Advanced Powder Technology 22 (2011) 493–497

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Advanced Powder Technology

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

Original Research Paper

Microwave-assisted hydrothermal synthesis of ZnO rod-assembled

microspheres and their photocatalytic performances
Zhenfeng Zhu *, Dong Yang, Hui Liu
School of Materials Science and Engineering, Shaanxi University of Science and Technology, Xi’an 710021, PR China

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

Article history: ZnO rod-assembled microspheres were successfully fabricated by using the microwave-assisted hydro-
Received 18 January 2010 thermal method in the existence of the poly ethylene glycol (PEG) with the molecular weight of 2000.
Received in revised form 27 May 2010 The structure and morphology of as-prepared samples were characterized by X-ray diffraction (XRD),
Accepted 7 July 2010
scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS), transmission
Available online 19 July 2010
electron microscopy (TEM) and selected area electron diffraction (SAED). The experimental results exhi-
bit that the as-prepared ZnO microspheres with a diameter about 1.5–2.0 lm were composed of many
Keywords:
rods with the diameter of 300 nm and the length of 1 lm, respectively. Photoluminescene measurement
ZnO
Microwave
shows a broad visible emission band centered at around 500–560 nm. The improved catalytic activity
Hydrothermal may be attributed to structural difference, including morphology, surface orientation and surface defects.
Self-assembled Furthermore, the possible growth and photodegradation mechanism of the as-prepared sample is also
Photodegradation briefly discussed.
Ó 2010 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved.

1. Introduction thermal method, microwave hydrothermal synthesis has attracted

ZnO, as a potential semiconductor with a wide band gap
(3.37 eV) and a large exciton binding energy of 60 meV [1], is per-
vasively used in solar cells [2], gas sensors [3], optoelectronic de-
vices [4], light emitting diodes [5] and photocatalysts for
degradation of pollutants due to its eco-friendly and non-toxicity
nature [6]. Much effort has been recently devoted to investigate
ZnO as a very promising phtocatalyst for degradation of pollutants,
like waste effluents of dyes and pigments from industrial branches
such as textile finishing and dye producing. Mai’s research group
[7] reported that methyl green could almost be degraded by ZnO
particles under irradiation of visible light. The successful photocat-
alytic oxidation of dichlorvos was studied by Evgenidou and his
coworkers [8] using TiO2 and ZnO as catalysts, which showed that
illumination of ZnO could lead to the disappearance of dichlorvos
while the TiO2 could provide mineralization. However, researches
on the photodecompositions of many different kinds of dyes per-
formanced only by ZnO are still a promising field.
Up to now, a number of investigations have focused on the syn-
thesis of nano- and micro-architectures through different methods
like hydrothermal [9], sol–gel [10], electrochemical deposition [11]
and vapor-phase process [12]. Compared with conventional hydro-
* Corresponding author. Fax: +86 29 86168802.
E-mail addresses: zhuzf@sust.edu.cn (Z. Zhu), nmlab@sust.edu.cn (D. Yang),
liuhui@sust.edu.cn (H. Liu).
wide interests as a novel heating model in material science due to
its many advantages, including rapid heating, low reaction temper-
ature, homogeneous thermal transmission [13], and the phase pur-
ity with better yield. Previous studies on the microwave irradiation
synthesis of ZnO with a variety of morphologies, such as nanowires
[13], nanorods [14], nanoneedles [15], hollow structures and self-
assembled architectures [16], were widely reported. This method
is promising for fabricating nanomaterials with appropriate mor-
phology, and it is also generally a low-cost process for the large
preparation of nano- and micro-structures. In this work, we report
the successful synthesis of ZnO microspheres self-assembled by
several hexagonal rods in an aqueous solution via microwave-as-
sisted hydrothermal process. The as-obtained products exhibit
both excellent optical and photocatalysis characteristics because
of their special morphology and structures. At last, the possible
growth and photodegradation mechanism of the as-prepared sam-
ple is briefly discussed.
2. Experimental
2.1. Preparation of ZnO spherical microstructures
All chemical agents are analytical grade and are directly used
without further purification. In a typical procedure, first, 3 mmol
of Zn(NO3)26H2O and 60 mmol of NaOH were dissolved in 5 mL
of deionized water, respectively. This solution was marked as solu-

