698 © IWA Publishing 2016 Water Science & Technology | 74.

3 | 2016

Facile one pot synthesis of zinc oxide nanorods and

statistical evaluation for photocatalytic degradation of a
diazo dye
Suvanka Dutta, Ananya Ghosh, Humayun Kabir and Rajnarayan Saha

ABSTRACT
Suvanka Dutta
In the present work zinc oxide nanorods (ZNRs) have been synthesized to estimate its photocatalytic
Ananya Ghosh
degradation potential on an industrially used diazo dye and optimization of the total treatment Rajnarayan Saha (corresponding author)
Department of Chemistry,
process has been designed. Response surface methodology (RSM) has been used to model the National Institute of Technology Durgapur,
Durgapur 713209,
operational parameters for this photocatalytic degradation. The crystallite size (101 plane) of the India
E-mail: rnsahanitd@gmail.com
synthesized ZNR has been found to be 20.99 nm having a band gap energy of 3.45 eV. At elevated pH,
Humayun Kabir
the rate of degradation of the photocatalyst was found to be higher than that of acidic pH. The
Department of Earth and Environmental Science,
independent variables of the model are time (9.6–122 min), pH (2–12.2), catalyst dose (0.2–0.4 g/L) National Institute of Technology Durgapur,
Durgapur 713209,
and dye concentration (88–512 mg/L). It was seen that the degradation efficiency was significantly India

affected by the initial dye concentration and the pH, the optimal values of the parameters being a pH
of 10.67, an initial concentration of 150 mg/L and ZnO dose of 0.37 g/L, the time taken being
88.52 min. The actual degradation efficiency of the dye reached 96.9% at optimized condition, which
is quite close to the predicted value of 98.07%.
Key words | kinetics, optimization, reactive dye, RSM, ZnO nanorod

INTRODUCTION

Textile industries are an ever increasing business not only
providing occupation to over millions of individuals but
also causing one of the biggest water footprints on the
earth, and dyeing poses an especially serious drawback
which adds to the already prevailing problem of water pol-
lution of the world. One of the significant classes of
synthetic organic dye is the azo dye, which is characterized
by the presence of one or more azo bonds (
N¼N
). These
dyes have become the most important commercial colorants
because of their wide color range, good fastness properties
and color density. These dyes represent approximately
50% of the worldwide production and are extensively used
in a number of industries with the textile industry being
the largest consumer (Sanmuga et al. ). Due to their
increasing popularity and unrestricted usage, azo dyes
started to adversely affect the water resources, aquatic
organisms and the entire ecosystem integrity (Kumar et al.
). The wastewater released by the dyeing industries con-
tains significant amounts of hazardous chemicals such as
tributyltin, pentabromodiphenyl ether, phthalates, perfluor-
ooctane sulfonate and aniline that are banned or strictly
doi: 10.2166/wst.2016.248
regulated in most countries because they are toxic, persist-
ent, bio-accumulative and hormone disruptive and can
even cause cancer (Absalan et al. ; Dasgupta et al.
; Dutta et al. a, b).
Photocatalysts offer great potential for environmental
purification and converting photon energy into chemical
energy (Xu et al. ; Lee et al. ). In the last decade het-
erogeneous photocatalysts such as ZnO, TiO2, WO3, ZnS,
ZrO2, SnO2 have been gaining huge importance due their
reusability, thermal stability and presence of multiple active
sites. These photocatalysts are generally semiconductive in
nature. The electronic structure of the semiconductors
made them act as sensitizers for light-induced redox pro-
cesses, which is characterized by a filled valence band and
an empty conduction band (Hu et al. ; Srivastava ;
Ludi & Niederberger ; Park et al. ; Zhang et al.
). Zinc oxide is a II–VI semiconductor with direct band
gap energy of about 3.4 eV and a large exciton binding
energy of about 60 meV which makes it thermally stable at
room temperature (Wu & Liu ; Nair et al. ). More-
over, being a II–VI semiconductor ZnO has a tendency to
 699 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR Water Science & Technology | 74.3 | 2016

show polytypism in two forms: one is cubic zinc blende form
and another is hexagonal wurtzite form (Hughes & Alivisatos
). Isotropic growth in zinc blende structure generates four
equivalent faces. Whereas anisotropic growth of wurtzite is
quite complicated and crystal growth along higher surface
energy plane (001) is greatly favored. Higher growth rate
along the c-axis results in quite fast disappearance of basal
plane and it leads to formation of nanorods (Manna et al.
; Peng et al. ). Nanorod structures of ZnO are poten-
tially ideal functional components for nanoscale electronics
and optoelectronics. Furthermore, nanorod structures of
semiconductors have a tendency to increase the band gap
energy comparative to nanoparticles, due to quantum con-
finement effects, which is in turn beneficial for
photocatalytic application as it decrease the recombination
rate between holes and electron pair. Moreover, higher
surface to volume ratio in nanorods, comparative to nanopar-
ticles, enhances the surface adsorption, thereby helping to
augment photocatalysis rate. ZnO nanoparticles are used
for multidisciplinary purposes including solar cells (Chakra-
barti & Dutta ), Gas sensors (Mohaghegh et al. ),
optoelectronic devices (Farzana & Meenakshi ), and
paints (Amorim et al. ) and as a photocatalyst for
microbial degradation (Puvaneswari et al. ). The reason
behind the widespread popularity of ZnO as an efficient
photocatalyst is that it can absorbs over a larger segment
of the solar spectrum, it is easily available, has low cost
and is relatively nontoxic (Klemola et al. ; Kant ;
Gnanaprakasam et al. , Thangavel et al. ).
Previously used conventional water treatment processes
were generally carried out using the one-factor-at-a-time
(OFAT) approach. This a method for designing experiments
involving the testing of factors, or causes, one at a time instead
due to the treatment with the deviation owing to random
errors, linked to the measurements of produced responses.
In this work zinc oxide nanorods (ZNRs) were syn-
thesized by simple alkaline hydrolysis method. A few
research works on factorial modeling of dye and different
organics degradation by zinc oxide nanoparticles have
been reported earlier (Soltani et al. ; Lee & Hamid
), but a comparatively less amount of work has involved
ZNRs and statistical modeling. Herein, the work covers a
simplistic one pot synthesis of ZNR requiring just two
easily available chemicals, a kinetics study utilizing the
nanorods and lastly the factorial design and process optim-
ization of photodegradation of the chosen dye.
MATERIALS
Zinc nitrate hexahydrate (ZnNO3.6H2O, 99%) and sodium
hydroxide (NaOH) used for the synthesis of ZNR, were pur-
chased from Merck (India). The chemicals were used as-
received without further purification. Deionized water
(18.2 mΩ) was used throughout the studies to prepare the
stock solutions and working solutions of dye. Details of
the model dye are given in Table 1.
Synthesis of ZNRs
For the preparation of the ZNRs the following process was
adopted: 0.7 M ZnNO3 solution was taken as the precursor.
Table 1 | Particulars of the selected dye
Name of dye Reactive Black 31

