Vacuum 101 (2014) 193e199

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Vacuum
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Modification of the antibacterial activity of Zn/TiO2 nano-materials

through different anions doped
Yuzheng Wang, Xiangxin Xue, He Yang*
Institute of Metallurgical Resources and Environmental Engineering, Northeastern University, Shenyang, China

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

Article history: Antibacterial activity of zinc-doped titania (Zn/TiO2) nano-materials through different anions (ZnCl2/
Received 19 June 2013 TiO2, Zn(Ac)2/TiO2, Zn(NO3)2/TiO2 and ZnSO4/TiO2) doped calcinated at 500
C under visible light irra-
Received in revised form diation and in the dark was investigated. A simple solegel method was used to synthesize TiO2 nano-
5 August 2013
materials. Samples ZnCl2/TiO2, Zn(Ac)2/TiO2, Zn(NO3)2/TiO2 and ZnSO4/TiO2 exhibit anatase phase TiO2
Accepted 8 August 2013
as the predominant crystalline phase and Zn ions exist in the form of ZnTiO3, Zn2Ti3O8, ZnO or ZnSO4
crystallites. The study on antibacterial effect of Zn/TiO2 nano-materials on fungal Candida albicans
Keywords:
(ATCC10231), Gram-negative Escherichia coli (ATCC25922) and Gram-positive Staphylococcus aureus
Anion
Zn-doped
(ATCC6538) shows that the antibacterial action is more significant on C. albicans than on E. coli and
TiO2 S. aureus. Under visible light irradiation, the antibacterial activity is superior to that in the dark.
Antibacterial activity Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Photocatalysis is a promising technology based on the interac-
tion between light and solid semiconductor particles and is able to
produce highly oxidative species that not only destroy bacteria, but
also destroy a large variety of chemical contaminants [1e3]. Mat-
sunaga et al. [4] reported for the first time the microbiocidal effect
of TiO2 photocatalytic reactions. Since then, research work on TiO2
photocatalytic killing has been intensively conducted on a wide
spectrum of organisms including viruses, bacteria and fungi [5,6].
Doping of TiO2 nano-materials with metals or nonmetals has
been widely studied for more than ten years. Most of the metal
doped (nonmetal-doped) TiO2 nano-materials have been explored
for photocatalytic activity. The dopant particles of nanosize
improved catalytic behavior, and were used for the degradation of
many compounds and this peculiar quality lead to enhanced anti-
bacterial property of doped TiO2 [7]. It was reported that TiO2
doped with Ag, Cu, Fe and rare earth element can effectively
improve antibacterial activity [8e11]. Zhao et al. reported Ag
nanoparticles are incorporated into TiO2 on Ti implants that can be
reduced by controlling the Ag release rate and the properties can be
further tailored to accomplish both long-term antibacterial ability
and biointegration [12]. Xue et al. [13] showed that boron-doped
TiO2 nano-material can destroy or inhibit the growth of
Escherichia coli and the order of the antibacterial activities of the B/
TiO2 materials obtained at different calcinations temperature is B/
TiO2-600
C > B/TiO2-500
C > B/TiO2-700
C > B/TiO2-800
C > B/
TiO2-900
C. Among them, zinc salts are commonly used because
they are inexpensive, stable and environmentally friendly [14,15].
For example, Chen et al. [16] reported zinc acetate loaded hy-
droxyapatite nanorods and amorphous calcium phosphate nano-
particles are investigated for oral antibacterial application. Zhang
[17] reported the synthesis of a zinc nitrate hexahydrate doped
TiO2 via Zn2þ introduction into a layered titanate followed by hy-
drothermal treatment and calcination, which showed its capability
for efficient electron transport in dye-sensitized solar cells due to
lower density of empty trap states. Prudencio et al. [18] reported
the effect of ZnSO4 addition to a conventional glass ionomer and a
resin-modified glass ionomer on solubility zinc release and Strep-
tococcus mutans growth inhibition. Indeed, the speciation forms of
soluble Zn ions (Zn2þ, Zn(OH)þ, ZnClþ, etc.) may considerably
change within the range of physiological conditions used in this
study depending not only on small variations of pH but also on
anions (Cl, SO24 ) as well as redox potential. However, most of
these studies have mainly focused on the zinc ion antibacterial, and
anion on zinc-doped TiO2 antibacterial property is seldom
reported.
In this paper, the impact of anions (Cl, Ac, NO 3 and SO4 )
2

doped TiO2 on antibacterial activity is investigated. Different zinc

salts-doped TiO2 nano-materials are prepared by a solegel method.
* Corresponding author. Tel.: þ86 02483681735. The antibacterial activity of zinc-doped TiO2 nano-materials is
E-mail address: yangh@smm.neu.edu.cn (H. Yang). examined against Candida albicans, Escherichia coli and

