Hydrothermal synthesis of ZnO nanopowder

and its photocatalytic performance under UV

and visible light irradiation
Cite as: AIP Conference Proceedings 2063, 040044 (2019); https://doi.org/10.1063/1.5087376
Published Online: 11 January 2019

G. Thirumala Rao, R. V. S. S. N. Ravikumar, N. Bakthavatchala Reddy, and Grigory V. Zyryanov

AIP Conference Proceedings 2063, 040044 (2019); https://doi.org/10.1063/1.5087376 2063, 040044

© 2019 Author(s).
 Hydrothermal Synthesis of ZnO Nanopowder and Its
Photocatalytic Performance under UV and Visible Light
Irradiation
G. Thirumala Rao1,a), R.V.S.S.N. Ravikumar2,b), N. Bakthavatchala Reddy3,c) and
Grigory V Zyryanov3,4,d)
1
Physics Division, Department of Basic Sciences & Humanities, GMR Institute of Technology, Rajam-532127, A.P.,
India.
2Department of Physics, Acharya Nagarjuna University, Nagarjuna Nagar-522510, A.P., India.
3Ural Federal University, Chemical Engineering Institute, Yekaterinburg, 620002, Russian Federation.
4I. Ya.Postovskiy Institute of Organic Synthesis, Ural Division of the Russian Academy of Sciences, 22 S.

Kovalevskoy Street, 620219 Yekaterinburg, Russian Federation.

a)Corresponding author: thirumalaphy@gmail.com, thirumalarao.g@gmrit.org
b)rvssn@yahoo.co.in
c)drbvreddyn@gmail.com
d)gvzyryanov@gmail.com

Abstract. ZnO nanopowder was synthesized by hydrothermal method and characterized by different spectroscopic
techniques. X-ray diffraction measurements reveal the hexagonal wurtzite structure of ZnO and the average crystallite size
is evaluated as 34 nm. Morphological and chemical compositional details were investigated by SEM, TEM and EDS
analysis. Optical absorption spectrum exhibited a characteristic exciton absorption band at 363 nm. PL spectrum exhibited
various bands in UV and visible regions. FT-IR spectrum exhibited the characteristic ZnO and other functional groups.
Visible light driven photocatalytic degradation of methylene blue (MB) dye in water was used to evaluate the photocatalytic
performance of the prepared ZnO nanopowder.

INTRODUCTION
Nanostructured metal oxide semiconducting materials such as TiO2 [1], ZnO [2], MgO [3] and SnO2 [4] have
attracted a lot of attentionin the field of photocatalysis. Among them, ZnO has been extensively investigated for the
degradation of many organic pollutants due to its high carrier mobility, ease of synthesis, and nontoxicity [5]. The
unique properties like physics, chemical, electrical, optical and photocatalysis of transparent ZnO semiconductor
material still prompted huge attention in various fields of industrial and technological applications [6]. ZnO is one of
the most applied semiconductor material due to its high solubility limit and huge application potential in various fields
such as solar cell, light emitting diode, biomedical application, antibacterial activity, sensors, super capacitors and
photocatalysis [7, 8]. However, several unfavorable drawbacks, such as a wide bandgap of 3.37 eV and fast internal
recombination of charge carriers, lead to low quantum yields and poor solar conversion efficiency. In this regard, it is
highly desirable to improve the photocatalytic efficiency of ZnO under visible light irradiation.Generally, in nanoscale
regime, material properties can be altered because of the grain size and increasing surface to volume ratio, which
modifies the electronic structure of the material compared to the bulk counterpart [9]. The attainment of nanoscience
to change the material properties is due to the quantum confinement effects [10]. In particular, ZnO nanostructures
process high quantum confinement effects as compared to the bulk material [11].
Various methods have been reported for the synthesis of ZnO nanostructures in order to modify its size and
morphology such as vapour transport process [12], sol-gel method [13], hydrolysis [14], chemical precipitation [15],
sonochemical synthesis [16] and hydrothermal method [17]. Among the above techniques the hydrothermal method

Modern Synthetic Methodologies for Creating Drugs and Functional Materials (MOSM2018)
AIP Conf. Proc. 2063, 040044-1–040044-5; https://doi.org/10.1063/1.5087376
Published by AIP Publishing. 978-0-7354-1791-5/$30.00

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is the most familiar, attractive and inexpensive method for the synthesis of ZnO nanopowders [18-20]. In the present
study, the ZnO nanopowder has been synthesized by hydrothermal method. As synthesized nanopowder was
characterized by various spectroscopic techniques like X-ray diffraction, SEM with EDS, TEM, optical absorption,
photoluminescence (PL), FT-IR and Photocatalytic activity.