of all concurrently. In this recent era, the OFAT method is get- Molecular formula C29H18CuN6Na4O17S4
ting replaced by chemometric methods like response surface Molecular weight 1,006.25
methodology (RSM) founded on statistical design of exper- Chemical structure
iments (Daniel ; Bezerra et al. ; Kasiri & Khataee
; Vaez et al. ). In order to overcome the problem
faced in the application of OFAT approach, the optimization
of analytical methods is carried out using multivariate statisti-
cal techniques like RSM. It is a collection of mathematical and
statistical procedures to analyze the influence of independent
variables (inputs) on a specific dependent variable (response)
(Ahmadi et al. ; Dutta et al. a, b). RSM utilizes
an experimental strategy such as the central composite
Maximum 549 nm
design (CCD) for the purpose of fitting a model by least squares absorbance (λmax)
technique (Bezerra et al. ; Khayet et al. ). The data
CAS no. 12731-63-4
obtained is analyzed by analysis of variance (ANOVA). The
Supplier Colour Chem, Clariant, Mumbai, India
fundamental concept of ANOVA is to compare the variation
 700 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR
NaOH (1 M) was taken as the source of the hydroxide ions
required for the hydrolysis of the salt. A hundred millilitres
of this solution was added to a round-bottom flask and
placed in an oil bath, maintained at a temperature of
W
110 C by a thermostat; the whole setup was then mounted
on a magnetic stirrer and rotated vigorously. This helped
homogenization of the reactant and even heat distribution
within the synthesis vessel. During the synthesis, after the
basic solution gained some momentum, 50 mL of zinc
nitrate solution was added drop-wise, keeping the tempera-
ture constant at 110 C. Zinc hydroxide is formed at first
W
and the solution turns turbid. Eventually with continuous
heating and stirring zinc hydroxide converts into zinc
oxide. The reaction pathway is given below
ZnNO3 þ NaOH ! ZnðOHÞ2 þNaþ þ NO

3 (1)
ZnðOHÞ2 ! ZnO ↓ þH2 O (2)
The entire reaction was carried out for a span of 2 hours;
after that the final product was filtered with a membrane
filter (0.2 μm pore size), washed with deionized water first
and then with absolute ethanol several times, and finally
the residue was dried at a temperature of 60 C in a
W
vacuum oven.
Particle characterization
Field emission scanning electron microscopy (FE-SEM) analy-
sis of the obtained ZNR was carried out by a Bruker XFlash
6160. That the nanorods were crystalline in nature was
proved by the X-ray diffraction (XRD) data, done by
PANalytical XPERT PRO, the scan range of the sample
being 35–100 (2θ) with the scan speed being 1.2 min
1.
W W
UV–visible (UV-Vis) absorption spectra of dispersed ZnO
nanorods solution were recorded by a UV-Vis spectropho-
tometer (1601 Shimadzu), for the evaluation of the band gap
energy of the sample. Fourier transform infrared (FT-IR) spec-
tra of the sample were recorded by a Thermo Nicolet iS10
spectrometer using KBr pellets in the range 4,000–400 cm
1.
The pH measurements of the dye solutions were carried out
by an Orion star A214 Thermo Scientific pH meter.
Preparation of synthetic wastewater
A synthetic wastewater solution was prepared using Reactive
Black 31 (RB 31) dye, which is widely used in the textile indus-
tries in India. The concentration of the stock dye solution was
Water Science & Technology | 74.3 | 2016
1,000 mg/L and was prepared by dissolving the dye in deio-
nized water. The dye concentration in the stock solution, the
intermediate dye solutions and the treated samples were all
measured using a UV-Vis spectrophotometer (1601 Shi-
madzu) at a λmax value of 549 nm wavelength for RB 31 dye.
The pH was adjusted by 0.1 N and 1 N HCl and 0.1 N and
1 N NaOH.
Experimental setup
Photo-oxidation of RB 31 dye was conducted in a batch
process. This experimental unit is configured with an annu-
lar cylindrical glass reactor (Figure 1) with a quartz tube at
the middle of the reactor to accommodate the UV light
source of 125 watt; the jacket was provided for cooling
purposes. Cooling medium (water) was continuously circu-
lated throughout the reaction time to prevent the UV bulb
from fusing. The reactor is provided with two ports: one
serves as inlet for reactants, and the second one for collec-
tion of treated samples. The reactor is in full contact with
air and homogenization is done by a magnetic stirrer.
The reactor is covered with a wooden box to prevent loss
of UV light. All the photo-induced experiments were per-
formed in this cylindrical photo-reactor whose total
volume is 500 mL. Samples were withdrawn from the
sampling port after certain fixed time intermissions and
were filtered (pore size <0.22 μm) to discard the suspended
ZnO particles present in the solution. Then the sample
solutions were analyzed for remaining dye. Before illumi-
nation, the suspension of RB 31 dye along with the
photocatalyst were magnetically stirred in the dark for
30 min, after dispersing in an ultrasonic bath for 5 min,
to ensure the establishment of an adsorption–desorption
equilibrium between ZnO and RB 31. Mineralization
efficiency (ME) is calculated by determining the total
organic carbon (TOC) at different time and the required
equation is given below ME (%)
ðTOC0
TOCt Þ
ME ð%Þ¼ ×100 (3)
TOC0
Here TOC0 and TOCt represent TOC of the dye solution
before photocatalysis process starts (t ¼ 0) and after time t
respectively.
RSM in experimental design
RSM has been widely applied for the optimization of several
chemical and physical methods (Cao et al. ). In this
 701 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR Water Science & Technology | 74.3 | 2016

Figure 1 | Design of the photo-reactor setup.

work, the optimization of process variables was done by Table 2 | Coded variables for RSM

using RSM combined with the most commonly used form

Range and level
of factorial experimental design, CCD. In the RSM
method, several influencing variables were studied along Variable Factors
1 þ1
α þα

with the responses by changing them concurrently and car- X1 Time (min) 26.00 105.00 9.64 121.36
rying out a limited number of experiments. The outcome of X2 pH 3.50 10.70 2.01 12.19
the experiments were analyzed using Design Expert7 soft-
X3 Dose (g/L) 0.23 0.36 0.20 0.41
ware, and the regression model was suggested. For the
X4 Dye concentration 150.00 450.00 87.87 512.13
evaluation purpose, four independent operating parameters, (mg/L)
influencing the removal efficiency of the dye, were chosen:
time (X1), pH (X2), dose of ZnO (X3) and dye concentration
(X4), with the percentage degradation efficiency of RB 31 as response surface delineating the relationship between the
the response (dependent variable). Additional parameters response of interest, that is, percentage dye removal
like stirring rate, temperature and light intensity were efficiency (Y1), and the independent process factors, could
taken as constant. Table 2 shows the ranges and level of not be adequately modeled using a first order model.’ The
independent variables. approximation of the real response function therefore
In their study involving photocatalytic degradation, necessitated the usage of a second order polynomial
Chakraborty et al. () stated ‘the curvature of the true model, i.e. a quadratic model using a standard RSM
 702 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR Water Science & Technology | 74.3 | 2016

