Superlattices and Microstructures 74 (2014) 279–293

Contents lists available at ScienceDirect

Superlattices and Microstructures

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

Structure, morphologies and dye removal

efficiency of ZnO nanorods grown on
polycrystalline Zn substrate
Tiantian Yin, Nan Chen, Yingying Zhang, Xiaoyan Cai, Yude Wang ⇑
Department of Materials Science and Engineering, Yunnan University, 650091 Kunming, People’s Republic of China

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

Article history: Rod-like ZnO with the different morphologies were grown on poly-
Received 28 May 2014 crystalline Zn substrate by a simple hydrothermal process in a
Received in revised form 9 June 2014 NaOH or NH4OH solution at the hydrothermal temperature range
Accepted 15 June 2014
from 80 to 150 °C for different reaction time. Variations prepara-
Available online 8 July 2014
tion in the different alkali solution concentration, hydrothermal
temperature, and reaction times were explored to shed light on
Keywords:
ZnO
the morphology of the rod-like nanostructures. The thorough
Nanostructures structural characterization including X-ray diffraction (XRD), scan-
Chemical synthesis ning electron microscopy (SEM), transmission electron microscopy
Electron microscopy (TEM), electron diffraction, and X-ray photoelectron spectrum
Surface reaction (XPS) were employed to examine the morphology and the micro-
structure of the final products. It was found that alkali solution
concentration, hydrothermal temperature and time have impor-
tant influence on the morphology of the rod-like nanostructures.
The dye removal efficiency of ZnO nanorods was explored by the
decoloration of azo dye Congo red (CR). In order to obtain the opti-
mum removal conditions of Congo red, the performance of remov-
ing CR with various initial concentrations by ZnO nanorods on Zn
substrates with different morphologies was tested under various
ambient conditions (visible light illumination and darkness). All
prepared samples showed an excellent dye removal efficiency for
organic pollutants CR from wastewater, making them promising
candidates for the wastewater treatment.
Ó 2014 Elsevier Ltd. All rights reserved.

⇑ Corresponding author. Tel.: +86 871 65031124; fax: +86 871 65153832.
E-mail address: ydwang@ynu.edu.cn (Y. Wang).

http://dx.doi.org/10.1016/j.spmi.2014.06.022
0749-6036/Ó 2014 Elsevier Ltd. All rights reserved.
280 T. Yin et al. / Superlattices and Microstructures 74 (2014) 279–293

1. Introduction

Due to the exponential increase of air, soil and water pollution, it is of paramount importance to
improve existing or to create novel materials for the pollutant removal. Moreover, the wastewater
treatment exhibits high priority in order to alleviate its influence to ‘‘clean’’ water and to open the pos-
sibility for its reuse, particularly at industrial scale. Organic dyes removal in wastewater has attracted
considerable attention because of their long-term environmental toxicity and short-term public
health damage [1,2]. Congo red (1-naphthalene sulfonic acid, 3,30-(4,40-biphenylenebis (azo)) bis
(4-amino-)disodium salt) with two azo bonds (AN@NA) is a well-known azo dye with high toxicity
and even carcinogenic to the animals and human because they are not readily degradable. On the
other hand, the traditional physical, chemical and biological means of wastewater treatments often
have little degradation effect on this anionic secondary azo dye pollutant due to its physicochemical,
thermal and optical stability upon the complex aromatic structures [3,4]. Compared with the conven-
tional wastewater treatment means, degradation has been proved to be an effective way, guaranteed
by its strong destructive power, to mineralize this pollutant into CO2 and H2O. To date, many materials
have been used for the degradation and removal of the Congo red from wastewaters, such as TiO2
[5–8], zeolite [9], Ni(OH)3 and NiO [10], Fe2O3 [11], CeO2 [3,12], carbon nanotubles [13], CdS [14],
Zn1xCuxS and Zn1xNixS [15], ZnO [16], WO3ATiO2/activated carbon [4], SnO2AZnO [17], and waste
materials (bottom ash and deoiled soya) [18]. However, their practical application and popularization
have been significantly constrained by their low catalytic activity under solar light, short-term stabil-
ity against photo- and chemical corrosion as well as potential toxicity. Thus, it is imperative to explore
a suitable material which is easily available and effective, to remove CR from wastewater.
As an important II–VI semiconductor, zinc oxide with wide band-gap of 3.3 eV and large excitonic
binding energy of 60 meV has been widely studied and used to various applications such as vacuum
fluorescent displays, transparent conductive contacts, solar cells, laser diodes, ultraviolet lasers, thin
film transistors, optoelectronic, and piezoelectric applications to surface acoustic wave devices [19].
Among these potential applications, nanostructured ZnO is highly of prospect for catalytic degrada-
tion. Additionally, nanostructured ZnO possesses higher surface area and rapid reaction rate without
light scattering than that of bulk counterparts [20].
Recently, one-dimensional (1D) ZnO nanomaterials, such as nanowires, nanorods, nanobelts and
nanotubes, have been extensively studied because not only they have larger surface area which
enlarges their contact surface during the reactions, but also their higher length–width ratio makes
them easily to be filtered out after the reactions [20]. Up to now, a variety of methods have been
applied to prepare 1D ZnO nanostructures including thermal evaporation [21], metal organic chemical
vapor deposition [22], template method [23], aqueous chemical growth [24], hydrothermal method
[25], etc. Among these methods, hydrothermal reaction presents some advantages, such as high yield,
uniform morphology, homogeneous size and simple and controllable process [26]. Until very recently,
1D nanostructured ZnO has reported to be directly grown on Zn substrate [27–33]. The properties of
the field emission, photocatalytic degradation, photoluminescence, and gas sensor based on these 1D
ZnO have been studied. However, to the best of our knowledge, the dye removal efficiency of ZnO NRs
grown on polycrystalline Zn substrate as a potential material for degradation or removal of the Congo
red from wastewaters has few been concerned. With this aim, in the present work we study the cat-
alytic degradation of organic dye CR utilizing ZnO NRs grown on polycrystalline Zn substrate. The
obtained data are discussed in connection with the differences in morphologies and removal
efficiency.

