Materials Science & Engineering B 248 (2019) 114405

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Materials Science & Engineering B

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

Enhanced photocatalytic performance of porous ZnO thin films by CuO T

nanoparticles surface modification
⁎
Linhua Xua,b, , Jing Sua,b, Gaige Zhenga,b, Lei Zhanga,c
a
School of Physics and Optoelectronic Engineering, Nanjing University of Information Science & Technology, Nanjing 210044, China
b
Jiangsu Key Laboratory for Optoelectronic Detection of Atmosphere and Ocean, Nanjing University of Information Science & Technology, Nanjing 210044, China
c
Physics Experiment Center, Nanjing University of Information Science & Technology, Nanjing 210044, China

A R T I C LE I N FO A B S T R A C T

Keywords: Improving the response of ZnO photocatalyst to visible light is a hot topic. In this work, the porous ZnO thin
Porous ZnO thin films films were first prepared by sol-gel method, and then CuO nanoparticles were deposited on the porous ZnO thin
CuO nanoparticles films to form CuO-ZnO heterojunction; the effect of CuO content on the photocatalytic activity of ZnO thin films
Sol-gel method were investigated. The results show that the formation of CuO-ZnO heterojunction effectively separates the
Photocatalytic performance
photogenerated electron-hole pairs, leading to significant decrease of ZnO ultraviolet emission. In addition, the
Heterojunction
ZnO thin films with CuO nanoparticles modified on the surface increase the absorptive capacity in the visible
range. Photocatalytic degradation of methylene blue shows that the photocatalytic activity of all CuO/ZnO thin
films is greatly improved. The improvement of photocatalytic performance should be attributed to the enhanced
separation efficiency of photogenerated electron-hole pairs by the CuO-ZnO heterojunction and the increased
light absorption in the visible range by CuO nanoparticles. This kind of CuO/ZnO thin films also shows good
photocatalytic reusability.

1. Introduction improve the photocatalytic performance of ZnO, some methods have

In recent years, with the rapid development of industry and agri-
culture, some negative effects also occur inevitably, such as environ-
mental pollution (especially water pollution and air pollution), which is
very serious in some emerging developing countries [1,2]. Water is the
basis of human survival, so how to solve the problem of water pollution
is crucial. However, the existing techniques can not completely remove
pollutants, especially organic pollutants in the water [3]. In recent
years, semiconductor photocatalysis technique has attracted wide at-
tention as a possible technique for the treatment of wastewater and
hydrogen production. The metal-oxide semiconductors used as photo-
catalysts include TiO2, ZnO, Fe2O3, SnO2 and so on. Among these
semiconductors, ZnO has a high photosensitivity and fast electron
transfer speed and thus is considered to be an important photocatalytic
material [4–10]. However, ZnO is a wide direct bandgap semi-
conductor. As a photocatalytic material, it shows two obvious defects:
(1) the recombination efficiency of photogenerated electrons and holes
is high; (2) ZnO can absorb only the ultraviolet light with energy higher
than the bandgap value. If the photocatalytic activity of ZnO is to be
enhanced, the above-mentioned defects must be overcome. In order to
been adopted by some researchers, such as doping ZnO with non-me-
tallic elements or metal elements [4,5,11,12], making ZnO thin films be
porous [13,14], noble metal nanoparticles surface modification
[3,9,15,16], forming a hybrid material or a coupled heterojunction with
a narrow bandgap material [10,17–20], etc. The last method has been
paid much attention because it not only can expand absorption to the
visible range but also improve the separation efficiency of photo-
generated electron-hole pairs.
Among the semiconductors with medium or narrow bandgaps such
as CdS, CdSe, In2O3, Cu2O, CuO, CuO has some attractive advantages,
such as chemical stability, p-type conductivity (being able to form
heterojunction with ZnO), abundant raw materials, and possessing the
suitable band edge position which can be coupled with ZnO. Some
CuO/ZnO composite materials have been prepared and investigated on
their photocatalytic performance. For example, Li et al. [21] prepared
nanostructured ZnO-CuO composite by homogeneous coprecipitation
method using zinc chloride and copper sulfate as raw materials. It was
found that the composite material showed high photocatalytic effi-
ciency for degradation of Rhodamine B with irradiation from the si-
mulated sunlight. Dai et al. [22] obtained ZnO-CuO nanoparticles by

