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Morphological evolution of ZnO nanostructures

and their aspect ratio-induced enhancement in
Cite this: RSC Adv., 2014, 4, 29249
photocatalytic properties†
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Faheem Ahmed, Nishat Arshi, M. S. Anwar, Rehan Danish and Bon Heun Koo*

Received 20th March 2014
Accepted 9th June 2014
DOI: 10.1039/c4ra02470b
www.rsc.org/advances
This work presented controllable growth of ZnO nanostructures with different aspect ratios by the
microwave irradiation method and investigated the photocatalytic degradation of methyl red (MR). X-ray
diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and selected area electron
diffraction (SAED) measurements showed that all ZnO nanostructures were of a hexagonal phase
structure. It was revealed by field-emission scanning electron microscopy (FESEM) and transmission
electron microscopy (TEM) images that the morphology of ZnO can be effectively controlled as sheet-
like, rod-like, brush-like, flower-like, prism-like, and pyramid-like only by changing the molar ratio (zinc
acetate: KOH) and reaction time. With the increase of molar ratio and reaction time, modification in the
E2(high) and E1(LO) Raman modes was observed. The energy band gap was found to be tuned by the
aspect ratio of ZnO nanostructures. Photoluminescence spectroscopy revealed the low-intensity NBE
emission and high and broad defect-related emission for high aspect ratio (14) nanorods. BET surface
area porosity analysis confirmed the presence of a mesoporous network in all the nanostructures,
showed high surface area and a uniform pore-size distribution for high aspect ratio nanorods. A
terephthalic acid assay study confirmed the formation of hydroxyl radicals (OH) in MR dye solution
treated with a ZnO nanostructures photocatalyst. The photodegradation of MR under UV light irradiation
showed that ZnO nanorods with a high aspect ratio of
14 showed superior photodegradation (
98%
degradation of MR within 60 min) than that of the lower aspect ratio nanostructures. The apparent
reaction rate constant for high aspect ratio (14) nanorods was higher than that of the lower aspect ratio
nanostructures. The enhancement in photocatalytic performance could be due to the high surface area
and enhanced charge separation and transfer efficiency of photoinduced charge carriers in the high
aspect ratio nanorods.

Nowadays, increased industrialization poses a threat to

Introduction
With a wide and direct band gap of 3.37 eV with a large exciton
binding energy of 60 meV, ZnO, which has been extensively
used in eld emission,1 short-wavelength optoelectronics,2
electroacoustic transducers,3 gas sensors,4 transparent con-
ducting coating materials,5 piezoelectric devices,6 and photo-
catalysis,7 has proven to be a unique functional material during
the past several years. Recently, the room temperature ferro-
magnetism (RTFM) behaviour with a Curie temperature (Tc)
value above room temperature in pure ZnO has been reported
by various groups,8,9 which has attracted enormous interest
from researchers for possible application in spintronic devices.
School of Nano and Advanced Materials Engineering, Changwon National University,
Changwon, Gyeongnam, 641-773, Korea. E-mail: bhkoo@changwon.ac.kr; Fax: +82-
55-262-6486; Tel: +82-55-264-5431
† Electronic supplementary information (ESI) available.
10.1039/c4ra02470b
human health in the form of environmental pollution. Envi-
ronmental remediation of organic pollutants by photocatalytic
degradation using wide bandgap semiconductors has attracted
considerable attention in recent times.10–13 Furthermore, these
materials in the nanostructured form exhibit enhanced prop-
erties, and therefore have potential applications such as in the
fabrication of nanodevices. Various semiconductors, including
ZnO and TiO2, are being used in photocatalytic application
because of their low cost, high photosensitivity, non-toxicity
and environmentally friendly nature.14–16 ZnO has been estab-
lished to be a more efficient photocatalyst than TiO2 because of
its high surface reactivity owing to its large number of active
surface defect states. It has also been shown that ZnO has high
reaction and mineralization rates17 because of its more efficient
hydroxyl-ion production.18 When ZnO is irradiated with UV
light, electrons are excited from the valence band to the
conduction band and electron–hole pairs are created. These
See DOI:
electron–hole pairs activate the surrounding chemical species,
and then promote the chemical reactions.19,20 The efficiency of