0042-207X/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.vacuum.2013.08.006
194 Y. Wang et al. / Vacuum 101 (2014) 193e199
Staphylococcus aureus. These microorganisms are selected because
of their relatively diverse make up in terms of biological structure,
in particular the cell walls of the organisms, coupled with their high
resistance to conventional antibacterial techniques.
2. Material and methods
2.1. Material synthesis
Material Zn/TiO2 particles were made by a solegel method as
described elsewhere [19]. TiO2 nano-materials were synthesized by
injecting acid solution (consisting of distilled water, ethyl alcohol
and acetic acid) into tetrabutyl titanate. The mixture was kept un-
der constant magnetic stirring for 3 h until the transparent sol was
obtained. The sol was then aged for 1 day and the gel was obtained.
The zinc ions doped nanoparticles were synthesized with the same
method mentioned above, except for adding the corresponding Zn
solution into the acid solution. The obtained gel was calcinated at
500
C for 2 h to remove residual organic compounds. For each
precursor solutions, the total amount of Zn was 0.0075 mol.
2.2. Characterization
An X-ray diffractometer (XRD, D/max-2550PC, Japan) employ-
ing Cu Ka radiation (l ¼ 0.1541 nm) at a scanning rate of
0.03537q s1 was used to measure crystallinity and determine the
phases present in the materials. The semi-quantitative XRD method
was base on relative intensity values, obtained by integrating
certain characteristic peaks of the component phases. Semi-
quantitative analysis of the phases, is performed by scaling the
intensities of the diffraction peaks in the sample to one diffracted
peak intensity of a certain reference phase, in this case corundum
(a-alumina). A reference intensity ratio (RIR) is thus applied to each
phase and the relative intensities compared. Therefore, the weight
fraction of particular crystal phase i in samples containing a
mixture of n materials can be determined by RIR method [20, 21]:
Ii =RIRi
Wi ¼ Pn  100% (1)
k ¼ 1 Ik =RIRk
where Ii is the integrated intensity of diffraction of the ith phase,
RIRi is the reference intensity ratio of the ith phase, Wi is the weight
content of the ith phase, and n is the phase number of the multi-
phase mixture.
The surface area of materials was measured using nitrogen (N2)
adsorption (BET, Quantachrome NOVA 1200e, USA). A transmission
electron microscope (TEM, TECNAI G2 F20, USA) was used to
examine the morphology and microstructure of the Zn-doped TiO2
materials. X-ray photoelectron spectroscopy (XPS, ESCALAB 250,
USA) analysis of the samples was measured with an X-ray source of
monochromated Al Ka (hv ¼ 1486.6 eV), operating at 15 kV and
150 W. The Zn(2p), O(1s), Ti(1s) and S(2p) peaks were deconvoluted
using Gaussian components, after a Shirley background subtrac-
tion. Infrared spectra were collected on a FT-IR spectrometer (FT-IR,
Quantachrome Nicolet 380, USA) using the standard KBr method.
The UV absorption properties of the materials were measured using
a diffused UVevis spectrophotometer (Shimadzu UV-2550, Japan),
at wavelengths in the range 200e600 nm. Atomic absorption
spectrometric was recorded on a PerkineElmer M2100 spectro-
photometer (AAS).
2.3. Zn2þ and SO2
4 release
0.1 g of dried powder of Zn-doped TiO2 nano-materials was
added into 25 mL deionized water, and then the suspension was
shaken for 2 h at a speed of 60 rpm using an oscillator in the arti-
ficial climate box at 37
C. The Zn2þ and SO2
4 release solution was