design. Hence, CCD was nominated as a proficient statisti- analysis, the main and interaction effects, the contour plot
cal tool for fitting second order empirical response surface and ANOVA were performed. The experimental outcomes
models. CCD was chosen to investigate the joint effect of of CCD were fitted to the second order (quadratic) poly-
the four independent variables by a set of 30 experiments, nomial equation as follows:
including six replications at the center points. The results
of experiments of dye removal efficiency percentage under Y% ¼ b0 þ b1 x1 þ b2 x2 þ b3 x3 þ b4 x4 þ b12 x1 x2
several experimental circumstances are shown in Table 3. þ b13 x1 x3 þ b14 x1 x4 þ b23 x2 x3 þ b24 x2 x4 þ b34 x3 x4
To examine the accuracy of the fitted model, a series of stat- þ b11 x21 þ b22 x22 þ b33 x23 þ b44 x24 (4)
istical analyses such as the normal plot, the residual

Table 3 | Matrix of CCD with its predictive value and experimental results (RE%, percentage removal efficiency)

Square root transformed

Experimental plans RE%

Run Time pH Dose g/L Concentration of dye mg/L Actual RE% Actual Predicted

1 26.00 10.70 0.23 450.00 18.67 4.32 4.31

2 65.50 7.10 0.30 300.00 31 5.57 5.56
3 65.50 7.10 0.30 300.00 31.3 5.59 5.57
4 65.50 7.10 0.30 87.87 79.21 8.90 8.92
5 65.50 7.10 0.40 300.00 34.7 5.89 5.85
6 121.36 7.10 0.30 300.00 35.76 5.98 5.96
7 105.00 3.50 0.23 150.00 69.4 8.33 8.31
8 65.50 7.10 0.30 300.00 31.2 5.59 5.57
9 26.00 10.70 0.38 450.00 24.21 4.92 4.96
10 105.00 10.70 0.38 150.00 99.16 9.96 9.99
11 26.00 3.50 0.38 150.00 44.82 6.69 6.71
12 105.00 3.50 0.23 450.00 28.65 5.35 5.36
13 65.50 2.01 0.30 300.00 43.03 6.56 6.61
14 105.00 10.70 0.23 150.00 85.54 9.07 9.06
15 105.00 10.70 0.23 450.00 46.66 6.83 6.84
16 26.00 10.70 0.23 150.00 36.87 6.07 6.09
17 65.50 7.10 0.30 300.00 30.8 5.55 5.57
18 65.50 7.10 0.30 300.00 30.7 5.54 5.57
19 9.64 7.10 0.30 300.00 6.24 2.50 2.51
20 65.50 7.10 0.30 512.13 25.91 5.09 5.07
21 105.00 10.70 0.38 450.00 47.21 6.87 6.88
22 26.00 3.50 0.23 150.00 29.16 5.40 5.36
23 105.00 3.50 0.38 150.00 82.26 9.07 9.06
24 26.00 3.50 0.23 450.00 9.2 3.03 3.02
25 65.50 7.10 0.20 300.00 23.23 4.82 4.86
26 65.50 7.10 0.30 300.00 31 5.57 5.57
27 26.00 10.70 0.38 150.00 55.95 7.48 7.45
28 105.00 3.50 0.38 450.00 29.01 5.39 5.39
29 65.50 12.19 0.30 300.00 67.69 8.23 8.18
30 26.00 3.50 0.38 450.00 13.6 3.69 3.67
 703 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR
where Y represents the response variable (decolorization
efficiency), bi, bij, and bii are the regression coefficients for
linear and quadratic effects and the coefficients of the inter-
action parameters, respectively, and xi are the independent
variables studied. Decolorization efficiency was calculated
by the following formula:
C0
Ct
Y% ¼ × 100
C0
where C0 is initial dye concentration and Ct is the dye con-
centration at time t.
RESULTS AND DISCUSSION
Characterization of zinc oxide nanoparticles
Phase and structural analysis by XRD
XRD diffraction pattern of the as-synthesized zinc oxide nano
powder is shown in Figure 2. The observed diffraction peaks
of ZnO at 2θ ¼ 32.12, 34.76, 36.64, 47.8, 57, 63.12, 66.64,
W
68.2, 69.9, 72.96 and 77.28 are associated with representa-
tive planes (100), (002), (101), (102), (110), (103), (200),
(112), (201), (004) and (202). The presence of several peaks
in the XRD patterns of as-grown sample revealed that the
nanostructures were polycrystalline in nature. All the diffrac-
tions can be assigned to the standard pattern for the pure
hexagonal phase (wurtzite structure) of ZnO. The values
have agreed well with the standard card for ZnO powder
Figure 2 | Powder XRD of nano ZnO particles at 2θ.
Water Science & Technology | 74.3 | 2016
sample (ICSD file No: 98000-9340). Diffraction patterns cor-
responding to impurities are found to be absent. This proves
that pure ZnO nanoparticles were synthesized. The crystallite
size (τ) of the as prepared nano powder can be calculated by
using Scherrer’s formula.
τ ¼ 0:94λ=β cosθ (6)
(5)
where λ is the wavelength of X-rays used (1.54060 Å), β is the
full width at half maximum and θ is the angle of diffraction.
Calculated crystallite size of prepared sample is found to be
around 20.99 nm (101 plane), which is in the order of nano
size.
Microstructural study by FE-SEM analysis
The FE-SEM image of the nanorods is shown in Figure 3(a). The
FE-SEM image discloses that the diameters of the ZnO nano-
rods are in the range 25–50 nm, and length is in the range of
300–400 nm. In a near similar process of synthesis, spherical
particles have been reported previously (Lanje et al. ; Rad-
zimska & Jesionowski ), whereas the little difference in our
process resulted in wurtzite nanorods. Energy-dispersive X-ray
(EDX) analysis (Figure 3(b)) reveals the presence of five
elements: Zn, O, C, Nb and N. Presence of Nb and N can be
due to instrumental error. Carbon source is mainly the grid
base of the SEM analysis and a little residual washing ethanol.
Atomic ratio between Zn and O is less than 1 (0.644) which
again corroborates the fact that the presence of washing ethanol
contributed to the excess oxygen. Major fraction of atoms are
zinc and oxygen (<81%); therefore we can confirm the for-
mation of ZnO nanoparticles from EDX data. Verification of
formation of ZnO particle by EDX analysis was also reported
by Gnanaprakasam et al. ().
FT-IR spectroscopy
The FT-IR spectrum of the as-prepared ZNRs shows
(Figure 4) the absorption at 901 cm
1, which is due to the
development of tetrahedral coordination of ZnO. Metal
oxides in general give absorption bands in their fingerprint
region, i.e. below 1,000 cm
1, occurring due to interatomic
vibrations (Rao ; Nadeem & Ahmed ). The peak at
925 cm
1 is due to overtone of water molecules (Mohan
et al. ). The band below 700 cm
1 is associated with
metal oxide (ZnO) bond. In the IR region, ZnO generally
shows discrete absorption bands about wavenumbers of
464 cm
1. The spectra should show a representative ZnO
absorption at 564 cm
1, blue-shifted to 512 cm
1 and there
 704 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR Water Science & Technology | 74.3 | 2016

