nanomaterials

Article
Preparation and Characterization of ZnO
Nanoparticles Supported on Amorphous SiO2
Ying Chen, Hao Ding * and Sijia Sun
Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory
of Mineral Materials, School of Materials Science and Technology, China University of Geosciences (Beijing),
Beijing 100083, China; chenying@cugb.edu.cn (Y.C.); 1012122105@cugb.edu.cn (S.S.)
* Correspondence: dinghao113@126.com; Tel.: +86-010-8232-2982

Received: 30 June 2017; Accepted: 24 July 2017; Published: 10 August 2017

Abstract: In order to reduce the primary particle size of zinc oxide (ZnO) and eliminate the
agglomeration phenomenon to form a monodisperse state, Zn2+ was loaded on the surface
of amorphous silica (SiO2 ) by the hydrogen bond association between hydroxyl groups in the
hydrothermal process. After calcining the precursors, dehydration condensation among hydroxyl
groups occurred and ZnO nanoparticles supported on amorphous SiO2 (ZnO–SiO2 ) were prepared.
Furthermore, the SEM and TEM observations showed that ZnO nanoparticles with a particle size of
3–8 nm were uniformly and dispersedly loaded on the surface of amorphous SiO2 . Compared with
pure ZnO, ZnO–SiO2 showed a much better antibacterial performance in the minimum inhibitory
concentration (MIC) test and the antibacterial properties of the paint adding ZnO–SiO2 composite.

Keywords: amorphous SiO2 ; load; monodisperse; ZnO nanoparticle; antibacterial

1. Introduction
Antimicrobial tests and environmental toxicity tests have been widely explored in order to
improve health, safety, and the environment [1–3]. Zinc oxide (ZnO), as a semiconductor material with
a band gap of 3.3 eV at room temperature [4], has high chemical stability, strong photosensitivity and
non-toxicity property and is widely used in antibacterial materials [5]. Compared with ordinary ZnO
powder, ZnO nanoparticles have a large specific surface area and small size effect, and show wide
application potential in microbial inhibition and mildew removal [6,7].
However, like most of the nanoparticles, ZnO nanoparticles are prone to forming serious
agglomeration, including hard agglomeration among the particles formed via the chemical reaction
of the surface groups and soft agglomeration formed by other physical effects [8]. It is difficult
to depolymerize the particles involved in hard agglomeration. Therefore, the apparent grain size
of the primary ZnO particles tends to increase to the micron scale and the normal performance of
ZnO nanoparticles is inhibited. In the preparation process of ZnO nanoparticles, in addition to the
control of the ZnO morphology and primary particle size, the agglomeration phenomenon of ZnO
particles should be suppressed to obtain dispersed nanoparticles. Wang et al. synthesized the doped
ZnO nanoparticles with the mixture of alcohol and water as the solvent according to a precipitation
method [9]. Chen et al. prepared ZnO nanocrystals via the reaction of zinc stearate with excessive
alcohol in the hydrocarbon solvent [10]. Weller et al. used the low-temperature solvent thermal method
to synthesize dispersible spherical ZnO nanoparticles and nano-rods with zinc acetate as precursors in
methanol [11]. However, these methods have low synthesis performance and limited control ability.
Especially, the solvent thermal process [12,13] is required to deal with organic solvents and it is difficult
to realize industrial production. Therefore, some nanoparticles (such as titanium dioxide, TiO2 ) [14,15]
are supported on the surface or pores of the inorganic carrier. In this way, the strong interaction
between the carrier surface and nanoparticles, and the forced isolation among the carrier particles

Nanomaterials 2017, 7, 217; doi:10.3390/nano7080217 www.mdpi.com/journal/nanomaterials

 Nanomaterials2017,
Nanomaterials 2017,7,7,217
217 22ofof12
12

strong interaction between the carrier surface and nanoparticles, and the forced isolation among the
efficiently preventefficiently
carrier particles the agglomeration
prevent the among the nanoparticles
agglomeration among theandnanoparticles
improve the and
dispersion
improve effects
the
and functions.
dispersion effects and functions.
AmorphousSiO
Amorphous SiO22,, commercially
commercially known as white carbon black, is an aggregate aggregate ofof SiO
SiO22 particles
particles
(SiO
(SiO 2 ·2 ·nH
nH 22 O)
O) and
and commonly
commonly used
used as
as a rubber reinforcing additive [16,17]. The
The primary
primary particle
particle size
sizeofof
SiO
SiO 2 2 particles
particles is
is generally
generally 10–100
10–100 nm.
nm. SiO
SiO 2
2 particles containing
containing rich
rich Si–OH
Si–OH groups,
groups, which
which can
can form
form aa
stronginteraction
strong interactionbetween
betweenthe theSiO
SiO22 carrier
carrier surface and Zn–OH (precursors
(precursors of of ZnO).
ZnO).This
Thisinteraction
interaction
reducesthe
reduces thecombination
combination betweenbetween Zn–OH
Zn–OH and and prevents
prevents its aggregation,
aggregation, thus
thus contributing
contributing to to the
the
formation of monodisperse ZnO nanoparticles. In addition, small amorphous
formation of monodisperse ZnO nanoparticles. In addition, small amorphous SiO2 particles have high SiO 2 particles have
high dispensability
dispensability and canand can further
prevent preventagglomeration
further agglomeration
of ZnO–SiO of2 ZnO–SiO
composite. 2 composite. Therefore,
Therefore, amorphous
amorphous
SiO 2 was SiO
selected 2 was
as selected
the carrieras
ofthe carrier
supported of supported
ZnO ZnO
nanoparticles.nanoparticles.
Basedon
Based onthe
theabove
aboveresults,
results,
in in this
this paper,
paper, thethe environmentally
environmentally friendly
friendly hydrothermal
hydrothermal method
method was
was adopted to prepare ZnO–SiO by loading
2+ Zn 2+ on the surface of amorphous SiO2 and calcining
adopted to prepare ZnO–SiO2 by loading Zn on the surface of amorphous SiO2 and calcining active
2

active products
products at high temperatures.
at high temperatures. Moreover, Moreover, the structures
the structures and antibacterial
and antibacterial properties
properties of as-
of as-prepared
prepared ZnO–SiO
ZnO–SiO2 were explored. 2 were explored.

