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CERAMICS
INTERNATIONAL

Ceramics International 40 (2014) 5629–5633
www.elsevier.com/locate/ceramint

Enhanced photocatalytic performance of ZnO/multi-walled carbon nanotube
nanocomposites for dye degradation
Ping Liua,n, Yanqing Guoa, Qingwei Xua, Fengge Wanga, Yanbin Lia, Keran Shaob
a

School of Electric and Information Engineering, Zhongyuan University of Technology, No. 41 Middle Zhongyuan Road, Zhengzhou 450007, China
b
College of Electrical and Electronics Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
Received 13 October 2013; received in revised form 30 October 2013; accepted 31 October 2013
Available online 8 November 2013

Abstract
The ZnO nanowire/multi-walled carbon nanotube (MWNT) nanocomposites have been successfully synthesized by one-step hydrothermal
method using zinc chloride as Zn source. Their photocatalytic degradation performances on methylene blue and Rhodamine 6G have been
investigated under UV irradiation. Experimental results show that the photocatalytic efficiency of the as-synthesized ZnO/MWNT
nanocomposites is 3 times higher than that of pure ZnO nanowires. The enhanced photocatalytic activity is attributed to the fast transfer of
photo-generated electrons from ZnO to MWNTs, leading to low recombination rate of photo-induced electron–hole pairs.
& 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: B. Nanocomposites; D. Carbon; D. ZnO; E. Functional applications

1. Introduction
The photocatalytic degradation of dye wastewaters by
semiconductor nanostructures has attracted much attention
due to its high efficiency, low-cost and nontoxic end products
[1–4]. Zinc oxide (ZnO) is a wide band-gap semiconductor
oxide and has been widely used to degrade organic dyes in
water under UV irradiation due to their strong oxidizing
power, and being non-toxic, and low cost [5–7]. However,
the recombination rate of the photo-induced electron–hole
pairs in ZnO is usually faster than surface redox reactions
[8], resulting in the low photocatalytic efficiency. To enhance
the photocatalytic efficiency, many efforts have been made to
suppress the electron–hole recombination by means of noble
metal loading [9,10] and incorporation of electron-accepting
materials [7,11,12].
Multi-walled carbon nanotubes (MWNTs) are considered to
be a good electron acceptor [13], which have been demonstrated to greatly improve the photocatalytic activity of
TiO2 for the degradation of azo dyes, phenol, etc. [14–16].
n

Corresponding author. Tel./fax: þ 86 371 62506070.
E-mail address: liuping1980@gmail.com (P. Liu).

In semiconductor oxide/MWNT nanocomposites, MWNTs act
as an excellent electron-acceptor/transport material to remarkably enhance the migration of photo-induced electrons in the
photocatalytic process, suppressing the recombination rate of
electron–hole pairs, which will enhance the photocatalytic
performance. Although the photocatalytic properties of ZnO/
MWNT nanocomposites have been investigated in previous
researches [13,17], the photocatalytic efficiency still remains
low. In this paper, we have demonstrated a one-step synthesis
of the ZnO/MWNT nanocomposites by hydrothermal method,
which has been widely applied to synthesize nanomaterials due
to the tunable control of reactive parameters [18]. The
photocatalytic properties of the as-synthesized ZnO/MWNT
nanocomposites have also been investigated through the
degradation of methylene blue (MB) and Rhodamine 6G
(Rh6G) under UV irradiation.
2. Experimental
All the chemical reagents are of analytical grade and used
without further purification. The ZnO/MWNT nanocomposites
have been synthesized by one-step hydrothermal method.
In a typical experiment, 2 mmol ZnCl2 (Sinopharm Chemical

0272-8842/$ - see front matter & 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2013.10.157

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P. Liu et al. / Ceramics International 40 (2014) 5629–5633

