Powder Technology 287 (2016) 439–446

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Powder Technology

journal homepage: www.elsevier.com/locate/powtec

Synthesis & characterization of silica coated and functionalized silica

coated zinc oxide nanomaterials
Issa M. El-Nahhal a,⁎, Jamil K. Salem a, Sylvia Kuhn b, Talaat Hammad a, Rolf Hempelmann b, Sara Al Bhaisi a
a
Department of Chemistry, Al Azhar University of Gaza, PO box 1277, Palestine
b
Physical Chemistry, Saarland University, D-66123 Saarbrucken, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Silica or meso silica or silica-meso silica coated zinc oxide microspheres were prepared based on base hydrolysis
Received 5 May 2015 of tetraethylorthosilicate (TEOS) in the presence of CTAB. Functionalization with amine or thiol organofunctional
Received in revised form 26 September 2015 groups were conducted onto pure zinc oxide, silica, meso silica or silica-meso silica coated zinc oxide micro-
Accepted 29 September 2015
sphere. The silica coated ZnO composites and their amine or thiol functionalized materials have been character-
ized by modern techniques, TEM, XRD, TGA, 13C NMR, FTIR, and UV/VIS spectroscopy. TEM analysis showed that
Keywords:
ZnO nanostructure
the ZnO nanoparticles were encapsulated and dispersed into the silica or meso silica microspheres. XRD analysis
Synthesis of zinc oxide nanoparticles indicated that the size of ZnO nanoparticles before and after coating with silica has been maintained almost un-
Silica coated ZnO changed. CP/MAS 13C NMR and FTIR spectra indicated that the coated meso silica zinc oxide materials have been
X-ray diffraction of coated ZnO successfully grafted by amine and thiol organofunctional groups.
Microstructure of silica coated ZnO © 2015 Elsevier B.V. All rights reserved.
Optical properties zinc oxide nanoparticles

1. Introduction
Zinc oxide is an inorganic multifunctional material with very useful
properties, it is used in various applications in catalysis, in cosmetics
as UV absorber, in biomedical applications, in chemical sensors, electro-
luminescent and photochemical properties [1–12]. Zinc oxide nano ma-
terials can be prepared by several methods: hydrothermal methods
[13], electrochemical depositions [14], sol–gel method [15], chemical
vapor deposition [16], thermal decomposition [17], and combustion
method [18,19]. Recently, ZnO nanoparticles were prepared by ultra-
sound [20] and co-precipitation [21]. Silica coated structured ZnO
nanomaterials have recently been used to improve their stability and
their dispersibility in suspensions [22] and therefore they can be used
for wide range of applications [22–25]. Silica-based coatings are of par-
ticular interest because they have good environmental stability with dif-
ferent materials [26], ease of surface modification [27] and reduce
potential for photocatalysis and formation of free radicals [28]. Silica
coating of metal oxide nanoparticles has been widely studied such as
Fe2O3, TiO2 and others [26,29,30]. However, the introduction of silica
coating on ZnO nanomaterial is substantially rather difficult, due to its
high surface energy activity and its large surface area and therefore
⁎ Corresponding author.
E-mail address: issanahhal@hotmail.com (I.M. El-Nahhal).
zinc oxide nanoparticles could be easily aggregated. There were some
reported articles in which dispersant agents were used as coupling
agents for the fabrication of silica coated ZnO nanoparticles [23,31].
Two main strategies were recently applied for the fabrication of silica
coating of zinc oxide nanoparticles using modified Stöber method. The
first strategy is to incorporate silane precursors during the growth pro-
cess of zinc oxide as coating agent [32,33], the second strategy is to use
sol–gel process for coating of previously prepared zinc oxide nanoparti-
cles [33]. In our research article, we used the second strategy, where
ZnO nanoparticles were firstly ultrasonicated in an ethanolic solution
containing base in order to decrease aggregation and activate ZnO nano-
particles, followed by sol–gel coating process. CTAB was used as a cou-
pling agent to incorporate with zinc oxide nanoparticles and also in
formation of meso silica microspheres. Nine different silica or meso sil-
ica and their functionalized silica coated ZnO microspheres are pre-
pared. Several techniques are used for structural determination.
Several methods and techniques were used for structural characteriza-
tion of these new materials. These methods include: X-ray diffraction
(XRD), transition electron microscopy with energy dispersive X-ray
Spectrometer (TEM-EDX), CP/MAS 13C nuclear magnetic resonance
(NMR) spectra, Fourier transform infrared spectroscopy (FTIR), Ultra vi-
olet-visible spectra(UV/VIS) and thermal analysis (TGA). TEM, XRD and
UV/VIS are used to provide information about morphology and optical
properties of pure and silica coated zinc oxide nanomaterials. 13C
NMR, FTIR and TGA analyses are used to examine the surface ligand con-
taining groups.