0921-8831/$ - see front matter Ó 2010 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.
doi:10.1016/j.apt.2010.07.002
494 Z. Zhu et al. / Advanced Powder Technology 22 (2011) 493–497

tion A. Secondly, 1 mmol of poly ethylene glycol (PEG, Mw 2000,

99%) was dissolved in a mixed solution of 50 mL of anhydrous eth-
anol and 10 mL of deionized water with vigorous stirring. This
solution was called as solution B. After several minutes of stirring
on the mixture of solution A and B, it experienced 10 min super-
sonic (40 kHz) treatment in a sonic oscillator. Then the mixed solu-
tion was transferred into a 100 mL Teflon-lined autoclave, treated
at 180 °C for 30 min in a MDS-8 microwave hydrothermal system
(manufactured by Shanghai Sineo Microwave Chemistry Technol-
ogy Co. Ltd), and allowed to cool to room temperature naturally.
The resulting precipitates were isolated by centrifugation, followed
by washing with distilled water and ethanol for several times to re-
move the possible residues, then dried in vacuum at 80 °C for 10 h
to obtain final products. Deionized water was used for making all
solutions.

2.2. Photodegradation test procedures

All photoreactions were carried out in glass breakers. Each con-

tained 100 mL dye aqueous solution (1.25 mg l1) and 0.2 g of the
as-prepared ZnO microspheres as photocatalyst. The mixture was
sonicated for 30 min to reach adsorption equilibrium. After that,
the reaction system was placed about 5 cm below the 365 nm light
source of a UV lamp (WFH-203, 220 V, 50 Hz), and irradiated for
different hours in dark at room temperature. The dye solution
was continuously stirred with a magnetic stirrer. Dye samples
were drawn periodically from reaction solution for the UV analysis,
ZnO catalysts were separated by simple centrifugation, washed
with ethanol to remove the organic residuals, and reused for the
next run. The chemical dyes involved are methylene blue
(C16H18N3SCl), methyl orange (C14H14N3NaO3S) and rhodamine B
(C28H31ClN2O3), respectively. They have many uses in a range of
different fields, like chemical indicator and biological tracer dye.
In this test, we use them as photocatalytic indicators to estimate
the photocatalytic activities of ZnO by monitoring their variations
in concentrations.
2.3. Characterization
X-ray diffraction patterns were obtained on a Rigaku D/max
diffractometer with Cu Ka radiation (k = 0.15418 nm). The micro-
structures of the sample were analyzed by scanning electron
microscopy (SEM; JEOL JSM-6360) coupled with energy disper-
sive spectroscopy (EDS) and transmission electron microscopy
(TEM; JEOM JSM-3010). The photoluminescence (PL) spectrum
was recorded at room temperature using a Xe lamp with an
excitation wavelength of 325 nm by a Hitachi F-4500 fluores-
cence spectrometer. The degradation process was analyzed by
monitoring dye absorption intensity at the maximum absorption
wavelength using a UV/Vis/NIR spectrometer (Perkin Elmer,
Lambda 950).
3. Results and discussion
3.1. Morphology and structure
XRD pattern of the as-obtained sample is summarized in Fig. 1.
All the diffraction peaks of samples can be indexed as the wurtzite-
structured hexagonal ZnO with lattice constants of a = 0.3249 nm
and c = 0.5206 nm (JCPDS, No.36-1451), which indicated that the
as-prepared sample is pure ZnO. The high intensities of the XRD
peaks of the as-obtained samples suggest that the ZnO phase syn-
thesized in this work is highly crystalline. No significant character-
istic peaks of impurities could be detected. In addition, the EDS of
the sample confirmed the presence of Zn and O in sample without
Fig. 1. The XRD pattern of the as-prepared ZnO, the inset EDS was taken from an
arbitrary microsphere.
any other elemental contamination, and the atomic percent ratio of
O and Zn in as-prepared sample is 0.559:1, which might indicated
that there are a large content of oxygen vacancy defects on the sur-
face of as-obtained product. The morphology of the as-synthesized
sample was examined by SEM and TEM as shown in Fig. 2. It can be
seen from Fig. 2 that the as-obtained ZnO product is mainly com-
posed of large quantity of quasi-spherical microspheres with diam-
eters of 1.5–2.0 lm. The high-magnification SEM (Fig. 2b) and TEM
(Fig. 2c) images further indicate these microspheres were assem-
bled by ZnO rods with the diameter and length of 300 and 1 lm,
respectively. In addition, SEM results also show that the ends of
ZnO rods are even and regular hexagon which is the typical char-
acteristic of hexagonal wurtzite structure of ZnO crystalline. A typ-
ical TEM image of one ZnO microsphere is shown in Fig. 2c. It is
