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Article history: ZnO-Al x% nanoparticles (NPs), with x ¼ 0, 1, 3, 5 or 10 mol% Al3þ, were synthesized by a modified sol-gel
Received 12 April 2017 method. The effects of Al3þ content on the structure, morphology and optical properties of Al-doped ZnO
Received in revised form were investigated by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman
24 August 2017
spectroscopy, photoacoustic absorption spectroscopy (PAS), photoluminescence spectroscopy (PL) and
Accepted 12 September 2017
Available online 15 September 2017
specific surface area determination. A single crystalline phase characteristic of ZnO with wurtzite
structure was detected for all synthesized oxides. With increasing dopant content, the average crystallite
size of the NPs decreased from 25 to 7 nm. ZnO-Al x% NPs exhibited enhanced optical properties with the
Keywords:
Nanostructured materials
absorption slightly shifted to the visible region and with the band gap energy (Eg) decreased from 3.12
Sol-gel processes (undoped ZnO) to 2.95 eV (ZnO-Al 3%). Undoped ZnO showed intense PL above 430 nm, which was
Optical properties considerably decreased with the insertion of Al3þ. Despite the increase of the surface area with Al3þ
X-ray diffraction doping of ZnO NPs, its catalytic activity in the decomposition reaction of Congo red showed a decrease
with doping. Research has shown that ZnO NPs can selectively target and kill cancer cells and that its
cytotoxicity is dependent of the concentration. The doping can be a method of shape the cytotoxicity of
ZnO NPs and their optical and photocatalytic properties. In-vitro cytotoxicity studies showed that both
undoped ZnO and Al-doped ZnO NPs synthesized were highly cytotoxic for fibroblast cells, suggesting
that these nanomaterials could be promising anticancer agents.
© 2017 Elsevier B.V. All rights reserved.
1. Introduction treat diseases, for example, cancer [1]. Similarly, the field of het-
erogeneous photocatalysis has expanded rapidly in recent decades.
Semiconductors nanostructured with suitable chemical, bio- It can be defined as the acceleration of a photoreaction in the
logical, structural, optical, cytotoxic and photocatalytic properties presence of a catalyst. In recent years, interest in photocatalysis has
are becoming increasingly important in biomedical and photo- focused on the use of semiconductor materials as photocatalysts for
catalytic applications, and have been the subject of significant the removal of ambient concentrations of organic and inorganic
research. Nanomedicine is the biomedical application of nano- species from aqueous or gas phase systems in environmental clean-
technology in which engineered nanoparticles (NPs) are used to up operations, drinking water treatment, and industrial and health
applications [2].
The extensive use of dyes in several fields, such as the food,
* Corresponding author.
cosmetics, pharmaceuticals, paper and textile industries, leads to a
E-mail address: jessika_delara@hotmail.com.br (J.L. Andrade). large consumption of water. It is estimated that the textile industry
https://doi.org/10.1016/j.jallcom.2017.09.128
0925-8388/© 2017 Elsevier B.V. All rights reserved.
J.L. Andrade et al. / Journal of Alloys and Compounds 729 (2017) 978e987 979
alone uses about 378 billion liters per year in various processes, like Al is low cost and has high abundance in the earth, so the effect
mercerization, desizing, scouring, dyeing, rising and so on [3]. The of Al-doping of ZnO on the photocatalytic performance has been
excessive consumption of water in these industries makes waste- studied extensively. Lee et al. [31] synthesized Al-doped ZnO (AZO)
water treatment more important. Presently, a selection of biolog- by a precipitation method with different dopant contents and
ical, physical and chemical traditional methods are used for studied their photocatalytic properties. It was verified that AZO
wastewater treatment, for example, biological oxidation [4], with 3 mol% of Al presented the highest photocatalytic perfor-
membrane filtration [5], adsorption [6], coagulation [7] and mance for the degradation of the methyl orange (MO) under UV
advanced oxidation processes (AOPs) [8]. irradiation. This maximum photocatalytic activity was assigned to
Congo red (CR) is a common harmful dye that has been used in the dopant content that could effectively reduce the recombination
the textile, paper, printing, leather and plastic industries [9]. CR is a between photo-induced electron-hole pairs.