2. Experimental procedure

2.1. Preparation of ZnO NRs grown on polycrystalline Zn substrate

All the chemical reagents used in the experiments were obtained from commercial sources as guar-
anteed-grade reagents and used without further purification.
 T. Yin et al. / Superlattices and Microstructures 74 (2014) 279–293 281

Zinc foils (2 cm  2 cm) were used as the substrate as well as the source of zinc. Zn foils were firstly
cleaned successively by sonication in deionized water, ethanol and acetone for duration of 10 min in
each. The whole process was repeated twice.
The typical procedure for the preparation of ZnO NRs was as follows: initially, 25 mL NaOH of
certain concentration was mixed with 25 mL NH3H2O or (NH4)2S2O8. After that, the solutions men-
tioned above were transferred to the autoclaves. Then the Zn foils were added into the mixtures,
sealed and heated at corresponding temperature for a suitable time duration. The experimental
details were exhibited in Table 1 for the purpose of clarity. After the elapsed reaction time, the auto-
claves were taken out from the oven and left to cool-down spontaneously to the room temperature.
The resulting products were washed with distilled water to remove reaction mixture, and then dried
in drier. Before the above procedures, the Zn foil substrate of the sample ZZ-6 was heated in 200 °C
for 2 h in advance.

2.2. Characterizations of ZnO NRs grown on polycrystalline Zn substrate

X-ray diffraction (XRD, Rigaku D/MAX-3B powder diffractometer) with copper target and Ka radi-
ation (k = 1.54056 Å) was used for the phase identification, where the diffracted X-ray intensities were
recorded as a function of 2h. The sample was scanned from 20° to 80° (2h) in steps of 0.02°. Scanning
electron microscopy (SEM) images of the prepared samples were obtained with XL30ESEM-TMP
microscope. Transmission electron microscopy (TEM) measurement was performed on a Zeiss EM
912 X instrument at an acceleration voltage of 120 kV, while high-resolution transmission electron
microscopy (HRTEM) characterization was done using JEOL JEM-2010 Electron Microscope (with an
acceleration voltage of 200 kV). The samples for TEM were prepared by dispersing the prepared sam-
ples in distilled deionized water and then dropped on carbonAcopper grids covered by an amorphous
carbon film. To prevent agglomeration of nanostructures the copper grid was placed on a filter paper
at the bottom of a Petri dish.

2.3. Water treatment with ZnO NRs grown on polycrystalline Zn substrate

Congo red (C32H22N6Na2O6S2, molecular weight: 696.67 g mol1, from Guangzhou Reagent
Corporation, China) was used as a model dye to evaluate the dye removal efficiency of ZnO NRs
grown on polycrystalline Zn substrate. The removal efficiency was carried out in an aqueous solu-
tion at ambient temperature. In a typical degradation experiment, an area of 2 cm  2 cm Zn sub-
strate covered with ZnO NRs was placed into 50 mL Congo red aqueous solutions (CRS) with
different concentrations (50, 70, and 100 mg L1) in a quartz beaker. At a certain interval, 4 mL of
the dispersion was extracted and subsequently centrifuged to separate some suspended particles
and dye solution at 4000 rpm for 30 min. The changes of the concentration of the centrifuged solu-
tions were recorded by a UV-2401PC spectrophotometer. The concentration (C) of the centrifuged
solution and the initial concentration (Co) of CR solution were monitored immediately by measuring
the absorbance of the supernatant at 498 nm using a spectrophotometer (Model No. JH722N). The
removal rate was calculated as C/Co.

Table 1
Preparation conditions of the ZnO nanorods on the zinc substrate.

Samples Alkaline solutions Temperature (°C) Time (h)

ZZ-1 NaOH (2.0 M) (NH4)2S2O8 (0.4 M) 150 18
ZZ-2 NaOH (0.48 M) NH3H2O (1.0 M) 150 24
ZZ-3 NaOH (0.48 M) NH3H2O (0.1 M) 150 48
ZZ-4 NaOH (0.48 M) NH3H2O (0.6 M) 120 24
ZZ-5 NaOH (0.48 M) NH3H2O (2.0 M) 120 24
ZZ-6 NaOH (0.48 M) NH3H2O (2.0 M) 120 24
282 T. Yin et al. / Superlattices and Microstructures 74 (2014) 279–293