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ZnO as a photocatalyst has been limited due to the recombi-
nation of photogenerated charge carriers, which is typically
faster than the rate of production of reactive oxidation species.
Thus, improving the charge separation efficiency needs a
rational design of the photocatalyst structure. As photocatalytic
activity of metal-oxide nanostructures depends on structures,
including the morphology, surface area and surface defects,
one-dimensional (1D) nanostructures such as nanorods, nano-
wires, and nanotubes are ideal candidates for the application in
photocatalysis since they offer a larger surface-to-volume ratio
than nanoparticulate thin lms.21 1D nanostructures with high
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aspect ratios have been shown to promote the separation of
photogenerated charge carriers due to an increased delocal-
ization of electrons in the 1D nanostructures, which is impor-
tant for improving the efficiency of the photocatalysts.
Therefore, it is very important to develop a shape and size-
controlled synthesis method for ZnO nanostructures. In recent
years, rapid progress has been made in the preparation of ZnO
nanostructures, including nanowires,22 nanosheets,23 nano-
tubes24 and nanoowers.25 Numerous approaches were
employed to fabricate ZnO nanostructures, which can be
usually classied into two categories, including physical
methods and the solution phase route. Physical methods
include thermal evaporation, chemical vapour deposition and
metal organic vapour phase epitaxy.26–28 However, the physical
process requires high temperature, a complex procedure, and
sophisticated equipment, which make the procedure expensive,
and thereby restricts possibilities of applications. In contrast,
the solution phase approaches, including microemulsion, sol-
vothermal, hydrothermal, precipitation, self-assembly and
template-assisted sol–gel processes, can allow for the growth of
ZnO nanostructures at much lower temperatures (<200  C) and
large-scale production.29–34 Among them, the hydrothermal
technique is a relatively simple, low temperature process, but it
requires longer reaction time (from a few hours to several days).
Thus, a simple and fast route for the synthesis of ZnO materials
under ambient conditions to full economic and industrial
requirements is still required. Recently, the synthesis of nano-
structured materials via microwave irradiation has been intro-
duced. In comparison with conventional heating, microwave
heating has unique effects such as rapid and homogeneous
volumetric heating, high reaction rate, short reaction time,
enhanced reaction selectivity, energy savings and low cost.9 The
effect of some synthesis parameters on the morphology of ZnO
nanostructures has been studied. Vayssieres et al. reported that
the size of the ZnO nanostructures was decreased, and the
aspect ratio was increased with a decrease in the solution
concentration.29 The reaction time in the solution reaction is
another important parameter reecting the thermodynamic
and/or kinetics processes because of its close relation to the
change of concentration and reaction rate in the reaction
process.35 Recently, work has been reported on the growth of
ZnO nanorods using a hydrothermal method and their photo-
catalytic activity dependent on aspect ratio.36 However, the
growth of ZnO nanorods required hydrothermal treatment for
6–48 h in order to obtain nanorods with different aspect ratios.
Similarly, in another report,37 photocatalytic properties of ZnO
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nanorods were studied. The nanorods were prepared by auto-
clave conditions at 120  C for 2–6 h. These reports showed that
the preparation method used for ZnO nanostructures is both
time- and energy-consuming and does not full the economic
and industrial requirements of ZnO nanostructures-based
photocatalysts. Nevertheless, the morphological evolution of
ZnO nanostructures from nanosheets to nanorods, nano-
brushes, nanoowers, nanoprisms, and nanopyramids with
high aspect ratios and the enhancement of photocatalytic
properties by aspect ratio have not been reported to the best of
our knowledge.
In this paper, we described the growth of ZnO with a diversity
of well-dened morphologies with different aspect ratios via the
simple microwave-assisted solution route within a few minutes,
and the photocatalytic activity of these nanostructures were
investigated by measuring the degradation of MR. The experi-
mental results showed that the as-obtained ZnO nanorods with
high aspect ratios exhibited excellent photocatalytic activity
compared with the low aspect ratio nanostructures. This study
will provide the platform to tune the morphology of ZnO
nanostructures using a microwave irradiation method, in which
various dimensional nanostructures such as 1D, 2D, and 3D can
be prepared simultaneously for future applications. Moreover,
the detailed structural, morphological, and optical character-
ization of ZnO nanostructures will provide helpful information
on the structure–property relationship. We envisage that this
work will help to develop new photocatalysts based on high
aspect ratio ZnO nanorods for practical application due to the
excellent photocatalytic behaviour, and this simple and one-
step method can suitably be scaled up for large-scale synthesis.
Experimental section
All the reagents involved in the experiments were of analytical
grade and utilized as-received without further purication. Zinc
acetate dihydrate (Zn(CH3COO)2$2H2O; 99.999%), and potas-
sium hydroxide (KOH; 99.99%) were purchased from Sigma
Aldrich. The synthesis was carried out in a domestic microwave
oven (Samsung, 750 W). In a typical experiment, different molar
ratios (ZnM : KOHM; 1 : 10, 1 : 15, 1 : 20 and 1 : 25) of
Zn(CH3COO)2$2H2O to KOH were dissolved in 100 mL distilled
water in a round-bottomed ask, and then placed in a domestic
microwave oven. Microwave irradiation proceeded at 300 W
(irradiation 12 s, stop 10 s) for different time intervals (10, 20,
30, 40 and 60 min). Aer microwave processing, the solution
was cooled to room temperature. The resultant precipitate was
separated by centrifugation, and then washed several times
with deionized water and absolute ethanol, and then dried in an
oven at 80  C for 24 h.
Methyl red (MR) was used as the test contaminant for the
photocatalysis experiments. A 10 mM aqueous solution of MR
was prepared in which 10 mg of ZnO catalysts were suspended.
Before illumination, the suspension was magnetically stirred in
the dark for 30 min to attain an adsorption–desorption equi-
librium. A high-pressure mercury lamp was used as a light
source. The beaker containing MR and ZnO catalysts was then
placed under the UV light for the photodegradation of MR. At
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certain time intervals, 5 mL of aliquot was sampled and
centrifuged immediately to remove the photocatalyst particles.
Then, the supernatant solution was analyzed by monitoring the
maximum absorption peak at 428 nm (lmax for MR) using a UV-
vis spectrophotometer (Agilent 8453). In order to estimate the
photocatalytic stability of the ZnO nanostructures, the time
courses of the photocatalytic degradation of MR using photo-
catalyst were conducted.
The phase purity of the as-obtained product was character-
ized by X-ray diffraction using a Phillips X'pert (MPD-3040) X-ray
diffractometer with Cu Ka radiations (l ¼ 1.5406 Å) operated at
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aqueous solution was replaced by the 5  104 M terephthalic
acid with a concentration of 2  103 M NaOH solution. The
generated 2-hydroxy terephthalic acid (TAOH) was measured by
a JASCO FP-6500 uorescence spectrophotometer using an
excitation wavelength of 315 nm.
Results and discussion
Fig. 1 shows typical XRD patterns of ZnO nanostructures
prepared at different molar ratios of zinc acetate and KOH aer

a voltage of 40 kV and a current of 30 mA. Field-emission 20 min of microwave irradiation. All the diffraction peaks can
scanning electron microscopy (FESEM) images were obtained be readily indexed using POWDER-X soware to the hexagonal
using a MIRA II LMH microscope. The elemental composition wurtzite ZnO phase in the standard data (JCPDS 89-1397) with
of ZnO was determined by energy dispersive X-ray spectroscopy calculated lattice parameters a and c of 0.324 and 0.520 nm,
(EDX, Inca Oxford, attached to the FESEM). Transmission respectively, and it can be clearly seen from the patterns that all
electron microscopy (TEM) micrographs, selected area electron of the samples showed a single-phase nature with a wurtzite
diffraction (SAED) pattern and high-resolution transmission structure except for the sample prepared at the 1 : 10 molar
electron microscopy (HRTEM) images were obtained using a FE- ratio. Zn(OH)2 phases are present in the sample for the 1 : 10
TEM (JEOL/JEM-2100F version) operated at 200 kV. To prepare molar ratio, which is in good agreement with the standard data
samples for TEM examination, ZnO nanostructures were JCPDS no. 38-0385 of Zn(OH)2. With the increase in molar ratio
dispersed in an ethanol solution, followed by an ultrasonic to 1 : 15 and 1 : 20, the diffraction peaks of Zn(OH)2 dis-
treatment for 10 min. A minute drop of ZnO suspension was appeared completely, and only the peaks of ZnO were materi-
cast onto a carbon-coated copper grid with subsequent drying alized. In addition, the intensity of the peaks increased with an
in air before transferring it to the microscope. In order to increase in the molar ratio. It can be clearly seen from Table 1
perform the phonon vibrational study of the ZnO nano- that with the increase in molar ratio, the FWHM corresponds to
structures, micro-Raman spectrometer (NRS-3100) was used decrease in (101) peak, which revealed the increase in the
with a 532 nm solid-state primary laser as an excitation source crystallinity. The crystallite sizes of the prepared samples esti-
in the backscattering conguration at room temperature. Room mated from X-ray line broadening of (101) peak using Scherrer's
temperature optical absorption spectra were recorded in the equation38 were found to be 25 nm, 28 nm, and 34 nm for
range of 200–800 nm using a UV-vis spectrophotometer (Agi-
lent-8453). The Brunauer–Emmett–Teller (BET) specic surface
area measurements were carried out by nitrogen adsorption
using an Autosorb®-1 (Quantachrome Instruments, Boynton
Beach, FL, USA). The photoluminescence measurements were
carried out using a luminescence spectrometer (JASCO, FP-
6500) with a xenon lamp as the excitation source at room
temperature. The excitation wavelength used was 325 nm.
Electrochemical and photoelectrochemical measurements were
performed on standard three-electrode quartz cells containing
0.2 M sodium sulphate (Na2SO4) of electrolyte solution and
measured by an electrochemical system (Versa STAT 3, Prince-
ton Research, America). The as-fabricated ZnO nanostructures
with various aspect ratios served as the working electrode.
Platinum wire was used as the counter electrode, and Ag/AgCl
(saturated with KCl) was used as the reference electrode. The
photoresponses of the photocatalysts as UV light on and off
were measured at 0.0 V. Electrochemical impedance spectra Fig. 1 XRD pattern of ZnO nanostructures for different molar ratios of
(EIS) were measured at 0.0 V over the frequency range of zinc acetate and KOH.
1–5000 Hz.
The generation of hydroxyl radicals (cOH) on the surface of
photo-illuminated ZnO nanostructures were detected by the PL Table 1 Change in FWHM ((101) peak) with the molar ratio
technique using terephthalic acid (TA) as a probe molecule.
Molar ratio FWHM (degree)
Terephthalic acid readily reacts with cOH to produce a highly
uorescent product, 2-hydroxyterephthalic acid, which exhibits 1 : 10 0.33
a PL signal at 425 nm. Experimental procedures were similar to 1 : 15 0.29
the measurement of photocatalytic activity, except that the MR 1 : 20 0.24