benzidine-based anionic diazo dye with a pKa value of 4.1 [10,11] Ahmad et al. [34] synthesized Al-doped ZnO by a combustion
(Fig. 1). CR is difficult to degrade due to its chemical structures method whilst varying the proportion of dopant from 0.5 to 6.0 mol
and stability, ensured by its highly conjugated system [12]. Benzi- %. The authors observed that the band gap energy (Eg) decreased
dine is a toxic metabolite of CR and is a human carcinogen, in with doping from 3.21 (pure ZnO) to 3.12 eV (AZO with 6 mol% Al).
addition to being an irritant to the skin and eyes [13,14]. Therefore, These oxides were employed in MO photodegradation under visible
there is a necessity to develop methods for CR removal from light and the best results were observed with AZO with 4 mol%,
environmental samples. Among the AOPs, heterogeneous photo- which degraded 100% of the MO dye after 1.5 h of irradiation, while
catalysis is indicated as a promising technique for the degradation the undoped ZnO degraded only 23%. These reports that reveal the
of this toxic dye [15]. application potential of Al-doped ZnO on the photodegradation of
Heterogeneous photocatalysis has the advantages of being able organic pollutants under sunlight or visible light motivated the
to degrade inorganic and organic pollutants completely via free current study.
hydroxyl radicals ($OH) generated in the reaction medium itself, Furthermore, due to the unique properties of ZnO, including
occurring at room temperature and is low cost, together with a low high chemical and physical stability, and highly efficient UVeVis
or minimum secondary impact on the environment and ecosys- absorption [35], its application has been reported for sunscreens
tems [16]. With the use of heterogeneous photocatalysis increasing, [36], food packaging [37], antibacterial agents [38] and drug de-
the development of new catalyst materials becomes very livery systems [39]. However, when a nanostructured material is
important. projected for biomedical applications, its potential cytotoxicity
Current and past research on photocatalytic processes has must be considered. Therefore, in-vitro studies have investigated
revealed several photocatalysts and their properties. Ideally, a the exposure effects on several cell lines [40]. Buerki-Thurnherr
photocatalyst should possess the following properties: photo- et al. [41] studied the cytotoxicity effect of ZnO towards Jurkat
activity, chemical inertness, stability toward photo-corrosion, cells, and their results revealed that even for very low concentra-
suitability for visible or near UV light energy harnessing, low cost tions of ZnO, it was highly toxic to these cells due to the release of
[17] and be easily removed from the medium. In recent years, this high amounts of Zn2þ into the cells. Zanni et al. [42] studied the
research field has focused on the use of broad gap semiconductors cytotoxicity effect of ZnO nanorods and microrods towards two
based on metal oxides as photocatalysts, such as TiO2 [18], Fe2O3 different human cell lines (MCF7 and HaCat). They demonstrated
[19], MgO [20], ZnO [21] and so on, for the removal/degradation of that these materials did not cause reduction of viable cells
organic and inorganic species from aqueous or gas phase systems compared to the control, but both cell lines exposed to ZnO showed
[22]. changes in cell morphology. Thus, more studies are evidently
Among the semiconductors that have been extensively investi- required to better understand the cytotoxic properties of undoped
gated, ZnO is a n-type semiconductor with the crystalline wurtzite and doped ZnO. We believe that the doping can be a method of
structure and with a wide band gap, reported to be around 3.3 eV shape the cytotoxicity of ZnO NPs and their optical and photo-
[23]. ZnO has been used in substitution to TiO2 in the photo- catalytic properties.