http://dx.doi.org/10.1016/j.powtec.2015.09.042
0032-5910/© 2015 Elsevier B.V. All rights reserved.
440 I.M. El-Nahhal et al. / Powder Technology 287 (2016) 439–446
2. Materials and methods
2.1. Materials
Tetraethylorthosilicate (TEOS), cetyltrimethylammonium bro-
mide (CTAB) alkyl hydroxyethyl dimethyl ammonium chloride
(HY, R = 12–14) were purchased from Merck and used as
received. The organoalkoxysilanes selected for the functionalization
process were 3-aminopropyltrimethoxysilane (APTS, 99%) and 3-
thiolpropyltrimethoxysilane (TPTS, 99%), these reagents were pur-
chased from Aldrich company and used without further purification.
Toluene and ethanol (spectroscopic grade) were purchased from Al-
drich company and were used as received. Zinc sulfate pentahydrate
and ammonium hydroxide solutions (28%) were obtained from Merck.
2.2. Methodology
Infrared spectra for the materials were recorded on a Perkin–Elmer
FTIR spectrometer using KBr disk in the range of 4000 to 400 cm− 1.
Thermogravimetric analysis (TGA) was carried out using Mettler
Toledo TGA/SDTA851e analyzer in the range of 25–600 °C of heat rate
10 °C/min. The system was purged with nitrogen using a flow rate of
50 mL/min. The X-ray diffraction (XRD) patterns of the dried as-prepared
samples were obtained using an X-ray diffractometer with Cu Ka
radiation (0.154 nm wavelength) under 40 kV and 200 mA. The TEM
analysis was done with JEM2010 (JEOL) transmission electron
microscope with energy dispersive X-ray Spectrometer INCA
(Oxford Instruments). UV/VIS spectra were obtained on a Shimadzu-
1601 UV/VIS spectrophotometer in a quartz cell with optical length
1 cm in the range of 700–200 nm.
2.3. Synthesis
2.3.1. Synthesis of ZnO nanoparticles
In typical synthesis of ZnO nanopowders [21], (20 mmol) of zinc sul-
fate pentahydrate ZnSO4.7H2O was dissolved into 25 mL of deionized
water. (20 mmol) of oxalic acid was dissolved in an equal volume of de-
ionized water and dropwise added to zinc sulfate solution under mag-
netic stirring for 60 min, white precipitate of zinc oxalate was isolated,
washed with water several times and dried at 100 °C for 24 h . The
dried material was grounded using mortar and pestle to produce fine
powder precursor. Subsequently, the precursor, zinc oxalate was
annealed in muffle furnace under air at 500 °C for 4 h to form ZnO
nanostructure.
2.3.2. Synthesis of ZnO@SiO2 microspheres
The coated silica zinc oxide microspheres labeled as ZnO@SiO2 were
prepared in similar reported method [26] through a simple sol–gel pro-
cess. Briefly, 0.10 g of ZnO particles were dispersed in a mixture of eth-
anol (40 mL), deionized water (10 mL), and concentrated ammonia
solution (28 wt.%, 1.2 mL) by ultrasonication for 1 h. To the solution,
0.43 mL of tetraethylorthosilicate (TEOS) was added dropwise. After
stirring for 6 h, the product was collected and washed with ethanol
and deionized water. The product was dried under vacuum at 60 °C
for 8 h.
2.3.3. Synthesis of ZnO@mSiO2 microspheres
Coated meso silica zinc oxide microspheres labeled as ZnO@mSiO2
were prepared by dispersed 0.10 g of ZnO nanoparticles in 60 mL etha-
nol and 1.2 mL concentrated ammonia solution (28 wt.%), then
ultrasonicated for 1 h. An ethanolic solution of 0.30 g CTAB was added
to the zinc oxide nanoparticles mixture under constant stirring at
room temperature. To the solution, 0.43 mL of TEOS was then added
dropwise under constant stirring for further 6 h. The product was sepa-
rated by centrifuge of 4000 rpm and washed with deionized water.
Finally the product was dried at 100 °C for 12 h and calcinated at
500 °C for 3 h.
2.3.4. Synthesis of ZnO@SiO2@mSiO2 microspheres
A two layer microspheres labeled hereafter as ZnO@SiO2@mSiO2
composite was prepared in a similar method described [26] by dis-
persed 0.10 g of ZnO@SiO2 in 60 mL ethanol and 1.2 M concentrated am-
monia solution (28 wt.%), then the mixture was ultrasonicated for 1 h.
An ethanolic solution containing 0.3 g CTAB was added to the mixture
under constant stirring for 6 h. Afterwards, 0.43 mL of TEOS was
added dropwise under mechanical agitation for further 6 h, the obtain-
ed particles were separated by centrifuge at 4000 rpm and washed with
deionized water. Finally the product was dried at 100 °C, then calcinated
at 500 °C for 3 h. Silica spheres free of zinc oxide were obtained by
treating ZnO@SiO2@mSiO2 materials with 2 M HCl, washed with excess
of water and dried in vacuum at 80 °C overnight.
2.3.5. Synthesis of amine-functionalization of ZnO–NH2, ZnO@mSiO2–NH2,
ZnO@SiO2@mSiO2–NH2
Amine-functionalized of ZnO or ZnO@mSiO2 microspheres were
prepared as previously described [26] by disperse 1.0 g of pure ZnO,
ZnO@mSiO2, ZnO@mSiO2 or ZnO@SiO2@mSiO2 with the appropriate
amount (0.37 g, 0.002 mol) of 3-aminepropyltrimethoxy silane cou-
pling agent in 20 ml of dry toluene. The mixture was refluxed for 24 h
at 110 °C. The material was filtered off washed with ethanol and dried
in vacuum at 80 °C.
2.3.6. Synthesis of thiol-functionalization ZnO@mSiO2–SH and