Figure 3 | (a) FE-SEM analysis of ZnO nanorods; (b) EDX data of ZNRs.

will be an additional maximum at wavenumbers smaller than
500 cm
1, which cannot be identified by our spectrometer
(Wu et al. a, b). The fundamental mode of vibration
at 3,399 cm
1 corresponds to O-H stretching frequency,
which is due to the presence of the water molecules bound
to the surface of the prepared sample. The peak at
2,847 cm
1 corresponds to C-H stretching frequency. The
presence of residual ethanol from the washing process can
be the only reason behind this peak. The peak at
1,635 cm
1 corresponds to an overtone of water molecule.
Optical study by UV-Vis spectroscopy
The UV optical spectra of ZnO nanorods, suspended
in deionized water, were obtained in the range of
200–800 nm by a 1601 Shimadzu spectrophotometer. Opti-
cal absorption spectrum of ZNRs is shown in Figure 5 (see
the inset in Figure 5). ZNR shows a small but sharp absorp-
tion peak at 356 nm in the UV-Vis region, which is blue-
shifted when compared to bulk ZnO particles having
absorption at about 380 nm (Yong-hong et al. ; Wu
 705 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR Water Science & Technology | 74.3 | 2016

portion of the plot of (αhυ)2 vs. hυ with the abscissa axis

(Cao et al. ), where hυ and α accounts for the photon
energy and the absorption coefficient, respectively. α is
derived from the Lambert–Beer relation, α ¼ 2.303 A/d,
where d is the path length of the quartz cuvette and A is
the UV-Vis absorbance. The band gap has been calculated
to be about 3.45 eV. Quantum size effect could be the
reason behind increased band gap (Devaraj et al. ).
Enhanced band gap of ZNR compared with the zinc oxide
nanoparticles is useful for the photocatalytic process as it
will help to reduce the recombination rate.

Preliminary experiments

The time-dependent total scan in the absorbance spectra of

Figure 4 | FT-IR plot of nano ZnO nanorods. the dye solution throughout the reaction was also examined
with initial dye concentration of 100 mg/L and catalyst load-
ing of 0.2 g/L at pH 7. As seen in Figure 6, the reductions in
five absorbance peaks at 257, 322, 413, 472 and 571 nm indi-
cate the degradation of the dye molecules. As no new
absorption peaks appeared during the reaction, it supports
the hypothesis that, if any intermediate product/s are
formed during the dye degradation, they are also efficaciously
degraded towards a full mineralization process; around 90%
reduction in the absorbance under 549 nm is also a strong
sign of degradation of intermediates.
In order to assess the substantial role of photocatalysts in
the photodegradation process, photolysis and catalyst adsorp-
tion in the dark were performed. As shown in Figure 7, 31%

Figure 5 | UV-Vis absorption spectrum (inset) and band gap energy determination of the
prepared ZnO nanoparticle.

et al. a, b). This blue shift may be attributed to the

crystallite size of the synthesized nanorods, which is below
30 nm. The absorption in the near-UV region is because of
near band edge emission occurring due to exciton recombi-
nation. The band gap energy of ZNRs has been calculated
from the UV-Vis absorption spectrum recorded in their col-
loidal state in absorbance mode (Figure 5) using the Tauc
plot. The required equation is αhυ ¼ A (hυ
Eg)n’, where
A is a constant, hν is photon energy, Eg is the allowed
energy gap, n ¼ ½ for allowed direct transition and n ¼ 2
for allowed indirect transition. The direct band gap (Eg), rep- |
Figure 6 UV-Vis spectra of photocatalytic degradation of RB 31 dye under different time
resents the junction point of the extrapolated straight interval, ZnO loading ¼ 0.2 g/L, dye concentration ¼ 100 mg/L, pH ¼ 7.
 706 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR
Figure 7 | Photocatalytic degradation of RB 31 dye under various conditions, ZnO load-
ing ¼ 0.2 g/L, dye concentration ¼ 100 mg/L, pH ¼ 7.
of the dye solution was photolyzed by only UV irradiation.
The sorption of dye solution by ZNR was trivial (9.4%).
Although 97.97% of the dye solution was degraded in the
presence of ZNR under UV illumination within 2 hours.
This indicated the synergistic effect between ZNR photocata-
lyst and UV light for the photocatalytic degradation.
Figure 8 presents the mineralization efficiency of TOC
of RB 31 dye photocatalysis by ZnO nanorods with
120 min of time. Results proved that 76.6% of TOC was
removed within this time limit. Therefore it can be inferred
that ZnO nanorods are very effective for RB31 dye degra-
dation as well as for the mineralization process.
Figure 8 | Plot of mineralization efficiency determined by removal of TOC of RB 31 dye by
ZNRs.
Water Science & Technology | 74.3 | 2016
Kinetics study
Before executing an experimental design, it is essential to
study the extent of photocatalytic degradation in RB 31 deco-
lorization. The rate of degradation of RB 31 in the presence of
ZNR, under UV illumination, was estimated at different pH
values with fixed dye concentration of 100 mg/L and catalyst
dosage of 0.2 g/L. The effect of pH on the dye photodegrada-
tion method is pretty challenging since it has various roles.
Due to the amphoteric nature of most semiconductor
oxides, pH of the dispersion becomes the significant par-
ameter dominating the rate of reaction taking place on the
semiconductor surface, as it affects the surface-charge proper-
ties of the photocatalysts. Moreover, industrial effluents are of
various pH ranges. Hence, the effect of pH on the rate of
degradation should be examined. Here, the experiments
were performed in the pH range of 3–12. Decay models of kin-
etics in photocatalysis usually follow pseudo zero order,
pseudo first order and second order models. Among these
the most common forms are zero and first order reaction.
Surface saturation on photocatalyst results in the zero
order kinetics model (Gaya ). If a change in concen-
tration does not affect the reaction rate, it is denoted as a
zero order reaction. A first order reaction rate depends on
a single reactant. A bi-component reaction or a second
order reaction converts into a pseudo first order reaction
when the concentration of one reactant remains more or
less the same throughout the reaction (Auguliaro et al.
). In the case of the photocatalysis process of a com-
pound, the two reacting species (the compound and
photocatalyst) result in a single compound P (assuming):
CþD!P (7)
The rate equation can be written as
d ½C 

¼ k ½C ½D  (8)
dt
where k represents the observed first order reaction rate
constant (min
1) and t is time. Now, if the concentration
of D remains the same throughout the reaction or
[D] > >> [C], or in other words [D] becomes constant:
d ½C 

