Environ Sci Pollut Res
DOI 10.1007/s11356-016-7750-6
RESEARCH ARTICLE
Photocatalytic degradation of methylene blue dye by zinc oxide
nanoparticles obtained from precipitation and sol-gel methods
Abebe Balcha 1 & Om Prakash Yadav 1 & Tania Dey 2
Received: 14 February 2016 / Accepted: 18 September 2016
# Springer-Verlag Berlin Heidelberg 2016
Abstract Zinc oxide (ZnO) nanoparticles were synthesized by
precipitation and sol-gel methods. The aim of this study was to
understand how different synthetic methods can affect the pho-
tocatalytic activity of ZnO nanoparticles. As-synthesized ZnO
nanoparticles were characterized by X-ray diffraction (XRD)
and UV-Visible spectroscopic techniques. XRD patterns of
ZnO powders synthesized by precipitation and sol-gel methods
revealed their hexagonal wurtzite structure with crystallite sizes
of 30 and 28 nm, respectively. Their photocatalytic activities
were evaluated by photocatalytic degradation of methylene
blue, a common water pollutant, under UV radiation. The ef-
fects of operational parameters such as photocatalyst load and
initial concentration of the dye on photocatalytic degradation of
methylene blue were investigated. While the degradation of
dye decreased over the studied dye concentration range of 20
to 100 mg/L, an optimum photocatalyst load of 250 mg/L was
needed to achieve dye degradation as high as 81 and 92.5 % for
ZnO prepared by precipitation and sol-gel methods, respective-
ly. Assuming pseudo first-order reaction kinetics, this
corresponded to rate constants of 8.4 × 10 − 3 and
12.4 × 10−3 min−1, respectively. Hence, sol-gel method is pre-
ferred over precipitation method in order to achieve higher
photocatalytic activity of ZnO nanostructures. Photocatalytic
activity is further augmented by better choice of capping ligand
Responsible editor: Philippe Garrigues
* Tania Dey
taniadey@hotmail.com
1
Chemistry Department, Haramaya University, Post Box 138, Dire
Dawa, Ethiopia
2
Department of Mechanical Engineering, Limerick Institute of
Technology, Moylish Park Campus, Limerick, Ireland
for colloidal stabilization, starch being more effective than
polyethylene glycol (PEG).
Keywords Pollutant degradation . Methylene blue . Zinc
oxide nanoparticle . Photocatalyst . XRD
Introduction
Effluents from textile, paper, and agro-industries are contami-
nated with chemicals such as dyes, phenols, and pesticides.
These being toxic and carcinogenic in nature are not only seri-
ous hazard to human health but also adversely affect the eco-
system. As these chemicals are stable to natural decomposition,
their ever-increasing levels in the environment, specifically in
water bodies, are of much concern to the society as well the
regulatory authorities around the world. Most of the traditional
water treatment methods such as membrane filtration, adsorp-
tion, and chemical treatment are ineffective for the complete
removal of dyes. On the contrary, these methods also generate
secondary pollutants such as toxic gases and sludge as solid
wastes that require further treatment.
Photocatalysis, using nanosized semiconductor
photocatalysts, is a newly emerging clean and cost-effective
alternative for a large-scale treatment of water polluted with
dyes and other organic compounds (Dey 2012; Danion et al.
2007; Rauf et al. 2007; Skorb et al. 2008; Abu Tariq et al. 2008;
Guesh et al. 2013; Nibret et al. 2015). The advantages of using
metal-oxide semiconductors, such as titania (TiO2) and zinc
oxide (ZnO), are not only their high photocatalytic efficiency
but also their high photosensitivity, non-toxic nature, low cost,
and eco-friendliness. But, the above photocatalysts have their
limitations; in that, these have high band gap (>3.0 eV), there-
fore can only be photoexcited in the ultra-violet (UV) region of
electromagnetic radiation. As the UV component of solar