Reagent Co., Ltd.) was first dispersed into 30 ml deionized
water, and then 2 ml MWNT aqueous solution (10 wt%,
Chengdu Organic Chemistry Co., Ltd.) was added into the
above-mentioned Zn2 þ solution under ultrasonication. The pH
value of the mixed solution was adjusted to 11 using NaOH.
After ultrasonication for 30 min, the mixed aqueous solution
was transferred to a 50-ml Teflon-lined autoclave and heated at
120 1C for 12 h. Finally, the ZnO/MWNT nanocomposites
were collected after washing, centrifugation and drying.
The microstructural morphologies of the as-synthesized ZnO/
MWNT nanocomposites were characterized by field emission
scanning electron microscope (FESEM, JEOL-JSM-6700F, Japan)
and energy dispersive spectrometer (EDS). The crystal structure
identification was performed by X-ray diffraction (XRD, Philips
1700X) with Cu-Kα radiation (λ¼ 0.154178 nm) after drying
nanocomposite film on silicon substrate. The UV–vis absorption
spectra of the aqueous ZnO/MWNT nanocomposite solution were measured on a UV/vis spectrophotometer (Hitachi,

U-2000). The photocatalytic properties of the as-synthesized
ZnO/MWNT nanocomposites (10 mg) were evaluated by
decomposing MB and Rh6G solutions (50 ml, 10 mg/l) at
ambient temperature under UV irradiation (λ¼ 365 nm, 150 W)
after 30 min adsorption equilibrium. The absorption spectra of MB
and Rh6G solutions were recorded using UV/vis spectrophotometer.
3. Results and discussion
The micro-morphologies of the as-synthesized ZnO/MWNT
nanocomposites were characterized by SEM, as shown in
Fig. 1a. It can be seen that the diameter of as-synthesized ZnO
nanowires (NWs) is 200–300 nm and the length is 5–10 mm,
which is similar to previous reports [19,20]. One can see that
ZnO NWs are plugged into the MWNTs closely. From lowresolution SEM image in Fig. 1b, the ZnO NWs are wellseparated from each other and well-mingled with MWNTs in

Fig. 1. (a) A typical SEM image, (b) low-resolution SEM image and (c) EDX mapping of the as-synthesized ZnO/MWNT nanocomposites.

P. Liu et al. / Ceramics International 40 (2014) 5629–5633

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Fig. 2. (a) XRD patterns and (b) UV–vis spectra of MWNTs, pure ZnO and the ZnO/MWNT nanocomposites.

Fig. 3. (a) UV–vis absorption spectra of the MB solution during the photodegradation. Inset is optical images before and after the photodegradation.
(b) Decomposition rate of MB solution with no catalysts, pure ZnO and ZnO/MWNT nanocomposites.

the nanocomposites. EDS mapping has also been performed to
characterize this uniformity, as shown in Fig. 1c. One can see
clearly that both MWNTs and ZnO NWs are well dispersed in
the nanocomposites, which will be beneficial for charge carrier
transfer between ZnO NWs and MWNTs.
Fig. 2a shows typical XRD patterns of MWNTs, pure ZnO
and the as-synthesized ZnO/MWNT nanocomposites. From
XRD pattern of pure ZnO NWs, five diffraction peaks at 32.51,
34.91, 36.71, 47.91and 56.41 can be observed clearly, corresponding to the (100), (002), (101), (102) and (110) planes of
the hexagonal wurtzite ZnO phase (JCPDS 65-3411), respectively [21]. Only one diffraction peak around 2θ ¼ 26.51 can be
seen from XRD pattern of MWNTs, which is attributed to
(002) peak of MWNTs. One can see clearly that all diffraction
peaks in the ZnO/MWNT nanocomposites are in good agreement with ZnO NWs and MWNTs [13].
The UV–vis absorption spectra of MWNTs, pure ZnO, and
the ZnO/MWNT nanocomposites are shown in Fig. 2b. It can
be seen that the MWNTs exhibit a very broad and featureless
absorption spectrum, while the pure ZnO and ZnO/MWNT
nanocomposites display sharp characteristic absorption peaks
at ca. 370 nm, indicating the existence of good crystalline and
impurity-suppressed ZnO NWs [5,22]. Compared with pure