⁎
Corresponding author at: School of Physics and Optoelectronic Engineering, Nanjing University of Information Science & Technology, Ningliu Road 219#,
Nanjing 210044, China.
E-mail address: congyu3256@sina.com (L. Xu).

https://doi.org/10.1016/j.mseb.2019.114405
Received 2 November 2017; Received in revised form 15 January 2019; Accepted 9 August 2019
Available online 19 August 2019
0921-5107/ © 2019 Elsevier B.V. All rights reserved.
L. Xu, et al.
two-solvent method and embedded them into mesoporous silica SBA-
15; they studied the effect of the loading dosage of ZnO-CuO nano-
particles on the photocatalytic efficiency of the (ZnO-CuO)/SBA-15
nanocomposites. It was found that too high or too low loading would
lower the photodegradation performance. Yang et al. [23] fabricated
CuO/ZnO hybrid nanostructures by the complex-directed hybridization
and subsequent calcinations, and investigated the photocatalytic
properties of the samples; they deemed that the enhanced photo-
catalytic activity of the CuO/ZnO-RT nanostructure could be ascribed to
the expanded absorption in the visible range. Samad et al. [24] pre-
pared the CuO/ZnO photocatalyst by mechanical mixing method and
photocatalytic oxidation and simultaneous removal of arsenite using
the photocatalyst was investigated; they found that the weight per-
centage of CuO in CuO/ZnO mixtures had a great effect on the photo-
catalytic activity. Taufik et al. [25] synthesized ternary CuO/TiO2/ZnO
nanocomposites with different CuO loadings by sol-gel method and
investigated the photocatalytic degradation of methylene blue; they
found that the ternary CuO/TiO2/ZnO nanocomposite with a molar
ratio of 0.5:1:1 exhibited the best photocatalytic activity. Although
some CuO/ZnO composites with different forms have been prepared,
most of them are unimmobilized (not easy to be recycled) or they have
been obtained by a relatively complicated preparation procedure.
However, the substrate-supported CuO/ZnO composites with low cost
and high visible response are rarely reported.
In a previous work of us [14], we obtained three-dimensional
porous ZnO thin films by a facile method, which exhibited higher
photocatalytic activity under irradiation of ultraviolet light compared
with compact ZnO thin films. However, the photocatalytic activity
under irradiation of visible light is still low. In order to further improve
the photocatalytic performance of the porous film under irradiation of
sunlight, in this work, CuO nanoparticles were deposited on the porous
ZnO thin films. It is found that the surface modification by CuO na-
noparticles can greatly enhance the photocatalytic performance of the
porous ZnO thin films and an optimal CuO loading dosage is also re-
vealed. Since both the preparation of porous ZnO thin films and de-
position of CuO nanoparticles are achieved by the low-cost sol-gel
method, this kind of CuO/ZnO nanocomposite thin films could be used
on a large scale. To the best of our knowledge, the photocatalytic be-
havior of this kind of special structured CuO/ZnO thin film has not been
reported. The detailed experimental results are described below.
2. Experiments
The porous Sr-doped ZnO thin films were first prepared by sol-gel
method. The preparation process has been described in detail elsewhere
[14]. Here the dopant concentration of strontium is 3 at.%. Then, CuO
nanoparticles were formed by spin-coating CuO sol on the porous ZnO
thin film and a suitable annealing treatment. The spin-coating was
carried out only one time. After the spin-coating, the sample was placed
under an infrared lamp for drying for 5 min and then put into a furnace
to be annealed at 450 ℃ for 30 min to form CuO-ZnO heterojunction. In
order to study the effect of CuO content on the photocatalytic perfor-