2.2.Experimental
ExperimentalProcedure
Procedure

2.1.
2.1.Materials
Materials
InInthis
thisstudy,
study,amorphous
amorphous SiO SiO22 was
was purchased
purchased from Henan Henan Jiaozuo
Jiaozuo Fluoride
Fluoride New New Energy
Energy
TechnologyCo.,
Technology Co.,Ltd Ltd(Jiaozuo,
(Jiaozuo,Henan,
Henan, China).
China). The properties of amorphous
amorphous SiO SiO22 are
are described
describedas as
follows:SiO
follows: SiO
2 content
content
2 of of 96.63%,
96.63%, whiteness
whiteness of of 96.76%,
96.76%, average
average aggregate
aggregate size size
of 20 of
µm, 20 μm,
primary primary
particle
particle
size size nm,
of 20–30 of 20–30 nm, andsurface
and specific specificarea
surface aream
of 59.54 of2 /g.
59.54 m2/g.
Zinc Zinc (Zn(NO
nitrate nitrate (Zn(NO 3)2·6H
3 )2 ·6H2 O) O) as
as 2the the
source
ofsource2+
Zn was of Zn 2+
from was fromYili
Beijing Beijing
Fine Yili Fine Chemical
Chemical Co., LtdChina).
Co., Ltd (Beijing, (Beijing,Sodium
China).polyacrylate
Sodium polyacrylate
(PAAS) as
a(PAAS)
dispersant as awas
dispersant
suppliedwas supplied byRun
by Changzhou Changzhou Run Yang
Yang Chemical Chemical
Co., Ltd Co., LtdJiangsu,
(Changzhou, (Changzhou,
China).
Jiangsu, China). Pure ZnO, as an antibacterial agent, was compared with the
Pure ZnO, as an antibacterial agent, was compared with the ZnO–SiO2 composite in antibacterial ZnO–SiO 2 composite in
antibacterial performance. It was produced by the Xi Long Chemical
performance. It was produced by the Xi Long Chemical Co., Ltd (Guangzhou, Guangdong, China) Co., Ltd (Guangzhou,
Guangdong,
and the size ofChina) and thewas
the particles sizeabout
of the200
particles was about
nm. Figure 1 shows200SEM
nm. images
Figure 1ofshows SEM images
amorphous of
SiO2 and
amorphous
pure ZnO. SiO 2 and pure ZnO.

Figure1.1.Micrographs
Figure Micrographsof
of(a,c)
(a,c) amorphous
amorphous SiO and (b)
SiO22 and (b) pure
pureZnO.
ZnO.

2.2.ZnO–SiO
2.2. ZnO–SiO22Precursor
Precursor
AmorphousSiO
Amorphous SiO22,, sodium
sodium polyacrylate
polyacrylate (1% of the weight of SiO22)) and and HH22OO were
were mixed
mixedandand
stirredtotoprepare
stirred preparethethe suspension
suspension with
with solid
solid content
content of 18%.
of 18%. Ceramic
Ceramic polishing
polishing ballsballs (diameter:
(diameter: 1–3
1–3 mm)
mm)added
were were added intosuspension
into the the suspension according
according to the
to the proportion
proportion of of
50%50%ofofthe
thesolid
solid content
content and
andthen
then
stirredatataaspeed
stirred speedofof1000
1000r/min
r/min for
for 11 h
h to
to prepare
prepare the
the depolymerized
depolymerized amorphous
amorphous SiO SiO22slurry.
slurry.AAzinc
zinc
nitratesolution
nitrate solution(0.09
(0.09 wt
wt %)%) was
was added
added into
into the
the slurry
slurry and
and the
the pH
pH ofof the
the mixture
mixture was
was respectively
respectively
 Nanomaterials 2017, 7, 217 3 of 12
Nanomaterials 2017, 7, 217 3 of 12

adjusted ◦
adjusted toto5.0
5.0and
and7.07.0by
byadding
adding 66 mol/L
mol/LNaOH
NaOH and and 66 mol/L HNO33.. The
mol/L HNO The mixture
mixture was
was stirred
stirredatat60
60 C
°Cfor
for11h.
h. The
The precursors were obtained
precursors were obtained after
after suction
suctionfiltration,
filtration,washing,
washing,and
anddrying
dryingand
and denoted
denoted asas
Zn–SiO
Zn–SiO 2 -pH5.0
2-pH5.0 (the
(the precursor
precursor was
was prepared
prepared with
with pHpH value
value at at 5.0)
5.0) andand Zn–SiO
Zn–SiO 2 -pH7.0
2-pH7.0 (the
(the precursor
precursor
was prepared with pH value at 7.0) respectively. The preparation process is shown in Figure 2.2.
was prepared with pH value at 7.0) respectively. The preparation process is shown in Figure

2.3.
2.3. Preparation
Preparation of of ZnO–SiO
ZnO–SiO 2 2

The precursors Zn–SiO ◦ C for 1 h to obtain the

The precursors Zn–SiO 2 -pH5.0
2-pH5.0 andand Zn-SiO
Zn-SiO 2 -pH7.0
2-pH7.0
were
were calcined
calcined at at
400400
°C for 1 h to obtain the
composite
composite particles
particles ofof ZnO
ZnO andSiO
and SiO 2 and
2 and
denoted
denoted asasZnO–SiO
ZnO–SiO 2 -pH5.0
2-pH5.0
(the
(the composite
composite obtained
obtained byby
calciningthe
calcining the precursor
precursor which
whichwas wasprepared with
prepared pH value
with at 5.0)atand
pH value ZnO–SiO
5.0) 2 -pH7.0 2(the
and ZnO–SiO composite
-pH7.0 (the
obtained by calcining the precursor which was prepared with pH value at 7.0).
composite obtained by calcining the precursor which was prepared with pH value at 7.0). The The loads of ZnO were
loads
4.51 and 11.26%, respectively.
of ZnO were 4.51% and 11.26%, respectively.

Figure 2. Preparation of composite particles of ZnO–SiO2 precursor.

Figure 2. Preparation of composite particles of ZnO–SiO2 precursor.