EXPERIMENTAL PROCEDURE
Materials

All the chemical reagents used were analytical grade (AR) without further purification. All the chemical reagents
were purchased from Merck chemicals, Mumbai, India. Zinc acetate and sodium hydroxide were used as precursors.
Deionized water was used for all dilution and sample preparation. All the chemicals were above 99% in purity. All
the glassware used in this experimental work was acid washed.

Synthesis of ZnO nanopowder

ZnO nanopowder was synthesized by hydrothermal method, in a typical procedure, 2.2 g (0.2 mol) of zincacetate
[Zn(CH3COO)2·2H2O] was dissolved in 50 mL of deionized waterandan equal molar amount of sodium hydroxide
[NaOH] was dissolved in another 50 mL of deionized water. The zincacetate solution was stirred magnetically to
obtain uniform solution. NaOH solution was added to the above solution drop-wise with continues stirring. After 10
min the temperature was raised to 80 oC, a homogeneous white precipitationwas obtained and then stirred for 4 h,
which indicates the formation of ZnO. The obtainedhomogeneous solution was transferred into the 100 mL Teflon
lined autoclave and kept in the furnace at 200oC for 12 h. After that the obtaineddispersion was washed severaltimes
with deionized water and ethanol to remove impurities. After washing, the solution was centrifuged at 10,000 rpm
about 30 min. The settled powder was collected and dried in a hot air oven at 120 oC for 2 h.

Characterization Techniques

Powder X-ray diffraction pattern was recorded on Shimadzu XRD 6000 diffractometer with CuKa radiation
(1.5406 Å). Scanning electron microscope (SEM) images were taken from ZEISS EVO 18. The chemical composition
was determined with an Oxford EDS analyzer attached with SEM instrument. Transmission electron microscope
(TEM) images were recorded on HITACHI H-7600 and CCD CAMERA system AMTV 600 by dispersing samples
in ethanol. Optical absorption (UV-Vis) spectrum was taken from JASCO V-670 spectrophotometer in the wavelength
region of 200–1400 nm. PL spectrum was obtained from Horiba Jobin-Yvon Fluorolog-3 Spectrofluorimeter with Xe
continuous (450 W) and pulsed (35 W) lamps as excitation sources. Fourier Transformed Infrared (FT-IR) spectrum
was recorded using KBr pellets on Shimadzu IR Affinity-1S in the range of 4000–400 cm–1.Photocatalytic activity
was performed using methylene blue as a pollutant under UV and Visible light irradiation.

Photocatalytic Activity

The photocatalytic activity of ZnOnanopowderwas calculated for the degradation of methylene blue (MB) as
amodel organic pollutant under UV and visible light irradiation. All photodegradation experimentswere performed at
ambient temperature. A halogen lamp(100 W, 220 V H-PAR30) with a 410 nm cut-off filter (UV L41 KenkoTokina
Japan) was fitted just below the lamp which served as a visiblelightsource to trigger the photocatalytic reaction. To
maintain theconstant temperature, a quartz photoreactor with a water circulationjacket was fixed in a steel container
along with a magnetic stirrer. Thelamp was kept 6 cm above the dye solution, different concentrations (5, 10 and 20
mg) of photocatalystwas added to an aqueous solution of MB (100 mL, 10 ppm).In a typical experiment, prior to light
illumination, the dye solutionwas stirred for 30 min in the dark to ensure adsorption-desorptionequilibrium between
the dye solution and the photocatalyst. After acertain time interval, 4.0 mL aliquots were collected from the
photoreactorand centrifuged to remove the small particles of the photocatalyst.A UV-vis-NIR double-beam
spectrophotometer was used tomonitor the concentration of the dye during the photoreaction. Theabsorbance of the
clear solution was recorded at Zmax of 663 nm. Toconfirm that the photocatalytic activity is due to the photocatalyst
only,we carried out blank experiments without a catalyst under light (photolysis)with a catalyst in the dark
(adsorption).

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 RESULTS AND DISCUSSION
Powder X-ray diffraction analysis

Figure 1 shows the X-ray diffraction pattern of ZnO nanopowder with the dominant peaks at 20 = 32.06, 34.69,
36.51, 47.84, 56.84, 63.11, 66.68, 68.22, 69.24, 72.78 and 77.10. All the diffraction peaks are indexed to the lattice
planes (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), (2 0 0), (1 1 2), (2 0 1), (0 0 4) and (2 0 2) of hexagonal wurtzite
structure of ZnO with lattice cell parameters a = 0.3239 and c = 0.5178 nm. Comparing with the standard data (JCPDS:
36-1451), the diffraction peals shifted toward higher angles which leads to the decrease of lattice cell parameters [21].
Average crystallite size is evaluated from the high intense peak using Debye-Scherrer’s formula [22],D = 0.9Z/þcos0,
where Z is X-ray wavelength (Cu Ka radiation), þ is full width at half maximum intensity (FWHM) and 0 is the
Bragg’s angle. Average crystallite size is found to be 16 nm.