mance of the porous ZnO thin film, four CuO sols with different con-
centrations were prepared. The concentration of the sols is 0.05, 0.1,
0.15 and 0.2 mol/L; accordingly, the resulted CuO/ZnO thin films are
labeled as sample B, C, D and E, respectively. For comparison, a bare
porous ZnO thin film is also characterized and tested; this sample is
labeled as sample A.
The surface morphologies and composition of the samples were
analyzed by a field emission scanning electron microscope (S4800)
equipped with an energy dispersive X-ray spectrometer. The crystal
phase of the CuO/ZnO thin films was determined by an X-ray dif-
fractometer (SmartLab). The microstructure of the CuO/ZnO thin films
is characterized by high-resolution transmission electron microscopy.
The surface composition and the chemical bonding states of the con-
stituent elements of the films were analyzed by an X-ray photoelectron
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Materials Science & Engineering B 248 (2019) 114405
spectrometer (Thermo escalab 250Xi). The optical absorption of the
samples was measured by a double beam spectrophotometer
(Cary5000). The photoluminescence spectra were recorded by a spec-
trometer (LabRAM HR800) using a He-Cd laser as the excitation source
with a wavelength of 325 nm. The photocatalytic activity of the samples
was tested using methylene blue as the model organic pollutant and a
Xe lamp of 150 W as the simulated sunlight source. The film area is
1.5 × 1.5 cm2; the methylene blue concentration in the aqueous solu-
tion is 5 mg/L. After the photocatalyst was put into the methylene blue
solution, the mixture was placed in the dark for one hour before the
irradiation of light so as to achieve the adsorption–desorption equili-
brium for the organic molecules on the sample surface. And then under
the Xe lamp irradiation, the photocatalytic degradation reaction
started. During the process, the photocatalytic reaction equipment is
cooled using circulating water; the methylene blue solution is at rest
without air or oxygen being pumped into it and without magnetic
stirring, so as to simulate the photocatalytic degradation process under
the natural conditions. The photodegradation efficiency is calculated by
the following formula:
C0 − C A −A
η= × 100% = 0 × 100%
C0 A0 (1)
where η is the degradation efficiency, C0 and A0 is the concentration
and absorbance of methylene blue solution before light irradiation, C
and A is the concentration and absorbance of methylene blue solution
after it is exposed to light irradiation for 120 min.
3. Results and discussion
3.1. The morphology, crystal phase and chemical composition of the CuO/
ZnO thin films
Fig. 1 shows the surface morphology image of the bare porous ZnO
thin film and the surface morphology images of porous ZnO thin films
modified by CuO nanoparticles formed by CuO sols with different
concentrations. Fig. 1(a) displays the surface morphology image of the
unmodified porous ZnO thin film, which exhibits a very uniform por-
osity. These pores are not only distributed on the film surface, but also
almost throughout the films [14], which show a three-dimensional
feature. This kind of pores makes the organic molecules in the liquid
environment can enter the interior of the ZnO thin film [21], which can
greatly increase the contact area between ZnO and organic pollutants,
being beneficial to improve the photocatalytic degradation efficiency of
ZnO thin films. In addition, some flat surfaces on ZnO grains are also
observed, which are similar to the flat upper surface of ZnO nanorods.
The flat surfaces are formed as a result of the preferential orientation of
the ZnO grains along the c-axis. From the Fig. 1(b), it can be apparently
seen that many spherical nanoparticles are formed on the ZnO thin film