3. Results and discussions

3.1. Structure and morphology study

The crystal structure of ZnO NRs was studied by XRD, as shown in Fig. 1. The diffraction peaks cor-
responded with the (1 0 0), (0 0 2), (1 0 1), (1 0 2) and (1 1 0) planes at 2h values of 31.78°, 34.42°, 36.26°,
47.54° and 56.61° can be indexed to the hexagonal wurtzite-structure of zinc oxide phase (JCPDS card
No. 70-2551) with space group of P63mc. It is noticeable that extra zinc phase diffraction peaks (JCPDS
card No. 87-0713) appear in the spectra of samples ZZ-2, ZZ-3, ZZ-4 and ZZ-6 arising from the bare
zinc substrate due to partial conversion of zinc surface. The existence of two sets of diffraction peaks
for above four samples and mono-phasic for sample ZZ-1 and ZZ-5, as well as no other detected dif-
fraction peaks from impurities proves the successful fabrication of ZnO grown on self-source sub-
strate. The narrow FWHM of the diffraction pattern indicates that all the samples are of excellent
crystal quality. Additionally, for sample ZZ-1, the (0 0 2) diffraction peak is highly enhanced and much
stronger than the other peaks, suggesting a preferential orientation of the crystals along the (0 0 2)
plane of the ZnO products. Remarkably, for other samples (from ZZ-2 to ZZ-6), the reaction between
zinc and alkaline solution are perhaps far from completion when changing component of solution sys-
tem from (NH4)2S2O8 to NH3H2O, giving rise to the strongest peaks at about 36.2° superimposed by
(0 0 2) plane of Zn and (1 0 1) plane of ZnO. However, the relative intensity of the (0 0 2) peaks of the
five samples are found to be much stronger than that reported in the JCPDS file, some of them (sample
ZZ-5 and ZZ-6) even nearly as strong as the superimposed peaks in intensity. The special feature of
(0 0 2) peaks indicate the preferential growth of ZnO along the c-axis, as demonstrated by further
structural analysis in the following sections.
The morphologies of as-prepared ZnO were characterized by SEM. Fig. 2 gives the images of the
typical samples, in which the morphologies of the nanorods change based on alkali solution concen-
tration, hydrothermal treatment temperature and time. As can be seen from Fig. 2(a), the surface of
zinc foil has been densely covered with quasi-oriented ZnO hexagonal prisms of nanorods prepared
in the solution containing 2.0 M NaOH and 0.4 M (NH4)2S2O8. The ZnO arrays are mainly composed
of uniform short nanorods with diameter of about 0.5 lm and length of 3–5 lm. By decreasing the

Fig. 1. X-ray diffraction patterns of the as-prepared ZnO nanorods on Zn substrate.

 T. Yin et al. / Superlattices and Microstructures 74 (2014) 279–293 283

Fig. 2. SEM images taken from as-prepared ZnO nanorods on Zn substrate: (a) ZZ-1, (b) ZZ-2, (c) ZZ-3, (d) ZZ-4, (e) ZZ-5, and (f)
ZZ-6, respectively.

concentration of NaOH from 2.0 M to 0.48 M, and simultaneously changing reaction solution constit-
uent with NH3H2O instead of (NH4)2S2O8, the orientation of the ZnO NRs altered dramatically. As a
result, an abundant number of free-standing nanorods are observed on the surface of the substrate.
In the case of sample ZZ-2, as shown in Fig. 2(b), it can be clearly seen that the products are substan-
tially constituted with the nanorods of 1 lm and mixed up with narrower nanorods of about 0.3 lm in
diameter. The average length of the nanorods in sample ZZ-2 is estimated to be 10 lm. High magni-
fication SEM image (inset in Fig. 2(b)) presents ZnO crystal shaped like a hexagonal prism with angles
284 T. Yin et al. / Superlattices and Microstructures 74 (2014) 279–293

between the two adjacent edges of 120°. Each of them has hexagonal pyramid-like sharp tip of well-
defined crystallographic faces, being identical to sample ZZ-1 (insert in Fig. 2(a)). The image of sample
ZZ-3 in Fig. 2(c) reveals that the length of nanorods is uniform to be about 10 lm with much wider
change in diameter. The thinner nanorods with diameter of only around 0.1 lm are uniformly distrib-
uted on the nanorods of about 2 lm in diameter. The sample ZZ-4 in Fig. 2(d) resembles the ZZ-3 in
clutter orientation. Compared with sample ZZ-3, the nanorods of ZZ-4 are narrower in diameter and
shorter in length of about 5 lm. Also, the top-view of these images is enlarged. They (inset in Fig. 2(c)
and (d)) appear as ZnO hexagonal prisms of nanorods, suggesting that each individual ZnO NR has pla-
nar tip on top. By increasing the NH3H2O concentration to 2.0 M, each nanorod of sample ZZ-5, as
observed as Fig. 2(e), has two branches and exhibits a special forcep shape with length of 20 lm. In
addition, it is distinguished from other samples in orientation. All samples are vertical or at certain
angle except for ZZ-5 with almost horizontal nanorods on the Zn substrate surface. Interestingly, with
heating Zn foil substrate in 200 °C for 2 h beforehand whereas keeping other experimental conditions
unchanged, the obtained nanorods in sample ZZ-6 ‘‘stand up’’ again and exhibit an obvious hexagonal
prism with hexagonal pyramid-like sharp tip. From Fig. 2(f), the diameter of nanorods ranges from
0.05 to 1 lm which is gradually diminished from bottom to top. In short, SEM observations reveal that
all our samples exhibit 1D rod-like nanostructures. So, it is reasonably concluded that the high aspect
ratio ZnO NRs can be expected.
Further structural characterizations of the ZnO hexagonal prism arrays with hexagonal pyramid
sharp tips grown on the zinc substrate were studied by TEM. The TEM samples were prepared by
scratching the ZnO NRs from Zn substrate, followed by dispersing them in water and casting them
on the copper grids. Typical TEM images (Fig. 3) of ZnO hexagonal prisms broken from sample ZZ-1
and ZZ-2 present an individual nanorod with sharp tips and a few impurities adhering on their surface.
The ZnO NRs are straight and their diameter is uniform along the entire length. Meanwhile, sharp tips
of the nanorods are about 80 nm and 800 nm in radii for sample ZZ-1 and ZZ-2, respectively, as
observed from Fig. 3(b) and (c), indicating the decreasing diameter at the tip regions has been carefully
identified. The corresponding selected area electron diffraction (SAED) patterns (inset in Fig. 3(b) and
(d)) of each single ZnO NRs appear as systematic bright spots, suggesting the single crystal nanorods.
Furthermore, the SAED patterns also confirmed that the nanorods possess wurtzite single crystal
structure without dislocations and stacking faults. The patterns are identified as the [1 1 0] electron
beam projection on the ZnO NRs [34]. By directly simulating the original SAED patterns, the a*, b*
and c* lattice vectors in the [1 0 0], [0 1 0] and [0 0 1] directions are in systematic arrays, which is in
good accordance with the results obtained by current interpretation [35]. Thus these two products
are really proved to be wurtzite ZnO, with the preferential growth of the ZnO NRs along the [0 0 0 1]
direction [36,37].
High resolution XPS studies were carried out to identify the oxygen chemical states of the ZnO NRs.
Fig. 4 shows the Gauss fitting curves of O1s spectra of the samples. The asymmetry of these peaks indi-
cated the appearance of multiple components. Two deconvoluted peaks centered at ca. 531.4 and
532.9 eV can be identified, implying the components lattice oxygen (Olattice) and adsorbed oxygen
ðOx Þ on the surface. The peak at 531.4 eV can be attributed to O
2
ion in wurtzite structure under a
fully oxidized stoichiometric condition [38,39]. The lattice oxygen could not be interacted with the
azo dyes, and unable to affect the formation of main charge-carrier holes in ZnO. The higher binding
energy of 532.9 eV results from the absorbed O x ions (O