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samples prepared at molar ratios of 1 : 10, 1 : 15, and 1 : 20,

respectively.
Fig. 2 shows the XRD patterns of ZnO nanostructures
prepared at the 1 : 20 molar ratio of zinc acetate and KOH for
different reaction times. All the samples showed a single-phase
nature with a hexagonal wurtzite structure. No characteristic
peaks of any impurities are detected, which demonstrates that
all of the samples have high phase purity, and the sharpness of
the peaks indicates the high crystallinity of the as-prepared
ZnO. The intensity and FWHM (see Table 2) of the diffraction
peaks were found to increase and decrease, respectively with an
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increase in reaction time, which indicates that the increase in

the reaction time improves the crystalline nature of prepared
ZnO nanostructures. The crystallite sizes of these nano-
structures estimated from X-ray line broadening of (101) peak
using Scherrer's equation38 were observed 26 nm, 29 nm, 32 nm,
and 39 nm for the samples prepared at 10 min, 20 min, 30 min,
and 60 min, respectively. Moreover, no remarkable shi of the
diffraction peaks among all of the samples reveals that lattice
expansion and/or shrinkage should be neglected.
Fig. 3 depicts the room-temperature Raman spectra of ZnO
nanostructures at different molar ratios of zinc acetate and
KOH for 20 min. The Raman spectrum ZnO nanostructures
show conventional vibration modes39 of E2(high)  E2(low),
A1(TO), E1(TO), E2(high) and longitudinal optical E1(LO),
centered at 332 cm1, 381 cm1, 408 cm1, 439 cm1, and 580
cm1 respectively, as shown in Fig. 3. However, for the sample
prepared at the 1 : 10 molar ratio, an extra mode appeared at
Fig. 3 Raman spectra of ZnO nanostructures for different molar ratios
of zinc acetate and KOH.
522 cm1, which may be due to the Zn(OH)2 intermediate
phase. With the increase in molar ratio from 1 : 10 to 1 : 15 and
then 1 : 20, this mode disappeared, indicating the complete
conversion of Zn(OH)2 into ZnO. These results are in good
agreement with the XRD analysis. It can be clearly seen from
Fig. 3 that the intensity of E2(high) mode increases with the
increase in molar ratio, which is due to the fact that an increase
in supersaturation resulted in the increase in the intensity of
Raman modes.40 However, the intensity of E1(LO) mode
remained the same for all samples.
The Raman spectrum of ZnO nanostructures prepared at the
1 : 20 molar ratio for different reaction times is shown in Fig. 4.
The peak intensity related to the E2(high) mode and E1(LO)
mode increases. The E1(LO) mode is well known, and it is
related to defects such as oxygen vacancies and zinc interstitials
in ZnO;41 thus, it may be expected that the change in the E1(LO)
mode for ZnO nanostructures may be due to defects introduced
by increasing the reaction time with minimum defects exhibi-
ted in 20 min irradiated sample. The large surface area and high
surface roughness indicate pronounced enhancement of the
surface activity compared with that of the bulk crystals, and may
activate the normally forbidden E1(LO) mode. Another note-
worthy feature is that the E2(high) mode is shied to a lower
wavenumber, which may be mainly due to the distortion of the
lattice and the defects.42

Fig. 2 XRD pattern of ZnO nanostructures for different reaction times.

Table 2 Change in FWHM (101 peak) with the reaction time

Reaction time (min) FWHM (degree)

10 0.31
20 0.28
30 0.26
60 0.21 Fig. 4 Raman spectra of ZnO nanostructures for different reaction
times.

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The morphological evolution of ZnO nanostructures in our
microwave-irradiation method is achieved by changing the
reaction time and molar ratio of zinc acetate and KOH.
Fig. 5 shows FESEM images of the basic ZnO nanostructures
with different morphologies synthesized from different molar
ratios of zinc acetate and KOH. The summarized morphologies
and reaction conditions are illustrated in Table 3. Fig. 5(a)
depicts morphology of ZnO without microwave process,
agglomerated particles with diameter ranging from 90–150 nm
can be seen. It is obvious that the size of the nanostructures
increases with an increase in the molar ratio. When the molar
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ratio of the solution is low (1 : 10), the ZnO nanosheets with
lateral dimensions of
1 mm and thicknesses of
30 nm (aspect
ratio
33) were formed (Fig. 5(b)). With an increase in the molar
ratio to 1 : 15 (Fig. 5(c)), ZnO NRs (length
1 mm and diameter

90–100 nm; aspect ratio
11) connected with nanosheets
(lateral dimension
1.5 mm, thickness
40–50 nm; aspect ratio

37) were obtained. These nanosheets grow in different
Fig. 5 FESEM images of ZnO (a) without microwave process (b) 1 : 10,
(c) 1 : 15, (d) 1 : 20 and (e) 1 : 25 molar ratio of zinc acetate and KOH. (f)
EDX spectrum of ZnO nanostructures.
Table 3 Summarized morphologies and reaction conditions
KOH concentration (M) Molar ratio Zn2+ : OH
0.5 1 : 10
0.75 1 : 15
1 1 : 20
1.25 1 : 25
1 1 : 20
1 1 : 20
1 1 : 20
1 1 : 20
1 1 : 20
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directions, and each nanosheet consists of numerous ZnO
nanorods. When the molar ratio is increased to 1 : 20, the
nanorods grow larger and exhibit improved crystal perfection,
which is shown in Fig. 5(d). These nanorods have a regular
hexagonal shape and a at end with a diameter of
150 nm and
a length of
2 mm (aspect ratio
14). Brush-like morphology
consisting of nanorods with a diameter of
90 nm and a length
of
4 mm (aspect ratio
20) was formed in the molar ratio of
1 : 25 (Fig. 5(e)). These results demonstrate that the molar ratio
plays a crucial role in the fabrication of ZnO morphology.
The elemental composition of the ZnO nanostructures was
investigated using energy dispersive X-ray spectroscopy (EDX).
The EDX plot as shown in Fig. 5(f) depicts peaks of Zn and O for
all of the ZnO nanostructures, which indicates that the ZnO
structures are composed of only Zn and O. No evidence of other
impurities was found, which also conrms the high purity of
the ZnO nanostructures.
In order to further investigate the morphological evolution of
ZnO, by keeping the molar ratio xed at 1 : 20, reaction time-
dependent experiments were carried out. The ZnO sample
reacted for 10 min exhibited ower-like morphology with
several symmetric petals consisting of a number of aggregative
nanorods with lengths
2.5 mm and diameters of
250 nm
(aspect ratio
10) (Fig. 6(a)). It can be clearly seen that the
branches of the single product grow in different directions and
are composed of symmetric nanorods extending radially from
the centre. With the prolongation of the reaction time to 20
min, the shape of the ZnO nanorods changed from sword-like
sharp tips to at ends having lengths of
2 mm and diameters of