after a CuO sol with a concentration of 0.05 mol/L is coated once and
annealed. It can be known from the below X-ray diffraction and
transmission electron microscopy results that these nanoparticles are
CuO nanoparticles. These CuO nanoparticles are very homogeneous
with a diameter of about 7–10 nm. When the CuO sol concentration is
low, these CuO nanoparticles are basically grown at the edge of ZnO
grains. This may be due to the higher energy of Zn and O atoms at the
edge of ZnO grains, which is more favorable for nucleation and crystal
growth of CuO. With the increase of CuO sol concentration, two obvious
changes are observed. One is that the CuO nanoparticles gradually in-
crease, and the other is that the pores on the ZnO film surface become
smaller due to the increase of CuO coverage area. For sample E, those
flat surfaces on ZnO grains are almost completely covered by CuO na-
noparticles.
Fig. 2 displays the typical elemental mapping images of sample D. it
can be seen that Cu element is uniformly distributed on the surface of
ZnO thin film, indicating that CuO nanoparticles are uniformly dis-
tributed on the surface of the porous ZnO thin film, which is consistent
L. Xu, et al.
Fig. 1. Surface morphology images of sample A (a), B (b), C (c), D (d) and E (e).
with the results observed directly by the scanning electron microscope.
In addition, the atomic percentages of Cu relative to Zn are calculated
from the energy dispersive X-ray spectroscopy spectra. The percentage
is 0.89%, 2.03%, 3.78%, and 4.59%, respectively, in sample B, C, D and
E. This is consistent with the trend of the gradually increased coverage
of CuO observed from the scanning electron microscopy image.
Fig. 3 presents a representative X-ray diffraction pattern of sample
D. The diffraction peaks in the pattern correspond to the diffraction
peaks of ZnO with a wurtzite phase and those of CuO with a monoclinic
structure (marked with an asterisk), respectively. Both the ZnO thin
film and the CuO nanoparticles show a polycrystalline nature. Except
the diffraction peaks of ZnO and CuO, no other peaks corresponding to
Cu, Zn or Cu2O are detected, indicating that this sample is composed
only of wurtzite ZnO and monoclinic CuO.
In order to further determine the contact state of CuO with ZnO, we
scraped part of sample D off the substrate and observed the high-re-
solution morphology image of the sample by a transmission electron
microscope. Fig. 4(a) shows the low-resolution morphology image of
the peeled coating. The inset is a selected-area electron diffraction
pattern. It can be seen that these diffraction patterns are circular shape,
meaning that both ZnO and CuO are mostly polycrystalline. This is
consistent with the X-ray diffraction result. Fig. 4(b) is an energy
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Materials Science & Engineering B 248 (2019) 114405
dispersive X-ray spectroscopy spectrum showing that the peeled coating
contains only three elements of Zn, O and Cu, further confirming that
the sample consists only of ZnO and CuO. Fig. 4(c) and (d) are high-
resolution images of two different areas as shown in Fig. 4(a). It can be
seen that the ZnO and CuO grains are closely connected together. They
all show clear ZnO and CuO lattice fringes, indicating that the ZnO-CuO
heterojunction has been formed. The clear lattice fringes also mean that
the crystalline quality of ZnO and CuO is relatively good.
In order to determine the surface composition and the chemical
state of the constituent elements, the X-ray photoelectron spectroscopy
spectra have been measured for sample D, as shown in Fig. 5. The
binding energy in the X-ray photoelectron spectroscopy spectra is ca-
librated by using that of C 1s (284. 8 eV). From the survey spectrum of