ZnO@SiO2@mSiO2–SH
Thiol-functionalized mesoporous materials were prepared by dis-
persed 0.10 g of the ZnO@mSiO2 or ZnO@SiO2@mSiO2 and the appropri-
ate amount (0.37 g, 0.0019 mol) of 3-thiolpropyltrimethoxy silane
coupling agent in 20 ml of dry toluene. The mixture was refluxed for
24 h at 110 °C. The material was filtered off washed with ethanol and
dried in vacuum at 80 °C.
2.3.7. Synthesis of zinc oxide free silica microspheres
Zinc oxide free silica spheres were obtained by treating 0.5 g ZnO@
mSiO2, ZnO@SiO2@mSiO2, ZnO@SiO2@mSiO2–NH2 with 20 mL 2 M hy-
drochloric acid with continuous stirring. Zinc oxide free silica materials
were separated, washed with distilled water and dried in vacuum at 60 °
C for 8 h.
3. Results and discussion
3.1. Synthesis
The following Schemes 1 & 2 represent the schematic views of the
synthesis of zinc oxide nanoparticles and its coating with silica, meso
silica coating and finally their functionalization. Zinc oxide nanoparti-
cles were prepared by the co-precipitation method [21] by the reaction
of zinc sulfate pentahydrate with oxalic acid, then the metal oxides were
obtained by calcinations at 500 °C (Scheme 1).
ZnO NPs were then dispersed in water/ethanol by ultrasonication for
1 h prior to TEOS coating through hydrolysis and subsequent polycon-
densation in the presence of NH4OH [26]. The ultrasonication in basic
media is to secure dispersion of ZnO particles into solution to be stabi-
lized by silica coating. The use of CTAB as cationic surfactant has two
functions, it acts as a coupling agent to incorporate with zinc oxide
nanoparticles to obtain well homogeneous dispersion and prevent
Scheme 1. Formation of ZnO nanoparticles.
 I.M. El-Nahhal et al. / Powder Technology 287 (2016) 439–446
Scheme 2. Descriptive of formation silica coated or encapsulation of metal oxide nanomaterials.
aggregations of zinc oxide nanoparticles, and the second function is to
form meso-wormlike silica [22,33]. In the sol–gel method, TEOS acts
as a silica coating precursor and NH4OH acts as the catalyst. In this
basic medium, the surface of the ZnO NPs was probably activated [33],
the TEOS silane precursor undergoes hydrolysis and polycondensation
process to establish ZnO–Si–O-linkages onto the nanoparticle surface
[26,33]. This leads to formation of ZnO@SiO2, and ZnO@mSiO2 micro-
spheres of diameter 260 nm and 300 nm, respectively. This depends
on the path of the synthesis. The ZnO nanoparticles were probably em-
bedded or encapsulated into the silica microspheres or introduced into
the mesopores of meso silica microspheres (Scheme 2) as confirmed
from TEM results. Synthesis of ZnO@SiO2@mSiO2 two-layer micro-
spheres of diameter over 300 nm were obtained by treating ZnO@SiO2
microspheres with concentrated ammonia solution (28 wt.%) and
CTAB and TEOS (Scheme 2) as confirmed from TEM results. The nano-
particles of ZnO were only embedded into the silica shell without ap-
pearance of zinc oxide nanoparticles in the meso silica shell as
confirmed by TEM discussed later.
Functionalization of ZnO or Zn@SiO2@m–SiO2 or Zn@m–SiO2 or Zn@
SiO2 nanomaterials was prepared by treating ZnO nanoparticles or their
silica coated materials with 3-aminopropyltrimethoxysilane (APTMS)
or 3-thiolpropyltrimethoxysilane (TPTMS) in dry toluene at 110 °C
(Scheme 2) [26]. It is found clearly that two shells, (meso and functional
silica) are formed around zinc oxide particles. Zinc oxide free spheres of
coated silica and zinc oxide free spheres of functionalized silica coated
materials are obtained easily by treating silica coated zinc oxide or
441
functionalized silica coated zinc oxide with hydrochloric acid
(Scheme 2). This was confirmed by TEM-EDX which confirms the ab-
sence of zinc contents after treatment with HCl acid. The experimental
data are summarized in Table 1.
3.2. FTIR spectra
Fig. 1a–d presents, the FT-IR spectra of ZnO, ZnO@SiO2, ZnO@SiO2@
mSiO2 and their amine functionalized ZnO@SiO2@mSiO2–NH2, re-
spectively. The peaks at 1550–1600 cm − 1 and 3100–3600 cm − 1
can be attributed to the hydroxyl groups (O–H) and amine (N–H)
bending and stretching vibrations, respectively. The Si–O–Si asym-
metric stretching vibration band of 980–1190 cm − 1 was found
only in the ZnO@SiO2 NPs spectrum compared to the ZnO NPs [33–
35]. The Si–ZnO bond formation was confirmed by the reduction in
peak intensity at 450–500 cm− 1 of Si–O–Si. This manifests the exis-
tence of a silica layer and successfully grafted over the ZnO NPs. The
absorption bands at 2980 and 1560 cm− 1 due to the ν(C–H) of ali-
phatic hydrocarbons and δ(N–H) (Fig. 1d) respectively as well as
the disappearance of the shoulder at 960 cm− 1 due to free silanol hy-
droxide groups (Si–OH) provide evidence for the introduction of the
organofunctional ligand groups onto the coated silica layers. The re-
moval of CTAB was confirmed from the FTIR spectra where the peaks
assigned due to CTAB at 2984 and 1475 cm− 1 due to ν(C–H) vibra-
tions are removed.
442 I.M. El-Nahhal et al. / Powder Technology 287 (2016) 439–446

