Materials Research Bulletin 46 (2011) 1207–1210

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Materials Research Bulletin

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

Structure and photocatalytic activity of Ni-doped ZnO nanorods

Jing Zhao a, Li Wang b, Xiaoqin Yan a, Ya Yang a, Yang Lei a, Jing Zhou a, Yunhua Huang a,
Yousong Gu a, Yue Zhang a,c,*
a
State Key Laboratory for Advanced Metals and Materials, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
b
School of Civil & Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China
c
Key Laboratory of New Energy Materials and Technologies, University of Science and Technology Beijing, Beijing 100083, China

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

Article history: The one-dimensional (1D) Zn1 xNixO (x = 0, 0.02, 0.05, 0.10) nanorods have been synthesized by a simple
Received 17 November 2010 hydrothermal method. New bands show at 130 cm 1 in the Raman spectra of Ni-doped ZnO nanorods
Received in revised form 19 March 2011 and their relative intensity depends on the doping concentration of nickel. The optical band gap of the
Accepted 12 April 2011
ZnO nanorods have been tuned by Ni-doping, which is revealed by absorption spectra. The
Available online 20 April 2011
photocatalytic activity of Zn1 xNixO was studied by comparing the degradation rate of rhodamine B
(RB) under UV-light irradiation. It was found that Zn0.95Ni0.05O exhibited the highest photocatalytic
Keywords:
degradation efficiency among the samples.
A. Nanostructures
C. Raman spectroscopy
ß 2011 Elsevier Ltd. All rights reserved.
D. Optical properties
D. Catalytic properties

1. Introduction Chang et al. presented promoted photocatalytic efficiency in Pd

The nano-semiconductor photocatalysts have attracted in-
creasing interest for its application in treating environment
pollutants [1–4]. Among the nanoscaled materials, the one-
dimensional (1D) photocatalysts have good performance. On the
one hand, they have larger surface area than microscale powders,
which enlarges their contact surface during the reactions. On the
other hand, compare to nano-particles, their higher length-width
ratio makes them easily to be filtered out after the reactions.
Among the II–VI subgroup photocatalysts, ZnO is a very
attractive semiconductor photocatalyst, for it has similar band
gap energy (3.37 eV) compared with TiO2 (3.20 eV), and its
quantum efficiency is larger than TiO2. There are many reports
of ZnO having higher photocatalytic activities than TiO2 in some
conditions [5–8]. The main factor influencing the photocatalytic
activity of ZnO is the quick recombination of charge carriers. In
order to improve the photocatalytic activity, different kinds of ions
were doped into ZnO to inhibit the recombination of photoinduced
electrons and holes. For instance, Qiu et al. reported Mg-doping
enhanced the decolorization of methylene blue in ZnO [9], and
modified ZnO [10].
Barick et al. have newly reported that the Ni-doped ZnO
exhibited better photocatalytic activity than ZnO in the degrada-
tion of methylene blue. The morphology of photocatalysts used in
their work is spherical aggregate with the size of about 1 mm [11].
But for the one-dimensional Ni-doped ZnO nano-structure, rarely
research has been done on their photocatalytic activities. And
whether the concentration of Ni-doping has effect on the
photocatalytic activities of ZnO has also not been discussed.
In this paper, we successfully fabricated Ni-doped ZnO
nanorods with different concentration, which are around 0%, 2%,
5%, and 10%. Raman scattering measurements were designed to
investigate the distortion of lattice after Ni-doping. Absorption
spectra were taken to derive the width of optical band gap of
Zn1 xNixO nanorods. The photocatalytic activity of Zn1 xNixO
samples was studied by analyzing the degradation of rhodamine B
(RB). This work investigated on a new aspect of 1D Ni-doped ZnO
for an overall insight in both fundamental researches and
technological applications.
2. Experimental

2.1. Preparation of Ni-doped ZnO nanorods

* Corresponding author at: State Key Laboratory for Advanced Metals and
Materials, School of Materials Science and Engineering, University of Science and
Technology Beijing, Beijing 100083, China. Tel.: +86 10 62334725;
The Ni-doped ZnO nanostructures were obtained through a
fax: +86 10 62333113. chemical method. The detailed experimental set-up has been
E-mail address: yuezhang@ustb.edu.cn (Y. Zhang). described elsewhere [12], the brief hydrothermal condition is as