withdrawn. The suspension was centrifuged for atomic absorption
spectrometric (AAS) analysis. At the same time, SO2
4 concentration
was determined by gravimetric method.
2.4. Measurement of antimicrobial property
C. albicans (ATCC10231), E. coli (ATCC25922) and S. aureus
(ATCC6538) were chosen as the bacteria in the antibacterial ex-
aminations. Antibacterial activity of Zn-doped TiO2 materials was
tested by an inhibition zone method and shaking flask method. All
glassware and materials were autoclaved at 120
C for 15 min to
ensure the sterility for testing. Microorganisms were inoculated
and grew aerobically in 25 mL liquid nutrient broth at 37
C on a
rotary shaker (120 rpm/min) for 18e24 h. They were adjusted to a
concentration of 104e105 CFU/mL in the antibacterial assay. The
experiments were carried out under two irradiation conditions:
visible light and dark. The visible light source was 15 common
fluorescent tubes, mounted on the inside of an artificial climate box
(with total power of 15  18 W).
The procedures of inhibition zone method were as follows. In-
hibition ring method was carried out by pouring agar into Petri
dishes to form 4 mm thick layers and the Petri dishes were left for
10 min to dry in the air. Dense inoculum of the tested microor-
ganisms was added to Petri dishes, and then the compacted powder
(0.70 g of samples, 14 mm in diameter) was arranged on the agar
surface and incubated at 37
C for 24 h in the artificial climate box
under the visible light. The diameters of inhibitory zones sur-
rounding the samples disks were observed. The plates were pho-
tographed and the average inhibition zone diameters were
measured.
The procedures of shaking flask method were as follows [22].
0.1 g of each sample was dispensed into 25 mL of a sterile 0.9 wt.%
saline water containing about 105e106 CFU/mL of C. albicans, E. coli
or S. aureus, and then shaken at 37  1
C under the visible light or
in the dark. 0.5 mL of the suspension was taken out from the test
tube after a contact for 120 min, and diluted to a certain volume (to
ensure the bacterial colonies grown could be counted easily and
correctly) by ten-fold dilution. The diluted solution was plated on
nutrient agar plates in triplicate and incubated at 37  1
C for 24 h.
The number of bacterial colonies on each plate was counted. The
killing rate (h) is relative to the viable bacteria counts as follows:
h ¼ (C0  C)  100%/C0, where C0 is the number of microorganism
colonies on the control tube (a sterile 0.9 wt.% saline water without
sample) and C is the number of microorganism colonies on the
samples.
3. Results and discussion
3.1. Morphologies and phase
Fig. 1 shows the recorded TEM images of the Zn-doped TiO2
materials. From the TEM micrographs, it is observed that different
anions doping doesn’t influence too far on the diameter and size
distribution of TiO2 materials. Particle size of ZnSO4 doping is
slightly smaller than that of the other three materials. The grains of
Zn-doped TiO2 are round-shaped and the particle size is about
20 nm. The BET surface areas of the Zn-doped are presented in
Table 1. It should be noted that the BET surface area of ZnSO4/TiO2 is
obviously higher than that of the other samples.
XRD was carried out to investigate the changes patterns TiO2
phase structure after zinc-doping. Fig. 2 shows the effect of anions
on the phase structure of Zn/TiO2 nano-materials calcinated at
500
C. It is found that material ZnCl2/TiO2 exhibits anatase phase
 Y. Wang et al. / Vacuum 101 (2014) 193e199 195