degradation of many organic pollutants [24,25], because it absorbs In the current study, Al-doped ZnO (ZnO-Al x% with x ¼ 0, 1, 3, 5
a larger fraction of the solar spectrum than TiO2 [26] and in many and 10 mol% Al3þ) nanostructures were synthesized by a modified
cases, due to its higher quantum efficiency [23]. sol-gel method [43]. The effects of dopant ion content on the
However, in order to improve the photocatalytic properties of structural organization and optical and morphological properties of
ZnO, this oxide has been doped with various metal ions, such as Ce ZnO were investigated. We also studied the effects of Al content on
[27], Mn [28], Cu [29], Mg [30], Al [31,32], Ga [33] and so forth. The the photocatalytic performance of Al-doped ZnO for the degrada-
insertion of dopant ions into the crystal lattice of ZnO enables tion of CR. In-vitro studies were also performed for evaluating the
suitable modifications to its properties. By molding the band cytotoxic effect of ZnO-Al x% NPs on fibroblast cells (ATCC L929),
structure of ZnO it is possible to shift its absorption to the visible with the aim of investigating their potential for biomedical appli-
region, and consequently, decrease its band gap energy [23]. cation in nanomedicine.
Undoped ZnO and Al-doped ZnO were synthesized by a modi- 2.2.1. Determination of pHpzc of ZnO-Al x% NPs
fied sol-gel method [43] and all the reagents used in this step were The pHpzc, known as the point of zero charge, was obtained by
of analytical grade without the need for further purification. mixing 0.50 g of each ZnO-Al x% oxide with 25 mL of 0.10 mol L1
Initially, a 10% (w/v) diluted aqueous solution of poly(vinyl alcohol) solution of NaCl in a falcon tube. Then, 1.00 mol L1 of HCl or NaOH
(98e99% hydrolyzed, Aldrich) and saturated metal nitrate solutions was added to each falcon tube in order to obtain the following pH
(Zn(NO3)2$6H2O and Al(NO3)3$9H2O, both Synth) were separately values: 2.0; 4.0; 6.0; 8.0; 10.0 and 12.0. The equilibrium pH of the
prepared and then mixed at specific metallic ion:monomer unit ra- mixture was measured after constant stirring for 24 h. After this,
tios. The solutions were maintained at room temperature under the pH of each solution was measured using a pHmeter and noted
stirring for 2 h and then heated under vigorous stirring until total as pHfinal. The pHpzc of the ZnO-Al x% oxides was estimated from
water evaporation. The temperature was maintained at 250e350 C curves of pH variation (DpH) versus initial pH (pHi), by linear
for the initial thermal degradation of the organic material. The extrapolation at DpH equal to zero (pHinitial ¼ pHfinal). The pHpzc is
nanostructured materials were obtained after calcination of the the point at which the extrapolated line (in DpH ¼ 0) intercepts the
precursor powder under air atmosphere at 500 C. As a result, experimental curve.
undoped ZnO and Al-doped ZnO NPs containing different concen-
trations of dopant ion (0, 1, 3, 5 and 10 mol%) were successfully 2.3. Photocatalytic performance of ZnO-Al x% NPs
prepared. These samples were labeled as ZnO-Al x% (with x mol%
Al3þ). The photocatalytic performance of the undoped and Al-doped
ZnO NPs was evaluated on the photodegradation of CR under
2.2. Characterization of ZnO-Al x% NPs UVeVis irradiation. The light source was a 125 W high-pressure Hg
lamp with a bulb (average fluency of 50.68 J m2 s1) at room
The structure of the ZnO-Al x% powder was analyzed by X-ray temperature (~300 K). The distance between the lamp and the
diffraction (XRD) using a Shimadzu XRD 7000 diffractometer (with suspension surface was fixed at 17 cm. Catalyst concentration and
Ka of 1.5406 Å radiation at 40 kV and 30 mA in the 2q range from solutions pH used were 1.00 g L1 and 12.0.