FIGURE 1. X-ray diffraction pattern of ZnO nanopowder

Figure 2 depicts the (a) SEM micrographsat different magnifications and (b) EDS pattern of ZnO nanopowder.
These morphologies reveal non-uniformly distributed stone like structures. The precise chemical composition details
of the prepared ZnO nanopowder has been investigated using EDS analysis. The EDS pattern of ZnO nanopowder
exhibited the peaks corresponding to the target elements only.Transmission electron microscope (TEM) is used to
investigate the morphology and internal structure of the materials. TEM images of ZnO nanopowder are shown in
Figure3. The TEM images reveal that the prepared nanopowder exhibited sphere like structures with average diameter
of 20 nm.

FIGURE 2.(a) SEM images of ZnO nanopowder, (b) EDS pattern of ZnO nanopowder

FIGURE3. TEM micrographs of ZnO nanopowder

Figure4shows the optical absorption spectrum of ZnO nanopowder. It is observed that the sample exhibited a
strong absorption band at 363 nm [23]. The room temperature photoluminescence (PL) spectrum of ZnO nanopowder
at Zex= 325 nm is shown in Figure 5 (a). The PL spectrum exhibited strong emission bands at UV and visible regions.

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 FIGURE 4. Optical absorption spectrum of ZnO nanopowder
The UV emission peak at 367 nm is attributed to the near band edge emission of ZnO arises from the radiative
recombination of electrons in the conduction band and holes in valency band [24]. The sharp emission band at 425
nm is related to the electron transition from the level interstitial Zn to the valence band or to the oxygen vacancy
defects [25]. The blue emission band centered at 443 nm is ascribed to the recombination of trapped electrons at the
extended level of interstitial Zn with photo generated holes. The bluish green emission centered at 468 nm attributed
to the electron transition from shallow donor level of oxygen vacancy to the valance band [26]. The green emission
band at 534 nm is ascribed to the recombination of electrons in the conduction band and holes at oxygen vacancy [27].
The CIE 1931 chromaticity diagram of ZnO nanopowder is shown in Figure 5(b). The chromaticity coordinates were
evaluated using corresponding PL data as (x = 0.1744, y = 0.2374), which indicates the blue emission of the sample.

FIGURE 5.(a) PL spectrum, (b) CIE chromaticity diagram of ZnO nanopowder

Photocatalytic activity

To study the photocatalytic activity of synthesized ZnO nanopowder, MB was used as an organic pollutant
for the photodegradation. Photodegradation of MB in absence of catalyst, 5, 10 and 20 mg of ZnO nanopowderunder
UV light irradiation is show in Figure 6 (a). The photodegradation of MB under UV light irradiation in absence of
catalyst was negligible. After 15 min of UV light irradiation, about 43, 82 and 20 % of MB was degraded by 5, 10, 20
mg of catalysts respectively. After 30 min of irradiation, 90, 93, 38 % of MB was degraded by 5, 10, 20 mg of catalysts
respectively. The low performance of 20 mg of catalyst may be arises due to the overloading of catalyst amount,
reduction of active sites and scattering of light. It is observed that 10 mg of catalyst loading gives better photocatalytic
performance for degradation of 10 ppm concentration of MB dye solution. For further investigation, 10 mg of catalyst
was taken as optimum condition. 10 mg of ZnO nanopowder was taken to investigate the photocatalytic performance
of ZnO under visible light irradiation.After 1 h 45 min of visible light irradiation, only 82 % of MB was degraded by
10 mg of catalyst. The photodegradation of MB under visible light irradiation is shown in Figure 6 (b).The result
shows that the ZnO shows better performance under UV light irradiation than visible light. The photocatalytic
performance of ZnO was need to be improve under visible light irradiation.

FIGURE 6. Photodegradation of MB under (a) UV light, (b) visible light irradiation of ZnO nanopowder

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 CONCLUSION
ZnO nanopowder was synthesized by hydrothermal method. The powder XRD pattern confirms the hexagonal
wurtzite structure of ZnO and average crystallite size was evaluated as 16 nm. SEM and TEM micrograph reveals the
irregular shaped stone like morphology of the prepared sample. The EDS spectrum shows only target elements, Zn
and O. Optical absorption spectrum exhibited band at 363 nm due to the exciton absorption of ZnO. PL spectrum
showed emission bands in UV, blue and green regions. CIE chromaticity coordinates reveal the blue emission.
Photocatalytic activity of ZnO nanopowder shows about 82% of degradation under visible light irradiation.
Photocatalytic activity of ZnO under visible light can be improved by doping or making composite materials.

ACKNOWLEDGMENTS
One of the author Dr. G. Thirumala Rao would like to GMR Institute of technology, Rajam for providing
financial support tocarry out the research work. Authors would also like to thank Department of Physics, Acharya
Nagarjuna University, Guntur.

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