150 nm (aspect ratio
14) (Fig. 6(b)). Interestingly, the shape
of the ZnO nanorods (at end) again changed from hexagonal to
tapered with lengths and diameters of
1.5 mm,
400 nm
(aspect ratio
3.75), respectively, and started to separate from
the bunch of owers as the reaction time was increased to 30
min (Fig. 6(c)). When the reaction time is further increased to 40
min, the crystal shape developed into a prism-like morphology
having a length and diameter of
2.2 mm,
500 nm (aspect ratio

4.5), respectively (Fig. 6(d)). Finally, aer increasing the reac-
tion time to 60 min, well-dispersed at-tip semi-porous nano-
rods (pyramid-like) with lengths of
3 mm and diameters of

600 nm (aspect ratio
5) were formed as shown in Fig. 6(e).
The semi-porous nature of the nanorods can be clearly seen
from the high-magnication image in Fig. 6(f). This shape
Reaction time (min) Morphology Aspect ratio
20 Nanosheets 33
20 Nanosheets; nanorods 37; 11
20 Nanorods 14
20 Nanorods (brush-like) 20
10 Nanorods (ower-like) 10
20 Nanorods 14
30 Nanorods (ower-like) 3.75
40 Nanorods (prism-like) 4.5
60 Nanorods (pyramid-like) 5
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Fig. 6 FESEM images of ZnO nanorods of (a) 10 min (b) 20 min, (c) 30 Fig. 7 TEM images of ZnO nanorods for (a) 20 min, (c) 30 min and (e)
min, (d) 40 min, and (e) 60 min and (f) high-magnification image of 60 60 min, respectively. Corresponding SAED patterns (b), (d) and (f), and
min microwave irradiation. HRTEM images are shown in the insets of (a), (c) and (e), respectively.

transformation can be explained in terms of the differences in is generally accepted that the nal morphology of ZnO crystals
the growth rates of various crystal faces. In general, the crystal is related to both their intrinsic crystal structure and external
plane with the highest growth rate disappears quickly, thus factors.44,45 The crystal formation process is divided into two
making the relative growth rate crucial to determine the stages of nucleation and growth. The overall reaction for the
morphology of the crystal. growth of ZnO nanocrystals may be expressed as follows:
Additional morphological characterization is achieved
Zn(CH3COO)2 + 2KOH / Zn(OH)2 + 2CH3COOK (1)
through the TEM, as shown in Fig. 7. Fig. 7(a) shows a typical
TEM image of a single ZnO nanorod prepared in 20 min in
Zn2+ + 2OH / Zn(OH)2 (2)
which a well-developed hexagonal phase with a at end can be
seen clearly. The TEM image of single nanorod prepared for 30 Zn(OH)2 + 2OH / [Zn(OH)4]2 (3)
min is shown in Fig. 7(c). From this TEM image, it can be seen
that the end of the ZnO nanorod is a sharp sword-like tip.
Fig. 7(e) shows the TEM image of a single ZnO semi-hollow
nanorod (pyramid-like). The atomic structures of ZnO nano-
structures were characterized by high-resolution transmission
electron microscopy (HRTEM). The HRTEM images in the
insets of Fig. 7(a), (c) and (e) show that all of the ZnO nanorods
are highly crystalline with a lattice spacing of about 0.26 nm,
corresponding to the distance between the (002) planes in the
ZnO crystal lattice. Moreover, the selected area electron
diffraction (SAED) patterns of the three ZnO structures
(Fig. 7(b), (d) and (f)) are indexed to hexagonal ZnO, indicating
that ZnO nanorods are single crystalline and have growth along
the [001] direction.
A schematic representation of the possible growth mecha-
nism of ZnO nanostructures is shown in Fig. 8. It is well known
that ZnO is a positively Zn2+-terminated (001) and negatively
O22-terminated (001) polar surfaces, which induces a net
dipole moment along the c axis.43 The growth habit of ZnO Fig. 8 A schematic representation of the possible growth mechanism
under solution conditions has been widely investigated, and it of ZnO nanostructures.

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[Zn(OH)4]2 / ZnO + H2O + 2OH (4)
when the KOH is rst introduced into the Zn2+ aqueous solu-
tion, the solution is observed to become turbid due to the
formation of white Zn(OH)2 colloids (reactions (1) and (2)). In
the solution environment, a part of the Zn(OH)2 colloids
dissolves into Zn2+ and OH. Large quantities of ZnO nuclei
form when the concentrations of Zn2+ and OH ions exceed the
critical value,46 and a subsequent crystal growth process
develops (reactions (3) and (4)). Based on the above discussion,
for the sample without the microwave process, large quantities
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of ZnO nuclei rst aggregate instead of exhibiting anisotropic
growth due to a lack of active sites around the circumference of
ZnO nuclei at low temperatures. Moreover, the number of
growth units Zn(OH)4)2 is still not enough; consequently, only
dispersive ZnO nanoparticles are obtained (see Fig. 8(a)). Under
the microwave process, at a lower molar ratio of 1 : 10, the OH
ligands are fewer, and the energy of the ions is high enough to
make the high-energy surface smoother, and thus the ions will
diffuse to low-energy surfaces.47 Under these conditions, the
growth is determined by dynamics instead of thermodynamics.
The 2D growth mode is more preferred under this nonequilib-
rium process.48 This is because of the fact that the growth
velocities are in the order V{010} > V{001}, and the nanosheets
(Fig. 8(b)) were formed at the 1 : 10 molar ratio of zinc acetate
and KOH. The formation of the nanosheets is attributed to the
close surface energy of 1D/2D crystals under proper experi-
mental conditions.49 When the molar ratio is increased to 1 : 15,
the quantity of Zn(OH)4)2 increases, and the anisotropic
growth is favourable, resulting in the ZnO nanorods growing
along the c-axis connected with the nanosheets (Fig. 8(c)). In the
proper molar ratio of 1 : 20, only (001)-oriented ZnO nuclei grow
preferentially along the c-axis, leading to the growth of (001)-
oriented hexagonal ZnO nanorods (Fig. 8(d)). For a higher molar
ratio of 1 : 25, the OH ligands are large enough, and they
promote crystal growth along the c-axis direction (Fig. 8(e)). This
anisotropy growth is supported by the abovementioned crys-
tallographic habit of ZnO; hence, the 1D growth of the nanorods
in the (001) direction is preferred.
With an increase in the reaction time from 10 min to 60 min,
as shown in Fig. 8, both the diameters and lengths of the ZnO
nanostructures increase. This indicates the transversal and
longitudinal growth of the single nanostructure with time.
Therefore, the different growth pattern should be considered.
Note that the uneven width change along the length for the
single nanostructure may be related to the anisotropy of the
ZnO material. The crystal planes, which have higher surface
energy, possess faster growth velocity. Because of the different
surface energy, the growth velocity of the (0001) planes is higher
than that of the (1000) planes. As a result, when different crystal
planes grow at different velocities, those surfaces with the faster
growth velocities ((001) planes) will continually decrease their
area and the surfaces with slower growth velocities ((100)
planes) will gradually dominate the morphology of crystal,
which results in the formation of 1D structure with uneven
width along its length. During the longer reaction time in our
experiments, the zinc species in the solution can be largely
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consumed. In this case, the Ostwald ripening will become
appreciable and the thermodynamics will dominate the reac-
tion process.35 The morphology of the ZnO nanostructures will
be directed to lower the system energy. The hollow structure
may have a lower energy than that of the solid structure due to
the higher energy at the polar surfaces.24 This may facilitate the
formation of the ZnO semi-hollow nanorods (pyramid-like).
The optical absorption spectra were employed to study the
effects of shape and aspect ratio on the optical properties of
ZnO nanostructures. The inset of Fig. 9 shows the absorption
spectra of the ZnO nanostructures with various aspect ratios.
The absorption edge of the high aspect ratio (14) ZnO nanorods
shis to shorter wavelengths; however, for low aspect ratio
nanostructures, the absorption band is shied toward higher
wavelengths.
Because the interband transition in ZnO is the allowed direct
transition, the optical-absorption coefficient a of ZnO can be
expressed by50
(ahv) ¼ A(hn  Eg)1/2, (5)
where A is a constant, hn is the photon energy, and Eg is the
optical bandgap energy. Fig. 9 shows the plots of (ahn)2 versus
(hn) for the ZnO nanostructures with various aspect ratios. The
band gap (Eg) values of the nanostructures were determined
from the intercept of (ahn)2 versus (hn) curves and found to be
3.47 eV for ZnO nanoower (A.R
10). Interestingly, the
increased bandgap of 3.48 eV was observed for high aspect ratio
(14) nanorods. In contrast, the band gap obtained decreased to
3.45 eV and 3.43 eV for nanoprisms (A.R
3.7) and nano-
pyramids (A.R
5), respectively (see Fig. 9). These results
indicated that the aspect ratio of ZnO nanostructures could give
rise to a negative/positive correction to the conduction and the
valence-band edges, leading to a bandgap tuning.
Photocatalytic properties of the ZnO nanostructures (1 : 20
molar ratio, 10–60 min reaction time) with different morphol-
ogies and aspect ratios (A.R) were examined by the
Fig. 9The plot of (ahn)2 versus hn for ZnO nanostructures. The inset
shows the corresponding UV-vis absorption spectra.
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decomposition of MR. The characteristic absorption of MR at