ZnO, the ZnO/MWNT nanocomposites exhibit an absorption
spectrum with smaller slope in the visible zone, which could
be attributed to the carbon doping effect [23].
To investigate the photocatalytic property of the assynthesized ZnO/MWNT composites, the photocatalytic degradations of MB solution (10 mg/L) have been tested under
365 nm using pure ZnO and ZnO/MWNT nanocomposites.
Fig. 3 shows typical absorption spectra of the MB solution and
the degradation rates with pure ZnO, ZnO/MWNT nanocomposites and no catalysts. From Fig. 4a, it can be clearly seen that
the absorption peaks of the MB solution diminished gradually as
the exposure time increased. Above 82% MB can be decomposed within 15 min using the nanocomposites. After UV
irradiation for 30 min, the relative intensity of the absorption
peaks disappears completely and the MB solution becomes
colorless, as illustrated by optical photograph (inset of Fig. 3a).
We have also measured the photodegradation rates of the MB
solution with pure ZnO NWs, ZnO/MWNT nanocomposites
and no catalysts, as shown in Fig. 3b. It can be seen clearly that
the degradation time using pure ZnO is 3 times longer than that
of ZnO/MWNT nanocomposites, confirming remarkably
enhanced photocatalytic efficiency of the nanocomposites, this
result is also much better than previous report [13].

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Fig. 4. (a) UV–vis absorption spectra of Rh6G solution during the photodegradation by the ZnO/MWNT nanocomposites. Inset is optical images before and after
the photodegradation. (b) Decomposition rate of Rh6G solution with no catalysts, pure ZnO and the ZnO/MWNT nanocomposites.

Fig. 5. Photocatalytic mechanism of the ZnO/MWNT nanocomposites.

To further characterize the photocatalytic property of the
as-synthesized ZnO/MWNT nanocomposites, the photocatalytic degradations of Rh6G solution (10 mg/L) have also been
tested under UV irradiation. After UV irradiation for 35 min,
the absorption peaks of Rh6G disappear completely and the
Rh6G solution become colorless, as illustrated by optical
photograph (inset of Fig. 4a). Fig. 4b shows the photodegradation rates of Rh6G solution with pure ZnO NWs, ZnO/MWNT
nanocomposites and no catalysts. It is observed that the
photodegradation rate using pure ZnO is much lower than
that of ZnO/MWNT nanocomposites, which further confirms
the enhanced photocatalytic efficiency.
Since the ZnO NW/MWNT nanocomposites exhibit much
higher photocatalytic activities than pure ZnO, the incorporation of MWNTs plays an important role in enhancing the
photocatalytic efficiency. According to the photocatalytic
mechanism based on the excitation of semiconductor [24],
Fig. 5 shows the enhanced photocatalytic degradation mechanism of the ZnO NW/MWNT nanocomposites, which includes
the generation of reactive oxygen species (ROSs) by exciting
semiconductor using UV irradiation and the oxidation of dye
molecules by these ROSs [24]. Under UV irradiation, the

photo-induced electrons (e  ) will transit from valence band
(VB) to conduction band (CB) and leave positive holes (h þ ) in
VB, forming the electron–hole pairs in ZnO NWs. Considering
the potential of the conduction band (  4.05 eV) and the
valence band ( 7.25 eV) of ZnO [22] and MWNTs (4.5–
5.0 eV) [25,26], direct electron transfer from ZnO NWs to
MWNT surface is thermodynamically favorable, which will
result in low recombination rate of the photo-induced e  /h þ
pairs [17,27]. These photo-generated electrons on MWNT
surface react easily with the dissolved oxygen (O2) adsorbed
on nanocomposite surface to form superoxide radical (dO2 ),
and the hydroxyl ions (OH  ) will be oxidized into hydroxyl
radicals (dOH) by photo-induced holes. The continuous
generation of these ROSs results in the degradation process
that the dye molecules decomposed into simple organics and
further converted into CO2 and H2O. Therefore, the enhanced
photocatalytic degradation of the ZnO NW/MWNT nanocomposites should be attributed to the electron transfer between
ZnO NWs and MWNTs under UV irradiation.

