Journal of Alloys and Compounds 729 (2017) 978e987

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Effects of Al3þ concentration on the optical, structural, photocatalytic

and cytotoxic properties of Al-doped ZnO
Jessica de Lara Andrade a, *, Angelica Gonçalves Oliveira a,
Vinícius Vaulei Gonçalves Mariucci b, Antonio Carlos Bento b,
Mychelle Vianna Companhoni c, Celso Vataru Nakamura c, Sandro Marcio Lima d,
Luis Humberto da Cunha Andrade d, Juliana Carla Garcia Moraes a,
Ana Adelina Winkler Hechenleitner a, Edgardo Alfonso Gomez Pineda a,
Daniela Martins Fernandes de Oliveira a
a
s-Graduaça
Programa de Po ~o em Química, Universidade Estadual de Maringa
, Av. Colombo 5790, 87020-900, Zona Sete, Maringa
, PR, Brazil
b
s-Graduaça
Programa de Po ~o em Física, Universidade Estadual de Maringa

, Av. Colombo 5790, 87020-900, Zona Sete, Maringa
, PR, Brazil
c
Departamento de Ci^
sicas da Saúde, Universidade Estadual de Maringa
encias Ba
, Av. Colombo 5790, 87020-900, Zona Sete, Maringa
, PR, Brazil
d
s-Graduaça
Programa de Po ~o em Recursos Naturais, Universidade Estadual de Mato Grosso do Sul, CP 351, 79804-970, Dourados, MS, Brazil

