Ali et al. Int. J. Res. Chem. Environ. Vol.

4 Issue 2 April 2014(161-165)

International Journal of Research in Chemistry and Environment

Vol. 4 Issue 2 April 2014(161-165)
ISSN 2248-9649
Research Paper

Synthesis and Characterization of ZnO/SiO2 Core-Shell Microparticles and

Photolytic Studies in Methylene Blue
Ali mran Vaizoullar, Ahmet Balc
Department of Chemistry, Mugla University, TURKEY

(Received 11th December 2013, Accepted 19th March 2014)

Available online at: www.ijrce.org

Abstract: ZnO and ZnO/SiO2 particles were synthesized. ZnO surface coated with SiO2. The
characterization of these particles was obtained by Fourier transform infrared spectroscopy (FT-IR), Xray diffraction (XRD), Scanning electron microscopy (SEM), and optical microscope. Compared
photoactivity pure ZnO and ZnO/SiO2 particles using Methylene Blue solutions in alkaline conditions, we
observed bare ZnO particles slightly degraded Metylen Blue but ZnO/SiO2 particles showed enhanced
photoactivity at the end of 90 minutes. This result that in the removal of organic pollutants, changing of
surface properties plays an important role.
Keywords: Nano synthesis, Fourier transform infrared spectroscopy, X-ray diffraction (XRD), Scanning electron
microscopy (SEM), optical microscope

Introduction

aminopropyltriethoxysilane under varying conditions

and found that the coating was controllable. Many
studies on the synthesis of composites, i.e. TiO2[12],
CaCO3 [13], Fe2O3[14] covered with SiO2 have been
reported. SiO2 is a most studied shell candidate due to
its relative ease in preparation, good environmental
stability and compatibility with other materials, which
motivated us to prepare the core/shell structured
composite of ZnO and SiO2 and expected to achieve
novel properties resulting from the synergic interaction
of these two chemical components[15].

In recent years the synthesis and

characterization of semiconductor particles attracted
great attention because of their usege in many areas
such as biomedicine, luminescence, photocatalysis,
solar cells, display panels, single-electron transistors [12]
. The synthesis of such particles and the geometric
consepts more relevant for its applications[3]. Although
ZnO is very good photocatalyst, there are some
problems in practice. ZnO is amphoteric, so it turns
Zn+2 and H2O in acidic medium[4-5], and formed
zincates in the alkaline medium[6].

In this study we synthesized core/shell

structured ZnO/SiO2 microcomposites via a facile
chemical route. The obtained samples were
characterized by transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron
microscopy (SEM). The photocatalytic performance of
samples were also studied with Methylenee blue.

So the photo-activity of ZnO varies depending

on the pH value in aqeous solution. For example
Daneshevar et al.[7] found that %65 removaling of
diazinon in neutral medium and they provided that
%49 removaling of diazinon in acidic medium(pH=3).
The coating of nanoparticles to enhance the
surface chemical and physical properties is the key for
the successful applications of nanomaterials[8]. For
example, Posthumus et al.[9], modified various oxidic
particles using 3-methacryloxypropyltrimethoxysilane
and improved that association of modified particles
with organic materials. Min et al.[10], stored ZnO rods
on the conformal Al2O3 and provided that Al2O3
cylindrical shells surrounds the ZnO rods. Grasset et
al.[11] coated commercial ZnO nanoparticles with

Material and Methods

Zinc acetate (Zn(CH3COO)22H2O), diethylene glycol (C4H10O3), polyethylene glycol (400),
tetraethoxysilane (C8H20O4Si) and anhydrous ethanol
(C2H5OH) were all bought from Merck. Methylene
Blue was purchased from Aldrich. All solutions were
prepared with distilled water.

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Ali et al. Int. J. Res. Chem. Environ. Vol.4 Issue 2 April 2014(161-165)
Preparation of ZnO microparticles: 1.5 g zinc
acetate were dispersed for 30 minutes in 100 ml DEG.
0.2 g of PEG and 100 ml ethanol was dispersed in a
separate place, each mixture was rapidly stirred in 500
ml beaker and it was stirred for 24 hours at 100 oC.
White precipitates were washed with ethanol for three
times and centrifugation. Finally, the precursors were
dried 24 h in oven and then ZnO microparticles were
obtained

1(b) which could be ascribed to the characteristic Si

OSi asymmetric stretching vibration [16]. Thus we can
infer that SiO2 shells syntesized from the condensation
of TEOS were nicely covered onto the ZnO surface[17].

Preparation of ZnO/SiO2 core/shell structured

nanoparticles: ZnO nanoparticles (obtained from the
above preparation in Section 2.2) were dispersed into
50 ml of ethanol and then slowly transferred into the
500 ml round bottom flask. An appropriate amount of
TEOS (5 ml) together with 25 ml of ethanol, 100 ml
water and 20 ml NH3H2O were then added into the
reaction flask. The mixture containing the ZnO,
TEOS, solvent, and NH3H2O was stirred for 20h.
Products washed with ethanol for several times, and
then dried in oven at 120 C for 4h.

