ISSN: 0970-020 X

ORIENTAL JOURNAL OF CHEMISTRY CODEN: OJCHEG

An International Open Free Access, Peer Reviewed Research Journal
2018, Vol. 34, No.(3):
Pg. 1333-1340
www.orientjchem.org

Synthesis, Characterization and Applications

of Zno/Tio2/Sio2 Nanocomposite
CHITRA MANOHARAN1, 2, VENCKATESH RAJENDRAN*2 and RAJESHWARI SIVARAJ2

Research Scholar, R&D Centre, Bharathiar University, Coimbatore – 641 046, India.
1

2
Department of Chemistry, Government Arts College, Udumalpet – 642 126, India.
*Corresponding author E-mail: [email protected]

http://dx.doi.org/10.13005/ojc/340319

(Received: November 16, 2017; Accepted: February 17, 2018)

Abstract

ZnO/TiO2/SiO2 nanocomposite was synthesized using microwave assisted sol-gel method

and characterized using UV–Visible spectroscopy, XRD, SEM, EDX, FT-IR and TEM analysis. XRD
results showed the crystallite in anatase phase. FT-IR reports bands that appeared at 1108 and 862
cm-1which shows the formation of Si-O-Si and Zn-O-Ti bonds. SEM and EDX analysis showed the
incorporation of ZnO nanoparticle with the TiO2/SiO2 nanocomposite which increase the separation
of electron-hole pairs and can enhance in photocatalytic activity on methylene blue dye under
sunlight irradiation. Ultrasound irradiation was applied for the impregnation of ZTS nanocomposite
with homogeneous distribution on cotton fabrics. The antibacterial activities of the ZTS impregnated
cotton fabrics observed against Escherichia coli (Gram negative) and Staphylococcus aureus (Gram
positive) cultures was significant. The effectiveness of fabric treatment is assessed by excellent
Ultraviolet protection factor (UPF).

Keywords: Nanocomposite, Microwave irradiation, X-ray diffraction,

SEM, TEM, Antibacterial activity.

Introduction materials with the addition of it4, 5. Kim et al.,6 also

proposed that, the introduction of silicondioxide to
Metal oxide nanoparticles have attracted other metaloxides increases the band gap energy.
great attention in recent years on account of their TiO 2 /SiO 2 composite has increased potential
special electronic and chemical properties1. Titanium application in the field of varied photocatalysis, as
dioxide (TiO2) is mostly used due to its high physical they show improved photocatalytic and thermal
and chemical stability, low cost and toxicity2,3. Due properties simultaneously when compared to pure
to the large band gap of silicon dioxide (SiO 2), TiO 27. Coupled semiconductor photocatalyst of
enhances the photocatalytic activity of other oxide TiO2/ZnO has been reported to enhance the photo

This is an Open Access article licensed under a Creative Commons Attribution-Non Commercial-Share Alike
4.0 International License (https://creativecommons.org/licenses/by-nc-sa/4.0/), which permits unrestricted
Non Commercial use, distribution and reproduction in any medium, provided the original work is properly cited.
1334 RAJENDRAN et al., Orient. J. Chem., Vol. 34(3), 1333-1340 (2018)