20 to 80 with a scan rate of 2 min1 and a step of 0.02 ). The The photocatalytic reactions were carried out using a Pyrex
average crystallite size was estimated using the Scherrer equation reactor (15 cm in diameter) containing 400 mL of 20 mg L1 CR
(Eq. (1)). solution. This solution with a catalyst was maintained under
magnetic stirring in the dark for 60 min to establish an adsorption-
0:9 l desorption equilibrium. After this, the pH was adjusted to 12.0 with
d¼ (1)
ðbhkl cos qB Þ a NaOH solution (1 mol L1) and the solution was irradiated under
constant stirring. During the photocatalytic reaction, aliquots were
where l is the wavelength, bhkl ¼ [(Bobs)2 e (Bstd)2]1/2, Bobs is the taken at different time intervals and immediately centrifuged to
observed full width at half maximum (FWHM) of the sample remove catalyst particles. The photocatalytic degradation of the CR
considered peak, Bstd is the instrumental contribution to the FWHM dye was monitored by measuring the absorbance of the solution
and qB is the Bragg angle. Micro-Raman measurements were per- samples at 498 nm using a UVeVis spectrophotometer (Cary 50).
formed using a Bruker Senterra Raman microscope using a 532 nm According to the Beer-Lambert Law, absorbance (A) is proportional
laser excitation and laser power of 20 mW at room temperature. to concentration.
Photoacoustic absorption (PA) spectra were performed using The percentage removal of CR was calculated using Eq. (3):
monochromatic light from a 1000 W xenon arc lamp (Model68820,
Oriel Corporation), a monochromator (Model 77250, Oriel In- A0 At
Degradation efficiency ð%Þ ¼ *100% (3)
struments) and a mechanical chopper (Model SR540, Stanford A0
Research Systems). The spectral range was between 200 and
800 nm. The band gap energy of the samples was determined using where A0 and At are the initial absorbance of the dye solution and
the Tauc relation (Eq. (2)): the absorbance at a certain reaction time (in min), respectively.
where a is the PA signal (directly proportional to the absorption Cell viability assays were performed using an in-vitro study
coefficient), A is a constant, h is Planck's constant, n is the photon employing fibroblast cells (ATCC L929). The fibroblasts cells were
frequency, Eg is the optical band gap and n is ½ for a direct semi- cultured in DMEM (Dulbecco's Modified Eagle Medium, Gibco
conductor [44]. Invitrogen) supplemented with 10% FBS (fetal bovine serum), 1%
Photoluminescence (PL) spectra were obtained with excitation penicillin and 1% streptomycin, and were incubated at 37 C in a
of the sample at 330 nm. The optical emission was collected with an humid atmosphere containing 5% CO2. The culture and co-
optical fiber and analyzed with a Jobin Yvon iHR550 mono- confluent were washed with PBS, trypsinized, resuspended and
chromator (1200 grooves/mm holographic grating) coupled to an seeded at an initial density of 2.5 105 cells/well in DMEM sup-
iCCD. All the measurements were performed at room temperature plemented with 10% FBS into a 96-well microplate. After 24 h of
(~300 K) with at least three repetitions. The morphology and incubation, the culture medium with ZnO, ZnO-Al 1% and ZnO-Al
microstructure of the samples were characterized by transmission 5% were prepared by serial dilution in concentrations of 800, 400,
electron microscopy (TEM, JEM-1400 JEOL, operated at 120 kV). 200, 100, 50 and 10 mg/mL, and 200 mL of this dispersion was added
Specific surface area measurements were carried out by N2 to each before being well incubated for 24 h. Two independent
adsorption-desorption isotherms at 77 K using a surface area experiments were performed in duplicate. The cell viability was
analyzer (QuantaChrome Nova 1200). The Brunauer-Emmett-Teller evaluated by the metabolic activity of the cells through a