[a]

Characterization of ZnO/SiO2 core/shell structured

nanoparticles: The particles were characterized using
Fourier transform infrared spectroscopy (FT-IR,
Thermo
Scientific
Nicolet-S10-ATR),
X-ray
diffraction (XRD, Rikagu-Smart Lab), Scanning
electron microscopy (SEM, JEOL JSM 7600-F) and
transmission electron microscope (JEOL JEM 2100F
HRTEM).
Photocatalytic activity experiment
The photocatalytic degradations of Methylene Blue
solutions using prepared ZnO and ZnO/SiO2 particles
were investigated with the following process:
photocatalysts were added into Methylene blue
solution (0,1gr, for 50ml), and the provided suspension
was kept in a dark environment with stirring for 30
min to allow the physical adsorption of Methylene
Blue on photocatalyst particles and then starting
photocatalytic working.

Figure 1: FT-IR spectra of pure ZnO particles(a)

and ZnO/SiO2 microparticles(b)
X-ray diffraction: The XRD spectra of pure ZnO,
and ZnO/SiO2 microparticles are shown in Figure 2.
From Figure 2(a), a series of characteristic peaks:
2.832 (100), 2.617 (002), 2.488 (101), 1.918 (102),
1.630 (110) and 1.481 (103) are observed, and they are
in accordance with the zincite phase of ZnO
(International Center for Diffraction Data, JCPDS).

After that, the mixture was taken into the

photoreactor for photocatalytic degradation. We
measured the UVvis absorption of the clarified
solution at the wavelength for 600nm. Finally, the
photocatalytic degradation was calculated using C/C0,
where C is concentration of Methylene Blue in
sampled solution, C0 is concentration of Methylene
Blue in original solution.

After covering with SiO2 layer, did not change

the characteristic peaks of ZnO/SiO2 particles with the
zincite phase of ZnO Figure 2(b), indicating that the
SiO2 did not affect the crystalline structure. As a
results, the diffraction peaks of amorphous SiO2 were
not observed. Similar to the working about
CaCO3@SiO2 coreshell nanoparticles reported no
peaks of SiO2 shell in XRD spectra [18].

Results and Discussion

FT-IR spectra: Figure 1 shows the FT-IR absorption
spectrum of pure ZnO, and ZnO/SiO2 microparticles,
respectively. The peak at 472cm1 is the characteristic
absorption of ZnO bond and the peaks at 3363 and
1567cm1 can be attributed to the absorption of water.
It is also found that the ZnO/SiO2 microparticles
exhibit absorptions at 7911046cm1 as shown in Fig.

The SEM images of ZnO, ZnO/SiO2

microparticles are shown in Figure 3. Figure 3(a)
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Ali et al. Int. J. Res. Chem. Environ. Vol.4 Issue 2 April 2014(161-165)
shows that ZnO microparticles are sized of 2-4m.
Figure 3(b) shows the SEM of the surface modified
ZnO/SiO2 particles.

particles is about 3-5 m. With the addition of SiO2

occurred in an increase in particle diameter, the
thickness of SiO2 shell increases to 35 m as shown
in Fig. 3(c,d).

The average diameter of ZnO nanoparticles is

determined to be 24 m and ZnO/SiO2 core shell

Figure 2: XRD spectra of pure ZnO(a) and ZnO/SiO2 core shell (b) particles

Figure 3: SEM image of ZnO particles(a) and ZnO/SiO2 core shell microparticles(b,c,d)
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Ali et al. Int. J. Res. Chem. Environ. Vol.4 Issue 2 April 2014(161-165)

Figure 4: TEM image of ZnO/SiO2 core shell microparticles (a,b)

PHOTOCATALYTC REMOVAL OF MM

PERCENTAGE OF
REMOVALNG

80
70
60
50

ZnO
ZnO/SiO2

40
30
20
10
0
0

20

40

60

80

100

120

RRADATON TME

Figure 5: Photocatalytic Degradation of Methylene Blue for ZnO and ZnO/SiO2 particles
The TEM images of ZnO/SiO2 microparticles
are shown in Figure 4. Figure 4 shows that ZnO
particles are in core and SiO2 particles are in surface.
We also that SiO2 particles are distributed on ZnO
surface homogenously.

weak photocatalytic activity in basic solution of

Methylene Blue. ZnO/SiO2 microparticles consisted of
ZnO core and SiO2 shell showed a better
photocatalytic performance in alkaline solutions of
Methylene blue, because of the improved stability
modified by the SiO2 shell. This is thought to be a
candidate particles in removing pollutants.

Photocatalytic Degradation: ZnO, and ZnO/SiO2

microparticles were used as photocatalysts
respectively to degrade Methylene Blue dissolved in
water. Figure 5 shows the relationship between C/C0
and irradiation time for Methylene Blue in basic
solution photocatalyzed by ZnO and ZnO/SiO2
microparticles. Within 90 minutes, the photocatalytic
degradation of Methylene Blue is 13 and 68% in the
presence of ZnO, and ZnO/SiO2 microparticles. This
means that the modified ZnO/SiO2 microparticles have
higher photocatalytic activity. Although ZnO
nanoparticles is a quite active photocatalyst, ZnO
reactions with excessive OH- in alkaline medium,
threrefore leading to the failure of photocatalytic
degradation of Methylene Blue. After ZnO was
modified with SiO2, the stability of core/shell
structured ZnO/SiO2 microparticles was improved due
to the reduced contact of ZnO with [OH][15].

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