Fig. 5(a), it can be seen that only the signals of Zn, O and Cu are shown
in this spectrum, which means that the sample surface is very pure and
does not contain other impurities. Fig. 5(b) shows the high-resolution
spectrum of Zn 2p. The two highly geometrically symmetric signal
peaks at 1044.78 and 1021.68 eV correspond to Zn 2p1/2 and Zn 2p3/2,
respectively, and the energy interval between them is 23.1 eV. The
above information indicates that Zn is completely oxidized and is +2
valence state [21,22]. Fig. 5(c) shows the high-resolution X-ray pho-
toelectron spectroscopy spectrum of O 1s, and it is clear that the peak is
L. Xu, et al.
Fig. 2. Typical elemental mapping images of sample D.
Fig. 3. X-ray diffraction pattern of sample D.
not geometrically symmetric. By Gaussian fitting, we can see that O
contains two components: one is at 529.9 eV which is assigned to Zn
and Cu-bonded lattice oxygen [22,26], and the other is at 531.5 eV
which derives from oxygen vacancies [3,26]. Fig. 5(d) shows the high-
resolution spectrum of Cu 2p. The two signal peaks at 933.8 and
953.8 eV are from Cu 2p3/2 and Cu 2p1/2, respectively, along with two
satellite peaks at 942.4 and 962.4 eV. This information indicates that Cu
ions are in the +2 valence state [21,22]. Therefore, the nanoparticles
on the ZnO films surface are CuO particles, which is consistent with the
results of X-ray diffraction and transmission electron microscopy.
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Materials Science & Engineering B 248 (2019) 114405
3.2. The optical properties and photocatalytic performance of CuO/ZnO
thin films
Fig. 6 shows the optical absorption spectra of the samples. All
samples show strong absorption in the ultraviolet region with wave-
length less than 380 nm, which is mainly due to the band-edge and
bandgap absorption of porous ZnO thin films. Compared with the bare
porous ZnO thin films, the ones modified by CuO nanoparticles also
show enhanced absorption in the range of 390–500 nm. This absorption
should be attributed to CuO, since the bandgap of CuO is in the range of
1.7~3.02 eV [22,27]. Extended optical absorption range is very im-
portant for improving the photocatalytic performance of ZnO-based
materials. Many studies have shown that one of the important factors
which have improved the photocatalytic performance of CuO-ZnO
composites is the increased utilization efficiency of visible light [23].
Fig. 7 shows the room-temperature photoluminescence spectra of
the CuO/ZnO thin films. As for the bare porous ZnO thin film, it exhibits
a strong ultraviolet emission centered at 381 nm as well as a wide
visible emission band which is formed by superposition of green, or-
ange and red emission peaks. Many researchers deem that the green
emission centered at 510 nm is related to oxygen vacancy defects in
ZnO [26,28]. Some scholars suggest that the red–orange emissions may
be associated with oxygen interstitials in ZnO or oxygen, hydroxide
adsorbed on the ZnO surface [29]. After the porous ZnO thin film is
modified by CuO nanoparticles, its ultraviolet emission obviously de-
creases. This is because the formation of CuO-ZnO heterojunction ef-
fectively separates the photo-generated electron-hole pairs, inhibiting
the rapid recombination. In addition, the visible emissions, especially
the orange emission is also significantly weakened; it may be due to
that CuO nanoparticle surface modification prevents the adsorption of
oxygen molecules, water molecules, hydroxide etc. which may cause
orange emission. The decline of green emission is due to the decrease of
oxygen vacancy defects on the surface of ZnO. Furthermore, a violet
emission at ~440 nm is also observed for CuO/ZnO thin films, but the
L. Xu, et al. Materials Science & Engineering B 248 (2019) 114405