0025-5408/$ – see front matter ß 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2011.04.008
1208 J. Zhao et al. / Materials Research Bulletin 46 (2011) 1207–1210
Fig. 1. The SEM image of Zn1 xNixO nanorods (a) x = 0, (b) x = 0.02, (c) x = 0.05, and (d) x = 0.10; The insets show the EDX spectra of the corresponding samples.
follows: 5 mmol zinc acetate [Zn(Ac)2
2H2O] and required amount
of nickel acetate [Ni(Ac)2
4H2O], which are 0, 0.1, 0.25, and
0.5 mmol, were dissolved into 175 ml absolute ethanol, then
40 mmol NaOH and 40.0 ml polyethylene glycol 400 (PEG-400)
were added into the above solution. The reaction was kept at 140 8C
for 24 h in a Teflon-lined stainless autoclave tank. After the reaction,
the precipitations were washed, filtered, and finally dried in air at
60 8C for 4 h.
2.2. Characterizations
The morphologies and component of as-prepared ZnO
products were characterized by scanning electron microscopy
(SEM) (Philips XL 30 FEG) equipped with an energy-dispersive X-
ray spectrometer (EDX). The crystal structure and phase of the
samples were determined by X-ray diffraction technique using
D8 Discover with GADDS. Raman scattering experiments were
measured at room temperature using a Raman spectroscope
meter (Jobin-Yvon, HR800) with the 514 nm line of an Ar+ laser.
The absorption spectra were recorded with a Hitachi spectro-
photometer (U-3010).
2.3. Measurement of photocatalytic activity
To investigate the photocatalytic activity of the Zn1 xNixO
samples, 2 mg of as-grown samples were dispersed in 100 mL
rhodamine B aqueous solution with the concentration of
1  10 5 M. The dispersion was added into a quartz beaker
under magnetic stirring, and kept in dark for 30 min to reach the
adsorption equilibrium. Then the dispersion was irradiated by a
300 W UV-light mercury lamp (Osram) with the central
wavelength of 365 nm. The surface of the dispersion was
maintained a distance of 15 cm from the light source to avoid
heat effect.
3. Results and discussion
3.1. Morphology and component
The morphologies and size of ZnO nanorods with various Ni
contents are nearly the same with a uniform diameter of 15–20 nm
and length of 150–400 nm, as shown in Fig. 1. The average Ni
contents in ZnO nanorods are determined to be 0%, 2  0.3%,
5  0.7% and 10  1.2% by EDX analyzing (see insets of Fig. 1), and the
test were repeated at three different spots for each sample to make
sure the distribution of Ni is homogeneous.
3.2. Structure characterization
The X-ray diffraction patterns of Zn1 xNixO nanorods are shown
in Fig. 2, and are vertically normalized for clarity. No extra peak
was found in all samples besides the signal of ZnO wurtzite
structure, suggesting no secondary phase in Zn1 xNixO. The
positions of the peaks of all samples are almost the same, which
have previous been observed in Ni-doped ZnO powders prepared
by sol–gel method [13] and rheological phase reaction-precursor
method [14]. The Shannon radius of Ni2+ ion (0.055 nm) is only
slightly less than that of Zn2+ion (0.060 nm). Therefore, the
substitution of Ni2+ion for Zn2+ will not result in much distortion
in the ZnO lattice, generally.
The Raman spectra further illustrate the structure of
Zn1 xNixO nanorods (in Fig. 3). The two strong bands at 100
and 438 cm 1 should be attributed to first-order modes E2low
and E2high, which are nonpolar modes caused by vibration
between Zn–Zn and O–O, respectively [15]. The band at
380 cm 1 is indicated to be A1(TO), which is also a first-order
optical mode. The peak at 333 cm 1 is usually considered to be
the second-order mode of E2high E2low [16]. There is hardly any
change of the peak positions in Raman spectra after doping,
 J. Zhao et al. / Materials Research Bulletin 46 (2011) 1207–1210 1209

a
101 x=0
100 201
002 110
102 103 112 x=0.02

Absorption (a.u.)
Intensity (a.u.)

x=0.10 200
x=0.05
x=0.05
x=0.10
x=0.02

x=0

30 40 50 60 70
2θ (deg.) 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8
Energy (eV)
Fig. 2. XRD patterns of Zn1 xNixO nanorods with x = 0, 0.02, 0.05, and 0.10.
b 3.32

Band gap (eV)

100 3.28

)
2
A( hua) 2( eV /cm
438 3.24

2
333 380
134
Intensity (a.u.)