2.4.
2.4. Characterization
Characterization
The
The X-ray
X-ray diffraction
diffraction (XRD)
(XRD) was
was measured
measured byby using
using a D/max-Ra
a D/max-Ra X-ray
X-ray diffractometer
diffractometer (Ouyatu,
(Ouyatu,
Japan, Cu Kα radiation = 1.54 Å) in an angular range of 10–80 ◦ (2θ) with a step of 0.02◦ (2θ). Scherer
Japan, Cu Kα radiation = 1.54 Å) in an angular range of 10–80° (2θ) with a step of 0.02° (2θ). Scherer
Equation
Equation [18]
[18] is is used
used toto calculate
calculate the
the average
average grain
grain size
size ofof ZnO
ZnO nanoparticles:
nanoparticles:

= Kλ,, (1)(1)
β=
Dcosθ 00
where K is the shape factor constant (0.94); λ is X-ray wavelength; D is the grain size; θ is the
where K is the shape factor constant (0.94); λ is X-ray wavelength; D is the grain size; θ is the diffraction
diffraction angle; β is the diffraction peak half width.
angle; β is the diffraction peak half width.
An X-ray fluorescence spectrometer (XRF Shimadzu-1800, Kyoto, Japan) was used to analyze
An X-ray fluorescence spectrometer (XRF Shimadzu-1800, Kyoto, Japan) was used to analyze the
the oxide content of samples. The particle size and size distribution of the composite particles of ZnO
oxide content of samples. The particle size and size distribution of the composite particles of ZnO
and SiO2 were characterized by transmission electron microscopy (TEM FEI Tecnai G220, Portland,
and SiO were characterized by transmission electron microscopy (TEM FEI Tecnai G220, Portland,
OR, USA).2 Scanning electron microscopy (SEM) was used to explore the morphology of ZnO–SiO2
OR, USA). Scanning electron microscopy (SEM) was used to explore the morphology of ZnO–SiO2 by
by a Hitachi field emission scanning electron microscope (Hitachi S4800, Tokyo, Japan) under the
a Hitachi field emission scanning electron microscope (Hitachi S4800, Tokyo, Japan) under the voltage
voltage of 10 kV. The Fourier transform infrared spectroscopy (FTIR, Madison, WI, USA)
of 10 kV. The Fourier transform infrared spectroscopy (FTIR, Madison, WI, USA) measurement was
measurement was carried out to explore the changes in functional groups of ZnO-SiO2 by Nicolet
carried out to explore the changes in functional groups of ZnO-SiO2 by Nicolet IS50. The samples
IS50. The samples were finely pulverized and then diluted in dried KBr to form a homogeneous
were finely pulverized and then diluted in dried KBr to form a homogeneous mixture according to the
mixture according to the sample-KBr ratio of 1/200. The X-ray photoelectron spectroscopy (XPS,
sample-KBr ratio of 1/200. The X-ray photoelectron spectroscopy (XPS, Manchester, UK) measurement
Manchester, UK) measurement was conducted on an Axis Ultra spectrometer with monochromatic
was conducted on an Axis Ultra spectrometer with monochromatic Mg Kα (1253.6 eV) radiation to
Mg Kα (1253.6 eV) radiation to investigate the valence state of Zn.
investigate the valence state of Zn.
2.5. Antimicrobial Test
2.5. Antimicrobial Test
The antimicrobial ability of ZnO–SiO2 under dark conditions was investigated through
The antimicrobial ability of ZnO–SiO2 under dark conditions was investigated through
antibacterial tests [19–21]. Different concentrations of ZnO–SiO2-pH5.0, ZnO–SiO2-pH7.0, and pure
antibacterial tests [19–21]. Different concentrations of ZnO–SiO2 -pH5.0, ZnO–SiO2 -pH7.0, and pure
ZnO were added to the agar medium, and then E. coli (CGMCC 1.2385) was inoculated on the
medium to observe the growth of bacteria and determine the minimum inhibitory concentration
(MIC) [22].
Nanomaterials 2017, 7, 217 4 of 12

ZnO were added to the agar medium, and then E. coli (CGMCC 1.2385) was inoculated on the medium
Nanomaterials 2017, 7, 217 4 of 12
to observe the growth of bacteria and determine the minimum inhibitory concentration (MIC) [22].
The antimicrobial coating was obtained by mixing 12 wt % styrene-acrylic emulsion, 34 wt %
The antimicrobial coating was obtained by mixing 12 wt % styrene-acrylic emulsion, 34 wt % of
of H2 O, 50 wt % of the filler (0–8 wt % of ZnO–SiO2 -pH7.0), and 4 wt % of paint additive.
H2O, 50 wt % of the filler (0–8 wt % of ZnO–SiO2-pH7.0), and 4 wt % of paint additive. The
The antibacterial property of ZnO–SiO2 was evaluated by testing the antibacterial property of the
antibacterial property of ZnO–SiO2 was evaluated by testing the antibacterial property of the coating.
coating. The antibacterial rate of the coating was tested according to Chinese national standard
The antibacterial rate of the coating was tested according to Chinese national standard GB/T21866-
GB/T21866-2008 [23]. The antibacterial rate (R) is calculated as:
2008 [23]. The antibacterial rate (R) is calculated as:
R=
R 100% × ×(A(A−−B)/A,
= 100% B)/A, (2)
(2)
where
where AA and
and BB are
are the
the average
average number
number of
of colonies
colonies of
of the
theblank
blankcontrol
control plate
plateand
andantibacterial
antibacterial coating
coating
plate
plate after
after 24
24 h.
h.