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

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
Semiconductors nanostructured with suitable chemical, bio-
logical, structural, optical, cytotoxic and photocatalytic properties
are becoming increasingly important in biomedical and photo-
catalytic applications, and have been the subject of significant
research. Nanomedicine is the biomedical application of nano-
technology in which engineered nanoparticles (NPs) are used to
* Corresponding author.
E-mail address: jessika_delara@hotmail.com.br (J.L. Andrade).
treat diseases, for example, cancer [1]. Similarly, the field of het-
erogeneous photocatalysis has expanded rapidly in recent decades.
It can be defined as the acceleration of a photoreaction in the
presence of a catalyst. In recent years, interest in photocatalysis has
focused on the use of semiconductor materials as photocatalysts for
the removal of ambient concentrations of organic and inorganic
species from aqueous or gas phase systems in environmental clean-
up operations, drinking water treatment, and industrial and health
applications [2].
The extensive use of dyes in several fields, such as the food,
cosmetics, pharmaceuticals, paper and textile industries, leads to a
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
alone uses about 378 billion liters per year in various processes, like
mercerization, desizing, scouring, dyeing, rising and so on [3]. The
excessive consumption of water in these industries makes waste-
water treatment more important. Presently, a selection of biolog-
ical, physical and chemical traditional methods are used for
wastewater treatment, for example, biological oxidation [4],
membrane filtration [5], adsorption [6], coagulation [7] and
advanced oxidation processes (AOPs) [8].
Congo red (CR) is a common harmful dye that has been used in
the textile, paper, printing, leather and plastic industries [9]. CR is a
benzidine-based anionic diazo dye with a pKa value of 4.1 [10,11]
(Fig. 1). CR is difficult to degrade due to its chemical structures
and stability, ensured by its highly conjugated system [12]. Benzi-
dine is a toxic metabolite of CR and is a human carcinogen, in
addition to being an irritant to the skin and eyes [13,14]. Therefore,
there is a necessity to develop methods for CR removal from
environmental samples. Among the AOPs, heterogeneous photo-
catalysis is indicated as a promising technique for the degradation
of this toxic dye [15].
Heterogeneous photocatalysis has the advantages of being able
to degrade inorganic and organic pollutants completely via free
hydroxyl radicals ($OH) generated in the reaction medium itself,
occurring at room temperature and is low cost, together with a low
or minimum secondary impact on the environment and ecosys-
tems [16]. With the use of heterogeneous photocatalysis increasing,
the development of new catalyst materials becomes very
important.
Current and past research on photocatalytic processes has
revealed several photocatalysts and their properties. Ideally, a
photocatalyst should possess the following properties: photo-
activity, chemical inertness, stability toward photo-corrosion,
suitability for visible or near UV light energy harnessing, low cost
[17] and be easily removed from the medium. In recent years, this
research field has focused on the use of broad gap semiconductors
based on metal oxides as photocatalysts, such as TiO2 [18], Fe2O3
[19], MgO [20], ZnO [21] and so on, for the removal/degradation of
organic and inorganic species from aqueous or gas phase systems
[22].
Among the semiconductors that have been extensively investi-
gated, ZnO is a n-type semiconductor with the crystalline wurtzite
structure and with a wide band gap, reported to be around 3.3 eV
[23]. ZnO has been used in substitution to TiO2 in the photo-
degradation of many organic pollutants [24,25], because it absorbs
a larger fraction of the solar spectrum than TiO2 [26] and in many
cases, due to its higher quantum efficiency [23].
However, in order to improve the photocatalytic properties of
ZnO, this oxide has been doped with various metal ions, such as Ce
[27], Mn [28], Cu [29], Mg [30], Al [31,32], Ga [33] and so forth. The
insertion of dopant ions into the crystal lattice of ZnO enables
suitable modifications to its properties. By molding the band
structure of ZnO it is possible to shift its absorption to the visible
region, and consequently, decrease its band gap energy [23].
Fig. 1. Acid-base equilibrium of CR.
979
Al is low cost and has high abundance in the earth, so the effect
of Al-doping of ZnO on the photocatalytic performance has been
studied extensively. Lee et al. [31] synthesized Al-doped ZnO (AZO)
by a precipitation method with different dopant contents and
studied their photocatalytic properties. It was verified that AZO
with 3 mol% of Al presented the highest photocatalytic perfor-
mance for the degradation of the methyl orange (MO) under UV
irradiation. This maximum photocatalytic activity was assigned to
the dopant content that could effectively reduce the recombination
between photo-induced electron-hole pairs.
Ahmad et al. [34] synthesized Al-doped ZnO by a combustion
method whilst varying the proportion of dopant from 0.5 to 6.0 mol
%. The authors observed that the band gap energy (Eg) decreased
with doping from 3.21 (pure ZnO) to 3.12 eV (AZO with 6 mol% Al).
These oxides were employed in MO photodegradation under visible
light and the best results were observed with AZO with 4 mol%,
which degraded 100% of the MO dye after 1.5 h of irradiation, while
the undoped ZnO degraded only 23%. These reports that reveal the
application potential of Al-doped ZnO on the photodegradation of
organic pollutants under sunlight or visible light motivated the
current study.
Furthermore, due to the unique properties of ZnO, including
high chemical and physical stability, and highly efficient UVeVis