Table 1
Experimental data.

Material Synthesis description Notes

ZnO@SiO2 ZnO + TEOS + NH4OH + Microspheres are formed,

sonication 1 h, annealed 260 nm diameter.
at 500 °C for 4 h.
ZnO@mSiO2 ZnO + TEOS + NH4OH + Microspheres, wormlike
CTAB + sonication 1 h, meso silica, 300 nm
annealed at 500 °C for 4 diameter, ZnO NPs are
h. dispersed into mesopores.
ZnO@SiO2@mSiO2 ZnO@SiO2 + TEOS + Microspheres of two layers,
NH4OH + CTAB + N300 nm diameter, ZnO
sonication for 1 h → NPs dispersed into silica
shell.
ZnO@mSiO2–NH2 ZnO@mSiO2 + amine Amine-functionalized and
silane, reflux in toluene at meso silica two layers are
110 °C → formed around ZnO.
ZnO@mSiO2–SH ZnO@mSiO2 + thiol Thiol-functionalized and
silane, reflux in dry meso silica two layers of 13
toluene at 110 °C → and 5 nm thickness
ZnO@SiO2@mSiO2–NH2 ZnO@SiO2@mSiO2 +
amino silane,reflux in dry
toluene at 110 °C →
ZnO–NH2 ZnO nanoparticles +
amine silane → reflux in
dry toluene at 110 °C →
ZnO free @SiO2@mSiO2 ZnO@SiO2@mSiO2 + 2 M Low density ZnO free silica
HCl → and meso layers, no Zn
content is observed
ZnO free@mSiO2 ZnO@mSiO2 + 2 M HCl → Low density ZnO free meso
silica layer, no ZnO is
present Fig. 2. CP/MAS 13C NMR spectra of ZnO@mSiO2–(CH2)3–NH2 and ZnO@mSiO2–(CH2)3–SH.

