Professional Documents
Culture Documents
Sythesis of Zinc Oxide Nanoparticles
Sythesis of Zinc Oxide Nanoparticles
3.1 INTRODUCTION
Nanomaterials find wide range of applications owing to their exciting physical, chemical
and catalytic properties [1]. The two approaches for nanomaterials synthesis are (i) top
down and (ii) bottom up approaches (Figure 3.1). Top down approach involves synthesis
of nanomaterials from bulk materials through size reduction using mechanical methods
such as mechanical milling [2,3] (Figure 3.1). Bottom up approach involves synthesis of
nanomaterials from the self-assembly of their constituent atoms into larger, organized
systems using chemical or physical methods (Figure 3.1). Bottom up approaches have
been widely used by the researchers due to advantages like reproducibility, relative ease
solvothermal techniques have been widely practiced. In the present work, room
temperature chemical precipitation method has been adopted for synthesis of ZnO
3.2.1 Materials
grade) were purchased from Merck, India and used as such without any further
Zinc oxide nanoparticles were synthesized by chemical precipitation method using zinc
Equimolar solutions of the reactants were used. Drop-wise addition of zinc nitrate
The white precipitate was collected by filtration and washed using deionized water
several times in order to remove the unreacted soluble reactants. The filtrate was then
washed with methanol to remove any organic impurities, if present and dried at 80 °C for
5 h [4].
The dried powder was annealed at high temperature in a muffled furnace for 2 hours in
order to facilitate the conversion of Zinc carbonate to Zinc oxide and improve the
nanomaterials prepared through chemical precipitation method. Any unmixed areas in the
117
Figure 3.2 shows the schematic representation of the ZnO synthesis and characterization
procedures.
Thermal analysis of the as-synthesized powder was carried out using a thermogravimetric
analyzer (SDT Q600, TA instruments, USA). About 2 mg of the sample was placed in an
118
alumina pan and subjected to controlled temperature increase from ambient temperature
to 1000 °C at a heating rate of 10 °C/min and the weight loss was recorded.
3.2.3.2 Morphology
The morphology of the synthesized ZnO powder was analyzed using scanning electron
temperatures were studied using a cold field emission electron microscope (JSM 6701F,
JEOL, Japan). The powder sample was sprinkled over a carbon tape affixed over a brass
stub. An ultra-thin film of gold was coated over the sample using sputter coating in order
to improve the conductivity of the sample. The gold coated sample was introduced into
the specimen chamber. The samples were imaged at an acceleration voltage of 3 kV and a
temperature) was studied using a transmission electron microscope (JEM 2100F, JEOL,
Japan). The powder sample was dispersed in water using bath ultrasonication for 10 min.
A drop of the dispersion was placed over a copper grid and dried. The sample was
calcination temperature was studied using an X-ray diffractometer (D8 Focus, Bruker,
119
Optical absorption spectra of the as-synthesized powder and powder annealed at optimum
750, Perkin Elmer, USA). The samples were scanned over the range from 250 to 800
nm.
The surface area of ZnO nanopowder was determined from BET isotherms recorded
The chemical reaction between Zinc nitrate and ammonium carbonate forms zinc
hydrate (hydrozincite) yields ZnO and the decomposition is significant above 200 °C [5].
results in incomplete decomposition and hence a mixture of ZnO and hydrozincite [5].
Figure 3.3 shows the change in weight of the as-synthesized powders subjected to the
controlled temperature rise. The onset of a rapid decrease in weight was observed at 125
°C which progressed upto 250 °C indicating the conversion of zinc carbonate hydroxide
to ZnO, which was inline with the observations of Kanari et al. [5]. The percentage loss
120
in weight from 125 to 250 °C is 20.3 %. The weight loss progressed upto about 550 °C,
3.3.2 Morphology
The as-synthesized powder (Zinc carbonate hydroxide hydrate) was irregular in shape
(Figure 3.4), which on calcination yielded regular spherical shaped ZnO particles. Since
the Zinc carbonate hydroxide hydrate to ZnO conversion occurs above 200 °C and
progresses upto 400 °C, there was an persistent increase in the fraction of particles with
regular morphology with increase in calcination temperature upto 550 °C (Figure 3.4).