clear that the morphology of samples is in accordance with the re-
sults of the SEM. A HRTEM image shown in Fig. 2d gives a lattice
fringe of about 0.26 nm, which agrees well with the (0 0 2) plane
of wurtzite ZnO, and indicates the [0 0 1] growth direction of
ZnO rods. The SAED pattern taken from one of the rod is shown
in the inset, and it further confirms the single-crystal nature of
the ZnO rod grown along the c-axis.
PL signals of the as-prepared ZnO sample is shown in Fig. 3. In
most cases, the PL spectra of ZnO consists of an ultraviolet emis-
sion peak in the range of 370–390 nm, and a broad visible emission
band centered at around 500–560 nm which is associated with
oxygen vacancies [1,17]. However, for as-prepared samples, Fig. 3
shows features different from many previous reports, it has an
UV emission band at about 371 nm, three strong blue light emis-
sion peaks at the range of 413–464 nm, and a blue-green and a
green light emission at around 481 and 520 nm, respectively. The
UV emission peak at 371 nm is due to the recombination of photo-
generated electrons and holes, while the blue and green emission
peaks at 413–464 nm and 481, 520 nm are possibly associated
with oxygen vacancies [18,19]. A low PL intensity at 371 nm indi-
cates that the rate of the recombination between photogenerated
holes and electrons might be lower on the surface of as-obtained
ZnO sample than common ZnO powder, which is beneficial for
the photocatalytic process [20]. In this work, the strong emission
peaks ranging from 400 to 500 nm are known to be related to radi-
ative defects, especially singly ionized oxygen vacancy for the blue-
green emission.
 Z. Zhu et al. / Advanced Powder Technology 22 (2011) 493–497
Fig. 2. (a) SEM overview of as-prepared ZnO samples. (b) SEM image of a singe spherical microstructure. (c) TEM image of a single assembled organization. (d) HRTEM image
and SAED pattern (inset) of a tip of a ZnO rod which is marked in inset of (c).
Fig. 3. PL spectrum of the as-prepared ZnO samples.
3.2. Photocatalytic tests
The photocatalytic activity of as-prepared ZnO was investigated
on the photodegradation of methylene blue, methyl orange and
rhodamine B under UV light irradiation. Fig. 4a–c show the varia-
tion in the UV–Vis absorption spectra of dye molecules at different
intervals for three dyes, respectively. It can be seen that the max-
imum absorbance at 665, 463 and 554 nm decreased gradually
with the irradiation time, implying that the dyes were being de-
graded. The decrease in absorbance was probably caused by the
495
destruction of the dye chromogen [21]. For a first order reaction,
Ln(C0/C) = kt, where C0 and C are the initial and actual concentra-
tion or absorbance of dyes, and k is the rate constant of the degra-
dation. In our tests, the values of k are found to be 0.752, 0.587 and
0.467 h1 for methylene blue, rhodamine B and methyl orange,
respectively. As shown in Fig. 4d, the photodegradation of methy-
lene blue by as-prepared ZnO microspheres was the most efficient
case, about 100% removal ratio of methylene blue was calculated
after illuminated by UV light for 7 h, while 9 h and 11 h needed
by rhodamine B and methyl orange, respectively. However, for
commercial ZnO powder, its photocatalytic activity to methylene
blue was inferior to as-prepared ZnO microspheres. This difference
was largely connected with specific surface of samples, the specific
surface areas of commercial powder and as-obtained sample were
7.02 and 12.56 m2/g respectively.
Without any catalyst, only a slow decrease in the concentration
of methylene blue was detected under UV irradiation. The addition
of catalysts leads to obvious degradation of organic dyes, and the
photocatalytic activity depends on the morphology and structure
of ZnO. As shown in Fig. 5, after five cycles, the as-prepared ZnO
still maintained a similar photocatalytic constant k to the photode-
composition of methylene blue, suggesting their reusability and
stability.
3.3. Mechanism of ZnO photocatalytic process
To answer the question of the cause of ZnO in photocatalytic
activity, it is important to understand the mechanism of semicon-
ductor photocatalysis. Upon irradiation, valence band electrons can
be excited to the conduction band leaving a hole behind (Eq. (1)).
The photoelectrons can be easily trapped by electronic acceptors
like adsorbed O2, to reduce molecular oxygen to superoxide radical
anion (Eq. (4)), whereas the holes at the ZnO valence band can oxi-
dize adsorbed water or hydroxide ions to produce hydroxyl radi-
496 Z. Zhu et al. / Advanced Powder Technology 22 (2011) 493–497