4. Conclusions
We have demonstrated a facile and one-step hydrothermal
approach to synthesize the ZnO NW/MWNT nanocomposites.
Their photocatalytic performances on MB and Rh6G have
been investigated under UV irradiation. Our results suggest
that the photocatalytic efficiency of the as-synthesized ZnO
NW/MWNT nanocomposites is 3 times higher than that of
pure ZnO NWs. This enhanced photocatalytic activity can be
attributed to the fact that the recombination process of photoinduced electron–hole pairs is suppressed due to the fast
transfer of photo-induced electrons from ZnO to MWNTs.

Acknowledgments
The authors thank the Foundation of Henan Educational
Committee (No. 2011A470015) and National Natural Science
Funds of China (No. 51177054).

P. Liu et al. / Ceramics International 40 (2014) 5629–5633

References
[1] W. Cun, J.C. Zhao, X.M. Wang, Preparation, characterization and
photocatalytic activity of nano-sized ZnO/SnO2 coupled photocatalysts,
Appl. Catal. B: Environ. 39 (2002) 269–279.
[2] Z.H. Zhang, Y. Yuan, Y.J. Fang, L.H. Liang, H.C. Ding, L.T. Jin,
Preparation of photocatalytic nano-ZnO/TiO2 film and application for
determination of chemical oxygen demand, Talanta 73 (2007) 523–528.
[3] H.W. Wei, L. Wang, Z.P. Li, S.Q. Ni, Q.Q. Zhao, Synthesis and
photocatalytic activity of one-dimensional CdS@ TiO2 core–shell heterostructures, Nano-Micro Lett. 3 (2011) 6–11.
[4] M. Boehme, W. Ensinger, Mixed phase anatase/rutile titanium dioxide
nanotubes for enhanced photocatalytic degradation of methylene-blue,
Nano-Micro Lett. 3 (2011) 236–241.
[5] T. Lv, L.K. Pan, X.J. Liu, Z. Sun, Enhanced photocatalytic degradation of
methylene blue by ZnO-reduced graphene oxide composite synthesized
via microwave-assisted reaction, J. Alloys Compd. 509 (2011)
10086–10091.
[6] C.G. Tian, Q. Zhang, A.P. Wu, M.J. Jiang, Z.L. Liang, B.J. Jiang,
H.G. Fu, Cost-effective large-scale synthesis of ZnO photocatalyst with
excellent performance for dye photodegradation, Chem. Commun. 48
(2012) 2858–2860.
[7] D.Y. Fu, G.Y. Han, Y.Z. Chang, J.H. Dong, The synthesis and properties
of ZnO–graphene nano-hybrid for photodegradation of organic pollutant
in water, Mater. Chem. Phys. 132 (2012) 673–681.
[8] T.G. Xu, L.W. Zhang, H.Y. Cheng, Y.F. Zhu, Significantly enhanced
photocatalytic performance of ZnO via graphene hybridization and the
mechanism study, Appl. Catal. B: Environ. 101 (2011) 382–387.
[9] L.L. Sun, D.X. Zhao, Z.M. Song, C.X. Shan, Z.Z. Zhang, B.H. Li,
D.Z. Shen, Gold nanoparticles modified ZnO nanorods with improved
photocatalytic activity, J. Colloid Interface Sci. 363 (2011) 175–181.
[10] J.W. Chiou, S.C. Ray, H.M. Tsai, C.W. Pao, F.Z. Chien, W.F. Pong,
C.H. Tseng, J.J. Wu, M.H. Tsai, C.H. Chen, H.J. Lin, J.F. Lee, J.H. Guo,
Correlation between electronic structures and photocatalytic activities of
nanocrystalline-(Au, Ag, and Pt) particles on the surface of ZnO
nanorods, J. Phys. Chem. C 115 (2011) 2650–2655.
[11] H.C. Qin, W.Y. Li, Y.J. Xia, T. He, Photocatalytic activity of heterostructures based on ZnO and N-doped ZnO, ACS Appl. Mater. Interfaces
3 (2011) 3152–3156.
[12] B.X. Li, T.X. Liu, Y.F. Wang, Z.F. Wang, ZnO/graphene-oxide
nanocomposite with remarkably enhanced visible-light-driven photocatalytic performance, J. Colloid Interface Sci. 377 (2012) 114–121.
[13] L.J. Jiang, L. Gao, Fabrication and characterization of ZnO-coated multiwalled carbon nanotubes with enhanced photocatalytic activity, Mater.
Chem. Phys. 91 (2005) 313–316.