3.3. 13C CP/MAS NMR results
The CP/MAS 13C NMR spectra for amine-functionalized coated silica-
meso silica zinc oxide and thiol-functionalized coated silica-meso silica
zinc oxide are depicted in Fig. 2a & b respectively. The spectrum of
amine-functionalized composite shows three methylene carbons at
11, 23 and 43 ppm corresponding to the Si–CH2, C–CH2 and CH2–N.
the signal at 165 ppm is probably due to absorbed CO2 [32]. The spec-
trum of thiol-functionalized composite shows three methylene carbons
at 11 and 28 ppm corresponding to the Si–CH2 and the two carbons C–
CH2 and CH2–S, respectively. The signal at 129 ppm is probably due to
the presence of some impurities. These assignments are based on spec-
tral data reported for similar systems [36].
3.4. XRD results
The XRD patterns for pure ZnO powder prepared by the co-pre-
cipitation method [21], silica, meso silica coated zinc oxide and
their amine or thiol functionalized materials are shown in Fig. 3a–i.
All the diffraction peaks are well indexed to the hexagonal ZnO
wurtzite structure (JCPDS no. 36–1451) [37]. Diffraction peaks corre-
sponding to the impurity were not found in the XRD patterns,
confirming high purity of the synthesized products. The mean

Fig. 3. XRD results of: a) ZnO free@SiO2@mSiO2, b) ZnO, c) ZnO@SiO2, d) ZnO@mSiO2, e)

Fig. 1. FTIR spectra of a) pure ZnO b) ZnO@mSiO2 c) ZnO@SiO2@mSiO2 and d) ZnO@SiO2@ ZnO@SiO2@mSiO2, f) ZnO@SiO2@mSiO2–(CH2)3–NH, g) ZnO@mSiO2–(CH2)3–SH, h)
mSiO2–(CH2)3–NH2. ZnO@mSiO2–(CH2)3–NH and i) ZnO free@mSiO2.
 I.M. El-Nahhal et al. / Powder Technology 287 (2016) 439–446 443

Fig. 4. TEM of a) ZnO, b) TEM-EDX of ZnO NPs, c) low resolution TEM of ZnO@mSiO2, d) high resolution TEM of ZnO@mSiO2, e) TEM of ZnO@SiO2, f) TEM of ZnO@SiO2@mSiO2, g) TEM of
ZnO@mSiO2–(CH2)3–SH, h) TEM-EDX of ZnO@mSiO2–(CH2)3–SH, i) TEM of ZnO@mSiO2–(CH2)3–NH2 and j) TEM-EDX of ZnO@mSiO2–(CH2)3–NH2.

crystallite size of ZnO particles was determined by Sherrer's equa-
tion (where D = 0.89λ/β cosθ where D is the crystallite size (nm),
λ is the wavelength of incident X-ray (nm), β is the full width at
half maximum, and θ is the diffraction angle). The obtained particle
size was 13 nm for pure ZnO. There was a small shift to lower angle
width and change in the line width revealing that silica coating was
successfully conducted (Fig. 3b–h). This leads in slight change of
the particle size of the coated zinc oxide. The zinc oxide free silica
(Fig. 3a & i) showed no XRD peaks, this may confirm that complete
removal of zinc oxide nanoparticles form silica coated zinc oxide mi-
crospheres, when treated with hydrochloric acid.
3.5. TEM results
TEM images along with EDX of pure ZnO, ZnO@SiO2, (ZnO@mSiO2
ZnO@SiO2@mSiO2 are given in Fig. 4a–g. TEM image of pure zinc oxide
shows different bar sizes of hexagonal shape of 20–70 nm length and
15–30 nm width (Fig. 4a). The TEM-EDX of ZnO nanomaterial shows
only zinc and oxygen peaks with no silicon is present (Fig. 4b). Fig. 4c
& d illustrates low and high resolution TEM images of ZnO@mSiO2 mi-
crospheres of 300 nm diameter. The meso silica microsphere was evi-
dent from the gray wormlike structure with zinc oxide appearing as
dark nanoparticles (dark color) which were capsulated into silica
444 I.M. El-Nahhal et al. / Powder Technology 287 (2016) 439–446

Fig. 4 (continued).

mesopores as shown in Fig. 4d. The small particles of zinc oxides are TEM-image Fig. 4e, that roughly microspheres of size 260 nm of silica,
probably formed through the ultrasonication process of colloidal solu- in which ZnO nanoparticles are dispersed. EDX confirms the presence
tion in the presence of CTAB, so these small particles are fitted into the of peaks due to components of silicon and oxygen and zinc. In the case
mesopores of the meso silica [22]. For ZnO@SiO2, it can be seen from of ZnO@SiO2@mSiO2 microspheres, it can be seen from TEM