3.
3. Results
Resultsand
andDiscussion
Discussion

3.1.
3.1. Structure
Structure and
and Characterization
Characterization of
of ZnO–SiO
ZnO–SiO22

3.1.1. Phase
3.1.1. Phaseand
and Chemical
Chemical Constitution
Constitution of
of ZnO–SiO
ZnO–SiO22
Figure 33 shows
Figure shows the
the XRD
XRD patterns
patterns of of ZnO–SiO
ZnO–SiO22. .Table
Table11shows
showsthetheXRF
XRFresults
resultsofofeach
eachsample.
sample.
The XRD
XRDpattern
patternofofthethe SiO ◦
The SiO 2 carrier
2 carrier shows
shows a strong
a strong bread bread
peakpeak
nearnear
2θ of2θ of indicating
23°, 23 , indicating
that thethat the
main
phase is an amorphous phase corresponding to amorphous SiO2. In the XRD patterns of ZnO–SiOof
main phase is an amorphous phase corresponding to amorphous SiO 2 . In the XRD patterns 2-
ZnO–SiO
pH5.0 and2 -pH5.0
ZnO–SiO and ZnO–SiO
2-pH7.0, -pH7.0, in
in 2addition to addition to the above-mentioned
the above-mentioned peak reflecting peak
thereflecting
amorphous the
amorphous
phase, phase,
the peaks at the peaks
31.8°, 34.5°, 31.8◦ , and
at 36.3°, 34.5◦47.5° ◦ , and 47.5◦ correspond to the ZnO diffraction
, 36.3correspond to the ZnO diffraction peak [24,25],
peak [24,25], indicating that Zn 2+ has been transformed into ZnO after the thermal
indicating that Zn has been transformed into ZnO after the thermal
2+ reaction with thereaction with
SiO2 carrier
the SiO
and 2 carrier and
calcination. The calcination.
ZnO diffraction The intensity
ZnO diffraction
of ZnO–SiOintensity of ZnO–SiO
2-pH7.0 2 -pH7.0 was
was significantly significantly
larger than that
larger
of than 2that
ZnO–SiO of ZnO–SiO
-pH5.0 due to the 2 -pH5.0
differentdueloadings
to the different
of ZnO. loadings of ZnO.
The contents of ZnO Thein contents
ZnO–SiO of 2ZnO in
-pH5.0
ZnO–SiO
and ZnO–SiO 2 -pH5.0 and ZnO–SiO
2-pH7.0 are respectively2 -pH7.0 are respectively 4.51 and 11.26% (Table
4.51 and 11.26% (Table 1). The SiO2 content in ZnO–SiO1). The SiO 2 content in
2-pH5.0
ZnO–SiO
is 2 -pH5.0
lower than that is
inlower than2-pH7.0.
ZnO–SiO that in ZnO–SiO
The results2 -pH7.0. The results
are consistent are the
with consistent
XRD results.with the XRD results.

Figure 3. XRD of (a) amorphous SiO22;; (b)

(b) ZnO–SiO
ZnO–SiO22-pH5.0;
-pH5.0;and
and(c)
(c)ZnO–SiO
ZnO–SiO22-pH7.0.
-pH7.0.
Nanomaterials 2017, 7, 217 5 of 12

Nanomaterials 2017, 7, 217 5 of 12

Table 1. XRF of amorphous SiO2 , ZnO–SiO2 -pH5.0 and ZnO–SiO2 -pH7.0.
Table 1. XRF of amorphous SiO2, ZnO–SiO2-pH5.0 and ZnO–SiO2-pH7.0.
Samples SiO2 /% ZnO/% Na2 O/%
Samples SiO2/% ZnO/% Na2O/%
amorphous SiO2 96.63 0 0.98
amorphous SiO2 96.63 0 0.98
ZnO–SiO2 -pH5.0 92.78 4.51 1.05
ZnO–SiO2-pH5.0 ZnO–SiO292.78
-pH7.0 84.22 4.51
11.26 2.68 1.05
ZnO–SiO2-pH7.0 84.22 11.26 2.68

According
According to
tothe
the XRD
XRD data
data in
in Figure
Figure 3,
3, the
the grain
grain size
size of
of ZnO–SiO -pH7.0was
ZnO–SiO22-pH7.0 wascalculated
calculatedtotobe
be
3.63
3.63nm
nmaccording
accordingtotothe
theScherer
Scherer Equation.
Equation.
3.1.2. Microstructure of ZnO–SiO2
3.1.2. Microstructure of ZnO–SiO2
Figure 4 shows the distribution of three elements (O, Si, and Zn) in ZnO–SiO2 -pH5.0 and
Figure 4 shows the distribution of three elements (O, Si, and Zn) in ZnO–SiO2-pH5.0 and ZnO–
ZnO–SiO2 -pH7.0. The distributions of these three elements are consistent with the distribution
SiO2-pH7.0. The distributions of these three elements are consistent with the distribution of ZnO–
of ZnO–SiO2 particles. The distribution densities of O and Si are larger than that of Zn. The Zn density
SiO2 particles. The distribution densities of O and Si are larger than that of Zn. The Zn density in the
inelemental
the elemental distribution
distribution of ZnO–SiO
of ZnO–SiO 2 -pH7.0 is greater than that of ZnO–SiO2 -pH5.0. The results
2-pH7.0 is greater than that of ZnO–SiO2-pH5.0. The results
indicate
indicate that
that the
the main
main components
components of of ZnO–SiO
ZnO–SiO22 are are SiO
SiO22.. The
Thecontent
contentofofZnOZnOisislow,low,butbutevenly
evenly
distributed on the surface of SiO
distributed on the surface of SiO22 particles.particles.
Figure
Figure 55 shows
showsthethe TEM TEMimagesimages
of theofamorphous
the amorphous SiO2ZnO–SiO
SiO2 carrier, carrier, 2-pH5.0,
ZnO–SiO and2 -pH5.0,
ZnO–SiO and
2-
ZnO–SiO 2 -pH7.0. At a small scale, all the samples are regular particle aggregates.
pH7.0. At a small scale, all the samples are regular particle aggregates. The particle size is about 20– The particle
size is about
30 nm. 20–30these
Although nm. particles
Although these particles
overlap each other, overlap each other,
the overall the overall
dispersion effect isdispersion
good. These effect
unitis
good. These
particles areunit particles
obviously are obviously
amorphous SiO2 amorphous
particles. AtSiO particles.
the2 scale of 10Atnm,thethe
scale of 10morphology
surface nm, the surface of
morphology of
SiO2 particles in theSiO particles in the SiO
2 SiO2 carrier is uniform, 2 carrier is uniform, indicating that no other material
indicating that no other material is loaded. At the scale is loaded.
Atof the scale
2 nm, onlyof homogeneous
2 nm, only homogeneous
non-crystal phase non-crystal phase
particles are particles
observed.are observed.
Dark spots with Dark spots
a size of with
3–8
anmsizeare
of uniformly
3–8 nm aredistributed
uniformlyin distributed
ZnO–SiO2-PH5.0in ZnO–SiO 2 -PH5.0 and
and ZnO–SiO ZnO–SiO
2-pH7.0 -pH7.0
at the 2scale at the
of 10 nm.scale
Theseof
10 nm.spots
dark Theseare dark spotsphase
crystal are crystal
particlesphase particles
at the largerat the larger magnification.
magnification. The stripe
The stripe spacing canspacing can
reflect the
reflect
latticethe
size.lattice size. The
The stripe stripeofspacing
spacing ZnO–SiO of2-pH5.0
ZnO–SiO and2 -pH5.0
ZnO–SiO and2-pH7.0
ZnO–SiO -pH7.0 are respectively
are2 respectively measured
measured
to be 2.45toand be 2.45
2.59and
nm.2.59 nm.(101)
ZnO ZnO plane
(101) plane
spacingspacing
and and ZnOZnO (002)
(002) plane
plane spacing
spacing arerespectively
are respectively
measured
measuredtotobe be2.45
2.45and
and2.59
2.59Å,Å,which
whichare arealmost
almostconsistent
consistentwith withstandard
standardZnO ZnO(101)
(101)plane
planespacing
spacingof
2.47 Å and
of 2.47 Å and ZnO ZnO(002) plane
(002) planespacing
spacing ofof2.60
2.60ÅÅ(ICDD
(ICDDcard card##89-7102).
89-7102). These datadata indicate
indicatethat
thatthese
these
ZnO
ZnOnanoparticles
nanoparticles were monodispersedly
monodispersedlyloaded loadedon onthetheSiO
SiO surface.
2 surface.
2 TheThe
sizesize
of of
ZnO ZnO particles
particles is 3–is
3–8 nm, which is consistent with the average particle size of 3.63 nm obtained
8 nm, which is consistent with the average particle size of 3.63 nm obtained in the XRD test [18]. in the XRD test [18].