¼ k 0 ½C  (9)
dt
Here, k0 is the rate constant of the pseudo first order
reaction. Now, if within the limit of t ¼ 0 to t ¼ t,
 707 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR
concentration of C changes from C0 to Ct, upon integration
within this limit
ð Ct ðt
dC=C ¼
k0 dt
C0 0 power function, σ ¼ f (μα), where sigma (σ) is the standard
LnCt =C0 ¼
k0 t
Now it can be written as
0
Cdye ¼ Cdye × e
kt
C0dye is the initial concentration (mg/L) of dye, and Cdye
is the concentration (mg/L) of dye at time t. Finally k indi-
cates the empirical rate constant (min
1). The constant k,
for the various reactions, was obtained by linear regression.
R2 denotes the regression coefficient (1.0 denotes ideal first
order kinetics; the larger the deviation from unity, the less
the equation fits the first order kinetics). Table 4 summarizes
rate constants from all the diverse experiments executed.
The rate of photocatalytic reaction increased with increasing
pH. The decrease in the photocatalytic degradation at acidic
pH may be because of dissolution of ZnO at low pH. At
higher pH range, there is enough hydroxyl (OH
) anions,
which assist photogeneration of hydroxyl radicals (OH•).
Development of regression model equation and its
validation for optimization
Model fitting and statistical analysis
Development of the model initially necessitates accurate
power transformation of the responses. In this work, the
response ranges from 6.24% to 99.16%, and the ratio of
maximum to minimum is 15.891 (>10), thereby
Table 4 | Rate constants and regression coefficient of dye degradation process at differ-
ent pH
pH K R2
3 0.0204
5 0.0251
7 0.0331
9 0.0273
11 0.0311
12 0.0472
Water Science & Technology | 74.3 | 2016
necessitating a power transformation. The Box–Cox plot
has been utilized as a tool to describe the best suitable
power transformation applicable to response data. Most
of the data transformations can be designated by the
(10)
deviation, mu (μ) is the mean and alpha (α) is the power.
(11) Lambda (λ) is (1
α) in all these cases. If the standard
deviation connected with an observation is proportionate
to the mean elevated to the power, then transforming the
observation by 1
α (or l) as the exponent value gives a
scale satisfying the equal variance requisite of the statisti-
(12) cal model. The bottom point on the Box–Cox plot
indicates the value of λ that results in the minimum
residual sum of squares in the transformed model. The
potential for progress is greatest when the range of the
maximum to minimum response value is greater than
three. According to the responses of the current work
the best power transformation can be affected by an expo-
nent of 0.53 which indeed recommends the square root
(0.5) transformation (Figure 9).
The experimental matrix design and the responses cen-
tered on experiments projected by CCD for the
degradation of RB 31 are given in Table 3. On the foun-
dation of the experimental design presented in Table 3, a
quadratic response surface model was designated by the
software prompted sequential model sum of squares studies,
so as to aptly estimate the response surface function for the
responses of concern. Similarly, the final regression model
0.944
0.996
0.983
0.959
0.931
0.972
Figure 9 | Box–Cox plot for power transformation.
 708 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR Water Science & Technology | 74.3 | 2016

equation, which is fitted to the experimental data is pre- residual or real error) of 5,191.91 implies that the model is
sented in terms of the actual variables as: significant. Now, there could be only 0.01% chance that a
model F-value this large could arise due to any noise.
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Removal efficiency ¼ þ4:00726 þ 0:10840 time Values of ‘Prob > F’ less than 0.0500 show that model

0:94603 pH þ 25:88086 dose
0:02321 concentration terms are significant. It can be inferred that A, B, C, D,
  AB, AC, AD, BD, CD, A2, B2, C2, and D2 are significant
þ 3:48039 × 10−4 × time × pH
0:053511 × time × dose
  model terms. Furthermore, values greater than 0.1000

2:61821 × 10−5 × time × concentration specify the model terms are not significant. The ‘Lack of
   
þ 8:35066 × 10−3 × pH × dose þ 2:56923 × 10−4 Fit F-value’ of 4.09 implies that the lack of fit is not signifi-
× pH × concentration
0:016337 × dose × cocentration cant relative to the pure error. There is a 6.68% chance
  that a ‘Lack of Fit F-value’ could happen due to noise. The

4:2721 × 10−4 × time2 þ 0:070272 × pH2
‘Predicted R-Squared’ value of 0.9989 is in rational agree-
 

20:920019 × dose2 þ 3:16220 × 10−5 × concentration2 ment with the ‘Adjusted R-Squared’ value of 0.9996,
(13) endorsing decent predictability of the model. ‘Adequate Pre-
cision’ measures the signal to noise ratio. A ratio greater
Further, the statistical suitability of the quadratic than 4 is desirable. Here the ratio of 295.375 indicates an
response surface model was investigated by Fisher’s statisti- adequate signal. This model can be used to navigate the
cal test (F-test) for ANOVA (Markova-Deneva ). The design space. The statistical significance of the model was
ANOVA outcomes for the recommended RSM model are furthermore verified through plotting the experimental
summarized in Table 5. The model F-value (ratio of mean observations against statistically anticipated responses for
square because of regression to the mean square due to dye removal efficiency (Figure 10(a)). Data points narrowly

Table 5 | ANOVA summary for the empirical quadratic response surface model

P-value
Source Sum of squares Degrees of freedom Mean square F-value Prob > F

Model 93.24 14 6.66 5,191.91 <0.0001

A: time 29.68 1 29.68 23,136.28 <0.0001
B: pH 6.17 1 6.17 4,807.38 <0.0001
C: dose 2.45 1 2.45 1,906.31 <0.0001
D: concentration 37.10 1 37.10 28,922.02 <0.0001
AB 0.039 1 0.039 30.55 <0.0001
AC 0.37 1 0.37 288.90 <0.0001
AD 0.39 1 0.39 300.18 <0.0001
BD 0.31 1 0.31 240.10 <0.0001
CD 0.50 1 0.50 388.32 <0.0001
A2 4.15 1 4.15 3,232.90 <0.0001
2
B 7.74 1 7.74 6,035.08 <0.0001
C2 0.11 1 0.11 85.58 <0.0001
2
D 4.72 1 4.72 3,683.39 <0.0001
Residual 0.019 15 1.283 × 10
3
Lack of fit 0.017 10 1.714 × 10
3 4.09 0.0668