Fig. 4. Transmission electron microscopy images of sample D.

origin of this violet emission in ZnO is not yet conclusive. Some re- factors: (1) the formation of CuO-ZnO heterojunction improves the se-
searchers consider it to be related to zinc interstitials [30], and other paration efficiency of photogenerated electron-hole pairs [21,22]; (2)
researchers deem it to be associated with copper ions incorporated into CuO increases the utilization efficiency of visible light. The mechanism
ZnO [31]. Since the violet emission has been found in many Cu-doped for the photocatalytic reaction of CuO-ZnO heterojunction is shown in
ZnO materials [31,32], we tend to believe that the violet emission Fig. 9. The process of photocatalytic reactions involved can be ex-
centered at 440 nm results from transitions related to Cu ions in ZnO pressed by the following equations:
lattice. During the formation process of CuO nanoparticles, some Cu
ZnO(e-+h+) + CuO(e-+h+) + hv → ZnO(e-+e-) + CuO(h++h+) (2)
ions are probably doped into ZnO lattice due to thermal diffusion,
which resulted in the violet emission. e-+O2→·O2– (3)
Fig. 8(a) shows the absorbance curves of methylene blue solution –
with the increase of reaction time using sample A as the photocatalyst. h +OH →·OH
+
(4)
It can be seen that as the reaction time increases, the concentration of –
·O2 +H2O → HO2·+OH– (5)
methylene blue in the aqueous solution gradually decreases; it is ap-
parent that the photocatalyst plays a role in the degradation of me- HO2 +H2O → H2O2OH
·
(6)
thylene blue. Although the ultraviolet light only accounts for a small
H2O2+·O2–→OH–+·OH + O2 (7)
part in the Xe lamp radiation, sample A still shows a certain photo-
catalytic activity, which is mainly due to the porous structure and nu- ·OH + MB → H2O + CO2 + inorganicmolecules (8)
merous surface oxygen vacancy defects [33]. Fig. 8(b) shows the pho-
Equation (2) shows that when the light is irradiated onto the CuO-
tocatalytic degradation efficiency of the five different samples with
ZnO heterojunction, ZnO absorbs ultraviolet light and generates elec-
reaction time of 2 h and the self-photodegradation efficiency of me-
tron-hole pairs, CuO absorbs visible and ultraviolet light and generates
thylene blue under the Xe lamp irradiation without photocatalysts. It is
electron-hole pairs. Since the position of the CuO conduction band and
clear that the natural degradation rate of methylene blue is very slow in
the valence band are higher than those of ZnO, it is thermodynamically
the absence of photocatalyst. When the porous ZnO thin films are
favorable for the transfer of photogenerated electrons and holes
modified by CuO nanoparticles, the photocatalytic degradation effi-
[22,24]. Electrons are transferred to ZnO, and holes are transferred to
ciency of the samples is remarkably improved compared with that
CuO. Then the photogenerated electrons and holes migrate to the sur-
without surface modification. The improvement of the photocatalytic
face of the semiconductors, respectively, reacting with the surface ad-
activity of these CuO/ZnO thin films is mainly due to the following
sorbed oxygen and hydroxide to produce superoxide radicals and