and O2 ) in the oxygen deficient regions
within the matrix of ZnO [39–41] caused by oxygen vacancy (VO), oxygen interstitial (Oi), and oxygen
antisite (OZn) [38]. In contrast, the absorbed O x ions are in favor of degradation reactions to promote
the oxidation of organic substances [42]. It is illustrated that ZnO NRs with different morphologies on
Zn substrate have the similar oxygen chemical states, which facilitates the oxidation of organic
substances.

3.2. Growth mechanism of ZnO NRs

To deeply understand the characteristics of ZnO, its growth mechanism must be involved. The reac-
tion accounts for the ZnO NRs growth is essentially a surface oxidation process [32]:
 T. Yin et al. / Superlattices and Microstructures 74 (2014) 279–293 285

Fig. 3. TEM and HRTEM images of as-prepared ZnO nanorods peeled off from Zn substrate: (a) and (b) ZZ-1, (c) and (d) ZZ-2. The
insets are their corresponding SAED patterns, respectively.

Zn þ 4NHþ4 þ 4OH ! ½ZnðNH3 Þ4 ðOHÞ2 þ 2H2 O þ H2 ð1Þ

½ZnðNH3 Þ4 ðOHÞ2 ! ZnO þ H2 O þ 4NH3 ð2Þ
The illustration of the growth mechanism of ZnO nanostructures with different morphologies is
shown in Fig. 5. The morphologies of the obtained ZnO crystals are evidently affected by alkaline solu-
tion concentration, hydrothermal reaction temperature and time. In this specific dual alkali solution of
synthetic approach, [Zn(NH3)4](OH)2 serve as basic growth units for the formation of ZnO nuclei. Dur-
ing hydrothermal condition, Zn react with OH ions of NaOH and NH+4 ions of (NH4)2S2O8 (or NH3H2O)
simultaneously to form [Zn(NH3)4](OH)2. Subsequently, [Zn(NH3)4](OH)2 decomposes to yield ZnO
molecular species and nucleate as ZnO nuclei on Zn substrate. These ZnO nuclei further grew to form
hexagonal nanorod seeds. The hexagonal wurtzite ZnO with polar structure is hexagonal close packing
of oxygen and zinc atoms in 3m point group and P63mc space group with zinc atoms in tetrahedral
sites. Thus, the crystal characteristics of wurtzite ZnO exhibit well defined crystallographic faces:
(0 0 0 1) base and nonpolar low symmetry ð1 0 1  0Þ faces, with C6v symmetry. In case of wurtzite
ZnO polar crystal, each Zn2+ ion lies inside a tetrahedron of four oxygen ions. The Zn and O atoms
are arranged alternatively along the c-axis, which results in the formation of top Zn-terminated
 plane. The inherent asymmetry along the c-axis leads
(0 0 0 1) plane and bottom O-terminated ð0 0 0 1Þ
to the anisotropic growth of 1D ZnO crystallites. The formation of hexagonal prisms in the present
study is attributed to the difference in growth rates of different crystal faces. The hydrothermal
 0Þ > ð1 0 1
growth rates of different planes are as follows: (0 0 0 1) > ð1 0 1  1Þ The more rapid of the
plane grows, the faster of its disappearance becomes. Therefore, the relative growth rate of these crys-
talline faces determines the aspect ratio and final shape of the ZnO nanorods [35]. The (0 0 0 1) plane
286 T. Yin et al. / Superlattices and Microstructures 74 (2014) 279–293

Fig. 4. XPS spectra of as-prepared ZnO nanorods on Zn substrate: the high-resolution spectrum of O1s for (a) ZZ-1, (b) ZZ-2, (c)
ZZ-3, (d) ZZ-4, (e) ZZ-5, and (f) ZZ-6, respectively.

disappeared due to its most rapid growth rate leading to the sharp tip at the end of the c-axis. Growth
 1Þ plane is at the slowest, hence, the rods remain to form hexagonal prisms with pla-
rate of the ð1 0 1
nar tips with the (0 0 0 1) plane at lower solution pH and treatment temperature for sample ZZ-3
(0.48 M NaOH + 0.1 M NH3H2O, 120 °C) and ZZ-4 (0.48 M NaOH + 0.6 M NH3H2O, 120 °C), but the
 T. Yin et al. / Superlattices and Microstructures 74 (2014) 279–293 287

Fig. 5. Schematic illustration of the possible growth mechanism for the formation of different ZnO nanorods grown at different
reaction conditions.