5633

[14] Y.S. Luo, J.P. Liu, X.H. Xia, X.Q. Li, F. Tao, S.Q. Li, Q.F. Ren, J.L. Li,
Z.J. Jia, Fabrication and characterization of TiO2/short MWNTs with
enhanced photocatalytic activity, Mater. Lett. 61 (2007) 2467–2472.
[15] Y. Ying, J.C. Yu, J.G. Yu, Y.C. Kwok, Y.K. Che, J.C. Zhao, L. Ding, W.
K. Ge, P.K. Wong, Enhancement of photocatalytic activity of mesoporous TiO2 by using carbon nanotubes, Appl. Catal. A: Gen. 289 (2005)
186–196.
[16] S.M. Lam, J.C. Sin, A.Z. Abdullaha, A.R. Mohamed, Photocatalytic
TiO2/carbon nanotube nanocomposites for environmental applications: an
overview and recent developments, Fuller. Nanotub. Carbon Nanostruct.
(2013)http://dx.doi.org/ 10.1080/1536383X.2012.690458.
[17] T.A. Saleh, M.A. Gondal, Q.A. Drmosh, Preparation of a MWCNT/ZnO
nanocomposite and its photocatalytic activity for the removal of cyanide
from water using a laser, Nanotechnology 21 (2010) 495705–495708.
[18] J. Xie, H. Wang, M. Duan, L.H. Zhang, Synthesis and photocatalysis
properties of ZnO structures with different morphologies via hydrothermal method, Appl. Surf. Sci. 257 (2011) 6358–6363.
[19] R. Wahab, S.G. Ansari, Y.S. Kim, M.W. Song, H.S. Shin, The role of pH
variation on the growth of zinc oxide nanostructures, Appl. Surf. Sci. 255
(2009) 4891–4896.
[20] B. Cheng, E.T. Samulski, Hydrothermal synthesis of one-dimensional
ZnO nanostructures with different aspect ratios, Chem. Commun. 8
(2004) 986–987.
[21] T.Q. Chang, Z.J. Li, G.Q. Yun, Y. Jia, H.J. Yang, Enhanced photocatalytic activity of ZnO/CuO nanocomposites synthesized by hydrothermal method, Nano-Micro Lett. 5 (2013) 163–168.
[22] G. Yang, H.S. Wang, C.L. He, L.J. Qiu, X.B. Cao, Uniform carboncoated ZnO nanorods: microwave-assisted preparation, cytotoxicity, and
photocatalytic activity, Langmuir 25 (2009) 4678–4684.
[23] Z.Y. Zhan, L.X. Zheng, Y.Z. Pan, G.Z. Sun, L. Li, Self-powered, visiblelight photodetector based on thermally reduced graphene oxide–ZnO
(rGO–ZnO) hybrid nanostructure, J. Mater. Chem. 22 (2012) 2589–2595.
[24] B.J. Li, H.Q. Cao, ZnO@graphene composite with enhanced performance
for the removal of dye from water, J. Mater. Chem. 21 (2011)
3346–3349.
[25] P. Liu, Y. Wei, K.L. Jiang, Q. Sun, X.B. Zhang, S.S. Fan, Thermionic
emission and work function of multiwalled carbon nanotube yarns, Phys.
Rev. B 73 (2006) 235412–235415.
[26] M. Shiraishi, M. Ata, Work function of carbon nanotubes, Carbon 39
(2001) 1913–1917.
[27] K. Dai, G. Dawson, S. Yang, Z. Chen, L.H. Lu, Large scale preparing
carbon nanotube/zinc oxide hybrid and its application for highly reusable
photocatalyst, Chem. Eng. J. 191 (2012) 571–578.