Figure4.
Figure 4. SEM
SEM images
images of
of ZnO–SiO
ZnO–SiO22 and
and corresponding
correspondingmapping
mappingresults.
results.
Nanomaterials 2017, 7, 217 6 of 12
Nanomaterials 2017, 7, 217 6 of 12

Figure 5.5.TEM
Figure TEMmaps
mapsofof
(a)(a)
amorphous SiO2SiO
amorphous ; (b)
2; ZnO–SiO2 -pH5.0;
(b) ZnO–SiO (c) ZnO–SiO
2-pH5.0; 2 -pH7.0
(c) ZnO–SiO at different
2-pH7.0 scales.
at different
scales.
3.1.3. Formation Mechanism of ZnO–SiO2
3.1.3. Formation Mechanism of ZnO–SiO2
Figure 6 shows the XPS pattern between 1015 and 1050 eV of the ZnO–SiO2 . The peaks of
Figure
ZnO–SiO 6 shows
2 -pH5.0 andthe XPS pattern
ZnO–SiO 2 -pH7.0 between
at 1046.01015 andand 1045.51050eVeV of the ZnO–SiO
correspond to Zn2p21/2 . The peaksthe
orbital; of peaks
ZnO–
SiO -pH5.0 and ZnO–SiO -pH7.0 at 1046.0 and 1045.5 eV correspond
at 1023.0 and 1022.5 eV correspond to the Zn2p3/2 orbital [26]. These peaks are equivalent to the
2 2 to Zn2p 1/2 orbital; the peaks at
1023.0
2p 1/2 andand2p 1022.5
3/2 energy eV correspond
peaks (1044.2 to theand Zn2p
1021.23/2 orbital
eV) of[26].ZnOThese peaks are equivalent
[27]. Moreover, the energy to the 2p1/2
difference
and 2p3/2Zn2p
between energy 1/2 peaks
and (1044.2
Zn2p 3/2 and
orbitals1021.2is 23eV)
eV, of ZnO
which [27].
is the Moreover,
same as the
that energy
of ZnO. difference
Therefore, between
it can be
Zn2p and Zn2p orbitals is 23 eV, which is the same as that
determined that the valence of Zn in ZnO–SiO2 -pH5.0 and ZnO–SiO2 -pH7.0 is +2, which is consistent
1/2 3/2 of ZnO. Therefore, it can be determined
that the results
with valenceofofXRD, Zn inXRF, ZnO–SiOand TEM. 2-pH5.0 and ZnO–SiO2-pH7.0 is +2, which is consistent with the

results
Tableof XRD,
2 shows XRF, theand TEM. of the amorphous SiO2 carrier, composite precursors (pH 5.0 and 7.0)
percentages
Table 2 shows
and ZnO–SiO 2 based the on percentages
XPS. Compared of the amorphous
with the amorphousSiO2 carrier,SiO composite
2 carrier, the Zn2+(pH
precursors 5.0 and
composite
7.0) and ZnO–SiO
precursors show the 2 based
increasing on XPS. ratioCompared
of O/Si with with thethe amorphous
increase in the SiO carrier, The
Zn 2content. the Zn 2+
change composite
may be
interpreted as follows. Hydroxyl groups generated by the hydrolysis of Zn form hydrogen bondsmay
precursors show the increasing ratio of O/Si with the increase in the Zn content. The change be
on the
interpreted
SiO 2 surface,as follows.
thus resulting Hydroxyl groupsin
in an increase generated
the amount by oftheO.hydrolysis
Comparedof withZn theform hydrogenZnO–SiO
precursors, bonds on 2
the SiO2 surface,
products thus resulting
show a decreased O/Si in an because
ratio increasethe in amount
the amount of O. Compared
of oxygen is decreasedwith by thethedehydration
precursors,
ZnO–SiO2 products
condensation reactionshow among a decreased
the –OH bonds O/Si onratiothebecause
surface of theprecursors
amount of oxygen
during is decreased
calcination. The by the
above
dehydration
analysis suggestscondensation reaction among
that ZnO nanoparticles wasthe loaded–OHonbonds on the
the surface surface of precursors
of amorphous SiO2. during
calcination.
Figure 7The shows above the analysis
infrared spectra suggestsofthat ZnO nanoparticles
the amorphous SiO2 carrier,was Zn 2+ composite
loaded on the surfaceprecursor of
amorphous SiO
(Zn–SiO2 -pH5.0 and Zn–SiO2 -pH7.0), and the final products (ZnO–SiO2 -pH5.0 and ZnO–SiO2 -pH7.0).
2.