radiation, reaching the Earth surface, is merely 4 to 5 % of the
solar spectrum, therefore, the photocatalytic efficiency of the
above photocatalysts is low under sunlight. In the recent years,
efforts have been made to modify the high band gap
photocatalysts by doping with metals and non-metals to enhance
their photocatalytic performance (Anandan et al. 2007;
Welderfael et al. 2013; Getaye et al. 2015). Alternatively, the
coupling of semiconductors having different band gap have also
lead to improve their photocatalytic performance (Hoffmann
et al. 1995). Further, the morphology of a photocatalyst such
as its shape and size may also affect its photocatalytic efficiency.
It is demonstrated in the literature that the photoactivity of cat-
alysts is influenced by their morphological characteristics such
as phase composition, crystalline quality, particle size, size dis-
tribution, and specific surface area.
Nanosized ZnO with larger specific area and more active sites
owing to large number of surface defects is thought as a low-cost
alternative to the commonly used titania (TiO2) photocatalyst for
degradation of organics in aqueous solutions (Daneshvar et al.
2004). Zinc oxide nanoparticles can be prepared by various
methods such as alkali precipitation (Rodriguez-Paez et al.
2001), hydrothermal synthesis (Baruwati et al. 2006), organo-
zinc hydrolysis (Perez-Lopez et al. 2005), spray pyrolysis (Bian
et al. 2004), microwave irradiation (Parida et al. 2006), and
plasma heat decomposing (Zhang et al. 2003). The shape, size,
and crystallite nature of the photocatalyst material is a function
of the method used for its synthesis.
Methylene blue (MB) is a heterocyclic aromatic chemical
compound used as a dye and as a pharmaceutical drug. It
enters water bodies through effluents from textile, paper, and
pharmaceutical industries and adversely affects eco-system
and aquatic life. Presence of methylene blue in drinking water
is a health hazard as it causes eye and skin irritation, hemolytic
anemia, nausea, vomiting, and abdominal pain. Therefore, its
removal from the polluted water is of significant importance.
The present work reports the photocatalytic degradation of
methylene blue in aqueous solution using ZnO nanoparticles as
photocatalyst. A comparative photocatalytic activity of ZnO
powders, synthesized by precipitation and sol-gel method, for
degradation of methylene blue dye in aqueous solutions under
UV radiation have been investigated. Effects of photocatalyst
load and substrate initial concentration on the degradation of
dye have also been studied along with their reaction kinetics. A
root cause analysis has been made on what synthetic factors
contribute towards better photocatalytic activity.
Materials and methods
Chemicals
Zinc nitrate hexahydrate [Zn (NO3)2·6H2O], MW 297 g/mol,
98 % pure was obtained from Fisher Scientific Laboratory,
Environ Sci Pollut Res
USA. Ammonia hydroxide (NH4OH), MW 35 g/mol, 98 %
pure was purchased from BLULUX, Maharashtra, India.
Ethyl alcohol (C2H5OH), MW 46 g/mol, 99 % pure; polyeth-
ylene glycol (PEG), MW 62 g/mol, 98 % pure; starch
(C6H11O5), MW 163 g/mol 97 %; and ammonium carbonate
(NH4)2CO3, MW 96 g/mol, 95 % pure were obtained from
BDH. Zinc acetate Zn (Ac)2, MW 183 g/mol, 99 % pure was
bought from Mart, India. Methylene blue (C16H18ClN3S),
MW 319.85 g/mol, 95 % pure was purchased from Jiangxi,
China. The structure of methylene blue is shown in Fig. 1.
Methods
Preparation of zinc oxide nanoparticles
ZnO nanoparticles were prepared by the following two
methods:
Domain 1: Precipitation method
Equal volume aqueous solutions of zinc acetate (2.1 %, w/v)
and ammonium carbonate (0.96 %, w/v) were poured into
100 mL aqueous PEG solution (5 %, w/v) with vigorous stir-