Fig. 2. XRD patterns of ZneTiO2 nano-materials.

Fig. 1. TEM images of (a) ZnCl2/TiO2, (b) Zn(Ac)2/TiO2, (c)Zn(NO3)2/TiO2 and (d) ZnSO4/
TiO2.
TiO2, rutile phase TiO2 and hexagonal ZnTiO3. Huang et al. [23]
reported the critical temperature for the crystal transfer from
anatase-type TiO2 to rutile-type of TiO2 was 600
C. This shows the
ZnCl2 doping promotes the phase transformation of TiO2 from
anatase phase to rutile phase. Both Zn(Ac)2/TiO2 and Zn(NO3)2/TiO2
nano-materials exhibit an anatase phase as the predominant
crystalline phase. In addition, some peaks characteristic of Zn2Ti3O8
and ZnO exist in Zn(Ac)2/TiO2 and Zn(NO3)2/TiO2 nano-materials,
respectively. The phase of ZnSO4/TiO2 nano-material is compos-
ited of anatase TiO2, rutile TiO2 and orthorhombic ZnSO4. According
to the line width analysis of anatase diffraction peak based on the
Scherrer equation [24], the average grain size of the samples are
estimated for Zn-doped TiO2 nano-materials and the results are
shown in Table 1.
The percentage content of phase composition extracted from
XRD spectra, which is often used to quantify the anatase-to-rutile
transformation, is calculated with the semi-quantitative calcula-
tion of XRD analysis. Table 1 shows the percentage content of phase
composition. It is observed the amount of ZnSO4 phase is higher
into Zn/TiO2 composition. Literatures [25] reported that Zn2Ti3O8 is
formed by the solid reaction of surrounding ZnO with anatase TiO2
crystals, and further transformed to ZnTiO3. The solid reaction is
influenced by reaction temperature, pressure and reactant activity.
However, ZnSO4 phase formation maybe because Zn ions and SO2 4 cording to literature [30], the peaks around 1025e1210 cm1,
can’t incorporate into the TiO2 lattice or react with TiO2, Zn ions and
SO2
4 ions recombined into ZnSO4, thus dispersion on the surface of
Table 1
Effect of various anions on phase structure and the BET surface areas of Zn/TiO2.
the material. This process is easier to carry out than solid reaction.
So XRD analysis detects the higher amount of ZnSO4 phase.
To further understand the relationship between the various Zn
content in the materials and their antibacterial activity, the amount
of Zn ions released from the materials are measured by AAS and the
amount of SO2 4 released from the ZnSO4/TiO2 was determined by
gravimetric method. The amount of Zn ions released are shown
in Table 2. The amount of zinc ions released from ZnSO4/TiO2 is
much higher than the other three materials, and the molar ratio of
Zn2þ and SO2 4 ions is nearly 1:1. The pH value of the released so-
lution from the ZnSO4/TiO2 is about 5.7 and that of released solu-
tion from the other materials is about 6.2. The reason of pH value
decrease for ZnSO4/TiO2 is a part of SO24 ions released.
To analyze the composition of the materials, we took FT-IR
spectra of the materials. The FT-IR spectra of zinc-doped TiO2 ma-
terials are shown in Fig. 3. The peaks at 1390 cm1, 1460 cm1 and
in the range 2850e3000 cm1 belong to the asymmetric and
symmetric CH3 vibrations [26]. The stretching vibration of CeH in-
plane bending vibrations has been identified at 1120 cm1 [26,27].
The bands at 2370 cm1 can be assigned to interference peak CO2
[28]. A broad peak centered at 3400 cm1 and 1650 cm1 corre-
sponding to eOH stretching [29]. Another peak near 500 cm1
could be attributed to TieO stretching vibration. But the intensities
of the TieO stretching vibration from the ZnSO4/TiO2 material are
significantly stronger than that from the other three spectra. Ac-
620 cm1 and 460 cm1 belong to SO2 4 stretching. So the peak
becoming strong near 500 cm1 may be due to overlapping SO2 4
stretching. In addition, a peak near 1095 cm1 is also attributed to
SO2
4 stretching. The result is just consistent with XRD analysis
results. Derived from the XRD analysis results, ZnSO4/TiO2 material
mainly exhibit ZnSO4 phase.

Catalysts Phase composition and Crystallite BET/(m2/g)

mass percentage diameter/nm Table 2
The content and existing form Zn/TiO2 released solution (analyzed by AAS).
ZnCl2/TiO2 Anatase TiO2: 49%; 18 64.636
Rutile TiO2: 29%; Sample no. Zn2þ pH AAS-determined AAS-determined
ZnTiO3: 22% initial doped content [mg/L] content [mmol]
Zn(Ac)2/TiO2 Anatase TiO2: 90%; 19 44.418 amount [mmol]
Zn2þ SO24 Zn2þ SO2
4
Zn2Ti3O8: 10%
Zn(NO3)2/TiO2 Anatase TiO2: 85%; 20 55.962 ZnCl2/TiO2 7.5 6.2 53.60 0.020 e
ZnO: 15% Zn(Ac)2/TiO2 7.5 6.3 47.90 0.018 e
ZnSO4/TiO2 Anatase TiO2: 50%; 15 100.668 Zn(NO3)2/TiO2 7.5 6.2 48.10 0.018 e
Rutile TiO2: 3%; ZnSO4: 47% ZnSO4/TiO2 7.5 5.7 448.5 540 0.172 0.140
196 Y. Wang et al. / Vacuum 101 (2014) 193e199

Table 3
Surface element content of zinc-doped TiO2 nano-materials (at.%).