J.L. Andrade et al. / Journal of Alloys and Compounds 729 (2017) 978e987 981
colorimetric method that is based on the ability of mitochondria of different Al3þ ion contents, in the range of 2q ¼ 20e80 are shown
viable cells to reduce MTT (tetrazolium salt) into a purple insoluble in Fig. 2(a). For all Al-doped ZnO samples, only the peaks charac-
compound called formazan. After 24 h, the 96-well cell culture teristics of ZnO with wurtzite structure [45] were observed, in
plates were observed under an optical microscope. Afterwards, a accordance with the standard card JCPDS 36-1451, which can be
40 mL MTT solution at a concentration of 2.5 mg/mL was added to indexed to the space group P63mc [46]. This indicates that the Al3þ
each well, and the cells were incubated for 4 h at 37 C and 5% CO2. ions were incorporated into the crystalline structure of ZnO, at least
The supernatant was removed and 100 mL of DMSO was added to partially occupying Zn2þ sites [47], and that the dopant levels
each well and the reading was performed in ELISA spectropho- investigated were lower than the limit solubility of Al3þ into the
tometer (Bio-Tek FL-600 Microplate Fluorescence Reader) at ZnO matrix. However, the positions of the diffraction peaks at 31.7
540 nm with a reference at 630 nm. Cells grown in the absence of (100), 34.5 (002) and 36.2 (101) were slightly shifted to higher
ZnO-Al x% oxides were used as a negative control and taken as 100% angles (as shown in Fig. 2(b)) and a baseline shift was exhibited
growth. The number of viable cells was calculated based on the with increasing Al3þ content. Similar behavior was also observed
absorbance value obtained. for the peaks at 66.3 (200), 68.0 (112) and 69.0 (201) in the XRD
pattern of the Al-doped ZnO.
These changes observed in the XRD patterns are associated to
3. Results and discussion the differences in the size radius of Zn2þ (0.74 Å), Al3þ (0.53 Å) and
in the valence charges. Since Al3þ ions are smaller than Zn2þ, when
3.1. Structure, morphology and optical properties of ZnO-Al x% NPs Al3þ occupy sites previously occupied by Zn2þ ions, the lattice
constants decreases, promoting alterations in the diffraction peaks
XRD diffractograms of undoped ZnO and ZnO-Al x% NPs with [47,48]. The unit cell volume estimated for the hexagonal crystal-
line system [34] of the undoped ZnO NPs decreased from 47.51 to
46.84 Å3 when it was doped with 10 mol% Al3þ ions.
Table 1 shows the average crystallite diameters estimated by the
Scherrer equation (Eq. (1)) using a 2q value equal to 47 (102) for
the synthesized oxides. It is clear that the average crystallite size
decreased from 25 to 7 nm with increasing Al3þ content up to
10 mol%. This result indicates that the doping occurred successfully,
where Al3þ ions substituted Zn2þ ions in the crystalline lattice
structure of ZnO, causing a decrease in the lattice parameter, and
consequently, a reduction in the average crystallite size.
The influence of Al3þ content on the structural organization of
the synthesized nanostructured oxides was investigated by Raman
spectroscopy (Fig. 3). Wurtzite-type ZnO belongs to the C6v 4 (P6 mc)
3
space group with two formula units per primitive cell, where all
atoms occupy C3v sites. In the Raman spectra of all ZnO-Al x%
samples, it was possible to identify Raman active mode character-
istics of ZnO [49e51]. Furthermore, in the spectra of Al-doped ZnO
the Elow
2 mode at 100 cm1, assigned mainly to Zn2þ motion in its
crystal lattice, and Ehigh
2 mode at 438 cm1, assigned to oxygen
displacement in the hexagonal phase of ZnO, are strongly
decreased in intensity with increasing Al3þ content in relation to
undoped ZnO. Raman signals at 331 and 380 cm1 are attributed to
the optical phonon overtone with A1 symmetry [52] and the A1
transverse optical phonon (TO) [49], respectively.