3
Pure error 2.097 × 10 5 4.194 × 10
4
Total 93.26 29
Standard deviation ¼ 0.036 Mean ¼ 6.13 Coefficient of variation ¼ 0.58
2 2
Predicted R ¼ 0.9989 Adjusted R ¼ 0.9996 Adequate precision ¼ 295.375
 709 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR
Figure 10 | (a) Predicted vs actual plot of dye degradation efficiency. (b) Normal prob-
ability plot of the residuals.
fell at around the diagonal of the plot, which further vali-
dated the statistical consistency of this predictive response
surface model. Moreover, the appropriateness of the
model can be estimated from the residuals, calculated by
defining the variance between the experimental and pre-
dicted decolorization efficiency. Figure 10(b) illustrates the
internally studentized residuals and normal probability
plot for decolorization efficiency. From the figure it is
Water Science & Technology | 74.3 | 2016
fairly evident that the obtained data points steadily appear
on a straight trend line, showing that there is no evident
dispersion.
Response surface analysis
The performance of the quadratic model estimated
response surface with the RB 31 dye removal efficacy as
the response, when exposed to the fluctuations of the
model environment, was graphically presented by means
of the three-dimensional response surface plots shown in
Figure 11. These plots can be utilized to evaluate any vicis-
situdes in the response surface founded on a polynomial
function. In this process, two parameters are held as con-
stant and two other parameters are varied within the
experimental ranges (Soltani et al. ). The variation in
dye removal efficiency (%) as functions of ratios of pH to
time concentration to time, and dose to concentration
have been validated by the response surface plots displayed
in Figure 11(a)–11(c), respectively.
The results in Figure 11(a) establish that the rate of
decolorization increases with increase in pH, presenting
maximum rate of removal at pH 10. Using an azo dye
namely Acid Brown 14, Sakthivel et al. () and Akyol
et al. () reported an analogous trend with ZnO, observ-
ing that the acid–base property of the metal oxide surfaces
can have substantial consequences on their photocatalytic
activity. The reported pHpzc for ZnO is 8.5–9.0 (Zhou &
Keller ), this means that above this pH, ZnO surface
gets negatively charged as the surface will be covered
with adsorbed OH
ions. These accumulated OH
ions
on the particle surfaces and in the reaction medium
favors the formation of OH• radical, which is now widely
accepted as the principal oxidizing species responsible for
the dye decolorization process. Lizama et al. () also
found out that pH 11 was the optimum value for reactive
Blue-19 dye removal, in presence of ZnO and TiO2 as
the photocatalysts. They commented that textile processes
using reactive dyes produce effluents with high pH, suit-
able for the use of ZnO as a catalyst. The effect of initial
dye concentration on decolorization efficiency is depicted
by Figure 11(b) at an initial pH 7.1 and catalyst dosage
of 0.3 g/L. The plot shows that decreasing initial dye con-
centration from 450 mg/L to 150 mg/L results in an
increase in the decolorization efficiency. As the initial
dye concentration decreases, more hydroxyl radicals are
available to degrade the dye, such that the decolorization
efficiency increases. Furthermore, it can be stated that
OH• concentration decreases as a result of decreasing
 710 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR
Figure 11 | (a) Effects of pH and time on removal efficiency at 0.3 g/L catalyst dosing and
300 mg/L dye concentration; (b) effects of concentration and time on removal
efficiency at 0.3 g/L catalyst dosing and pH of 7.1; (c) effects of dose and
concentration on removal efficiency at pH of 7.1 and reaction time of
65.5 min.
Water Science & Technology | 74.3 | 2016
path length of the photons entering the dye solution to
excite the surface of the photocatalyst, as the initial dye
concentration increases (Zhu et al. ). Figure 11(c)
depicts the influence of ZnO loading and initial RB 31
dye concentration on the degradation efficiency while
keeping pH at 7.10 and time duration of 65.5 min. As illus-
trated in the plot, the degradation percentage increased
with increasing catalyst dosage. This is based on the fact
that as the dye molecules get adsorbed onto the catalyst
surface, competitive adsorption of the OH
ions on the cat-
alyst active sites declines leading to the reduction in OH•
radical generation, which is the prime oxidant essential
for a high degradation efficiency (Zhu et al. ). On the
other hand, considering the Lambert–Beer law, as the
initial dye concentration increases, penetration of photons
into the solution decreases, which this results in lower
photon absorption by the catalyst particles and leads to
consequent lower photocatalytic reaction rate.
Process optimization and model validation and
confirmation
Process optimization was executed on the basis of the desir-
ability function to define the optimal conditions for the
degradation of RB 31 dye. Design Expert7 software was
used here to recognize the specific points that maximize the
desirability function (Table 6). The program utilizes five
options as an objective to build desirability indices: none,
maximum, minimum, target, and within range. The norms
for all variables in correspondence with percentage removal
efficiency are shown in Table 6. The importance gives added
weight to upper or lower bounds or accentuates target values.
As a higher degradation efficiency is the main goal for such
studies, an ‘importance’ value of 5 has been denoted as the
maximum goal. On the basis of the settings and limits desig-
nated above, the optimum situations for maximum
degradation efficacy (98.07%) were observed at pH value of
10.67, an initial dye concentration of 150 mg/L, ZnO dose
of 0.37 g/L and time duration of 88.52 min (Figure 12).
To test the suitability of the model in predicting the
maximum removal percentage of RB 31, an authentication
experiment was performed in a 500 mL reactor at the opti-
mum conditions. A mean of maximum degradation of
96.9% was obtained from three replicate tests, as shown in
Table 7. A good agreement between the predicted value
and the experimental value confirms the validity of the
model in simulating the photocatalytic degradation of
RB 31.
 711 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR Water Science & Technology | 74.3 | 2016

Table 6 | Optimization of individual responses to obtain overall desirability response

Name Goal Lower limit Upper limit Lower weight Upper weight Importance

Time (min) minimize 40.00 70.00 1 1 3

pH maximize 5.00 10.70 1 1 3
Catalyst dose (g/L) minimize 0.23 0.38 1 1 3
Dye concentration (mg/L) maximize 150.00 450.00 1 1 3
Removal efficiency (%) maximize 6.24 99.16 1 1 5

Figure 12 | Desirability ramp for numerical optimization.