Fig. 5. Thermograms for (a) ZnO@SiO2@mSiO2 and (b) ZnO@SiO2@mSiO2-NH2. Fig. 6. UV/VIS spectra for a) ZnO, b) ZnO@SiO2@mSiO2, and c) ZnO@SiO2.
 I.M. El-Nahhal et al. / Powder Technology 287 (2016) 439–446
Fig. 7. UV/VIS spectra for a) ZnO@SiO2 and b) ZnOfree@SiO2.
image Fig. 4f that zinc oxide nanoparticles of different sizes are dis-
persed only into the silica microspheres and none are present in the
meso silica shell. This is in consistence with experimental work, where
zinc oxide nanoparticles were firstly accommodated into the silica mi-
crosphere, and later coated with a meso silica shell. The size distribution
histogram of ZnO nanoparticles coated silica showed that ca. 85% of ZnO
nanoparticles has mean particle size of 16.1 nm, whereas ca. 8% of ZnO
nanoparticles has particle size of 5 nm and 7% have particle size of
40 nm. The TEM-EDX of ZnOfree@mSiO2 and ZnOfree@SiO2@mSiO2
microspheres showed only the presence of silicon and oxygen and ab-
sence of zinc content which is evident for complete removal of ZnO
core upon treatment with HCl. This also was confirmed by UV/VIS spec-
tra discussed below. The TEM and TEM-EDX images Fig. 4(g & i) and
(h & j) of ZnO@mSiO2–SH and ZnO@mSiO2–NH2 NPs, respectively
showed ZnO core bare covered with distinguishable meso silica layer,
13 nm in thickness covered by thin layer of functionalized thiol-silane
precursor layer, 5 nm in thickness resulting from the condensation of
thiol-silane over the meso silica layer [33,37,38] as marked in Fig. 4g.
This was also evident from TEM-EDX (Figs. i & j) in which the silicon con-
tent has increased from 1.3% for ZnO@mSiO2 to 9.13% after coating with
thiol-silane and the zinc content has decreased from 96% to 68% after.
3.6. TGA analysis
Thermogravimetric analysis (TGA) and differential thermogravimet-
ric analysis (DTA) for ZnO@SiO2@mSiO2 and its amine functionalized
ZnO@SiO2@mSiO2–NH2 nanoparticles were examined under nitrogen
atmosphere at 20–600 °C at rate 10 °C/min. The thermogram of the
ZnO@SiO2@mSiO2 nanomaterial (Fig. 5a) shows two peaks, the main
peak occurs at ~75 °C due to loss of 9.9% of its initial weight. This attrib-
uted to loss of physisorbed water and alcohol from the system pores
[37]. The second peak is at ~390 °C due to loss of 3.6%, which is probably
due to dehydroxylation and loss of water or alcohol from silica [37]. The
total loss of weight was 13.3%. Fig. 5b shows the thermogram of the
ZnO@SiO2@mSiO2–NH2 nanomaterial, three peaks were observed, the
first peak occurs at ~75 °C due to loss of 7.2% of its initial weight. This at-
tributed to loss of physisorbed water and alcohol from the system pores
[37]. The second peak and third peak at 350 °C and at 450 °C, respective-
ly are due to lost of the amine functional groups from the system loss
17.6% and dehydroxylation and loss of water or alcohol from silica [3].
The total loss of weight was 23.8%. The difference between the total
loss of the two materials (10.5%) is probably due to the amine
organofunctional group.
445
3.7. UV/VIS spectra
The UV/VIS spectra for the solution contain ZnO@SiO2 and ZnO@
SiO2@mSiO2 NPs in HY surfactant Fig. 6(a–c). HY surfactant was used
to obtain a homogenous solution of un-coated and coated silica zinc
oxide particles. Two peaks at 359, 290 nm are shown in Fig. 6(a–c),
that characteristic for the presence of ZnO nanoparticles [22,33]. It is
found that there is a decreasing of the absorption band intensities as
the number of shells of coated silica is build up on zinc oxide (ZnO@
SiO2 to ZnO@SiO2@mSiO2). There was a shift of the absorption band at
307 nm for the free uncoated ZnO to shorter wavelength at 290 nm
for ZnO@SiO2 and at 283 nm for ZnO@SiO2@mSiO2 . The blue shift of
the absorption band 307 nm to shorter wavelength is probably due to
decreasing of the particle size. No peaks are observed for the ZnO free
coated silica-mesosilica indicating the absence of the shell core of zinc
oxide (Fig. 7b) when treated with HCl acid in comparison with that of