degradation efficiency of TiO2 catalyst and studies (THF) ((CH2)4O, 99.5%, Merck & Co.) and potassium
on improving the photocatalytic efficiency have been hydroxide (KOH) (85.0%, Merck & Co.) were used
reported8-11. Zinc oxide has achieved applications in this study.
in various areas such as optical, magnetic and gas
sensing and apart from these, zinc compounds Synthesis of ZnO/TiO2/SiO2 nanocomposite
have been generally regarded as safe12. In recent Firstly, ZnO nanoparticle were synthesized
years, ZnO and TiO2 nanostructures have attracted by alkali precipitation method from the aqueous
great attention in both fundamental studies and solution of Zn (CH3COO)2•2H2O and KOH22.
applications13.
TiO2/SiO2 sol was prepared by mixing the
The rapid heat transfer of microwave sols of TiO2 and SiO2, which were prepared by stirring
irradiation allows the chemical reactions much HCl, ethanol and TTIP (Titanium tetraisopropoxide)
faster as compared to usual heating methods, (1:4:2 ratio) and silicic acid with THF (Tetrahydrofuran)
ensuing increased product yield. 14 The kinetic (1:2 ratio)23.
or thermodynamic pathways of the temperature
sensitive reactions can be selectively tuned by The ZnO suspension was prepared by
microwave irradiation14. Microwave synthesis is the dispersing the calculated amount of ZnO in 100 ml
convenient method for the synthesis of metal oxide deionised water, and isopropanol was added to the
semiconductor nanoparticle15. Nano coating on the mixture in order to immerse ZnO thoroughly. Then
surface of textiles and clothing enhance the material the suspension was added to the TiO2/SiO2 sol,
for UV blocking; antimicrobial and self-cleaning stirred magnetically for 30 minutes. The resulting
properties have also been reported16. aqueous solution was introduced in microwave
irradiation for 15 minutes. The reaction products were
Sonochemical irradiation has been proven filtered and washed with deionised water followed
as an effective technique for the synthesis17, as well by ethanol to remove the ions probably left over in
as for the deposition and insertion of nanoparticle the final product and dried in hot air oven at 80 0C
on/into fabrics18-20. The deposition of nanoparticles to obtain the ZTS nanocomposite.
on fabrics involves the formation of microjets from
auditory bubble, which push the nanoparticle onto the Characterization of synthesized nanocomposite
surface of the fabric at a high speed causes21. The optical properties of the synthesized
ZnO/TiO2/SiO2 nanocomposite were analysed using
The aim of this work is to synthesize and UV-Visible spectrophotometer (UV-1700 Series,
characterize the ZTS nanocomposite using microwave Shimadzu), the crystalline structure analysed
assisted sol-gel method. The photocatalytic studies by D8 Advance X-ray diffraction (Shimadzu lab
were performed for methylene blue dye and X-6000). Surface morphology was determined by
antibacterial activity of the sonochemically coated scanning electron microscopy (SEM) (Model JSM
cotton fabrics has also been investigated. 6390LV, JOEL, USA), the elemental analysis by
EDX and the functional groups by Fourier transform
Materials and methods infrared spectroscopy (FTIR) (Bruker, Germany).
The morphology and size were determined by
Materials transmission electron microscopy (TEM) (JEOL
The chemicals such as titanium JEM-3100F).
tetraisopropoxide (TTP) (Ti{OCH(CH3)2}4 ,99.9%,
Merck & Co.), as a titanium precursor, Silicic acid The photocatalytic activity of the
(H2SiO3, 99.9%, Merck) as silica source, zinc acetate synthesized ZTS nanocomposite was studied by the
dihydrate (Zn (CH3COO)2•2H2O, 98.0%, Merck & Co. ) decolourization of the aqueous solution of methylene
as zinc oxide source, Congo red (Merck & Co.), blue under sunlight. All the experiments were carried
ethanol (C2H5OH, 99.9%, Merck & Co.), hydrochloric out in an open 100 ml Pyrex vessel under identical
acid (HCl) (99.9%, Merck & Co.), isopropanol conditions24. The experiments were conducted at
((CH3)2CHOH, 99.0%, Merck & Co.), tetrahydrofuran different concentrations (20, 40, 60, 80, 100 mg/l)
1335 RAJENDRAN et al., Orient. J. Chem., Vol. 34(3), 1333-1340 (2018)

of dye solutions at a photocatalyst load from 0.1 to dispersed tetrahedral coordinated TiO4 unit. Anbo
0.5 g. The efficiency of the catalyst was calculated et al., have reported that the tetrahedral coordination of
using the following equation titanium oxides can be chemically supported onto silica
matrix 28. An excitonic absorption peak is found at
R (%) = (A0 - (A/A0)) × 100 (1) about 248 nm due to the ZnO nanoparticle which
Where A0 and A are the absorbance lie much higher than the band gap wavelength of
of dye solution before and after decolourization 358 nm (Eg=3.46 eV) due to the inverse relationship
respectively25. of the energy of a photon (E) and the wavelength of
the light (λ)29.
The coating process was carried out by
using ultrasonicator.1 piece of 10 X 10 cm fabric FT-IR spectrum of the ZTS nanocomposite
(100% cotton) and ZTS nanocomposite was added (Fig. 2) has two distinctive bands that appeared at
to the solution of 4:1 ethanol/ ethylene glycol in a around 862 cm-1 and 1108 cm-1 which are responsible
100 ml sonication flask. The sonication was for TiO2, ZnO and SiO2 matrix in the nanocomposite.
conducted by 70% amplitude of 750W booster
sonicator (Ti-horn, 20 kHz). The reaction mixture was
irradiated for 2 h with high intensity ultrasonic horn
and the fabric was washed with ethanol and dried
out under vacuum21.