Sample no. Zn Ti O S

ZnCl2/TiO2 12.55 14.17 43.08

Zn(Ac)2/TiO2 11.7 10.13 42.43
Zn(NO3)2/TiO2 9.95 10.37 43.28
ZnSO4/TiO2 6.73 10.17 47.51 6.28

doped TiO2 is presented in Fig. 4(b) where two peaks at about

Fig. 3. FT-IR spectra of Zn/TiO2 calcinated at 500
C.
3.2. XPS analysis
We know that the XPS is a surface inspection measurement. All
the structures detected by the XPS are present on the materials
surface or subsurface. The high-resolution XPS spectra of the Zn 2p,
O 1s, Ti 2p and S 2p region on the surface of material are shown in
Fig. 4(a)e(d), respectively.
XPS characterizations show that the Ti 2p spectrum of doped
TiO2 exhibits two peaks at 458.6 eV and 464.5 eV assigned to the
two spin-orbit components of Ti 2p3/2 and Ti 2p1/2, indicating that
Ti is 4þ valence in the doped TiO2 [31]. The Zn 2p spectrum in the
1022 eV and 1045 eV are assigned to the 2p3/2 and 2p1/2 electronic
states of Zn(Ⅱ), respectively [31,32]. It indicates that Zn exists as the
2þ oxidation state in the doped system.
The O 1s XPS (Fig. 4(c)) spectra are wide and asymmetric,
indicating that there are at least two kinds of chemical states ac-
cording to the binding energy range from 526 eV to 536 eV. In our
investigation two peaks are identified for materials ZnCl2/TiO2,
Zn(Ac)2/TiO2, Zn(NO3)2/TiO2. After curve fitting, besides the peak
corresponding to metaleO (OM), the other peak at higher binding
energy can be identified. This peak should be attributed to the
surface species such as TieOH and TieOeO resulting from the
chemisorbed water (OH) [33]. However, there are third peaks pre-
sent in the sample ZnSO4/TiO2. The peak at about 532.5 eV is related
to oxygen (OS) in the [SO2 4 ] crystal lattice. Furthermore, the XPS
spectrum for the sample exhibits one peak in the S 2p region
(Fig. 4(d)). BE for S 2p3/2 peak in ZnSO4 is 169.4 eV, thus further
confirming that there is existence of the compound ZnSO4. The
results of Zn, Ti, O and S content are showed in Table 3.
3.3. UVevis diffuse reflectance spectra (DRS)
The DRS of zinc-doped nano-materials are illustrated in Fig. 5. It
can be clearly observed that the absorption edge positions of ZnCl2/
TiO2, Zn(Ac)2/TiO2, Zn(NO3)2/TiO2 and ZnSO4/TiO2 doped materials

Fig. 4. XPS spectra of the Zn/TiO2 nano-materials: (a) Ti 2p, (b) Zn 2p, (c) O 1s, and (d) S 2p regions.
 Y. Wang et al. / Vacuum 101 (2014) 193e199
Fig. 5. UVevis diffuse reflection spectra for Zn/TiO2 materials calcinated at 500
C: (a)
ZnCl2/TiO2, (b) Zn(Ac)2/TiO2, (c) Zn(NO3)2/TiO2 and (d) ZnSO4/TiO2.
extend into the visible region. It is clear that the incorporation of
zinc results in a red-shift of the absorption of TiO2 materials. What
is more, the absorption edge of ZnCl2/TiO2 can shift to longer
wavelength than the other materials, indicating that ZnCl2/TiO2 is
more helpful to photocatalytic reaction. However, the absorption
edge positions of ZnSO4/TiO2 basically no change compare with
pure TiO2 (the absorption edge of pure TiO2 is 387 nm).
Because TiO2 is an indirect gap semiconductor, the Indirect
Transition Model was used to calculate the band gap energy of TiO2,
the equation as follows [34]:
 