Fig. 4. (a–c) Variation of the UV absorption spectra for methylene blue, methyl orange and rhodamine B solution in the presence of as-prepared ZnO. (d) The curves of Ln(C0/
C) vs. irradiation time.

cals (Eq. (2) and (3)), to further oxidize organic pollutants into
harmless products (Eq. (5)) [22,23]. In general, if the photogenerat-
ed electron–hole pairs were recombined, the photocatalytic activ-
ity would be decreased or eliminated. Defects of oxygen vacancy in
ZnO crystallinity, can act as the recombination centers to capture
photo-induced electrons, but the low PL intensity at UV region
(371 nm) indicates the rate of recombination of electrons and holes
is comparatively low, so that the photocatalytic activity can be sta-
bilized or improved in some way. The mechanism of ZnO photocat-
alytic process can be given as followings:

þ
ZnO þ hmðUVÞ ! eCB þ hVB ð1Þ

þ
hVB þ H2 O ! Hþ þ OH ð2Þ

þ
hVB þ OH! OH ð3Þ

eCB þ O2 ! O
2 ð4Þ

O 
2 þ OHads þ dye ! degraded product ð5Þ
Fig. 5. Plot of rate constant k vs. photodecomposition cycle for methylene blue.
 Z. Zhu et al. / Advanced Powder Technology 22 (2011) 493–497
4. Conclusions
In summary, ZnO rod-assembled microspheres have been
successfully synthesized via a simple microwave-assisted hydro-
thermal method. The structure, morphology, PL property, photo-
catalytic application and possible growth mechanism of products
were investigated in detail. The experimental results demonstrated
that the as-prepared ZnO had an excellent optical property and
higher photocatalytic activity than that of commercial ZnO for deg-
radation of methylene blue under UV irradiation, which can be
attributed to the structural difference, including morphology, sur-
face orientation and surface defects. In addition, this kind of ZnO
material displays good recyclability and stability, and may provide
guidance for the application of ZnO in the treatment of organic
pollutants.c
Acknowledgements
This work was financially supported by the National Science
Foundation of China (No. 50772064), China Postdoctoral Science
Foundation Founded Project (No. 20080440185, 200902584), and
Postgraduate Innovation Fund of Shaanxi University of Science
and Technology.
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