(1 0 1 0) planes remain to form hexagonal pyramid-like shapes. However, the polar (0 0 0 1) face is
metastable and subjected to be etched at higher pH and temperature for sample ZZ-1 (2.0 M
NaOH + 0.4 M (NH4)2S2O8, 150 °C) and ZZ-2 (0.48 M NaOH + 1.0 M NH3H2O, 150 °C), resulting in hex-
agonal pyramid tips on top of ZnO nanorods [43,44]. On the other hand, it seems that with the con-
tinual increases in the solution pH until to the highest value (0.48 M NaOH + 2.0 M NH3H2O), so
many quantity of [Zn(NH3)4](OH)2 emerged at the initial reaction procedure that the ZnO nuclei
grown on Zn substrate through nonuniform nucleation would stack more than one tier. At the stage
of crystal growth, supernatant nuclei grow along c-axis to from hexagonally prismatic shaped ZnO
crystals firstly but ‘‘fall down’’ ultimately due to the weak interaction force between roots of nanorods
and the substrate. Possibly, Zn atoms of the ð1 0 1  0Þ polar face react with the excess OH ions to pro-
duce hydroxide species, which etch the hexagonal prisms from their hexagonal pyramid tips to bot-
toms, remaining as the forcep-like morphology of sample ZZ-5. For the case of heating Zn foil in
advance, a thin layer of ZnO grows by oxidation at the surface, functioning as nucleation sites for fur-
ther hydrothermal treatment. For this reason, one can believe that the alignment of the ZnO NRs onto
the ZnO/Zn substrate of sample ZZ-6 is better than those grown on the bare Zn substrate under the
same growth conditions.

3.3. Dye removal efficiency of ZnO NRs

To estimate the dye removal efficiency of the as-prepared ZnO samples with different structures,
the degradation of CR was carried out in an aqueous solution with the immersion of Zn foil covered
by ZnO NRs. For a comparison, varying different parameters, such as lighting conditions, initial dye
concentration and treatment time, were examined in details. The comparisons of the decolorization
of CR as a function of ZnO morphologies, are depicted in Fig. 6. The value of C/Co is used to describe
the dye removal efficiency which stands for the concentration ratio after and before a certain period
of reaction time, as such, the process of removal can be clearly assigned from the curves. The reduction
in the concentration of CR decreased with reaction time indicates the removal of the organic dye. As
shown in Fig. 6(a), the results of the removal experiments under visible light irradiation verified that
CR can be effectively removed by the ZnO nanostructures. The order of color bleaching rate is ZZ-
1 > ZZ-2 > ZZ-4 > ZZ-3 > ZZ-6 > ZZ-5. Sample ZZ-1, nanorod arrays with hexagonal pyramid-like sharp
tips of the best orientation, is found to be the most active remover, followed by another kind of
288 T. Yin et al. / Superlattices and Microstructures 74 (2014) 279–293

Fig. 6. Removal activity for CR in the presence of various ZnO nanorods on Zn substrate: (a) Congo red solutions (CRS)
(100 mg L1, 50 mL) upon visible light irradiation, and (b) CRS (70 mg L1, 50 mL) under dark condition.

hexagonal prisms of arrays with similar sharp tips, i.e. sample ZZ-2. The less efficiency results are
found to be sample ZZ-4 and ZZ-3 with hexagonal pyramid-like nanorod arrays and planar tips on
top. Forceps-like ZnO NRs paralleling to Zn substrate (sample ZZ-5) exhibit the poorest dye removal
efficiency. Approximately 83% color removal takes place within the first 49 h in ZZ-1 as compared
to 70%, 60%, 42%, 37% and 26% for those in sample ZZ-2, ZZ-4, ZZ-3, ZZ-6 and ZZ-5, respectively.
The sample ZZ-1 is able to fully bleach CR within 110 h of illumination. However, sample ZZ-5 shows
significant less efficiency in the same period of time. Certainly, the highest removal efficiency and
capacity (12,476.38 mg CR per m2 ZnO film grown on Zn substrate) for CR dye in aqueous solution
is shown by sample ZZ-1. Interestingly, ZnO nanorod arrays grown on self-source substrates synthe-
sized via a simple hydrothermal route in our studies are discovered to have the ability of dislodging CR
from aqueous solution under dark conditions without stirring or ultrasound, providing that the dura-
tion is long enough, that is ca. 3–6 days. One can note that a similar phenomena reported by Wu using
a layered perovskite, which degraded CR with very striking in the dark [45]. It means that he
discoloration process reported herein requires no external energy input. As seen from Fig. 6(b), the
 T. Yin et al. / Superlattices and Microstructures 74 (2014) 279–293 289

concentration of CR decreases even without light illumination, giving description that the decolour-
ation of dye by ZnO NRs can be also carried out in the absence of light. This presents the removal
of CR will not be subjected to the constraint of time (day and night) and space (indoor and outdoor),
which hence provides a potentially low-cost alternative for the remediation of azo-dye effluents. The
rate of CR decolorization by various ZnO nanostructured materials without light exposure is gradually
slowing down with the time of experiment, and sample ZZ-3 exhibits the highest removal efficiency
and capacity. It is worth mentioning here that the control experiments including the exposure and
preservation of CR aqueous solution under visible light irradiation and dark condition without ZnO,
and substitution of pure Zn foils for that with ZnO NRs, do not lead to any significant decolorization
of the dye solution.
The relationship between the removal percentage of CR in the presence of sample ZZ-1 and ZZ-3
and time is illustrated in Fig. 7. The bar graphs compare the removal curves of dye decolorization