Figure 7 shows
The absorption peaksthe infrared
of each sample spectra
at 450 ofand
the 1062 cm−1 are
amorphous SiO 2 carrier, Zn
respectively 2+ composite precursor
ascribed to symmetrical
and antisymmetric stretching vibration of Si–O–Si. The absorption peak at 799 cm 1 corresponds
(Zn–SiO 2-pH5.0 and Zn–SiO 2 -pH7.0), and the final products (ZnO–SiO 2 -pH5.0 and −
ZnO–SiO 2-pH7.0).

The
to absorption
bending peaks reflecting
vibration, of each sample at 450 and 1062
the characteristics cm 2 [28].
of SiO −1 are respectively
As shown in ascribed
Figure to 7, symmetrical
the infrared
−1 corresponds −
spectra of Zn2+ composite
and antisymmetric stretching vibration
precursors of Si–O–Si.
(Zn–SiO 2 -pH5.0 The absorption
and Zn–SiO 2peak
-pH7.0) at 799
at cm
3317 and 3319 cm to 1

bending vibration,
correspond to Zn–OH reflecting
stretching thevibration.
characteristics of SiO2 [28].
The absorption As shown
peaks in Figure
of hydroxyl 7, the
groups ininfrared spectra
zinc hydroxide
of Zn composite
(Zn(OH)2+ precursors −
1347 cm(Zn–SiO 1 2-pH5.0 and Zn–SiO effect2-pH7.0) at 3317 and 3319 cm product,
−1 correspond
2 ) at 1345 and reflect the bridging of the hydroxyl group in the and
to Zn–OH
the stretching
Si–OH bending vibration.
vibration peakTheinabsorption
the two products peaks of hydroxyl
moves fromgroups
958 cmin −1zinc
(the hydroxide
vibration peak (Zn(OH) 2)
of the
at 1345 and 1347 cm −1 reflect the bridging − 1 effect of the hydroxyl
raw material SiO2 ) to 952 and 954 cm , respectively. The changes indicate that in the hydrothermal group in the product, and the Si–OH
bendingduring
reaction vibrationthe peak in the process
preparation two products of Zn–SiO moves from Zn
2 -pH5.0, 9582+ cm −1 (the vibration peak of the raw
forms a complex of Zn(OH)2 , which
material SiO ) to 952 and 954 cm −1, respectively. The changes indicate that in the hydrothermal
yields hydrogen bonds with Si–OH on the surface of amorphous SiO2 [29–31]. In addition, the –OH
2

reaction vibration
bending during the preparation
peaks of water processadsorbed ofonZn–SiO 2-pH5.0,
the surface Zn2+ forms
of Zn–SiO 2 -pH5.0a complex
and Zn–SiO of Zn(OH)
2 -pH7.0 2, which
occur
yields
at 1413hydrogen
and 1411 cm −
bonds 1 with Si–OH The
, respectively. on the
–OH surface
shear of amorphous
vibration peaksSiO 2 [29–31].
occur at 1580Inand addition,
1579 cm the−1 –OH
[32].
bending vibration peaks of water adsorbed on the
The Zn–OH and Si–OH of calcined products and the –OH bond of adsorbed water disappeared surface of Zn–SiO 2 -pH5.0 and Zn–SiO 2 -pH7.0
occurthe
after at 1413 and 1411
calcination of cmthe−1,precursors.
respectively. The –OH the
Therefore, shear vibration peaks occur
high-temperature at 1580resulted
calcination and 1579 incmthe−1
[32]. The Zn–OH and Si–OH of calcined products and the –OH bond of adsorbed water disappeared
after the calcination of the precursors. Therefore, the high-temperature calcination resulted in the
Nanomaterials 2017, 7, 217 7 of 12
Nanomaterials2017,
Nanomaterials 2017,7,7,217
217 77of
of12
12

evaporation of
evaporation of
evaporation SiO
of SiO surface
SiO222 surface water
surface water and
water and the
and the dehydration
the dehydration condensation
dehydration condensation reaction
condensation reaction between
reaction between Si–OH
between Si–OH and
Si–OH and
and
Zn–OH, and
Zn–OH,and
Zn–OH, yielded
andyielded Si–O–Zn
yieldedSi–O–Zn chemical
Si–O–Znchemical bond.
chemicalbond.
bond.

Figure6.
Figure
Figure 6.XPS
6. XPSof
XPS of(a)
of (a)ZnO–SiO
(a) ZnO–SiO222-pH5.0;
ZnO–SiO -pH5.0;(b)
-pH5.0; (b)ZnO–SiO
(b) ZnO–SiO222-pH7.0.
ZnO–SiO -pH7.0.
-pH7.0.

Table2.
Table
Table 2.Element
2. Elementanalysis
Element analysisbased
analysis basedon
based onXPS
on XPSresults
XPS results
results

Samples
Samples C1s(%)
C1s (%) Zn2p(%)
Zn2p (%) Si2p(%)
Si2p (%) O1s(%)
O1s (%) O/Si
O/Si
Samples C1s (%) Zn2p (%) Si2p (%) O1s (%) O/Si
AmorphousSiO
Amorphous SiO22 2.74
2.74 00 31.27
31.27 65.84
65.84 2.11
2.11
Amorphous SiO2 2.74 0 31.27 65.84 2.11
Zn–SiO22-pH5.0
Zn–SiO -pH5.0 6.18
6.18 2.24
2.24 27.55
27.55 62.04
62.04 2.25
2.25
Zn–SiO2 -pH5.0 6.18 2.24 27.55 62.04 2.25
ZnO–SiO 2 -pH5.0
ZnO–SiO2-pH5.0
ZnO–SiO2 -pH5.03.48
3.48 3.48 2.472.47
2.47 30.03
30.03
30.03 63.68
63.68
63.68 2.12 2.12
2.12
Zn–SiO22-pH7.0
Zn–SiO -pH7.0
Zn–SiO2 -pH7.06.90
6.90 6.90 6.246.24
6.24 24.38
24.38
24.38 60.84
60.84
60.84 2.50 2.50
2.50
ZnO–SiO ZnO–SiO2 -pH7.0
ZnO–SiO22-pH7.0
-pH7.0 5.96
5.96 5.96 10.55
10.55 10.55 25.18
25.18
25.18 58.39
58.39
58.39 2.31 2.31
2.31