ring. The suspension was stirred for 2 h at room temperature.
The precipitate was filtered, washed with ammonia solution
and absolute ethanol several times, and then dried for 12 h at
room temperature. The product was calcined at 550 °C for 3 h
and crushed to get fine powder (Meruvu et al. 2011).
Domain 2: Sol-gel method
Hexahydrate zinc nitrate, Zn(NO3)2·6H2O, aqueous solu-
tion (9.8 %, w/v) was mixed with 30 g of starch under vigor-
ous stirring. The mixture was heated at 90 °C for 3 h to get a
translucent gel and kept at 4 °C for 24 h and then treated with
95 % alcohol. The product was dried at 80 °C for 12 h, cal-
cined at 600 °C for 4 h, and grinded (Shen et al. 2008).
X-ray diffraction analysis
X-ray diffraction pattern of each as-synthesized photocatalyst
was obtained using an X-ray diffractometer (BRUKER D8
Advance X-ray diffraction (XRD) from Bruker AXS GMBH,
Karlsruhe, Germany) equipped with a Cu target generating a
Cu Kα radiation (wavelength 0.15406 nm). The measurements
were carried at room temperature using accelerating voltage
Fig. 1 Structure of methylene blue or 3,7-bis(dimethylamino)phenothiazin-
5-ium chloride
Environ Sci Pollut Res
and current as 40 kV and 30 mA, respectively. The instrument
was operated under step time and 2θ degree as 1 s and 0.02°,
respectively, over a 2θ range of 4° to 64°.
UV-Visible absorption spectroscopic study
UV-Visible absorption spectra of 0.1 % (w/v) aqueous dis-
persion of each synthesized photocatalyst powder were re-
corded over a wavelength range of 200–800 nm using a
spectrophotometer (SANYO Gallenkamp, SP65).
Photocatalytic degradation study
Methylene blue aqueous solution (100 mL) of given con-
centration was mixed with a known amount of
photocatalyst powder in a reactor tube made of quartz.
The reaction mixture was kept under dark for 30 min to
attain sorption-desorption equilibrium. A UV lamp (Philips,
12 W) was placed 10 cm above the reactor tube. The
reaction mixture was irradiated while continuously being
stirred and simultaneously purged with air. Five milliliter
of reaction mixture was collected at a regular interval of
20 min. The suspension was centrifuged at 3000 rpm for
10 min, and absorbance of the clear supernatant was re-
corded at 665 nm using a spectrophotometer (SANYO
Gallenkamp, SP65) (Kwon et al. 2004).
Fig. 2 X-ray diffraction pattern
of ZnO photocatalysts
synthesized by a precipitation
method and b sol-gel method
Results and discussion
XRD analysis
X-ray diffraction patterns of ZnO powders synthesized by
precipitation and sol-gel methods are shown in Fig. 2. The
identical XRD pattern of the two ZnO samples each exhibiting
diffraction peaks at 2θ = 31.8, 34.5, 36.4, 47.6, 56.8, and 63.0
due to crystal planes (100), (002), (101), (102), (110), and
(103), respectively, reveal their hexagonal wurtzite structure
(Kang et al. 2010). As no additional diffraction peaks were
observed which may come from impurity, it was concluded
that the synthesized ZnO photocatalyst samples were pure.
XRD results also indicated (101) plane to be the preferred
growth plane, as (101) peak was the most intense peak. The
intensity ratio of (101)/(002) peaks remained invariant, imply-
ing that solvent viscosity had no effect on ion diffusion.
The average crystallite size of each synthesized
photocatalyst was determined using Scherrer’s equation
(Zheng and Wu 2009).
D ¼ K:λ=ðβ:cosθÞ ð1Þ
where D is the crystallite size in nm, K is the shape factor (taken
as 0.94), λ is the wavelength of X-ray (λ = 0.154056 nm), β is
the full width at half maximum (FWHM) for the most intense
diffraction peak in the XRD pattern (at 2θ = 36.4°), and θ is the
Bragg’s angle. The calculated average crystallite sizes (D) of
studied photocatalysts are given in Table 1.
 Environ Sci Pollut Res