ZnO@SiO2(Fig. 7b).
4. Conclusion
Silica or meso silica or both silica coated ZnO microspheres were
synthesized by modified Stöber method. The ZnO particles are dis-
persed into the silica microspheres or into the mesopores of the meso
silica shell confirmed from TEM analysis. Functionalized of the meso sil-
ica shell with amine or thiol silane coupling agent, two shells, meso and
functional silica layers of 13 nm and 5 nm thickness are formed, respec-
tively. XRD results found for free ZnO NPs and the silica coated zinc
oxide materials showed hexagonal ZnO wurtzite structure with mean
average crystallite size of 13 nm. Zinc oxide free silica materials which
have low density silica spheres showed no XRD peaks due to complete
etching of core ZnO. TGA and FTIR spectra revealed that the amine and
thiol organofunctional groups are covalently attached to the meso silica
layer. TGA revealed that 10.5% of the weight of the functionalized coated
silica zinc oxide is due to organofunctional groups. These materials have
been testing for removal of toxic of heavy metals and dyes as proposed
coming further research.
References
[1] Q.B. Meng, K. Takahashi, X.T. Zhang, I. Sutanto, T.N. Rao, O. Sato, A. Fujishima, H.
Watanabe, T. Nakamori, M. Uragami, Fabrication of an efficient solid-state dye-sen-
sitized solar cell, Langmuir 19 (2003) 3572–3574.
[2] L.F. Dong, J. Jiao, D.W. Tuggle, J.M. Petty, S.A. Elliff, M. Coulter, ZnO nanowires formed
on tungsten substrates and their electron field emission properties, Appl. Phys. Lett.
82 (2003) 1096–1098.
[3] A. Shimizu, S. Chaisistsak, T. Sugiyama, A. Yamada, M. Konagai, Synthesis of silica
coated zinc oxide–poly(ethylene-co-acrylic acid) matrix and its UV shielding evalu-
ation, Thin Solid Films 361 (2000) 193–197.
[4] M.L. Curridal, R. Comparelli, P.D. Cozzli, G. Mascolo, A. Agostiano, Colloidal oxide
nanoparticles for the photocatalytic degradation of organic dye, Mater. Sci. Eng.
C23 (2003) 285–289.
[5] V.P. Kamat, R. Huehn, R. Nicolaescu, J. Phys. Chem. B 106 (2002) 788–794.
[6] T. Gao, T.H. Wang, Synthesis and properties of multipod-shaped ZnO nanorods for
gas-sensor applications, Appl. Phys. A 80 (2005) 1451–1454.
[7] R.S. Yadav, P. Mishra, A.C. Pandey, Growth mechanism and optical property of ZnO
nanoparticles synthesized by sonochemical, Ultrason. Sonochem. 15 (2008)
863–868.
[8] N. Jones, B. Ray, K.T. Ranjit, A.C. Manna, Antibacterial activity of ZnO nanoparticle
suspensions on a broad spectrum of microorganisms, FEMS Microbiol. Lett. 279
(2008) 71–76.
[9] G. Singh, E.M. Joyce, J. Beddow, T.J. Mason, Evaluation of antibacterial activity of ZnO
nanoparticles coated sonochemically onto textile fabrics, J. Microbiol. Biotechnol.
Food Sci. 2 (2012) 106–120.
[10] P.T. Kumar, V.K. Lakshmanan, R. Biswas, S.V. Nair, R. Jayakumar, Synthesis and bio-
logical evaluation of chitin hydrogel/nano ZnO composite bandage as antibacterial
wound dressing, J. Biomed. Nanotechnol. 8 (2012) 891–900.
[11] X. Tang, E.S. Choo, L. Li, J. Ding, J. Xue, Synthesis of ZnO nanoparticles with tunable
emission colors and … via a polyol hydrolysis route and their cell labeling applica-
tions, Langmuir 25 (2009) 5271–5275.
[12] A.S. Dussert, E. Gooris, J. Hemmerle, Characterization of the mineral content of a
physical sunscreen emulsion and its distribution onto human stratum corneum,
Int. J. Cosmet. Sci. 19 (1997) 119-12.
[13] Y.H. Ni, X.W. Wei, J.M. Hong, Y. Ye, Hydrothermal synthesis and optical properties of
ZnO nanorods, Mater. Sci. Eng. B Solid State Mater. Adv. Technol. 121 (2005) 42–47.
446 I.M. El-Nahhal et al. / Powder Technology 287 (2016) 439–446
[14] S. Chang, S.O. Yoon, H.J. Park, A. Sakai, Luminescence properties of Zn nanowires
prepared by electrochemical etching, Mater. Lett. 53 (2002) 432–436.
[15] M. Ristiac, S. Musiac, M. Ivanda, S. Popoviac, Sol–gel synthesis and characterization
of nanocrystalline ZnO powders, J. Alloys Compd. 397 (2005) L1–L4.