Figure
Figure 7.
Figure FTIR
FTIR spectra
7.7. FTIR spectraof
spectra ofamorphous
of amorphousSiO
amorphous 22,2, ,Zn–SiO
SiO
SiO Zn–SiO22-pH5.0,
Zn–SiO -pH5.0,ZnO–SiO
2-pH5.0, -pH5.0,
ZnO–SiO222-pH5.0,
ZnO–SiO Zn–SiO
-pH5.0, Zn–SiO -pH7.0,
Zn–SiO222-pH7.0, and
-pH7.0, and
and
ZnO–SiO
ZnO–SiO 2 -pH7.0.
ZnO–SiO22-pH7.0.
-pH7.0.

Figure888shows
Figure
Figure showsaaaschematic
shows schematicdiagram
schematic diagramofofthe
thesynthesis
synthesisprocess
synthesis processof
process ofZnO–SiO
of ZnO–SiO222by
ZnO–SiO byloading
loadingZn
loading Zn2+
Zn 2+on the
2+
on the
amorphous SiO carrier via the hydrothermal reaction and composite
amorphous SiO22 carrier via the hydrothermal reaction and composite
2 precursor
composite precursor calcination.
precursor calcination. Due
calcination. Due toto
to
thelarge
the largenumber
numberof ofSi–OH
Si–OHbonds
bondson
onthe
thesurface
surfaceofofSiO
SiO22and
andthe
thestrong
strongactivity
activityof
ofSi–OH
Si–OHbonds,
bonds,thethe
Nanomaterials 2017, 7, 217 8 of 12

Nanomaterials 2017, 7, 217 8 of 12

the large number of Si–OH bonds on the surface of SiO2 and the strong activity of Si–OH bonds, the
interaction
interaction between
between Si–OH
Si–OH and
and Zn–OH
Zn–OH isis greater
greater than
than the
the interaction
interaction in
in Zn–OH
Zn–OH(multinuclear
(multinuclearions).
ions).
Therefore, Zn 2+
2+ is immobilized on the surface of SiO 2 and dispersed ZnO nanoparticles are formed
Therefore, Zn is immobilized on the surface of SiO2 and dispersed ZnO nanoparticles are formed
after
after the
the calcination
calcination of
of precursors.
precursors.

Figure 8. Synthesis of the ZnO–nSiO22 Complex

Complex

3.2.
3.2. Antibacterial
Antibacterial Properties
Properties of
of ZnO–SiO
ZnO–SiO22
ZnO
ZnO has
has antibacterial
antibacterial activity
activity under
under light
light and
and dark
dark conditions
conditions and
and is
is mostly
mostly applied
applied under
under dark
dark
conditions. In order to investigate the antibacterial properties of ZnO–SiO under
conditions. In order to investigate the antibacterial properties of ZnO–SiO2 under dark conditions,
2 dark conditions,
ZnO–SiO
ZnO–SiO22-pH5.0,
-pH5.0,ZnO–SiO
ZnO–SiO2-pH7.0, and pure ZnO were respectively prepared. Figure 9 shows the
2 -pH7.0, and pure ZnO were respectively prepared. Figure 9 shows the
bacterial growth profiles obtained
bacterial growth profiles obtained by the by the plate
plate test.
test. Obvious
Obvious colonies
colonies werewere formed
formed in in the
the blank
blank
control
control without
without the antimicrobial material
the antimicrobial material (Figure
(Figure 9a).
9a). When
When the
the concentration
concentration of of ZnO–SiO
ZnO–SiO22-pH5.0
-pH5.0
was
was 1010mg/mL,
mg/mL,obvious
obvious colonies
colonieswere
wereobserved
observedon the
on culture plate;plate;
the culture whenwhenthe concentration of ZnO–
the concentration of
SiO -pH5.0 was 20 mg/mL, the number of colonies decreased but colonies
ZnO–SiO2 -pH5.0 was 20 mg/mL, the number of colonies decreased but colonies did not completely
2 did not completely
disappear;
disappear; when
when the concentration of
the concentration of ZnO–SiO
ZnO–SiO22-pH5.0
-pH5.0 was was increased
increased toto 3636 mg/mL,
mg/mL, no no colony
colony was
was
formed (Figure 9b). The concentrations of ZnO–SiO -pH7.0 and pure ZnO
formed (Figure 9b). The concentrations of ZnO–SiO2 -pH7.0 and pure ZnO required for colony-free
2 required for colony-free
results
results were respectively 19
were respectively 19 mg/mL
mg/mL and and 20 mg/mL (Figure
20 mg/mL (Figure 9c,d).
9c,d). Based
Based on on the
the above
above results,
results, the
the
minimum
minimum inhibitory
inhibitory concentration
concentration (MIC)
(MIC) of of each
each sample
sample was was determined
determined and and converted
converted into
into the
the
minimum
minimum inhibitory concentration of ZnO based on the content of ZnO in the composite (Table 3).
inhibitory concentration of ZnO based on the content of ZnO in the composite (Table 3).
The MIC values
The MIC values of of ZnO–SiO
ZnO–SiO22-pH5.0 and ZnO–SiO
-pH5.0 and ZnO–SiO22-pH7.0
-pH7.0 were
were respectively
respectively 1.60 and 2.14
1.60 and 2.14 mg/mL,
mg/mL,
which
which were equivalent to
were equivalent to 10%
10% ofof the
the MIC
MIC ofof pure
pure ZnO
ZnO (20 (20 mg/mL),
mg/mL), indicating
indicating that
that the
the antimicrobial
antimicrobial
ability of ZnO nanoparticles loaded on the SiO surface was about 10
ability of ZnO nanoparticles loaded on the SiO2 surface was about 10 times that of pure ZnO.
2 times that of pure ZnO.
Obviously,
Obviously,
the formation theofformation
dispersedofnanoparticles
dispersed nanoparticles
(3–8 nm) loaded (3–8 on
nm) loaded onSiO
amorphous amorphous SiO2 greatly
2 greatly improved its
improved its antimicrobial
antimicrobial performance. performance.