CONCLUSION

Table 7 | Decolorization efficiency at optimum values of the process parameters In the present study ZnO nanorods were synthesized by simple
alkaline hydrolysis method at elevated temperature. Morpho-
Optimum value Experimental
Variables predicted value logical and optical analysis revealed that at (101) plane the
nanorods have crystallite diameter of 20.99 nm and the band
Time (min) 88.52 89.00
gap energy is 3.45 eV. Photocatalytic degradation of the
pH 10.70 10.60
model reactive dye RB 31 by ZnO nanorod under UV
ZnO dose (g/L) 0.37 0.37
irradiation in an aqueous medium is investigated here in the
Dye concentration 150.00 150.00
context of RSM. Kinetics study at different pH presented an
(mg/L)
increasing trend in the rate of reaction with respect to increas-
Removal efficiency (%) 98.07 96.90
ing pH. The model showed that the decolorization efficiency
 712 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR
increases with increasing pH and doses of ZnO nanorods,
whereas the removal efficiency is inversely related to initial
dye concentration. Optimization of the process by RSM
based on CCD showed 96.9% removal efficiency under opti-
mized operational conditions. This is quite consistent with
the software-predicted 98.07% removal efficiency. The results
obtained indicated applicability of the present process for effi-
cient removal of dye from aqueous media.
ACKNOWLEDGEMENTS
Authors are grateful to the infrastructure provided by the
National Institute of Technology (NIT) Durgapur. Assistance
for TOC analysis was given by Gargi Biswas and Dr Susmita
Dutta from Chemical Engineering Department, NIT Durga-
pur. Professor D. Mal from Department of Chemistry of IIT
Kharagpur provided assistance for FE-SEM and EDX analy-
sis. Indrani Thakur, Ram Chandra Maji and Jhilli Dasgupta,
fellow research scholars, helped us throughout the work.
REFERENCES
Absalan, G., Asadi, M., Kamran, S., Sheikhian, L. & Goltz, D. M.
 Removal of reactive red-120 and 4-(2-pyridylazo)
resorcinol from aqueous samples by Fe3O4 magnetic
nanoparticles using ionic liquid as modifier. J. Hazard. Mater.
192, 476–484.
Ahmadi, M., Vahabzadeh, F., Bonakdarpour, B., Mofarrah, E. &
Mehranian, M.  Application of the central composite
design and response surface methodology to the advanced
treatment of olive oil processing wastewater using Fenton’s
peroxidation. J. Hazard. Mater. 123 (1–3), 187–195.
Akoyl, A., Yatmaz, H. C. & Bayramoglu, M.  Photocatalytic
decolorization of Remazol Red RR in aqueous ZnO
suspensions. Appl. Catal. B. 54, 19–24.
Amorim, C. C., Leão, M. M. D., Moreira, R. F. P. M., Fabris, J. D. &
Henriques, A. B.  Performance of blast furnace waste for
azo dye degradation through photo-Fenton-like processes.
Chem. Eng. J. 224, 59–66.
Augugliaro, V., Coluccia, S., Loddo, V., Marchese, L., Martra, G.,
Palmisano, L. & Schiavello, M.  Photocatalytic oxidation of
gaseous toluene on anatase TiO2 catalyst: mechanistic aspects
and FT-IR investigation. Appl. Catal. B: Environ. 20 (1), 15–27.
Bezerra, M. A., Santelli, R. E., Oliveira, E. P., Villar, L. S. & Escaleira,
L. A.  Response surface methodology (RSM) as a tool for
optimization in analytical chemistry. Talanta 76, 965–977.
Cao, J., Wu, Y., Jin, Y., Yilihan, P. & Huang, W.  Response
surface methodology approach for optimization of the
removal of chromium (VI) by NH2-MCM-41. J. Taiwan Inst.
Chem. Eng. 45, 860–868.
Water Science & Technology | 74.3 | 2016
Chakrabarti, S. & Dutta, B. K.  Photocatalytic degradation of
model textile dyes in wastewater using ZnO as
semiconductor catalyst. J. Hazard. Mater. 112 (3), 269–278.
Chakraborty, S., Dasgupta, J., Farooq, U., Sikder, J., Drioli, E. &
Curcio, S.  Experimental analysis, modeling and
optimization of chromium (VI) removal from aqueous
solutions by polymer-enhanced ultrafiltration. J. Membr. Sci.
456, 139–154.
Daniel, C.  ‘One-at-a-Time Plans’. J. Am. Stat. Assoc. 68, 353–360.
Dasgupta, J., Singh, M., Sikder, J., Padarthi, V., Chakraborty, S. &
Curcio, S.  Response surface-optimized removal of
Reactive Red 120 dye from its aqueous solutions using
polyethyleneimine enhanced ultrafiltration. Ecotoxicol.
Environ. Saf. 121, 271–278.
Devaraj, R., Karthikeyan, K. & Jeyasubramanian, K.  Synthesis
and properties of ZnO nanorods by modified Pechini
process. Appl. Nanosci. 3, 37–40.
Dutta, S., Ghosh, A., Satpathi, S. & Saha, R. a Modified
synthesis of nanoscale zero-valent iron and its ultrasound-
assisted reactivity study on a reactive dye and textile industry
effluents. Desalin. Water Treat. DOI: 10.1080/19443994.
2015.1096833.
Dutta, S., Ghosh, A., Moi, C. S. & Saha, R. b Application of
response surface methodology for optimization of reactive
azo dye degradation process by Fenton’s oxidation. Int. J.
Environ. Sci. Dev. 6 (11), 818–823.
Farzana, M. H. & Meenakshi, S.  Visible light-driven photoactivity
of zinc oxide impregnated chitosan beads for the detoxification of
textile dyes. Appl. Catal. A (General) 503, 124–134.
Gaya, U. I.  Heterogeneous Photocatalysis using Inorganic
Semiconductor Solids. Springer, Amsterdam.
Gnanaprakasam, A., Sivakumar, V. M., Sivayogavalli, P. L. &
Thirumarimuruganv, M.  Characterization of TiO2 and ZnO
nanoparticles and their applications in photocatalytic
degradation of azo dyes. Ecotoxicol. Environ. Saf. 121, 121–125.
Hu, Y., Jiang, Z., Xu, C., Mei, T., Guo, J. & White, T. 
Monodisperse ZnO nanodots: synthesis, characterization, and
optoelectronic properties. J. Phys. Chem. C 111 (27), 9757–9760.
Hughes, S. M. & Alivisatos, P. A.  Anisotropic formation and
distribution of stacking faults in II–VI semiconductor
nanorods. Nano Lett. 13 (1), 106–110.
Kant, R.  Textile dyeing industry an environmental hazard.
Nat. Sci. 4 (1), 22–26.
Kasiri, M. B. & Khataee, A. R.  Photooxidative decolorization of
two organic dyes with different chemical structures by UV/H2O2
process: experimental design. Desalination 270 (1–3), 151–159.
Khayet, M., Zahrim, A. Y. & Hilal, N.  Modelling and
optimization of coagulation of highly concentrated industrial
grade leather dye by response surface methodology. Chem.
Eng. J. 167 (1), 77–83.
Klemola, K., Pearson, J. & Lindstrom-Seppä, P.  Evaluating
the toxicity of reactive dyes and dyed fabrics with the HaCaT