0 2 4 6 8 10
x=0.10 Ni content (%)
x=0
x=0.05
x=0.10
x=0.02
x=0.02
x=0 x=0.05
2.8 2.9 3.0 3.1 3.2 3.3 3.4 3.5
100 200 300 400 500 600 700 Energy (eV)
Raman shift (cm-1)
Fig. 4. (a) Absorption spectra of Zn1 xNixO nanorods dispersed in aqueous solution.
(b) The plots of (hna)2 vs photon energy used to estimate optical band gap. The inset
Fig. 3. Raman spectra of Zn1 xNixO at room temperature.
shows the change of optical band gap energy due to Ni-doping.

indicating no stress in the Zn1 xNixO lattice. We conclude that Ni
doping causes little or no lattice distortion in the ZnO lattice,
which is consistent with the XRD results.
It is worth noting that an additional mode at 134 cm 1 appears
in the Ni-doped ZnO nanorods and becomes stronger along with
the increase of Ni content. Such mode was observed by Yadave
et al. in Ni-doped ZnO only at the temperature below 220 K [17]. In
their work, the peak at around 130 cm 1 is assigned to be TA mode
of ZnO, which has been enhanced due to the zone-boundary effect.
In our case, the tests were operated at higher temperature (298 K),
and the mode at 130 cm 1 appears as well, we do not attribute it
to TA mode for the peak value of TA mode is nearly coincide with
E2low, which should be very close to 100 cm 1 [18,19]. We conclude
the mode at around 130 cm 1 is caused by the Ni–Ni vibration.
Since the atoms mass of Zn is only slightly larger than Ni, the
vibrating frequency of Ni–Ni vibration should be a little faster than
Zn–Zn vibration which should appear at 100 cm 1. As more and
more Ni2+ ion replace the position of Zn2+, the long-range ordered
Ni2+ ions form a special symmetry in ZnO lattice, awoke the Ni–Ni
vibration.
3.3. Band gap
Measurements of the optical band gaps of the ZnO nanorods
with various Ni contents were also performed. The absorption
spectra are shown in Fig. 4(a). The optical band gaps of Zn1 xNixO
are estimated from the plots of (hna)2 versus hn in Fig. 4(b),
where hn is photon energy and a is the absorption coefficient
[20]. When the concentration of Ni-doping rises, the band gap
first increases and then decreases (see inset of Fig. 4(b)), which is
different from the report made by Bhat et al. Their study shows
that the optical band gap of the Ni-doped ZnO prepared in
aqueous solution maintains a decrease with the rise of Ni content
[21]. In our case, the absorption edge of Ni-doped ZnO samples
gets blue shift while the doping level is relatively low (x < 0.02)
which is caused by that the excess carriers provided by doping
can fill some energy level on the edge of conduction band and
cause the transition energy increase [22]. As the Ni content
increase, more and more Ni2+ replace the position of Zn2+
(x > 0.02), the strong sp–d exchange interaction cause the
absorption edge shift to red side [23].
3.4. Photocatalytic activity
In order to evaluate the photocatalytic activity of the Zn1 xNixO
nanorods, we chose rhodamine B (RB) for the photodegradation
investigation, which was widely used to investigate the photo-
catalytic activity of un-doped and doped ZnO photocatalysts [5,24–
26]. Although there are reports about the transitional metal ions
doped into II–VI subgroup photocatalysts can cause deep impurity
levels appear in the bandgap, which enable the photocatalyst to
absorb visible light [4,27,28], we did not observe such a strong
absorption in visible light region in our study of Ni-doped ZnO (see
absorption spectra in Section 3.2 and the PL spectra in Appendix B),
so we use an UV-light lamp as the irradiate source. Fig. 5(a) shows
the degradation rates of RB using Zn1 xNixO as photocatalysts, and
the In (C0/C) versus time curves of the RB photocatalytic activities
are shown in Fig. 5(b). For the intervals between tests are 10 min,
1210 J. Zhao et al. / Materials Research Bulletin 46 (2011) 1207–1210

a 1.0 gaps of Zn1 xNixO samples are estimated from the absorption
x=0 spectra. The photocatalytic activity of Zn1 xNixO is studied by the
x=0.02 degradation of rhodamine B (RB), and it is found that Zn0.95Ni0.05O
0.8
x=0.05 has the best photocatalytic activities among the samples. These
x=0.10 results show the nickel dopant has a positive effect on the
0.6 promising application of ZnO nanorods for the photocatalytic
degradation in the future.
C/C0

0.4

Acknowledgements
0.2
This work was supported by the National Basic Research
0.0
Program of China (No. 2007CB936201), the Major Project of
0 20 40 60 80 International Cooperation and Exchanges (No. 2006DFB51000) and
Time (min) the Research Fund of Co-construction Program from Beijing
Municipal Commission of Education.
b x=0
4 x=0.02 Appendix A. Supplementary data
x=0.05
3
x=0.10 Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.materresbull.2011.04.008.
In( C0/C)

2
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