The morphology of the cotton fabric alone

and the nanocomposite coated cotton fabrics were
studied by SEM analysis. The UPF (Ultraviolet
protecting Factor) of ZTS nanocomposite coated
cotton fabric was assessed by using the most
accepted standard AATCC test method 183.

The antibacterial activity of the cotton fabrics

against Staphylococcus aureus (Gram positive) and
Escherichia coli (Gram negative) bacteria strains Fig. 1. UV-Visible spectra of ZTS nanocomposite
were tested using well diffusion method26,27.
The peak at 1108 cm -1 show Si-O-Si bending
Results and discussion vibrations23 and the peak around at 862 cm−1 can
be devoted to symmetric stretching vibration mode
Characterization of synthesized ZTS nanocomposite of Zn-O-Ti groups25,30,31. Stretching vibrations of
UV-Vis absor ption spectra of ZTS Zn-O-Si was found to be absent as no band appeared
nanocomposite is shown in Fig. 1. The peak observed at 950 cm-1 32. The peaks observed at 1621 cm-1
at about 222 nm can be attributed to the transfer and at above 3000 cm-1 indicates the bending and
of an electron from O2- to Ti4+ ions of the highly stretching vibrations of –OH groups23.

Fig. 2. FT-IR Spectra of ZTS nanocomposite

1336 RAJENDRAN et al., Orient. J. Chem., Vol. 34(3), 1333-1340 (2018)

Figure 3 shows the XRD pattern of ZTS

nanocomposite which confirms the phase formation
and crystalline nature of the samples. The size of the
nanoparticle (D) has been calculated by the most
intense XRD line using Scherer’s formula.

D = k λ / b Cos q (2)

Where λ is the wavelength of X-ray, β is

the full width half maxima, θ is Bragg’s angle, k is
the shape factor which has the value 0.9. The most
intense peak (2θ) at 25.30 assigned for anatase TiO2
(d101) was observed in the ZTS nanocomposite23. Fig. 4. SEM Analysis of ZTS nanocomposite
The broad peaks observed (2θ) at about 20.6, 22.20
indicates that the overlapping of 100 plane (quartz)
and the amorphous state of SiO2 respectively33, 34.
The diffraction peaks observed (2θ) at 37, 47.9o are
indexed as 101 and 102 planes of ZnO hexagonal
wurzite phase and 54.4, 63o for ZnTiO31,24,35.The
crystallite size of ZTS nanocomposite, calculated
from the most intense peak was about 46 nm.

Figure 4 shows the SEM image of ZTS

nanocomposite in which TiO2 nanoparticle are
deposited on the surface of the SiO 2 spheres
and there were no isolated TiO2 particles formed
Fig. 5. EDAX of ZTS nanocomposite
separately36. ZnO nanoparticle was coordinate with
the surface of the TiO2/SiO2 nanocomposite as view Photocatalytic activity
as white patches. The EDAX results showed the The photocatalytic activity of ZTS
n a n o c o m p o s i t e w a s m e a s u r e d by p h o t o
atomic ratio of Zn/Ti/Si as 52.54/19.66/8.05. The
decomposition of methylene blue by using sunlight
results show ZnO to be incorporated into TiO2/SiO2 as the light source by taking into consideration of
to form ZTS nanocomposite (Figure 5). various parameters such as contact time, catalyst
dosage and pH.

Fig. 3. XRD Analysis of ZTS nanocomposite

Fig. 6. TEM analysis of ZTS nanocomposite
Figure 6 clearly refers the morphology of
the composites to be spherical shape and some Effect of contact time and initial concentration
of the composites as agglomerates with the mean of the dye
crystallite size of 46-50 nm which is approximately The removal of methylene blue was
in conformity with XRD. evaluated for various concentrations of dye ranging
1337 RAJENDRAN et al., Orient. J. Chem., Vol. 34(3), 1333-1340 (2018)