cytotoxicity test. AUTEX Res. J. 7 (3), 217–223.
Kumar, A. N., Reddy, C. N. & Mohan, S. V.  Biomineralization
of azo dye bearing wastewater in periodic discontinuous
batch reactor: effect of microaerophilic conditions on
treatment efficiency. Bioresour. Technol. 188, 56–64.
 713 S. Dutta et al. | Statistical evaluation for photocatalytic dye degradation by ZNR
Lanje, A. S., Sharma, S. J., Ningthoujam, R. S., Ahn, J. S. & Pode,
R. B.  Low temperature dielectric studies of zinc oxide
(ZnO) nanoparticles prepared by precipitation method. Adv.
Powder Technol. 24, 331–335.
Lee, K. M. & Hamid, S. B. A.  Simple response surface
methodology: investigation on advance photocatalytic
oxidation of 4-chlorophenoxyacetic acid using UV-active
ZnO photocatalyst. Materials 8, 339–354.
Lee, K. M., Lai, C. W., Ngai, K. S. & Juan, J. S.  Recent
developments of zinc oxide based photocatalyst in water
treatment technology: A review. Water Res. 88, 428–448.
Lizama, C., Freer, J., Baeza, J. & Mansilla, H. D.  Optimized
photodegradation of Reactive Blue 19 on TiO2 and ZnO
suspensions. Catal. Today 76, 235–246.
Ludi, B. & Niederberger, M.  Zinc oxide nanoparticles:
chemical mechanisms and classical and non-classical
crystallization. Dalton Trans. 42, 12554–12568.
Manna, L., Scher, E. C. & Alivisatos, A. P.  Synthesis of soluble
and processable rod-, arrow-, teardrop-, and tetrapod-shaped
CdSe nanocrystals. J. Am. Chem. Soc. 122 (51), 12700–12706.
Markova-Deneva, I.  Infrared spectroscopy investigation of
metallic nanoparticles based on copper, cobalt, and nickel
synthesized through borohydride reduction method. J. Univ.
Chem. Technol. Metall. 45, 351–378.
Mohaghegh, N., Tasviri, M., Rahimi, E. & Gholami, M. R. 
Nano sized ZnO composites: preparation, characterization
and application as photocatalysts for degradation of AB92
azo dye. Mater. Sci. Semiconduct. Proc. 21, 167–179.
Mohan, R., Krishnamoorthy, K. & Kim, S.-J.  Diameter
dependent photocatalytic activity of ZnO nanowires grown by
vapor transport technique. Chem. Phys. Lett. 539–540, 83–88.
Nadeem, M. Y. & Ahmed, W.  Optical properties of ZnS thin
films. Turk. J. Phys. 24, 651–659.
Nair, M. G., Nirmala, M., Rekha, K. & Anukaliani, A.  Structural,
optical, photo catalytic and antibacterial activity of ZnO and
Co doped ZnO nanoparticles. Mater. Lett. 65 (12), 1797–1800.
Park, H., Chang, S., Jean, J., Cheng, J. J., Araujo, P. T., Wang, M.,
Bawendi, M. G., Dresselhaus, M. S., Bulović, V., Kong, J. &
Gradecak, S.  Graphene cathode-based ZnO nanowire
hybrid solar cells. Nano Lett. 13 (1), 233–239.
Peng, X., Manna, L., Yang, W., Wickham, J., Scher, E.,
Kadavanich, A. & Alivisatos, A.  Shape control of CdSe
nanocrystals. Nature 404, 59–61.
Puvaneswari, N., Muthukrishnan, J. & Gunasekaran, P. 
Toxicity assessment and microbial degradation of azo dyes.
Ind. J. Exp. Biol. 44, 618.
Radzimska, A. K. & Jesionowski, T.  Zinc oxide – from
synthesis to application: a review. Materials 7 (4), 2833–2881.
Rao, C. N. R.  Chemical Applications of Infrared Spectroscopy.
Academic Press, New York.
Sakthivel, S., Neppolian, B., Shankar, M. V., Arabindoo, B.,
Palanichamy, M. & Murugesan, V.  Solar photocatalytic
degradation of azo dye: comparison of photocatalytic efficiency
of ZnO and TiO2. Sol. Energ. Mat. Sol. Cell 77, 65–82.
First received 21 December 2015; accepted in revised form 9 May 2016. Available online 1 June 2016
Water Science & Technology | 74.3 | 2016
Sanmuga, P. E., Senthamil, S. P. & Umayal, A. N. 
Biodegradation studies on dye effluent and selective remazol
dyes by indigenous bacterial species through spectral
characterization. Desalin. Water Treat. 55 (1), 241–251.
Soltani, R. D. C., Rezaee, A., Godini, H., Khataee, A. R. &
Hasanbeiki, A.  Photoelectrochemical treatment of
ammonium using seawater as a natural supporting
electrolyte. Chem. Ecol. 29, 72–85.
Soltani, R. D. C., Rezaee, A., Khataee, A. R. & Safari, M. 
Photocatalytic process by immobilized carbon black/ZnO
nanocomposite for dye removal from aqueous medium:
optimization by response surface methodology. J. Ind. Eng.
Chem. 20, 1861–1868.
Srivastava, V. C.  Photocatalytic oxidation of dye bearing
wastewater by iron doped zinc oxide. Ind. Eng. Chem. Res.
52, 17790–17799.
Thangavel, S., Thangavel, S., Raghavan, N., Krishnamoorthy, K. &
Venugopal, G.  Visible-light driven photocatalytic
degradation of methylene-violet by rGO/Fe3O4/ZnO ternary
nanohybrid structures. J. Alloys Compounds 665, 107–112.
Vaez, M., Moghaddam, A. Z. & Alijani, S.  Optimization and
modeling of photocatalytic degradation of azo dye using a
response surface methodology (RSM) based on the central
composite design with immobilized titania nanoparticles.
Ind. Eng. Chem. Res. 51 (11), 4199–4207.
Wu, J. J. & Liu, S. C.  Low-temperature growth of well-aligned
ZnO nanorods by chemical vapor deposition. Adv. Mater. 14,
215–218.
Wu, L., Wu, Y., Pan, X. & Kong, F. a Synthesis of ZnO
nanorod and the annealing effect on its photoluminescence
property. Opt. Mater. 28, 418–422.
Wu, L., Wu, Y., Shi, Y. & Wej, H. b Synthesis of ZnO
nanorods and their optical absorption in visible-light region.
Rare Metals 25 (1), 68–73.
Xu, T., Zhang, L., Cheng, H. & Zhu, Y.  Significantly enhanced
photocatalytic performance of ZnO via grapheme
hybridization and the mechanism study. Appl. Catal. B:
Environ. 101, 382–387.
Yong-hong, N., Xian-wen, W., Jian-ming, H. & Yin, Y. 
Hydrothermal preparation and optical properties of ZnO
nanorods. Mater. Sci. Eng. B 121, 42–47.
Zhang, W., Wang, S., Wang, Y., Zhu, Z., Gao, X., Yang, J. &
Zhang, H. X.  Zno@ZnS core/shell microrods with
enhanced gas sensing properties. RSC Adv. 5, 2620–2629.
Zhou, D. & Keller, A. A.  Role of morphology in the aggregation
kinetics of ZnO nanoparticles. Water Res. 44, 2948–2956.
Zhu, H. Y., Xiao, L., Jiang, R., Zeng, G. M. & Liu, L. 
Adsorption removal of Congo red onto magnetic cellulose/
Fe3O4/activated carbon composite: equilibrium, kinetic and
thermodynamic studies. Chem. Eng. J. 172, 494–502.
Zhu, H., Jiang, R., Fu, Y., Guan, Y., Yao, J., Xiao, L. & Zeng, G.
 Effective photocatalytic decolorization of methyl orange
utilizing TiO2/ZnO/chitosan nanocomposite films under
simulated solar irradiation. Desalination 286, 41–48.