428 nm was chosen to monitor the photocatalytic degradation
process. Fig. 10 illustrates the time-dependent absorption
spectra of MR aqueous solutions during UV light irradiation in
the presence of ZnO nanorods (A.R ¼ 14). As a control, the
absorbance peak of the MR solution was monitored under two
different conditions: (i) with a photocatalyst in the dark and (ii)
without photocatalysts under UV light illumination (ESI* 1†).
The change in the absorbance peak of MR under these condi-
tions is found to be negligible, indicating that there is no loss of
MR without an irradiated photocatalyst. For ZnO nanorods (A.R
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¼ 14) placed in an MR solution, the maximum absorption of the

MR solution was found to decrease with illumination time and
disappeared almost completely aer irradiation for about 60
min. In particular, the photocatalytic performance of
50% was
rapidly achieved within 10 min of photoirradiation for ZnO
nanorods, whereas aer 60 min illumination of UV light, MR
was almost completely (
98%) removed over ZnO nanorods. In
order to evaluate the relationship between photocatalysis and
aspect ratio, nanoowers, nanoprisms, and nanopyramids were
used as the contrast examples. Fig. 11 shows the relative
concentration (C/C0) of MR as a function of time for various
nanostructures, where C is the concentration of MR at the
irradiation time (t) and C0 is the concentration of the dye before
irradiation. When the suspensions were magnetically stirred in
the dark for 30 min to ensure the establishment of an adsorp-
tion/desorption equilibrium of MR on the sample surface, only
a slight decrease in the MR solution concentration was
observed. This demonstrates that the adsorption of MR on the
samples is limited aer the adsorption–desorption equilibrium
is reached. A control experiment revealed negligible decolor-
ization of the dye solution treated with photocatalysts in the
dark. The extent of decolorization was similar to the blank
sample comprising a dye solution illuminated with UV light
without a photocatalyst (ESI* 1†). It is clear from Fig. 11 that for
all ZnO nanostructures placed in the MR solution, the
concentration of the MR solution is observed to decrease with
irradiation time, indicating that all of the nanostructures show
Fig. 11 Temporal evolution of MR absorption spectra with various
ZnO nanostructure photocatalysts.
UV-light photocatalytic properties in the degradation of MR.
The catalytic activity of the these nanostructures possesses a
sequence of nanorods > nanoowers > nanopyramids > nano-
prisms for 60 min of irradiation.
The kinetic behavior of these photocatalysts was further
studied, and the results are shown in Fig. 12. There is an
obvious linear relationship between the value of ln(C0/C) and
the irradiation time. The photocatalytic process can be regarded
as pseudo rst-order reaction, and the rate equation is
expressed as ln(C0/C) ¼ Kt, where t is the reaction time, K is the
apparent reaction rate constant, and C0 and C are the concen-
trations of MR at the time of 0 and t, respectively. The apparent
reaction rate constant K for the degradation of MR was calcu-
lated to be 6.32  102 min1, 2.91  102 min1, 1.53  102
min1 and 1.05  102 min1, respectively, for ZnO nanorods
(A.R
14), nanoowers (A.R
10), nanopyramids (A.R
5) and
nanoprisms (A.R
3.7), respectively. The inset of Fig. 12 shows
the relationship between k and different aspect ratios

Fig. 12 Kinetic relationship of ln(C0/C) versus irradiation time for

Fig. 10 UV-visible absorbance spectra of photodegradation of MR in various ZnO nanostructure photocatalysts. The inset shows the plot of
the presence of ZnO nanostructures. rate constant versus the aspect ratio of nanostructures.