Fig. 7. Removal percentage for CR in the presence of ZnO nanorods on Zn substrate under various ambient environments: (a)
CRS (100 mg L1, 50 mL) in the presence of sample ZZ-1, and (b) CRS (70 mg L1, 50 mL) in the presence of sample ZZ-3.
290 T. Yin et al. / Superlattices and Microstructures 74 (2014) 279–293

under visible light irradiation with those in dark ambient environment. As seen, ZnO NRs decolorize
CR under visible light faster than those in darkness, regardless of the morphology of ZnO nanostruc-
tured arrays or the initial concentration of CR solutions. It is observed that about 81% of CR is dislodged
within 48 h of exposure time by sample ZZ-1 while it takes the same period of time for the same
remover to bleach only half the same quantity of CR (42%) as disposed without light illumination
(shown in Fig. 7(a)). It is also observed that sample ZZ-3 under visible light reach 75% of dye removal
in 48 h, however, the removal of dyes decrease to 47% with eliminating the illuminant in lamphouse
and keeping it dark (shown in Fig. 7(b)).
The continuous UV–Vis spectra of the centrifuged solution after decoloration processing at the dif-
ferent intervals are used to record and contrast with that of the initial CR solution. Fig. 8 shows the
UV–Vis absorbance spectra of the CR solutions with different initial concentrations (50, 70 and
100 mg/L, respectively) bleached by sample ZZ-1 under vis-light exposure, which further depicts
the dye removal efficiency of the ZnO NRs and demonstrates the effect of initial CR concentration.
As seen in Fig. 8, the absorption spectra of the original CR solutions are characterized by one main
band in the visible region with its maximum absorption at 498 nm corresponding to the azo bonds
of the CR molecule, which is responsible for the dark red color of the aromatic rings pertaining to
the azo groups. The other two bands in the ultraviolet region located at 236 nm and 343 nm, respec-
tively, are attributed to the benzene ring and naphthalene ring structure [46,47]. The characteristic
absorption peaks of CR at 343 nm and 498 nm was chosen as the parameters to be monitored. In
Fig. 8, the degradation rate (C/Co) increases with respect to the treatment time, and correspondingly,
the amplitude of the peak decreases with time increase. The color of the CR aqueous solutions were
bleached when the ZnO nanostructures are used to dispose the CR and the absorption of the solution
at 498 nm is close to zero. As it can be observed, the disappearance of the visible band is accompanied
by total discoloration of the solutions from insets of Fig. 8, which also displays the degradation process
of CR. By comparing the figures, one can see that the main absorption peaks of the dye in the UV–Vis
region basically disappeared in 95–110 h, depending on the initial concentration of CR. However, even
if the concentration of CR increased exponentially, the corresponding removal efficiency do not
decreased multiply. For instance, the respective consuming time for discoloration of approximately
total CR with initial concentration of 50, 70 M and 100 mg L1 are 95, 101 and 110 h, rather than cor-
responding multiple of 95, 122 and 190 h. Similar phenomena can be observed in bleaching of CR by
other five samples under various surroundings involving brightness and darkness (not shown here).
Hence, the rod-like ZnO arrays have satisfactory ability to remove both low and high concentration
of azo dyes under ambient conditions, and their excellent degradation performances make them a
promising degradation material to remove organic pollutants in industrial wastewater treatment.
To investigate the removal mechanism of CR, regenerated ZnO NRs and Congo red dye were char-
acterized by XRD. A comparative combination of XRD patterns of the ZnO nanostructures on Zn sub-
strate after decolorization processing in darkness regenerated by simply taking them out from treated
dye solutions and drying in air is presented in Fig. 9. It can be seen that all samples show the reflec-
tions of hexagonal wurtzite structural ZnO and polycrystalline Zn, which originated from ZnO NRs and
their substrates, respectively. Comparing with the pure CR diffraction peaks, no CR peaks are observed
from regenerated ZnO NRs, suggesting that no CR dye adsorption on the surface of ZnO NRs after the
removal treatment. Moreover, it is acceptable that the adsorption process is controlled by a multi-step
process, involving adsorption on the external surface and diffusion to the surface of the adsorbent.
Surface adsorption mechanism is dominant in first several minutes of contact time, thereafter, diffu-
sion became a rate-limiting process. The third one ascribes to the equilibrium stage [48–51]. However,
neither rapid adsorption nor equilibrium is observed in our dye removal experiments. These basically
suggest that the decoloration of the dye might be caused by catalytic reaction rather than adsorption.
As is well known, the subtotal photon-driven applications of ZnO require ultraviolet light (k < 387 nm)
for excitation because of its large band gap (3.2 eV). Many efforts have been made to overcome this
shortcoming and enhance photocatalytic activity of ZnO to the visible region, including noble metal
modifying, non-metallic elements doping (e.g. C, N, S), rare earth ion doping (e.g. Ce, La), transitional
metal ions doping (e.g. Ni, Mn, Co, Fe , Cu) and oxide semiconductors compositing [52]. All of them
take effect more or less owing to either narrowed band gap or more efficient charge separation. Inter-
estingly, Kaneva et al. [53] have reported that pure nanostructured ZnO thin film without Ni2+ doping
 T. Yin et al. / Superlattices and Microstructures 74 (2014) 279–293 291