ðahnÞ1=2 ¼ A hn  Eg
where a is the absorbance (arbitrary units), hn is photon energy
(eV), A is a constant, Eg is the band gap energy(eV). As showed in
Fig. 5, the x-axis intercept of the line tangent to the inflection point
of the curve provides the band gap values as 3.04 eV, 3.13 eV,
3.11 eV, and 3.24 eV for ZnCl2/TiO2, Zn(Ac)2/TiO2, Zn(NO3)2/TiO2
and ZnSO4/TiO2, respectively. In particular, the band gap for ZnCl2/
Fig. 6. Antibacterial experiments of Zn-doped TiO2 and pure TiO2 nano-materials under visible light irradiation by the inhibition zone method. (a) Candida albicans; (b) Staphy-
lococcus aureus; (c) Escherichia coli.
197
TiO2 can be greatly decreased because of appearing rutile phase.
Mixed crystal helps to the red-shift of the absorption edge. The
result is just consistent with XRD analysis results.
3.4. Antibacterial investigation
The antibacterial activity of the Zn-doped TiO2 materials was
tested by the method of inhibition zone. It is clearly observed that
materials show antibacterial activity against C. albicans, E. coli and
S. aureus. Fig. 6 shows that pure TiO2 had no antibacterial activities
against the three bacteria. The average inhibition zones against the
three bacteria are 7.21, 6.37, 6.21 and 9.70 mm for ZnCl2/TiO2,
Zn(Ac)2/TiO2, Zn(NO3)2/TiO2 and ZnSO4/TiO2, respectively. The
same molar ratio of Zn doping, their antibacterial activities are not
the same, indicating anion doping has an effect on the antibacterial
effect.
To further investigate the effect of zinc-doping on the antibac-
terial activity, we also choose shaking flask method to evaluate
antibacterial activity. Fig. 7 shows the results obtained by shaking
flask method under the visible light and in the dark. It can be clearly
observed that the percentage reduction of ZnSO4/TiO2 is the highest
under the visible light, indicating that ZnSO4/TiO2 has significant
antibacterial activity; antibacterial activity of ZnCl2/TiO2 is slightly
superior to Zn(NO3)2/TiO2; antibacterial activity of Zn(Ac)2/TiO2 is
the worst. This conclusion is similar to the Heinlaan [35]. He
pointed out that both ZnO and nano ZnO were much less toxic than
ZnSO4 although the amount of soluble Zn should be comparable.
The acute toxicity of both Zn oxides for Vibrio fischeri was almost
identical being 6-times less toxic than ZnSO4. On the other hand,
under visible light irradiation, their antibacterial activities are su-
perior to dark condition.
According to the results of antibacterial effect for Zn/TiO2 nano-
materials, we supposed that the antibacterial mechanism of Zn/
TiO2 was as follows:
(2)
(1) The order of the antibacterial activities of Zn/TiO2 material
through different anions doped in visible light irradiation is
ZnSO4/TiO2 > ZnCl2/TiO2 > Zn(NO3)2/TiO2 > Zn(Ac)2/TiO2.
Firstly, an antibacterial mechanism of photocatalyst (such as
TiO2, ZnO and ZnTiO3) under the visible light conditions has
been proposed to occur in several ways. The mechanical
destruction of cell membrane by reactive species such as the
198 Y. Wang et al. / Vacuum 101 (2014) 193e199
Fig. 7. Antibacterial result of Zn-doped TiO2 under visible light irradiation and in the dark by shaking flask method. (a) Candida albicans; (b) Staphylococcus aureus; (c) Escherichia
coli.