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Paper
nanostructures. It is clear from inset of Fig. 12 that the reaction
rate constant for high aspect ratio (14) nanorods is higher than
that of lower aspect ratio nanostructures, which reveals the
higher photocatalytic activities of higher aspect ratio (14) ZnO
nanorods.
Fig. 13 shows the percentage decolorization (degradation) of
MR dye as a function of aspect ratio. It can be clearly seen from
Fig. 13 that the percentage decolorization increases with the
increase in aspect ratio of nanostructures. The higher photo-
catalytic performances of
98% was achieved within 60 min of
photo-irradiation for high aspect ratio (14) nanorods, whereas
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only 80%, 58%, and 44% degradation efficiency of MR was
obtained with nanoowers (A.R ¼ 10), nanopyramids (A.R ¼ 5),
and nanoprisms (A.R ¼ 3.7), respectively. This indicates that
high aspect ratio ZnO nanorod photocatalysts a more superior
to than that of lower aspect ratio nanostructures. In addition, by
comparing the photocatalytic performance of the high aspect
ratio ZnO nanorods obtained in this study with other reported
nanostructures, ZnO nanorods showed better photocatalytic
properties. For example, Comparelli et al.51 showed the degra-
dation of MR under UV irradiation in the presence of nanosized
ZnO and TiO2. Their results revealed that ZnO degraded 50% of
MR for 140 min irradiation time, whereas about 90% of MR was
degraded with TiO2. In another report, Kanjwal et al.52 pre-
sented hierarchical nanostructures consisting of ZnO and TiO2
prepared by an electro-spinning process, followed by a hydro-
thermal technique for use as a photocatalyst for dye degrada-
tion. The results showed that the introduced ZnO–TiO2
hierarchical nanostructure can eliminate almost all the MR dye
within 90 min. They also showed that less than 30% of the MR
dye was removed using pure ZnO nanoowers, even aer 180
min. However, in the case of pristine TiO2 nanobers, up to
50% of dye was removed aer 180 min. The ZnO-doped TiO2
nanobers showed better results than the rst two catalysts and
removed more than 80% of dye aer 3 h.
In the present work, ZnO nanorods degraded more than 50%
of MR within 10 min and for 60 min of UV light irradiation, MR
Fig. 13 Percentage decolorization (degradation) of MR dye as a
function of aspect ratio on various ZnO nanostructure photocatalysts.
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was almost completely degraded. Therefore, the ZnO nanorods
obtained in the present work are photocatalytically more
superior than the others.
Photocatalytic stability is the main limitation in the devel-
opment of photocatalysts for organic dye degradation. To esti-
mate the photocatalytic stability of the ZnO nanostructure
photocatalysts, the time courses of photocatalytic degradation
of MR using high aspect ratio (14) nanorods were conducted
and are shown in Fig. 14. No noticeable degradation of MR was
observed in repeated runs for the photocatalytic reaction of 60
min, which reveals that ZnO nanorods have good stability and
reusability performance and can be a potential candidate for
practical photocatalysis applications.
The activation energy has been calculated from the Arrhe-
nius equation:53
k ¼ AeEa/RT, (6)
where Ea is the activation energy, k is the rate constant, A is the
pre-exponential factor, T is the temperature and R is the gas
constant, which equals to 8.314 J mol1 K1, respectively. In the
photocatalytic reaction, the activation energy is the energy
required to promote photoelectrons from the photo catalyst to
be trapped at surface by adsorbed oxygen molecules.54
The photocatalytic decolorization of MR dye using ZnO
nanostructures with different reaction temperatures ranging
from 300 K to 325 K was represented by a pseudo rst order, and
the activation energy (Ea) and pre-exponential factor (A) were
calculated by plotting ln(k) versus 1/T and found by using the
following equation:
Slope ¼ Ea/R, Intercept ¼ ln(A). The activation energy and
pre-exponential factor of various ZnO nanostructures were
obtained to be approximately 6.88 kJ mol1 and 1.8  102, 8.81
kJ mol1 and 5.5  102, 10.41 kJ mol1 and 2.4  103, and 11.35
kJ mol1 and 4.9  103 for nanostructures with aspect ratios of
14, 10, 5 and 3.7, respectively. The activation energy for high
aspect ratio (14) ZnO nanorods is lowest (6.88 kJ mol1);
therefore, the photocatalytic reaction is fast and ends at 60 min.
These results are consistent with the trend observed in the
photocatalytic activities of these nanostructures, showing the
Fig. 14 The stability of ZnO nanorods (A.R ¼ 14) for photodegradation
of MR.
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maximum photocatalytic activity for high aspect ratio (14) ZnO
nanorods.
The surface composition and chemical states of ZnO nano-
structures with various aspect ratios were investigated by XPS
analysis, and the results are shown in Fig. 15(a) and (b).
Fig. 15(a) shows the high-resolution XPS spectra of the ZnO
nanostructures recorded for the Zn 2p regions. The binding
energy of Zn 2p3/2 and Zn 2p1/2 of all ZnO nanostructures are
1021.47 eV and 1044.25 eV (Fig. 15 (a)), which are very well
matched with the standard values of ZnO.54 The binding ener-
gies of Zn 2p3/2 and Zn2p1/2 at 1021.47 eV and 1044.25 eV show
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an obvious shi to high energy with an increase in the aspect
ratio of the ZnO nanostructures.
The O 1s spectra from the nanorods are shown in Fig. 15(b).
An asymmetric prole of the O 1s region reveals the existence of
three different O species in the sample. The O 1s prole can be
deconvoluted using a Gaussian tting technique into three
different peaks located at binding energy values of 530.2 eV,
531.4 eV and 532.6 eV, respectively, (Fig. 15(b)) in all samples.
Fig. 15 XPS spectra of ZnO nanostructures with various aspect ratios:
(a) Zn-2p and (b) O-1s.
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The peak at 530.2 eV can be indexed to the O2 species in ZnO.
The higher energy peak at 531.4 eV can be assigned to oxygen
vacancies or defects (OV), and the peak at 532.6 eV can be
indexed as chemically absorbed oxygen (OC) species.55,56
Because the physically absorbed hydroxyl groups on ZnO can
be easily removed under the ultra-high vacuum condition of the
XPS system, ZnO nanorods with ne surface structures will not
give signicant signals in the XPS.57,58 Therefore, the distinct
signals of the hydroxyl groups observed should be due to
hydroxyl groups, i.e. Zn–OH and H2O, strongly bound to surface
defects on ZnO; i.e., the hydroxyl groups in XPS are associated
with surface defects, and the visible hydroxyl groups should
indicate the existence of surface defects on ZnO samples.
According to the XPS results, the OV (531.4 eV) and OC (532.6 eV)
values of O 1s are higher for the high aspect ratio nanorods
(Fig. 15(b)), which indicates that higher aspect ratios of ZnO
nanorods have higher amounts of surface defects and visible
hydroxyl groups. Furthermore, oxygen species around 532.6 eV
are caused by the surface hydroxyl group. The presence of
surface hydroxyl groups facilitates the trapping of photoin-
duced electrons and holes, thus enhancing the photocatalytic
degradation process.
Fig. 16 shows the room-temperature PL spectra of the ZnO
nanostructures with various aspect ratios. A near-band-edge
(NBE) emission at
369 nm and four visible light emission
bands: two weak blue bands at
407 and
431 nm, a weak blue-
green band at
465 nm and a strong and broad green band at