Table 3. MIC of ZnO–SiO2 -pH5.0, ZnO–SiO2 -pH7.0, and pure ZnO.

MIC (mg/mL) ZnO–SiO2 -pH5.0 ZnO–SiO2 -pH7.0 ZnO

E. coli 36 19 20
E. coli (ZnO) 1.60 2.14 20
Nanomaterials 2017, 7, 217 9 of 12
Nanomaterials 2017, 7, 217 9 of 12

Figure 9. Antimicrobial
Figure teststests
9. Antimicrobial of (a)
of blank control,
(a) blank (b)(b)
control, different concentrations
different concentrationsofofZnO–SiO -pH5.0in
ZnO–SiO22-pH5.0 in agar
medium, (c) different concentrations of ZnO–SiO -pH7.0 in agar medium, (d) different
agar medium, (c) different concentrations of ZnO–SiO2-pH7.0 in agar medium, (d) different
2 concentrations
of pure ZnO in agar
concentrations of medium.
pure ZnO in agar medium.

Figure 10 shows the Table 3. MIC of ZnO–SiO

antibacterial 2-pH5.0, ZnO–SiO2-pH7.0, and pure ZnO.
rate and colony growth conditions of E. coli on the plates added
with different amounts
MIC (mg/mL) of ZnO–SiO
ZnO–SiO2 -pH7.0 coating.
2-pH5.0 The antibacterial
ZnO–SiO 2-pH7.0 rate of ZnOthe coating without
ZnO–SiO2 -pH7.0 E. was
coli 0 and a large number 36 of colonies were19formed on the plate,20indicating that the
coating showed no(ZnO)
E. coli antibacterial property. 1.60 When the addition 2.14of ZnO–SiO2 -pH7.020in the coating was
only 2%, the antibacterial rate was increased above 70%, showing a good antibacterial effect; when
the dosage Figure
was10 shows theincreased
gradually antibacterial
to rate
8%,and
thecolony growth conditions
antibacterial rate of theofcoating
E. coli onto
the
E.plates added
coli was 90.48%,
with different amounts of ZnO–SiO2-pH7.0 coating. The antibacterial rate of the coating without
which met the requirements of the antibacterial effect of antibacterial coating in Chinese national
ZnO–SiO2-pH7.0 was 0 and a large number of colonies were formed on the plate, indicating that the
standard GBT21866-2008.
Nanomaterials 2017, 7, no
The increasing antibacterial rate of the paint indicated less colonies
217 antibacterial property. When the addition of ZnO–SiO2-pH7.0 in the coating10
and a
of 12
coating showed was
betteronly
antibacterial effect.
2%, the antibacterial rate was increased above 70%, showing a good antibacterial effect; when
the dosage was gradually increased to 8%, the antibacterial rate of the coating to E. coli was 90.48%,
which met the requirements of the antibacterial effect of antibacterial coating in Chinese national
standard GBT21866-2008. The increasing antibacterial rate of the paint indicated less colonies and a
better antibacterial effect.
The antimicrobial properties of the ZnO nanoparticles supported uniformly and dispersedly on
the surface of SiO2 were greatly improved, due to the large specific surface area and surface activity
of ZnO nanoparticles compared with the pure ZnO of large particles, and the contact and inhibition
with microbes is stronger. This should be considered as one of the means to enhance the function of
ZnO.

Figure 10.Effects
Figure10. Effectsof
ofdifferent additiveson
different additives onantibacterial
antibacterial rate
rate (E.(E. coli).
coli).

4. Conclusions
ZnO–SiO2 composite was prepared by an environmentally friendly hydrothermal method and
high-temperature calcination. In this composite, ZnO nanoparticles with a particle size of 3–8 nm
were uniformly and dispersedly loaded on the surface of amorphous SiO2. The size of the ZnO
Nanomaterials 2017, 7, 217 10 of 12

The antimicrobial properties of the ZnO nanoparticles supported uniformly and dispersedly on
the surface of SiO2 were greatly improved, due to the large specific surface area and surface activity of
ZnO nanoparticles compared with the pure ZnO of large particles, and the contact and inhibition with
microbes is stronger. This should be considered as one of the means to enhance the function of ZnO.

4. Conclusions
ZnO–SiO2 composite was prepared by an environmentally friendly hydrothermal method and
high-temperature calcination. In this composite, ZnO nanoparticles with a particle size of 3–8 nm were
uniformly and dispersedly loaded on the surface of amorphous SiO2 . The size of the ZnO particles
used in the industry is about 500 nm, and there is a certain degree of agglomeration among particles.
According to the analysis of relevant tests, the strong interaction between the SiO2 carrier surface and
Zn–OH (precursors of ZnO) reduced the combination between Zn–OH, prevented its aggregation and
formed monodispersed nanoparticles. Compared with pure ZnO, ZnO–SiO2 showed much better
antibacterial performance in the MIC test and the characterization test of paint properties.
In general, ZnO nanoparticles loaded uniformly and depressively on the surface of amorphous
SiO2 greatly enhanced its antibacterial function.

Acknowledgments: This work was supported by the Fundamental Research Funds for the Central
Universities of China (No. 2652016160) and the Project Commissioned by Shandong Private Enterprises
(No. 2015-KY19-139 20151224).
Author Contributions: Ying Chen and Hao Ding conceived and designed the experiments; Ying Chen
performed the experiments; Ying Chen, Hao Ding and Sijia Sun anamyzed the date; Hao Ding contributed
reagents/materials/analysis tools; Ying Chen wrote the paper.
Conflicts of Interest: The authors declare no competing financial interest.

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