Fig. 8. UV–Vis absorption spectra of CRS with various initial concentrations before and after treatment in the presence of
sample ZZ-1 under visible light irradiation: (a) CRS (50 mg L1, 50 mL), (b) CRS (70 mg L1, 50 mL), and (c) CRS (100 mg L1,
50 mL). Insets are the corresponding photographs of CRS before and after treatment with sample ZZ-1 at different time
intervals.
292 T. Yin et al. / Superlattices and Microstructures 74 (2014) 279–293

Fig. 9. XRD patterns of CR and ZnO nanorods on Zn substrate regenerated from treated CRS with initial concentration of
100 mg L1 under dark.

has the highest efficiency to remove malachite green in aqueous solutions upon UV-light illumination,
visible light and in darkness, in which they attributed the removal under vis-light and dark to the
effect of photocatalysis and adsorption, respectively. Nonetheless, no acceptable explanation or mech-
anism for visible light catalytic activity of pure ZnO film was proposed in their work. It is believed that
the morphology, surface area, and surface properties have a great influence on their catalytic activity
of ZnO nanostructures. Thus, the removal of CR by ZnO NRs grown on Zn substrate in our study pos-
sibly originates from the special well-aligned rod-like arrays morphology, high surface area and the
oxidizing O x ions adsorbed on the surface (shown in Fig. 4). Furthermore, catalysis is a very complex
process and strongly depends on many other factors such as crystallinity, size distribution, surface
compositions, and so on. Therefore, the detailed and accurate mechanism for the decoloration of CR
is still an open question. Certainly, a further study is required to clarify those factors affecting the
removal of CR dye.

4. Conclusion

In summary, ZnO NRs grown on polycrystalline Zn substrates with the different morphologies were
prepared through a facile hydrothermal method. The structural analysis indicated that ZnO created
from self-source substrates was 1D nanorods structure. A possible formation mechanism of these
ZnO nanostructures was proposed. The removal of azo dye Congo red (CR) with various initial concen-
trations in the presence of nanostructured ZnO was tested under visible light illumination and dark-
ness. All prepared samples show the excellent removal capacity for organic pollutants CR from
wastewater. The discoloration process reported herein requires no external energy input, and it can
be carried out under various ambient conditions (bright and dark), which is of potential importance
for the low-cost treatment of azo-dye effluents.

Acknowledgements

This work was supported by the Department of Science and Technology of Yunnan Province via the
Project for the Promotion of Science and Technology (Grant No. 2011FA001), National Natural Science
Foundation of China (No. 51262029), the Key Project of the Department of Education of Yunnan
 T. Yin et al. / Superlattices and Microstructures 74 (2014) 279–293 293

Province (ZD2013006), the Creative Experimental Project of National Undergraduate Students (No.
121067318), and Program for Excellent Young Talents, Yunnan University.