absorption [35], its application has been reported for sunscreens
[36], food packaging [37], antibacterial agents [38] and drug de-
livery systems [39]. However, when a nanostructured material is
projected for biomedical applications, its potential cytotoxicity
must be considered. Therefore, in-vitro studies have investigated
the exposure effects on several cell lines [40]. Buerki-Thurnherr
et al. [41] studied the cytotoxicity effect of ZnO towards Jurkat
cells, and their results revealed that even for very low concentra-
tions of ZnO, it was highly toxic to these cells due to the release of
high amounts of Zn2þ into the cells. Zanni et al. [42] studied the
cytotoxicity effect of ZnO nanorods and microrods towards two
different human cell lines (MCF7 and HaCat). They demonstrated
that these materials did not cause reduction of viable cells
compared to the control, but both cell lines exposed to ZnO showed
changes in cell morphology. Thus, more studies are evidently
required to better understand the cytotoxic properties of undoped
and doped ZnO. We believe that the doping can be a method of
shape the cytotoxicity of ZnO NPs and their optical and photo-
catalytic properties.
In the current study, Al-doped ZnO (ZnO-Al x% with x ¼ 0, 1, 3, 5
and 10 mol% Al3þ) nanostructures were synthesized by a modified
sol-gel method [43]. The effects of dopant ion content on the
structural organization and optical and morphological properties of
ZnO were investigated. We also studied the effects of Al content on
the photocatalytic performance of Al-doped ZnO for the degrada-
tion of CR. In-vitro studies were also performed for evaluating the
cytotoxic effect of ZnO-Al x% NPs on fibroblast cells (ATCC L929),
with the aim of investigating their potential for biomedical appli-
cation in nanomedicine.
980 J.L. Andrade et al. / Journal of Alloys and Compounds 729 (2017) 978e987
2. Experimental
2.1. Preparation of ZnO-Al x% NPs
Undoped ZnO and Al-doped ZnO were synthesized by a modi-
fied sol-gel method [43] and all the reagents used in this step were
of analytical grade without the need for further purification.
Initially, a 10% (w/v) diluted aqueous solution of poly(vinyl alcohol)
(98e99% hydrolyzed, Aldrich) and saturated metal nitrate solutions
(Zn(NO3)2$6H2O and Al(NO3)3$9H2O, both Synth) were separately
prepared and then mixed at specific metallic ion:monomer unit ra-
tios. The solutions were maintained at room temperature under
stirring for 2 h and then heated under vigorous stirring until total
water evaporation. The temperature was maintained at 250e350  C
for the initial thermal degradation of the organic material. The
nanostructured materials were obtained after calcination of the
precursor powder under air atmosphere at 500  C. As a result,
undoped ZnO and Al-doped ZnO NPs containing different concen-
trations of dopant ion (0, 1, 3, 5 and 10 mol%) were successfully
prepared. These samples were labeled as ZnO-Al x% (with x mol%
Al3þ).
2.2. Characterization of ZnO-Al x% NPs
The structure of the ZnO-Al x% powder was analyzed by X-ray
diffraction (XRD) using a Shimadzu XRD 7000 diffractometer (with
Ka of 1.5406 Å radiation at 40 kV and 30 mA in the 2q range from
20 to 80 with a scan rate of 2 min1 and a step of 0.02 ). The
average crystallite size was estimated using the Scherrer equation
(Eq. (1)).
0:9 l
d¼
ðbhkl cos qB Þ
where l is the wavelength, bhkl ¼ [(Bobs)2 e (Bstd)2]1/2, Bobs is the
observed full width at half maximum (FWHM) of the sample
considered peak, Bstd is the instrumental contribution to the FWHM
and qB is the Bragg angle. Micro-Raman measurements were per-
formed using a Bruker Senterra Raman microscope using a 532 nm
laser excitation and laser power of 20 mW at room temperature.
Photoacoustic absorption (PA) spectra were performed using
monochromatic light from a 1000 W xenon arc lamp (Model68820,
Oriel Corporation), a monochromator (Model 77250, Oriel In-
struments) and a mechanical chopper (Model SR540, Stanford
Research Systems). The spectral range was between 200 and
800 nm. The band gap energy of the samples was determined using
the Tauc relation (Eq. (2)):
ahn ¼ A (hn e Eg)n
where a is the PA signal (directly proportional to the absorption
coefficient), A is a constant, h is Planck's constant, n is the photon
frequency, Eg is the optical band gap and n is ½ for a direct semi-
conductor [44].
Photoluminescence (PL) spectra were obtained with excitation
of the sample at 330 nm. The optical emission was collected with an
optical fiber and analyzed with a Jobin Yvon iHR550 mono-
chromator (1200 grooves/mm holographic grating) coupled to an
iCCD. All the measurements were performed at room temperature
(~300 K) with at least three repetitions. The morphology and
microstructure of the samples were characterized by transmission
electron microscopy (TEM, JEM-1400 JEOL, operated at 120 kV).
Specific surface area measurements were carried out by N2
adsorption-desorption isotherms at 77 K using a surface area
analyzer (QuantaChrome Nova 1200). The Brunauer-Emmett-Teller
(BET) surface area (SBET) was calculated using QuantaChrome™
NovaWin software using the BET equation in a relative pressure
range of P/P0 ¼ 0.050e0.350.
2.2.1. Determination of pHpzc of ZnO-Al x% NPs
The pHpzc, known as the point of zero charge, was obtained by
mixing 0.50 g of each ZnO-Al x% oxide with 25 mL of 0.10 mol L1
solution of NaCl in a falcon tube. Then, 1.00 mol L1 of HCl or NaOH
was added to each falcon tube in order to obtain the following pH
values: 2.0; 4.0; 6.0; 8.0; 10.0 and 12.0. The equilibrium pH of the
mixture was measured after constant stirring for 24 h. After this,
the pH of each solution was measured using a pHmeter and noted
as pHfinal. The pHpzc of the ZnO-Al x% oxides was estimated from
curves of pH variation (DpH) versus initial pH (pHi), by linear
extrapolation at DpH equal to zero (pHinitial ¼ pHfinal). The pHpzc is
the point at which the extrapolated line (in DpH ¼ 0) intercepts the
experimental curve.