from 20 to 100 ppm (as per industry usage) at Effect of pH

different time periods were shown in Fig. 7(a). It The pH of the reaction has a significant
depicts that an increase in dye removal with increase effect on the surface properties of the catalyst,
in time and reached the optimal at 180 min. As the which include the surface charge of the particles.
dye concentration was increased from 20 to 100 ppm, The effect of pH on the photocatalytic degradation
the removal of dye decrease from 100% to 90% at of methylene blue showed higher the pH, higher
equilibrium. It is clear that the removal of dye depends is the decomposition of the dye, Fig. 7(c). at
on the time and initial concentration of the dye. pH 2, the maximum decomposition was11% and with
increase in the pH 12, the degradation percentage
Effect of Catalyst Loading reached 90%, at lesser time than equilibrium which
The dosage of the nanocomposite decides may be due to the surface charges. The electrostatic
the capacity of the photocatalyst for the concentration attraction of the negatively charged sites and the dye
of the dye solution. The results are shown in cation favoured the decomposition of the dye by the
Fig. 7(b) which shows that the percentage removal pH increases38.
of the dye increased rapidly with increase in catalyst
dose (0.1 to 0.5 g/l) and after optimum dose, Figure 8 shows the FT-IR spectrum of ZTS
the removal percentage remained constant. The nanocomposite after decomposition of methylene
availability of the active sites on the photocatalyst blue dye. The appearance of characteristic bands of
surface, increasing the number of OH radicals with ZTS (1100, 860 cm-1) and there is no band appeared
the increase in dosage, resulting the decolourisation at around 782 cm-1 which is the characteristic band
of dye solution37. for C-S functionality39, shows that the cleavage of the

Fig. 7. Effect of (a) contact time on removal of methylene blue (b) Dosage of catalyst on removal methylene
blue (c) pH on removal of methylene blue

C–S+=C functional group in methylene blue, by the

OH• radicals generated by the oxidation of water by
holes formed by ZTS .Columbic interaction with the
surface of ZTS and the cleavage of the bonds occur.
The conversion of C–S+=C to C–S (=O)–C induces
the opening of the central aromatic ring through the
heteroatoms, S and N40.

Structure and morphology of the nanocomposite

coated fabrics
Figure 9a and 9b shows the cotton fabrics
before and after sonochemical treatment. Fig.10b Fig. 8. FT-IR Spectra of ZTS after decomposition of
shows a uniform distribution of the particles along methylene blue
1338 RAJENDRAN et al., Orient. J. Chem., Vol. 34(3), 1333-1340 (2018)

the fibre which shows that ultrasound irradiation can Table1: Standard UPF Values
be used as an effective method for coating textiles.
UPF Range Protection UV-R
Category Transmission (%)
The UV-protection factor rating of the ZTS
coated cotton fabric was in the range of >50 and the 15-24 Good 6.7-4.2
25-39 Very good 4.1-2.6
transmission percentage was less than 2.5 which are
40-50, > 50 Excellent Less than 2.5
related to the standard UV-protection factors rating
(Table 1).
Figure 10 reports the antibacterial activity of
the ZTS nanocomposite coated cotton fabrics tested
The UPF values were obtained against
against Staphylococcus aureus and Escherichia
minimum transmission (i.e. Maximum UPF) of UV
coli bacteria strains. Strong bactericidal effect was
radiation in the range of 387-388 nm for five scans, observed for the nanocomposite coated clothes
thus conforming the ability of ZTS to work effectively for both bacteria strains (19 mm zone of inhibition
in UV-A range (320-400 nm), recognised as a major observed for Staphylococcus aureus and 18 mm for
cause of pigmentation and premature ageing41. Escherichia coli).

Fig. 9. SEM images of a) uncoated Cotton fabric b) ZTS Coated cotton fabric

Fig 10. Antibacterial activity of ZTS nano composite coated cotton fabric
against a) Staphylococus areas b) E.Coli
1339 RAJENDRAN et al., Orient. J. Chem., Vol. 34(3), 1333-1340 (2018)

Conclusion nanocomposite coated fabrics can comprise probable

applications in wound dressing, as bandages and
The ZnO based TiO2/SiO2 nanocomposite designing of UV protecting fabrics.
shows efficient photodegradation on methylene
blue dye at higher concentration under sunlight. The Acknowledgement
sonochemical coating method of nanocomposite
on fabrics provide a uniform deposition. Strong The authors are grateful to the Bharathiar
antibacterial activities and efficient UPF values University, Coimbatore and Karunya University,
were observed for the coated cotton fabrics. The Coimbatore for instrumentation facility.

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