O  
2 , OH , and H2O2 has been usually mentioned in many
publications [36]. These species are generally obtained from
the results of the photocatalytic reaction when photocatalyst
absorbs light. XPS analysis proves the surface of the samples
exist a large number of OH [37]. Secondly, XRD analysis
shows ZnCl2/TiO2 nano-material generates rutile phase TiO2.
As well known, mixed crystal helps to the photocatalytic
performance. And DRS analysis also shows ZnCl2/TiO2 is
more helpful to photocatalytic reaction compared with the
other materials. Zn(NO3)2/TiO2 nano-material exhibits
anatase phase TiO2 and ZnO. Moon et al. [38] pointed out
binary oxide catalysts often exhibited higher catalytic activ-
ity than what can be directly predicted from the properties of
their components. The interface between the two phases
may act as a rapid separation site for the photogenerated
electrons and holes due to the difference in the energy level
of their conduction bands and valence bands. It can also
promote the photocatalytic reaction. It is speculated photo-
catalytic activity caused by mixed crystal may be stronger
than that caused by binary oxide catalysts, so that photo-
catalytic activity of ZnCl2/TiO2 is stronger than that of
Zn(NO3)2/TiO2. Thirdly, antibacterial activity of ZnSO4/TiO2 is
the strongest. AAS analysis shows the released solution of
ZnSO4/TiO2 material contains large amounts of Zn ions and
SO24 . It is well established that Zn ions possesses excellent
antibacterial quality. On the other hand, TiO2-based solid
acids photocatalysts have been effectively introduced in the
field of photocatalysis. Zhimou et al. [39] reported sulfated
TiO2 was easier to improve the hydrophilic properties of
TiO2. The surface acidity was considered to exist in the form
of stronger surface hydroxyl groups and hydroxyl groups can
accept holes by illumination generated. Li et al. [40] also
reported SO2 4 -doped TiO2 photocatalyst prepared by treat-
ing the xerogel under supercritical conditions. They pointed
out that SO2 4 /TiO2 exhibited higher activity and longer life-
time than the corresponding undoped TiO2. So, in this paper,
SO24 -doped generate the more surface hydroxyl group so
that photocatalyst antibacterial activity is improved. In
addition, SO2 4 -doped makes decrease in the pH value of the
released solution. Strains grown require appropriate envi-
ronmental factors (temperature, pH, redox potential, DO,
solar radiation, the water activity, osmotic pressure and
surface tension, etc.) beside nutrients. The suitable pH value
of each strain is different. Optimum pH value of most bac-
terial is 6.5e7.5. In this experiment, the pH value of the
released solution is about 5.7 beyond the optimum pH. The
inappropriate pH can affect the activity of membrane and
microorganisms on the absorption of nutrients, which is not
conducive to the growth of bacteria. So it is speculated that
excellent antibacterial property of ZnSO4/TiO2 is due to the
synergistic effects of zinc ion antibacterial activity, photo-
catalytic and improvement of material surface acidity.
(2) In dark conditions, Zn/TiO2 nano-materials are still antibac-
terial activities due to Zn ions release. The order of the
amount of Zn ions released is ZnSO4/TiO2 > ZnCl2/
TiO2 > Zn(NO3)2/TiO2 ¼ Zn(Ac)2/TiO2. This is just consistent
with antibacterial activities of Zn/TiO2 in the dark.
(3) We can conclude that the antibacterial action of the Zn-doped
TiO2 material is more significant on Gram-positive bacteria
than on Gram-negative bacteria. The difference in activity
against these two types of bacteria can be explained by the
different structures and chemical composition of the cell
surfaces. The cell wall of Gram-negative bacteria is different
from the Gram-positive bacteria by having an outer mem-
brane that covers the peptidoglycan layer. It also helps the
bacteria to survive when considering the presence of external
substance that can harm the bacteria [24]. Fungal C. albicans is
highly resistant to photocatalytic degradation due to its thick
eukaryotic cell wall, while in our study, the antibacterial effect
of Zn-doped TiO2 nano-materials on C. albicans is well. This is
a promising result especially for simple preparation route
with incorporation of nano-materials.
4. Conclusion
The present study demonstrates antibacterial activity of Zn/TiO2
nano-materials through different anions (ZnCl2, Zn(Ac)2, Zn(NO3)2
and ZnSO4) doped under visible light irradiation and in the dark.
The order of the antibacterial activity of Zn/TiO2 materials through
different anions doped is ZnSO4/TiO2 > ZnCl2/TiO2 > Zn(NO3)2/
TiO2 > Zn(Ac)2/TiO2. Under visible light irradiation, the antibacte-
rial activity is superior to that in the dark. It is concluded that
antibacterial activity of ZnSO4/TiO2 materials is mainly due to the
zinc ions antimicrobial, photocatalytic and improvement of the
surface acidity and antibacterial activity of the other materials is
mainly attributed to photocatalysis antibacterial.
Acknowledgments
We gratefully acknowledge the support from National Natural
Science Foundation of China (No. 51090384).
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