation percent values of MB respectively are about 65%, 70%,
with the transfer of electrons to the neighboring oxygen vacancies.

Fig. 4. O1s XPS spectra of the pristine and reduced ZnO NARs. Fig. 5. Photoluminescence (PL) spectra of pristine and reduced ZnO NARs.
 C. Wang et al. / Applied Surface Science 325 (2015) 112–116
Fig. 6. (a) Photodegradation of MB under UV light by different samples and (b)
linear transform ln(C0 /C) = f(t) of the kinetic curves of MB disappearance for different
samples.
91% and 60% in the presence of pristine ZnO NRAs, N-15, N-30 and
N-45. The apparent first order kinetic equation ln(C0 /C) = kapp t is
used to fit experimental data in Fig. 6(a), where kapp is apparent
rate constant. The results showed that the results are fitted well
with the apparent first order because the relative constant are all
higher than 0.95. The kapp obtained from Fig. 6(b) are 0.017, 0.020,
0.040 and 0.015 min−1 in the presence of pristine ZnO NRAs, N-15,
N-30 and N-45, respectively. N-30 showed the best photocatalytic
activity. The apparent rate constant of N-30 was about 2.4 times as
that of pristing ZnO NRAs.
ZnO photocatalysis is based on the generation of an
electron–hole pair upon light irradiation. However, the photo-
induced electron–hole easily recombined in the photocatalysis
process. Therefore, it is important to reduce the surface recombi-
nation of electrons and holes. Oxygen vacancies can act as electron
acceptors during the photocatalytic reaction and thus reduce
the recombination rate. Oxygen vacancies can also facilitate the
adsorbed O2 to capture photo-induced electrons, synchronously
generating superoxide radical anions. Therefore, oxygen vacancies
115
Fig. 7. The mechanism of photocatalytic degradation of MB by reduced ZnO under
UV light irradiation.
can greatly enhance the photocatalytic properties [39–41]. Fig. 7
shows the degradation of MB by the reduced ZnO nanostructure
under UV light. Band gap excitation of the semiconductor results in
electron–hole separation. Highly reactive hydroxyl radicals can also
be formed either by the decomposition of water or by the reaction
of a hole with OH− . The hydroxyl radical and photogenerated holes
are extremely strong, non-selective oxidants that lead to the degra-
dation of MB at the surface of reduced ZnO. This can be attributed
to the high concentrations of oxygen vacancies created in reduced
ZnO.
Fig. 8 shows the transient photocurrent responses of the samples
(pristine ZnO NRAs, N-15, N-30 and N-45). The applied potential
biases were +0.3 V in the irradiation process. The rise and fall of
the photocurrents correspond well to the UV illumination being
switched on and off for the four samples. The response of N-30
was the highest among the samples. It shows that photocurrents
of all reduced ZnO NRAs are higher than that of pristine ZnO NRAs
and increase gradually with the increasing of the NaBH4 treatment
time from 15 to 30 min. The photocurrent of N-30 reaches a max-
imum. As the NaBH4 treatment time is further increased above 30
min, the photocurrent of the reduced ZnO NRAs decrease. The N-
45 shows an obvious decay. Kong and Li [42] reported that surface
oxygen vacancies serve as charge carrier traps as well as adsorption
sites where the charge transfer to adsorbed species, which can pre-
vent e− –h+ recombination. However, bulk oxygen vacancies tend to
act as charge carrier traps where e− –h+ recombination occurs. The
NaBH4 treatment introduces oxygen vacancies in ZnO, the number
of oxygen vacancies is proportional to treatment time, but when
Fig. 8. Photocurrent responses of different samples at +0.3 V under UV light irradi-
ation.
116 C. Wang et al. / Applied Surface Science 325 (2015) 112–116

fund of NSFC (No. 51422902), the National Natural Science Founda-

tion of China (No. 51108158), The outstanding youth fund of Jiangsu
Province (BK2012037), Research Fund for innovation team of Min-
istry of education (IRT13061), Fundamental Research Funds for the
Central Universities (2013B32114, 2013B14114).

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