Table 1 Average crystallite size (D) of photocatalysts synthesized by where Eg is the band gap energy in electron volts (eV) and λ is
method (A), i.e., precipitation method, and method (B), i.e., sol-gel
the wavelength (nm) corresponding to maximum absorption.
method
The Eg of photocatalyst synthesized using precipitation and sol-
Sample 2θ (deg) β (radians) D (nm) gel method methods were found as 3.44 and 3.35 eV, respec-
tively, which match well with literature (Berger 1997; Soosen
ZnO from method (A) 36.4 0.00496 30
et al. 2009). This shows that synthetic methods can play a vital
ZnO from method (B) 36.7 0.00545 28
role in changing the absorption characteristics of ZnO.

Photocatalytic degradation study

UV-Visible absorption study
Percentage degradation of methylene blue was calculated
Plots of absorbance versus wavelength for 0.1 % (w/v) aqueous using the equation (Kwon et al. 2004)
dispersion of photocatalysts synthesized using precipitation
Degradation ð%Þ ¼ ½ðA0 −At Þ=A0   100 ð3Þ
and sol-gel methods are presented in Fig. 3. The absorption
bands of photocatalysts prepared using the above two methods where A0 and At are the absorbance values at the initial stage
were 360 and 370 nm, respectively, attributed to band edge and at time Bt,^ respectively.
absorption of hexagonal wurtzite ZnO. Both of these absorp-
tion bands are blue shifted from the bulk value of 380 nm,
indicating decrease in particle size and increase in band gap Effect of calcination temperature
energy. Band gap energy (Eg) of each photocatalyst can be
obtained using the following relation (Zheng and Wu 2009): As calcination temperature increases, crystallites tend to ag-
glomerate, resulting in larger crystal particles with subse-
1240 quently decreased surface area and hence lesser photocatalytic
Eg ¼ ð2Þ
λ activity (Hayat et al. 2011; Ivetic et al. 2014). However,

Fig. 3 Plot of absorbance as a

function of wavelength (nm) for
0.1 % (w/v) aqueous dispersion of
synthesized photocatalysts. a
ZnO synthesized using
precipitation method (absorbance
wavelength = 360 nm) and b ZnO
synthesized using sol-gel method
(absorbance
wavelength = 370 nm)
Environ Sci Pollut Res

studies show that the decrease in particle size is nominal above

the calcination temperature of 500 °C (Yang et al. 2009). As
the calcination temperatures in our experiments were 550 and
600 °C, the possibility of calcination temperature having sig-
nificant effect on photocatalytic activity is ruled out.

Effect of photocatalyst load

Plots of percent degradation/adsorption of MB under dark,

using different photocatalyst load, as a function of time are
presented in Fig. 4. Such plots under UV radiation are shown
in Fig. 5. Each percent degradation value under UV is
corrected by subtracting from it the corresponding percent
adsorption value. Both adsorption (under dark) as well as
photocatalytic degradation under UV irradiation first increases
with increasing adsorbent/photocatalyst load, attains maxi-
mum value at an optimum adsorbent/photocatalyst load (here
250 mg/L), and then decreases at higher adsorbent/
photocatalyst load. The initial increase in the amount of cata-
lyst is due to increased number of active sites on the
photocatalyst surface. The observed decrease in the degrada-
tion at higher catalyst load above the limiting/optimum value
of 250 mg/L may be due to (a) agglomeration of photocatalyst
Fig. 5 Plots of percent photocatalytic degradation of MB under UV
particles resulting in decreased specific surface area of irradiation at varying catalyst load as a function of time. a Photocatalyst
synthesized by precipitation method and b photocatalyst synthesized by
sol-gel method

adsorbent and (b) decreased number of photons reaching at

the adsorbent active sites due to screening effect by excess
catalyst.
Maximum photocatalytic degradation of MB achieved at
3 h under UV irradiation using photocatalysts synthesized by
precipitation and sol-gel methods were 81.02 and 92.48 %,
respectively. Photocatalytic activity of ZnO nanoparticles syn-
thesized by sol-gel method is higher than that of synthesized
by precipitation method. This can be attributed to smaller
crystallite size obtained by sol-gel method, where the carriers
easily reach the surface to participate in photoactivity. An
increase in crystallite size increases probability of charge re-
combination outside the barrier region (Franco Arias et al.
2015), causing lower photocatalytic activity. Hence, sol-gel
method is more preferred over precipitation method, as far
as high photocatalytic activity is concerned.