[16] J.J. Wu, S.C. Liu, Low-temperature growth of well-aligned ZnO nanorods by chemical
vapor deposition, Adv. Mater. 14 (2002) 215–218.
[17] R.C. Wang, C.C. Tsai, Efficient synthesis of ZnO nanoparticles, nanowalls, and nano-
wires by thermal decomposition of zinc acetate at a low temperature, Appl. Phys.
A 94 (2009) 241–245.
[18] D.G. Lamas, G.E. Lascalea, N.E. Walsoc, Synthesis and characterization of nanocrys-
talline powders for partially stabilized zirconia ceramics, J. Eur. Ceram. Soc. 18
(1998) 1217–1221.
[19] S. Badhuri, S.B. Badhuri, Enhanced low temperature toughness of Al2O3–ZrO2 nano/
nano composites, Nanostruct. Mater. 8 (1997) 755–763.
[20] Z. Khorsand, A. Abid, W.H. Majid, H.Z. Wang, R. Yousefi, M. Golsheikh, Z.F. Ren,
Sonochemical synthesis of hierarchical ZnO nanostructures, Ultrason. Sonochem.
20 (2013) 395–400.
[21] O. Singh, N. Kohli, R.C. Singh, Precursor controlled morphology of zinc oxide and its
sensing behavior, Sens. Actuators B 178 (2013) 149–154.
[22] J. Wang, T. Tsuzuki, B. Tang, P. Cizek, L. Sun, X. Wang, Synthesis of silica-coated ZnO
nanocomposite, the resonance structure of polyvinyl pyrrolidone (PVP) as a cou-
pling agent, Colloid Polym. Sci. 288 (2010) 1705–1711.
[23] L. Spanhel, Colloidal ZnO nanostructures and functional coatings: a survey, J. Sol-Gel
Sci. Technol. 39 (2006) 7–24.
[24] M. Bitenc, G. Draži, Z. Crnjak, Orel, characterization of crystalline zinc oxide in the
form of hexagonal bipods, Cryst. Growth Des. 10 (2010) 830–837.
[25] K. Han, Z. Zhao, Z. Xiang, C. Wang, J. Zhang, B. Yang, The sol–gel preparation of ZnO/
silica core-shell composites and hollow silica structure, Mater. Lett. 61 (2007)
363–368.
[26] J.F. Wang, T. Tsuzuki, L. Sun, X.G. Wang, Reducing the photocatalytic activity of zinc
oxide quantum dots by surface modification, J. Am. Ceram. Soc. 922 (2009)
083–2088.
[27] D.K. Yi, A study of optothermal and cytotoxic properties of silica coated Au nano-
rods, Mater. Lett. 65 (2011) 2319–2321.
[28] M. Nakade, M. Ogawa, J. Mater. Sci. Technol. 42 (2007) 4254–4259.
[29] R. Gerhard, H. Werner, P. Holger, S. Heinrich, H.K. Seidlitz, H. Hohn, Elevated UV-B
radiation reduces genome stability in plants, Nature 406 (2000) 98–101.
[30] L. Fernandez, N. Garro, E.J. Haskouri, M. Perez-Cabero, J. Alvarez- Rodriguez, J.
Latorre, C. Guillem, A. Beltran, D. Beltran, P. Amoros, Mesosynthesis of ZnO–SiO2 po-
rous nanocomposites with low-defect ZnO nanometric domains, Nanotechnology
19 (2008) 10.
[31] C. Graf, D.L.J. Vossen, I. Arnout, A.V. Blaaderen, A general method to coat colloidal
particles with silica, Langmuir 19 (2003) 6693–6700.
[32] E.J. Tang, S.Y. Dong, Preparation of styrene polymer/ZnO nanocomposite latex via
miniemulsion polymerization and its antibacterial property, Colloid Polym. Sci.
287 (2009) 1025–1032.
[33] Mohankandhasamy Ramasamy, Yu Jun Kim, Haiyan Gao, Dong Kee Yi, Jeong Ho An,
Synthesis of silica coated zinc oxide–poly(ethylene-co-acrylic acid) matrix and its
UV shielding evaluation, Mater. Res. Bull. 51 (2014) 85–91.
[34] C.M. Halliwell, A.E.G. Cass, A factorial analysis of silanization conditions for the im-
mobilization of oligonucleotides on glass surfaces, Anal. Chem. 73 (2001)
2476–2483.
[35] P.B. Lihitkar, S. Violet, M. Shirolkar, J. Singh, O.N. Srivastava, R.H. Naik, S.K. Kulkarni,
Confinement of zinc oxide nanoparticles in ordered mesoporous silica MCM-41,
Mater. Chem. Phys. 133 (2012) 850–856.
[36] J.J. Yang, I.M. E1-Nahhal, G.E. Maciel, Synthesis and solid-state NMR structural char-
acterization of some functionalized polysiloxanes, J. Non-Cryst. Solids 204 (1996)
105–117.
[37] Y.-S. Li, J.S. Church, A.L. Woodhead, F. Moussa, Preparation and characterization of
silica coated iron oxide magnetic nano-particles, Spectrochim. Acta A 76 (2010)
484–489.
[38] D. Japi, I. Djerdj, M. Marinek, Z.C. Orel, In situ and ex situ TEOS coating of ZnO nano-
particles and the preparation of composite ZnO/PMMA for UV–VIS absorbers, Acta
Chim. Slov. 60 (2013) 797–806.