In addition, the Raman signal between 530 and 580 cm1 cor-
responds to the A1 and E1 symmetry species of the longitudinal
optical (LO) phonon [53]. This signal is associated with structural
disorders, such as oxygen vacancies [50], and its intensity increases
with Al3þ incorporation. Above 1000 cm1, there is a Raman signal
that corresponds to the E2 vibration modes LO [50,54]. The spectral
changes observed in the Raman spectra of the Al-doped ZnO in
relation to undoped ZnO, are mainly correlated to the characteristic
Raman signals of Zn2þ ion vibrations in the crystal lattice of ZnO
Table 1
Average crystallite diameter estimated by the Scherrer equation and optical band
gap energy (Eg) estimated by Tauc equation for undoped ZnO and ZnO-Al x%
samples.
Fig. 3. Raman spectra of undoped ZnO and ZnO-Al x% with different Al3þ contents.
Table 2
Specific surface area (SBET) and pHpzc estimated for undoped ZnO and ZnO-Al x%
with different Al3þ contents.
3.3. In-vitro cytotoxicity of synthesized ZnO-Al x% NPs Fig. 8. L929 cell viability expressed as a percentage of the viability of cells in the
control after incubation for 24 h with a culture in different concentrations of ZnO, ZnO-
The results of in-vitro studies of the cytotoxicity of the ZnO-Al x% Al 1% and ZnO-Al 5%. The in-vitro cytotoxicity test was carried out in an MTT assay.
J.L. Andrade et al. / Journal of Alloys and Compounds 729 (2017) 978e987 985
Fig. 9. Optical images of L929 cells cultured. (a) Control cells; (b), (c) and (d) exposed to ZnO; (e), (f) and (g) exposed to ZnO-Al 1%; (h), (i) and (j) exposed to ZnO-Al 5% at
concentrations of 200, 100 and 10 mg/mL, respectively.
ions caused considerable changes in the electronic, structural, op- interstitials, which was considerably decreased with the insertion
tical and morphological properties of the ZnO NPs, possibly of Al. The ZnO-Al x% oxides showed a broad and less intense
increasing the quantity of structural defects and the recombination emission band at the visible region, with maximum in the green
rate between photogenerated electron-hole pairs. We believe that region (at 550 nm) that may be assigned to intrinsic defects, such as
such changes significantly affected the photocatalytic efficiency of oxygen vacancies and Zn interstitials and vacancies. The insertion
each oxide tested as a catalyst for the CR photodegradation. How- of Al3þ ions into the crystalline structure of the ZnO NPs decreased
ever, in relation to cytotoxic effects, both systems, undoped ZnO their photocatalytic activity, probably due to the increase of the
and Al-doped ZnO, exhibited high cytotoxicity towards L929 recombination rate between photogenerated electron-hole pairs.
fibroblast cells. This effect is likely to be related to the toxic Zn2þ With respect to cytotoxicity, both undoped ZnO and Al-doped ZnO
ions released into the cells, since complementary studies revealed oxides inhibited the fibroblast cell viability and affected the cell
that Al3þ ions from undoped Al2O3 was not cytotoxic towards L929 morphology.
fibroblast cells. With the increase of Zn2þ released into the cells, the
ROS generation is also increased, leading to cytotoxicity of cells Acknowledgments
through oxidative stress. An interesting aspect is that the cytotox-
icity of these NPs can be molded by chemical modification on its The authors are grateful to Department of Physics/UEM, to
surface or immobilization into biocompatible polymers, or in core- COMCAP/UEM for providing the equipment used in this work, to
shell type nanostructure, aiming biomedical applications such as CAPES and to CNPq (Process n. 405381/2016-6) for financial
drug delivery system. The selective cytotoxicity of the ZnO-Al x NPs support.
against cancerous cells in vitro, compared to others NPs [1], is
another interesting aspect to be investigated in future studies.
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