Effect of initial concentration of dye

Using optimum photocatalyst load (250 mg/L) and differ-

Fig. 4 Plots of percentage degradation/adsorption of MB under dark at
varying catalyst load as a function of time. a Photocatalyst synthesized by
precipitation method and b photocatalyst synthesized by sol-gel method
ent initial concentration of dye, i.e., MB, the plots of
percent photocatalytic degradation of the dye as a func-
tion of time are presented in Fig. 6. In case of both the
photocatalysts, synthesized by precipitation and sol-gel

Fig. 6 Percentage degradation of MB dye under UV radiation as a
function of time using varying initial concentration of MB, catalyst
(ZnO) load 250 mg/L. a Photocatalyst synthesized by precipitation
method and b photocatalyst synthesized by sol-gel method
methods, degradation of dye decreases with its increasing
concentration. This is because a higher dye concentration
(a) decreases the path length of photon entering dye so-
lution and (b) absorbs significant amount of UV light
rather than the catalyst (Shanthi and Kuzhalosai 2012).
Fig. 7 Effect of capping ligand in colloidal stabilization of ZnO nanoparticle. a End-grafted polyethylene glycol or PEG and b surface-adsorbed starch
Environ Sci Pollut Res
Fig. 8 Plots of ln(C0/Ct ) as a function of time using MB initial
concentration of 20 mg/L and varying catalyst load. a Photocatalyst
synthesized by precipitation method and b photocatalyst synthesized by
sol-gel method
Effect of capping ligand
Both precipitation and sol-gel methods are cost-effective, sim-
ple, and suitable for industrial scale-up. However, the role of
capping ligand is crucial in these processes. For example, in
Environ Sci Pollut Res

Table 2 Photocatalytic degradation rate constant (k) under UV irradiation for MB initial concentration 20 mg/L and different catalyst load using
photocatalysts synthesized by precipitation and sol-gel methods

Catalyst load (mg/L) 100 150 200 250 300 350

Rate constant (k)/(min−1) using photocatalyst 3.8 × 10−3 5.8 × 10−3 7.4 × 10−3 8.4 × 10−3 5.6 × 10−3 5 × 10−3
synthesized by precipitation method
Rate constant (k)/(min−1) using photocatalyst 5 × 10−3 8 × 10−3 9.9 × 10−3 12.4 × 10−3 7 × 10−3 6.4 × 10−3
synthesized by sol-gel method

our sol-gel method, starch is used as capping ligand, which Kinetic study of photocatalytic degradation of methylene
stabilizes the ZnO nanoparticle. The –OH functional groups of blue
starch bind with the surface of ZnO nanoparticles during the
initial stage and hence prevent them from agglomerating. Photocatalytic degradation of MB under UV irradiation fol-
Similarly, the PEG molecules in precipitation method serve lows the pseudo first-order reaction kinetics expressed by the
as stabilizing agent, where colloidal stabilization occurs due to following equation:
van Der Waal’s interaction between O− groups in PEG and
C0
positively charged surface of ZnO nanoparticle. Hence, sur- ln ¼ k:t ð4Þ
face modification of nanoparticles can even cause charge re- Ct
versal based on number of –OH groups in the stabilizing where k is the reaction rate constant, C0 is the initial concen-
agent. But, PEG is an end-grafted polymer, whereas starch is tration of aqueous MB, and Ct is the concentration of aqueous
an adsorption polymer. Hence, in starch-stabilized ZnO nano- MB at the reaction time t.
particle, the entire surface is covered with tangled ribbon-like Using MB initial concentration of 20 mg/L and varying
ligands offering better dispersion, whereas in PEG-stabilized photocatalyst loads, plots of ln(C 0 /C t ) versus time are
ZnO nanoparticle, the surface coverage is poor with straight
chain ligands sticking out of the surface (Fig. 7). This causes
PEG-capped ZnO nanoparticles to grow readily and agglom-
erate through the uncovered sites like a template or cluster,
adsorbed water, and surface hydroxyl serving as growth pro-
moters. This in turn causes lower surface area and reduced
photocatalytic activity in PEG-stabilized nanoparticles. So,
the higher photocatalytic activity resulted from sol-gel method
of synthesis might have correlation with better capping ligand
being used. A systematic study of varying capping ligands for
each of these synthetic methods is necessary to further estab-
lish this point.