587 nm have been observed. The NBE emission is attributed to
a well-known recombination of free excitons through an
exciton–exciton collision process of the wide bandgap ZnO59
and the weak blue, blue-green and broad green light emissions
are resulted from the recombination of a photo-generated hole
with a singly ionized charge state of specic defect.60 It is
generally complicated in experiments to distinguish PL bands
caused by zinc interstitials (Zni) and oxygen vacancies (VO).
Theoretically, Kohan et al.61 and Van de Walle62 calculated the
formation energies and electronic structure of native point
Fig. 16 Room-temperature PL spectra of ZnO nanostructures with
various aspect ratios.
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defects in ZnO. Based on their results, oxygen and zinc vacan-
cies are the two most common defects in ZnO. In zinc-rich
conditions, the oxygen vacancies (VO) have lower formation
energy (1.2 eV) than the zinc interstitials (Zni) and will dominate
in the defect; however, in oxygen-rich conditions, zinc vacancies
(VZn) ought to dominate. In our microwave aqueous growth
condition, Zn source supplies from zinc salts and the O comes
from the OH. This aqueous growth method can be classied as
Zn-rich conditions due to the high solubility of the zinc salts.
Therefore, PL spectra indicate that the oxygen vacancies (VO)
may possibly be responsible for the green light emission,
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whereas zinc interstitials (Zni) and zinc vacancies (VZn) may be
excluded in the synthesized ZnO rods. These results are in good
agreement with the earlier report.63 We predict that the rapid
microwave heating might enhance the defects.
Generally, the NBE peaks directly reect the separation
situation of the photogenerated charge carriers; i.e., the
stronger the NBE peaks, the higher the recombination rate of
photogenerated charge carriers, which probably results in a
slower photocatalytic activity.64 High aspect ratio (14) ZnO
nanorods showed a decrease in the NBE intensity and hence, a
higher separation rate and lower recombination rate of photo-
induced charge carriers, which leads to higher photocatalytic
activity.
Two impurity levels, which can enhance the electron–hole
pair separation rate in ZnO nanorods, are generated in the
presence of oxygen vacancies and interstitial oxygen defects.65
As seen in Fig. 16, the green light emission intensity is higher
for high aspect ratio (14) nanorods; hence, the photocatalytic
activity of the ZnO nanorods can be enhanced with aspect ratio.
It can be concluded that abundant surface oxygen vacancies or
defects exist in ZnO nanorods, which may play a vital role in
photocatalytic activity.
To study the textural properties and nature of porosity of the
samples, BET analysis was carried out, and the parameters of
surface area obtained. BET analysis of the samples showed a
surface area of 28.2 m2 g1, 19.4 m2 g1, 9.6 m2 g1 and 6.1 m2
g1 for the ZnO nanostructures with aspect ratio of 14, 10, 5 and
3.7, respectively. The isotherm of the ZnO nanostructures with
various aspect ratios exhibit type IV isotherms, according to
IUPAC classications, characteristic of the porous materials,
which conrms the presence of mesoporous materials with a
narrow range of uniform pores. The pore volume distribution
determined by the BJH method was found to be 0.082 cm3 g1,
0.075 cm3 g1, 0.058 cm3 g1 and 0.046 cm3 g1 with an average
uniform pore-size distribution of
9.4 nm,
7.8 nm,
4.6 nm
and
3.7 nm for ZnO nanostructures with aspect ratio of 14, 10,
5 and 3.7, respectively.
The parameters that affect the photocatalytic activity include
the catalyst, band gap, surface area, porosity, crystal structure,
crystallinity, purity, density of surface, hydroxyl groups, e and h+
migration characteristics, surface acidity and size distribution.
The maximum photocatalytic degradation of MR was ach-
ieved for high aspect ratio (14) ZnO nanorods, in which the
surface area and pore volume were maximum. The amount of
dye adsorbed on the surface of the catalysts is directly related to
the surface area, which is available for adsorption. Therefore,
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the large specic surface area of high aspect ratio (14) ZnO
nanorods can improve the contact opportunity between the dye
and photocatalyst, which can accelerate the rate of the photo-
catalytic reaction. The advantage of nanopores in the high
aspect ratio (14) ZnO nanorods might be helpful to understand
the rapid photocatalysis performance. The nanoholes in ZnO
nanorods provide ideal channels for easy and fast diffusion of
the dye molecules to contact the different interplanar surfaces
of the nanoparticles, which greatly increases the chances and
velocities of the encounter of the produced electron–hole pair
with the dye molecules and thus enhances the photocatalytic
activity.
The transient photocurrent responses of a photocatalysis
may directly correlate with the recombination efficiency of the
photogenerated carriers.66–68 Fig. 17 shows the transient
photocurrent density responses of ZnO nanostructure elec-
trodes under UV light irradiation. A generation of photocurrent
with good reproducibility for all samples is observed via various
on–off cycles of intermittent illumination. This indicates that
the electrode is stable, and the photocurrent is quite reversible.
The photocurrent of the ZnO nanostructures electrode is found
to decrease with a decrease in aspect ratio, showing maximum
current for high aspect ratio (14) nanorods. The enhancement
in the photocurrent of the ZnO nanorod (14) photocatalyst
indicates an enhanced photoinduced electrons and holes
separation.
Complementary information regarding the interface charge
separation efficiency of the ZnO nanostructure photocatalysts
was investigated by the electrochemical impedance measure-
ments. Fig. 18 shows the representative electrochemical
impedance spectra (EIS), presented as a sum of real impedance
(Z0 ) and imaginary impedance (Z00 ) in the form of a Nyquist plot
for ZnO nanostructures. The radius of the arc on the EIS spectra
reects the interface layer resistance occurring at the surface of
electrode. The smaller arc radius indicates the higher efficiency
of charge transfer.69 Fig. 18 shows that the diameters of the arc
radius for the high aspect ratio (14) ZnO nanorod electrodes is
Fig. 17 The transient photocurrent density responses of ZnO nano-
structure photocatalyst electrodes with light on–off cycles under UV
light irradiation.
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Fig. 18 Nyquist plots for ZnO nanostructures with various aspect
ratios in light on/off cycles under UV light irradiation.
smaller than that of the lower aspect ratio nanostructure elec-
trodes. These observations indicated that both the solid-state
interface layer resistance and the charge-transfer resistance on
the surface of ZnO have signicantly decreased for high aspect
ratio (14) nanorods. This suggests that a high aspect ratio (14)
ZnO nanorods acts as nanoscale electrodes and accelerates
charge transfer, decreases the intragranular resistance, inhibits
recombination between charge carriers, and enhances photo-
catalytic efficiency.70 This result is in good agreement with the
transient photocurrent responses of these photocatalysts.
Fig. 19 presents the PL spectral changes observed during the
UV illumination of the different photocatalysts in the aqueous
basic solution of terephthalic acid. Usually, PL intensity at
about 425 nm is proportional to the amount of produced
hydroxyl radicals.71 In general, hydroxyl radicals (cOH) has been
regarded as the dominant active species responsible for the
photocatalytic oxidation reactions. Obviously, it can be seen
that the intensity of the generated 2-hydroxy-terephthalic acid
(TAOH) of high aspect ratio (14) nanorods was stronger than
that of lower aspect ratio nanostructures, indicating that the
formation rate of cOH radicals on high aspect ratio (14) nano-
rods was larger than that of the others.
Fig. 19 Detection of cOH radical by fluorescence method using ter-
ephthalic acid as trapping reagent.
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Thus, it can be concluded that high aspect ratio (14) nano-
rods could produce more cOH content than that of lower aspect
ratio nanostructures, thereby possessing higher photocatalytic
performance. Therefore, cOH experiments further conrm that
cOH is actually produced and indeed participates in photo-
degradation reactions.
The photocatalytic activity of a catalytic material is inu-
enced by several factors such as carrier recombination, size of
the particles, surface area, surface acidity, and presence of a