References

[1] H.Y. Xiao, Z.H. Ai, L.Z. Zhang, J. Phys. Chem. C 113 (2009) 16625–16630.
[2] J.B. Fei, Y. Cui, X.H. Yan, Y. Yang, K.W. Wang, Q. He, J.B. Li, Adv. Mater. 20 (2008) 452–456.
[3] Z.J. Yang, J.J. Wei, H.X. Yang, L. Liu, H. Liang, Y.Z. Yang, Eur. J. Inorg. Chem. 2010 (2010) 3354–3359.
[4] J.H. Sun, Y.K. Wang, R.X. Sun, S.Y. Dong, Mater. Chem. Phys. 115 (2009) 303–308.
[5] V.A. Sakkas, M.A. Islam, C. Stalikas, T.A. Albanis, J. Hazard. Mater. 175 (2010) 33–44.
[6] M.N. Chong, H.Y. Zhu, B. Jin, Chem. Eng. J. 156 (2010) 278–285.
[7] M.T.C. Sansiviero, D.S.D. Santos, A.E. Job, R.F. Aroca, J. Photochem. Photobiol., A 220 (2011) 20–24.
[8] G. Laeraa, B. Jin, H. Zhu, A. Lopez, Catal. Today 161 (2011) 147–152.
[9] A.K. Kondru, P. Kumar, S. Chand, J. Hazard. Mater. 166 (2009) 342–347.
[10] B. Cheng, Y. Le, W.Q. Cai, J.G. Yu, J. Hazard. Mater. 185 (2011) 889–897.
[11] A. Afkhami, R. Moosavi, J. Hazard. Mater. 174 (2010) 398–403.
[12] H. Li, G.F. Wang, F. Zhang, Y. Cai, Y.D. Wang, I. Djerdj, RSC Adv. 2 (2012) 12413–12423.
[13] S. Chatterjee, M.W. Lee, S.H. Woo, Bioresour. Technol. 101 (2010) 1800–1806.
[14] H.Y. Zhu, R. Jiang, L. Xiao, Y.H. Chang, Y.J. Guan, X.D. Li, G.M. Zeng, J. Hazard. Mater. 169 (2009) 933–940.
[15] H.R. Pouretedal, M.H. Keshavarz, J. Alloys Compd. 501 (2010) 130–135.
[16] A. Elaziouti, N. Laouedj, B. Ahmed, J. Chem. Eng. Process Technol. 2 (2011) 1–9.
[17] K. Melghit, M.S. Al-Rubaei, I. Al-Amri, J. Photochem. Photobiol., A 181 (2006) 137–141.
[18] A. Mittal, J. Mittal, A. Malviya, V.K. Gupta, J. Colloid Interf. Sci. 340 (2009) 16–26.
[19] X.Y. Chong, L.X. Li, X.L. Yan, D. Hu, H.S. Li, Y.D. Wang, Physica E 44 (2012) 1399–1405.
[20] J. Zhao, L. Wang, X. Yan, Y. Yang, Y. Lei, J. Zhou, Y. Huang, Y. Gu, Y. Zhang, Mater. Res. Bull. 46 (2011) 1207–1210.
[21] M. Li, D. Wang, Y. Ding, X. Guo, S. Ding, H. Jin, Mater. Sci. Eng. A 452–453 (2007) 417–421.
[22] M.C. Jeong, B.Y. Oh, W. Lee, J.M. Myoung, J. Cryst. Growth 268 (2004) 149–154.
[23] B.I. Seo, U.A. Shaislamov, M.H. Ha, S.W. Kim, H.K. Kim, B. Yang, Physica E 37 (2007) 241–244.
[24] T.L. Vayssieres, K. Keis, S.E. Lindquist, J. Phys. Chem. B 105 (2001) 3350–3352.
[25] J.P. Liu, C.X. Xu, G.P. Zhu, X. Li, Y.P. Cui, Y. Yang, X.W. Sun, J. Phys. D: Appl. Phys. 40 (2007) 1906–1909.
[26] X.Y. Cai, Y. Cai, Y.J. Liu, H. Li, F. Zhang, Y.D. Wang, J. Phys. Chem. Solids 74 (2013) 1196–1203.
[27] Z.K. Li, X. T Huang, J.P. Liu, H.H. Ai, Mater. Lett. 62 (2008) 2507–2511.
[28] Z.K. Li, X.T. Huang, J.P. Liu, Y.Y. Li, X.X. Ji, G.Y. Li, Mater. Lett. 61 (2007) 4362–4365.
[29] A. Dev, S. Kar, S. Chakrabarti, S. Chaudhuri, Nanotechnology 17 (2006) 1533–1540.
[30] C.H. Lu, L.M. Qi, J.H. Yang, L. Tang, D.Y. Zhang, J.M. Ma, Chem. Commun. (2006) 3551–3553.
[31] Y.P. Fang, Q. Pang, X.G. Wen, J.N. Wang, S.H. Yang, Small 2 (2006) 612–615.
[32] Q. Tang, W.J. Zhou, J.M. Shen, W. Zhang, L.F. Kong, Y.T. Qian, Chem. Commun. (2004) 712–713.
[33] N.K. Sarkar1, S.K. Bhattacharyya, Nanotechnology 24 (2013) 225502–225509.
[34] S. Jattukul, S. Thongtem, T. Thongtem, Ceram. Int. 37 (2011) 2055–2059.
[35] N. Ekthammathat, T. Thongtem, A. Phuruangrat, S. Thongtem, Superlattices Microstruct. 53 (2013) 195–203.
[36] S.P. Garcia, S. Semancik, Chem. Mater. 19 (2007) 4016–4022.
[37] M. Wang, S.H. Hahn, J.S. Kim, J.S. Chung, E.J. Kim, K.K. Koo, J. Cryst. Growth 310 (2008) 1213–1219.
[38] M. Chen, Z. Wang, D. Han, F. Gu, G. Guo, J. Phys. Chem. C 115 (2011) 12763–12773.
[39] J.C. Lin, K.C. Peng, H.L. Liao, S.L. Lee, Thin Solid Films 516 (2008) 5349–5354.
[40] M. Chen, X. Wang, Y.H. Yu, Z.L. Pei, X.D. Bai, C. Sun, R.F. Huang, L.S. Wen, Appl. Surf. Sci. 158 (2000) 134–140.
[41] J. Wang, Z. Wang, B. Huang, Y. Ma, Y. Liu, X. Qin, X. Zhang, Y. Dai, Appl. Mater. Interf. 4 (2012) 4024–4030.
[42] H. Liu, S. Cheng, M. Wu, H. Wu, J. Zhang, W. Li, C. Cao, J. Phys. Chem. A 104 (2000) 7016–7020.
[43] J.H. Yang, J.H. Zheng, H.J. Zhai, L.L. Yang, L. Liu, M. Gao, Cryst. Res. Technol. 44 (2009) 619–623.
[44] Q. Ahsanulhaq, A. Umar, Y.B. Hahn, Nanotechnology 18 (2007) 115603–115609.
[45] J.M. Wu, W. Wen, Environ. Sci. Technol. 44 (2010) 9123–9127.
[46] Y.Q. Cao, Y.Y. Hu, J. Sun, B. Hou, Bioelectrochemistry 79 (2010) 71–76.
[47] S.Y. Liu, Y. Cai, X.Y. Cai, H. Li, F. Zhang, Q.Y. Mu, Y.J. Liu, Y.D. Wang, Appl. Catal., A 453 (2013) 45–53.
[48] X.Y. Huang, H.T. Bu, G.B. Jiang, M.H. Zeng, Int. J. Biol. Macromol. 49 (2011) 643–651.
[49] L.H. Ai, C.Y. Zhang, Z.L. Chen, J. Hazard. Mater. 192 (2011) 1515–1524.
[50] L.H. Ai, C.Y. Zhang, F. Liao, Y. Wang, M. Li, L.Y. Meng, J. Jiang, J. Hazard. Mater. 198 (2011) 282–290.
[51] G. Crini, F. Gimbert, C. Robert, B. Martel, O. Adama, J. Hazard. Mater. 153 (2008) 96–106.
[52] X.Y. Cai, Y. Cai, Y.J. Liu, S.J. Deng, Y. Wang, Y.D. Wang, I. Djerdj, Ceram. Int. 40 (2014) 57–65.
[53] N.V. Kaneva, D.T. Dimitrov, C.D. Dushkin, Appl. Surf. Sci. 257 (2011) 8113–8120.