121
These results are inline with the thermal analysis of as-synthesized powders (Figure
3.3).The primary particle size of synthesized ZnO ranged between 25 and 40 nm.
However, the primary particle sizes of ZnO powders were larger for samples annealed at
calcination temperatures of 600 °C, 700 °C and 800 °C. There was no conversion of Zinc
carbonate to ZnO beyond 550 °C as evident from thermal analysis (Figure 3.3). The
122
larger primary particle size at higher calcination temperatures (below melting point) can
be attributed to growth of grains. At higher temperatures, fusion of more than one particle
due to melting of particle surfaces resulted in larger particle sizes [6]. With these
observations, 550 °C was chosen as the optimum calcination temperature due to the
ZnO.
The transmission electron micrograph of ZnO nanoparticles (Figure 3.5) shows the
spherical morphology of the particles and the size ranging between 25-40 nm
In order to investigate the role of mixing conditions on the morphology of the ZnO
(iii)Magnetic stirring in a baffled vessel (The reaction vessel was equipped with four
baffles with a width of about 1/10th of the diameter of the reaction vessel)
ZnO nanoparticles prepared using overhead stirrer (Mechanical stirring) were irregular in
shape with elongated aggregates (Figure 3.6 (a)). The use of magnetic stirring for mixing
of reactants yielded spherical particles. Though magnetic stirring without baffles yielded
spherical particles, the particle sizes were not uniform (Figure 3.6 (b)) probably due to
vortices. The use of baffles in the reaction vessel improved the uniformity of the shape of
the particles (Figure 3.6 (c)). This can be attributed to the more effective mixing of the
reactants in the baffled reaction vessel in which the detrimental effects of vortices are
minimal.
124
Figure 3.7 shows the X-ray diffraction patterns of as-synthesized powder and ZnO
annealed at 550 °C. X-ray diffraction pattern of as-synthesized powder was well in
The annealing of the synthesized powders at 550 °C resulted in the formation of highly
crystalline ZnO nanoparticles as evident from the X-ray diffractogram (Figure 3.7). The
125
diffraction peaks at 2 of 31.72°, 34.37°, 36.2°, 47.48°, 56.54° correspond to the planes
(100), (002), (101), (102), (110) with hexagonal wurtzite structure (JCPDS Card No. 89–
1397) with strong diffraction at 2 of 36.2°. The broadening of peaks shows the
Figure 3.7. X-ray diffraction patterns of as-synthesized powders and ZnO calcined at 550
°C.
126
The crystallite size of the ZnO nanoparticles was calculated using the scherrer formula
(Eq. (1))
0.9
D (3.1)
cos
In Eq. (3.1), ‘D’ is crystallite size, ‘’ is wavelength of incident X-ray (nm), ‘’ is full
width at half maximum intensity (radians), ‘’ is Bragg diffraction angle. Crystallite size
of ZnO nanoparticles calculated using Scherrer formula was found to be 25.78 nm, which
The absorption spectra of as-synthesized ZnO and ZnO calcined at 550 °C are shown
in Figure 3.8. The as-synthesized powder showed no specific peak between 250 and 800
nm, whereas ZnO nanoparticles calcined at 550°C showed a peak at 360 nm. The
electronic spectra (Figure 3.8) of the annealed sample was in good agreement with those
reported by Chang and Tsai [7]. The absence of any characteristic absorption in the
electronic spectra of as-synthesized sample indicates that the as-synthesized dried powder
did not contain ZnO nanoparticles. The thermal decomposition of the as-synthesized
dried powder (hydrozincite) yielded ZnO nanopowder, as evident from the characteristic
Figure 3.8. Electronic spectra of as-synthesized powder and ZnO annealed at 550 °C.
The surface area of ZnO nanoparticles annealed at 550 °C was found to be 29.58 m2/g
3.4 CONCLUSIONS
nanoparticles has been investigated, from which 550 °C was identified as the optimum
were spherical with a size range of 25-40 nm as confirmed using electron microscopy. X-
128
ray diffraction pattern of synthesized ZnO showed that the particles were highly
3.5 REFERNCES