5
L. Xu, et al.
Fig. 5. Typical X-ray photoelectron spectroscopy spectra of sample D: (a) survey spectrum, (b) high-resolution spectrum of Zn 2p, (c) high-resolution spectrum of O
1s and (d) high-resolution spectrum of Cu 2p.
Fig. 6. Absorption spectra of the samples.
hydroxyl radicals, as described in Eqs. (3) to (7). Hydroxyl radicals are
a strong oxidizing agent that decomposes methylene blue into H2O,
CO2, and harmless inorganic small molecules, as shown in Eq. (8).
Among the samples, sample D shows the best photocatalytic ac-
tivity, indicating that the CuO loading dosage has an important influ-
ence on the photocatalytic performance of CuO/ZnO thin films. The
similar results have been also reported by others [24,25,34]. For ex-
ample, Harish et al. [34] studied the effect of CuO loading dosage on
the photocatalytic performance of ZnO nanorods. They found that the
CuO/ZnO composite obtained the highest photocatalytic activity when
the addition of Cu relative to Zn was 1% in the growth solution.
However, they did not give a detailed explanation about the result. So,
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Materials Science & Engineering B 248 (2019) 114405
Fig. 7. Photoluminescence spectra of the samples.
why is the photocatalytic performance of CuO/ZnO composite mate-
rials reduced when the surface loading dosage of CuO is relatively high?
We think there are three main reasons: (1) when the loading dosage of
CuO is too high, the exposed area of ZnO is greatly reduced, as shown in
Fig. 1(e); (2) when the loading dosage of CuO is too high, a large
amount of ultraviolet light are absorbed by the upper CuO; as a result,
the ultraviolet light which can be utilized by ZnO is greatly decreased;
(3) Although some studies have reported that CuO has a certain pho-
tocatalytic activity, the quantum efficiency of CuO is much lower than
that of ZnO [24]; so, a high CuO loading will reduce the overall
quantum efficiency of the CuO/ZnO system. Therefore, in respect to the
CuO/ZnO composite materials, their photocatalytic performance can be
L. Xu, et al.
Fig. 8. (a) Ultraviolet–visible absorption spectra of methylene blue solution as a function of irradiation time using sample A as the photocatalyst and (b) the
photodegradation efficiency of the samples.
Fig. 9. The schematic diagram of the band structure of CuO/ZnO system and
the charge transfer process.
improved maximally only when a synergistic effect is realized, namely,
maximizing the utilization efficiency of irradiated light and the se-
paration efficiency of photogenerated electron-hole pairs. However, for
different forms of CuO/ZnO materials, such as powders, films, na-
norods, etc. the optimal loading dosage of CuO is not necessarily same
[24,25,34].
In order to decide the reproducibility of the photocatalytic perfor-
mance of porous ZnO thin films modified by CuO nanoparticles, we
carried out five tests for sample D on the photocatalytic degradation of
methylene blue under the same conditions. After a photocatalytic test is
finished, the sample will be withdrawn from the solution and then
rinsed with water and then placed in the sun to be dried, and then it will
be reused for the next time. The photodegradation efficiency is shown
in Fig. 10. With the increase of reaction times, the photodegradation
efficiency of the sample decreases slightly. Even so, it is still higher than
80% for the fifth time. This indicates that this kind of material has a
good reusability. Compared with the unimmobilized CuO/ZnO com-
posite materials, this kind of CuO/ZnO thin films is easier to be re-
cycled. Unlike the substrate-supported CuO/ZnO materials, the se-
paration process of the unimmobilized ones from the liquid after use is
laborious and the CuO-ZnO heterojunction is also easily destroyed after
multiple use and treatment.
From the above results, it is clear that the photocatalytic perfor-
mance of the porous ZnO thin films can be greatly improved with CuO
nanoparticles modification. This improvement of photocatalytic per-
formance is caused mainly by the extended light absorption range and
the reduced recombination efficiency of photogenerated electrons and
holes.
4. Conclusion
In this study, we systematically studied the effect of CuO loading on
7
Materials Science & Engineering B 248 (2019) 114405
Fig. 10. The reproducibility of photocatalytic performance of the CuO/ZnO
thin film.
the photocatalytic activity of porous ZnO thin films under simulated
solar radiation. The results show that the photodegradation efficiency
of all porous ZnO films modified by CuO nanoparticles is greatly im-
proved compared with that of porous ZnO thin films without surface
modification. This improvement in photocatalytic performance is
mainly due to the enhanced visible light absorption and improved se-
paration efficiency of photogenerated electron-hole pairs. Although the
photodegradation efficiency of all ZnO thin films loaded with CuO
nanoparticles is improved, it shows a strong dependence on the loading
dosage. It is found that the CuO/ZnO thin film exhibits the highest
photocatalytic activity when the atomic percentage of Cu to Zn in the
samples is 3.78%. In addition, the CuO/ZnO thin film also shows good
reproducibility. The results suggest that this kind of photocatalyst
(porous ZnO thin films modified by CuO nanoparticles) may have po-
tential application in wastewater treatment.
Acknowledgements
This work is supported by the Natural Science Foundation of the
Jiangsu Higher Education Institutions (Grant no. 16KJB430021,
17KJB430022) and the Natural Science Foundation of Jiangsu Province
(Grant no. BK 20180784). Dr. Jing Su thanks the financial support by
the “Six Talent Peaks” Project of Jiangsu Province (Grant no.
R2016L07).
L. Xu, et al.
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