Fig. 10 Plot of ln(C0/Ct) as a function of time using varying MB initial

concentration and catalyst load of 250 mg/L. a Photocatalyst synthesized
Fig. 9 Rate constant of photocatalytic degradation as a function of by precipitation method and b photocatalyst synthesized by sol-gel
catalyst load, with constant initial dye concentration of 20 mg/L method

Table 3 Photocatalytic degradation rate constant (k) under UV irradiation for different initial concentrations of MB and optimum catalyst load 250 mg/
L using photocatalysts synthesized by precipitation and sol-gel methods
Initial concentration of dye (mg/L) 20
Rate constant (k)/(min−1) using photocatalyst synthesized 7.9 × 10−3
by precipitation method
Rate constant (k)/(min−1) using photocatalyst synthesized 8.0 × 10−3
by sol-gel method
presented in Fig. 8. All the plots were linear with R2 (correla-
tion coefficient) values, mostly 0.98 and average 0.94 for
photocatalysts synthesized by precipitation and sol-gel
methods, respectively. This confirmed the applicability of the
pseudo first-order reaction kinetic model for MB photocatalyt-
ic degradation. One of the basic postulates of pseudo first-order
reaction is that one of the reactants should be present in large
excess, so that the concentration of that reactant remains effec-
tively constant. The slight deviation from linearity observed in
the plots in Fig. 8 indicates that one of the reactants may not be
present in sufficiently large excess. Alternatively, it might be
an indication that the ZnO nanoparticles were not quite mono-
disperse in size. The calculated rate constant (k) data obtained
from the slope of ln(C0/Ct) versus time linear plots are present-
ed in Table 2 as well as plotted in Fig. 9. Highest rate constants,
corresponding to optimum catalyst load of 250 mg/L, were
8.4 × 10−3 and 12.4 × 10−3 min−1 for photocatalysts prepared
by precipitation and sol-gel methods, respectively. The higher
dye degradation rate in case of photocatalyst synthesized by
sol-gel method can originate from its smaller particle size.
Moreover, this can be attributed to the higher density of
electron-deficient sites generated during sol-gel method that
can trap photogenerated electrons and reduce recombinations,
thereby improving the photocatalytic activity.
Fig. 11 Rate constant of photocatalytic degradation as a function of
initial dye concentration, with constant optimum catalyst load of
250 mg/L
Environ Sci Pollut Res
40 60 80 100
5.6 × 10−3 3.9 × 10−3 3.1 × 10−3 2.4 × 10−3
6.4 × 10−3 4.8 × 10−3 3.9 × 10−3 3.4 × 10−3
Using optimum photocatalyst load of 250 mg/L and
varying concentration of MB, plots of ln(C0/Ct) versus
time are presented in Fig. 10. All plots were linear with
correlation coefficient (R2) being mostly 0.98 and 0.99 for
photocatalysts synthesized by precipitation and sol-gel
methods, respectively. It was observed that degradation
rate of MB decreases with the increase in initial dye con-
centration over the studied concentration range. The calcu-
lated rate constant values are recorded in Table 3 as well
as plotted in Fig. 11.
Conclusion
Nanosized zinc oxide (ZnO) photocatalyst powders were
synthesized by precipitation and sol-gel methods and were
characterized by XRD and UV-Visible spectroscopic tech-
niques. Photocatalyst synthesized by sol-gel method had
sm aller crystallite size and higher wavelength
photoabsorption compared to that prepared by precipitation
method. The photocatalytic activities of ZnO nanoparticles
synthesized by precipitation and sol-gel methods were
evaluated using degradation of MB dye as a probe.
Photocatalytic degradation of MB increases with increase
in catalyst load up to a limiting value (250 mg/L) and
then decreases at higher catalyst concentrations. However,
at a fixed catalyst load, the degradation of MB decreases
with increase of dye concentration. Using dye initial con-
centration of 20 mg/L, maximum degradations of MB un-
der UV radiation, at 3 h, over photocatalysts prepared by
precipitation and sol-gel methods were 81 and 92.5 %,
respectively. Assuming pseudo first-order reaction kinetics,
this corresponded to a rate constant of 8.4 × 10−3 and
12.4 × 10−3 min−1, respectively. Hence, sol-gel method
is preferred over precipitation method in order to obtain
higher photocatalytic activity of ZnO nanostructures and
the choice of capping ligand is crucial in this process.
ZnO nanostructures of higher aspect ratio and intentional
inclusion of defects can lead to even higher photocatalytic
activity by appropriately modifying the synthetic routes.
This study offers a low-cost eco-friendly solution to water
purification problem.
Environ Sci Pollut Res
Acknowledgments The authors would like to thank the Geological
Survey of Ethiopia (GSE) for providing the XRD analysis facility.
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