higher number of hydroxyl groups. In this work, ZnO nanorods
with high aspect ratios show a higher percentage of degradation
as compared to the low aspect ratio nanostructures as well as
the previously reported work. The enhancement of photo-
catalytic activity was most likely due to the relative increase of
active morphological surfaces because of the increased surface-
to-volume ratio, as well as the low recombination rate of the
electron–hole pairs generated during optical exposure, owing to
largely available surface states. This is mainly due to changes in
space-charge regions because this is well-dened along the
longitudinal direction of the nanorods.72,73 The enhanced
oxygen adsorption in the high aspect ratio ZnO nanorods is
expected to be very effective in accepting photogenerated holes.
This leads to a reduction in the recombination probability of
photogenerated carriers, which in turn forms oxygen species74
and thus results in high photocatalytic activity. The superior
photocatalytic performance of ZnO nanorods can be extended
to remove other organic pollutants from wastewater.
Fig. 20 shows the schematic diagram of a UV light photo-
catalytic mechanism with ZnO nanorods. Photocatalytic
degradation was generally operated by the action of hydroxyl
radicals formed during the reaction.74 The photocatalytic
mechanism is proposed in the following manner: when the ZnO
nanostructures were illuminated with light, electrons were
excited from the valence band of ZnO to the conduction band,
leaving a hole in the valence band. The hydroxyl groups present
on the surface of the ZnO react with the photogenerated hole to
produce hydroxyl radicals. Similarly, peroxide (O2) is formed
when the dissolved oxygen interacts with photogenerated elec-
trons. This peroxide takes one proton to yield a superoxide
(HO2) followed by the formation of hydrogen peroxide (H2O2).
A hydroxyl radical was also produced by the attack of a photo-
generated electron to the hydrogen peroxide. These reactive
radicals and intermediate species react with dye and degrade
them into non-toxic organic compounds.
ZnO + hn / ZnO + e + h+ (7)
Fig. 20 Schematic representation of UV light photocatalytic process
in the presence of ZnO nanostructures.
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OH + h+ / OH (8)
O2 + e / O2 (9)
O2 + H+ / HO2 (10)
2HO2 / H2O2 + O2 (11)
H2O2 + e / OH + OH (12)
Mashkour et al.75 reported the effect of H2O2 addition on the
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reaction rate constant of photocatalytic degradation. Their
results showed that the apparent rate constant increased with
increasing the concentration of H2O2 due to the increase in the
formation of cOH radicals, in addition to inhibiting the
recombination of electron–hole pairs.76,77
In the present work, the reaction rate is higher for high
aspect ratio nanorods, whereas the reaction rate is lower for the
low aspect ratio. The reaction rate is dependent on the gener-
ation of hydroxyl radicals. In general, a hydroxyl radical (cOH)
has been regarded as the dominant active species responsible
for the photocatalytic oxidation reactions. Obviously, it can be
seen that the intensity of the generated 2-hydroxy-terephthalic
acid (TAOH) of high aspect ratio (14) nanorods was stronger
than that of the lower aspect ratio nanostructures, indicating
that the formation rate of cOH radicals on high aspect ratio (14)
nanorods was larger than that of the others. Thus, it can be
concluded that high aspect ratio (14) nanorods could produce
more cOH content than that of lower aspect ratio nano-
structures, thereby possessing higher photocatalytic perfor-
mance. Therefore, it is logical to state that, in the present work,
H2O2 formed in the photocatalytic reaction, which in turn
formed cOH radicals and degraded the organic dye, which is in
good agreement with the earlier report.75
It is well known that the photocatalytic process is determined
by the separation of electron–hole pairs,78 and the separation of
photogenerated carriers could be due to the crystalline phase,
the aspect ratio of the nanorods, and the electronic structure of
the facets and defects.79 Among these factors, surface defects
have to be considered for most cases, except for perfect single
crystals. Because the current ZnO nanorods were synthesized via
a microwave irradiation method at relatively low temperatures,
the diffusion lengths of atoms during the decomposition reac-
tion of the precursor is relatively short. It is therefore reasonable
to believe that a large number of surface defects exist in the nal
products, which result in visible emissions (400–700 nm).
Generally, the recombination probability of the photo-
generated carriers would be high, and the separation of the
electron–hole is the rate-limiting step for the photocatalytic
process.78 The aspect ratio of nanostructures is expected to
enhance the separation of photogenerated carriers. Therefore,
decreased recombination centers with a lesser number of
interparticle junctions and high electron delocalization in high
aspect ratio nanorods lead to higher efficiency.80 For 1-D
nanostructured crystals, the space-charge region is well con-
structed along the longitudinal direction of the ZnO
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nanocrystal, which indicates that photogenerated electrons can
ow in the direction of the crystal length. Increased delocal-
ization of electrons at 1-D nanostructured crystals can lead to a
remarkable decrease in charge carrier recombination proba-
bility. Consequently, larger numbers of electrons and holes
exist on the active sites of the nanocrystal surface, resulting in
higher activity.75 Therefore, in the present work, the higher
aspect ratio (14) ZnO nanorods exhibit higher photocatalytic
activity.
Conclusions
In summary, highly crystalline ZnO with different morphologies
have been successfully prepared by a convenient microwave-
assisted solution route. XRD, HRTEM and SAED measurements
showed that all of the ZnO nanostructures are of a hexagonal
phase structure. The exception of secondary phase formation
(Zn(OH)2) was observed for the sample prepared using the 1 : 10
molar ratio, which nally converted to ZnO upon increasing the
molar ratio. PL and XPS studies revealed the existence of defects
in the ZnO nanorods. FESEM and TEM images revealed that the
morphology of ZnO can be effectively controlled as sheet-like,
rod-like, brush-like, ower-like, prism-like, and pyramid-like,
which was ascribed to the process parameter-dependent tuning
of the nanostructures. The aspect ratio continued to change as a
consequence of changes in the reaction time and molar ratio,
showing maximum (14) for the nanorods prepared at the 1 : 20
molar ratio for 20 min. It is suggested that the zinc species and
environment, including OH and K+ as well as the reaction
time, are the crucial factors for the morphologies of obtained
ZnO. Such knowledge would allow for quick synthesis of ZnO
with anticipated morphology simply by selecting the appro-
priate molar ratio and reaction time. The photocatalytic prop-
erties of ZnO nanostructures with different aspect ratios toward
MR under UV light irradiation were found to be attractive. The
observed rates of degradation were found to be proportional to
the rates of formation of active hydroxyl radicals studied by the
emission spectra of 2-hydroxy-terephthalic acid. EIS study
shows that the high aspect ratio (14) ZnO nanorods minimized
charge recombination and effectively enhanced the photo-
catalytic activity. The enhanced percentage degradation of MR
with ZnO nanorods was found to be
98% within 60 min of UV
light illumination, which was due to the higher aspect ratio.
This enhancement in photocatalytic activity may be attributed
to the easy separation of photogenerated charge carriers in the
higher aspect ratio nanorods, which resulted to the enhanced
oxygen chemisorptions. For bridging between the laboratory
and industry, considering the excellent photocatalytic perfor-
mance and facile preparation method, the prepared ZnO
nanorods are believed to have potential applications in the eld
of environmental remediation and photocatalysis.
Acknowledgements
This work was supported by the National Research Foundation
of Korea (NRF) grant funded by the Korean Government (MSIP)
(no. 2011-0030058). This work was also supported by the MSIP
RSC Adv., 2014, 4, 29249–29263 | 29261

RSC Advances
(Ministry of Science, ICT & Future Planning), Korea. Under the
ITRC (Information Technology Research Centre) support
program supervised by the NIPA (National IT Industry Promo-
tion Agency) (NIPA-2014-H0301-14-1016).
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