2.3. Photocatalytic performance of ZnO-Al x% NPs
The photocatalytic performance of the undoped and Al-doped
ZnO NPs was evaluated on the photodegradation of CR under
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
temperature (~300 K). The distance between the lamp and the
suspension surface was fixed at 17 cm. Catalyst concentration and
solutions pH used were 1.00 g L1 and 12.0.
The photocatalytic reactions were carried out using a Pyrex
reactor (15 cm in diameter) containing 400 mL of 20 mg L1 CR
solution. This solution with a catalyst was maintained under
magnetic stirring in the dark for 60 min to establish an adsorption-
desorption equilibrium. After this, the pH was adjusted to 12.0 with
(1)
a NaOH solution (1 mol L1) and the solution was irradiated under
constant stirring. During the photocatalytic reaction, aliquots were
taken at different time intervals and immediately centrifuged to
remove catalyst particles. The photocatalytic degradation of the CR
dye was monitored by measuring the absorbance of the solution
samples at 498 nm using a UVeVis spectrophotometer (Cary 50).
According to the Beer-Lambert Law, absorbance (A) is proportional
to concentration.
The percentage removal of CR was calculated using Eq. (3):
A0  At
Degradation efficiency ð%Þ ¼ *100% (3)
A0
where A0 and At are the initial absorbance of the dye solution and
the absorbance at a certain reaction time (in min), respectively.
(2) 2.4. In-vitro cytotoxicity of ZnO-Al x% NPs
Cell viability assays were performed using an in-vitro study
employing fibroblast cells (ATCC L929). The fibroblasts cells were
cultured in DMEM (Dulbecco's Modified Eagle Medium, Gibco
Invitrogen) supplemented with 10% FBS (fetal bovine serum), 1%
penicillin and 1% streptomycin, and were incubated at 37  C in a
humid atmosphere containing 5% CO2. The culture and co-
confluent were washed with PBS, trypsinized, resuspended and
seeded at an initial density of 2.5  105 cells/well in DMEM sup-
plemented with 10% FBS into a 96-well microplate. After 24 h of
incubation, the culture medium with ZnO, ZnO-Al 1% and ZnO-Al
5% were prepared by serial dilution in concentrations of 800, 400,
200, 100, 50 and 10 mg/mL, and 200 mL of this dispersion was added
to each before being well incubated for 24 h. Two independent
experiments were performed in duplicate. The cell viability was
evaluated by the metabolic activity of the cells through a
 J.L. Andrade et al. / Journal of Alloys and Compounds 729 (2017) 978e987
colorimetric method that is based on the ability of mitochondria of
viable cells to reduce MTT (tetrazolium salt) into a purple insoluble
compound called formazan. After 24 h, the 96-well cell culture
plates were observed under an optical microscope. Afterwards, a
40 mL MTT solution at a concentration of 2.5 mg/mL was added to
each well, and the cells were incubated for 4 h at 37  C and 5% CO2.
The supernatant was removed and 100 mL of DMSO was added to
each well and the reading was performed in ELISA spectropho-
tometer (Bio-Tek FL-600 Microplate Fluorescence Reader) at
540 nm with a reference at 630 nm. Cells grown in the absence of
ZnO-Al x% oxides were used as a negative control and taken as 100%
growth. The number of viable cells was calculated based on the
absorbance value obtained.
3. Results and discussion
3.1. Structure, morphology and optical properties of ZnO-Al x% NPs
XRD diffractograms of undoped ZnO and ZnO-Al x% NPs with
Fig. 2. (a) XRD patterns of undoped ZnO and ZnO-Al x%, with x corresponding to
different Al3þ ion contents in mol% (indicated) and (b) zoom-in for the range
31.0e37.5 .
981
different Al3þ ion contents, in the range of 2q ¼ 20e80 are shown
in Fig. 2(a). For all Al-doped ZnO samples, only the peaks charac-
teristics of ZnO with wurtzite structure [45] were observed, in
accordance with the standard card JCPDS 36-1451, which can be
indexed to the space group P63mc [46]. This indicates that the Al3þ
ions were incorporated into the crystalline structure of ZnO, at least
partially occupying Zn2þ sites [47], and that the dopant levels
investigated were lower than the limit solubility of Al3þ into the
ZnO matrix. However, the positions of the diffraction peaks at 31.7
(100), 34.5 (002) and 36.2 (101) were slightly shifted to higher
angles (as shown in Fig. 2(b)) and a baseline shift was exhibited
with increasing Al3þ content. Similar behavior was also observed
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
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
Al3þ occupy sites previously occupied by Zn2þ ions, the lattice
constants decreases, promoting alterations in the diffraction peaks
[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.
Nanoparticles Diameter (nm) Band gap energy (eV)
ZnO 25 ± 1 3.12 ± 0.01
ZnO-Al 1% 15 ± 1 3.00 ± 0.01
ZnO-Al 3% 12 ± 3 2.95 ± 0.01
ZnO-Al 5% 8±4 2.99 ± 0.01
ZnO-Al 10% 7±3 3.07 ± 0.01
982 J.L. Andrade et al. / Journal of Alloys and Compounds 729 (2017) 978e987

Fig. 3. Raman spectra of undoped ZnO and ZnO-Al x% with different Al3þ contents.

and oxygen vacancy displacement. This suggests that some Zn2þ

ions were replaced by Al3þ. As previously discussed, the different
ionic radius and valences of zinc and aluminum ions may have
promoted structural changes in the crystalline structural lattice of
the ZnO host [55,56]. These evidences are in accordance with the
XRD results (Fig. 2).
TEM images obtained for the NPs are shown in Fig. 4. The
undoped ZnO NPs (Fig. 4(a)) exhibited sizes of around 30e50 nm
and no uniform morphology, with some hexagonal, cubic and
spherical particles. The ZnO-Al 10% NPs (Fig. 4(b)) showed a fairly
particulate form with uniform size distribution and with an average
diameter of around 10 nm. It can be seen from the TEM images that
the average particle size of the samples decreases with increasing
Al dopant content, consistent with the data estimated by the
Scherrer equation.
Fig. 5(a) shows the UVeVis PA spectra obtained at room tem-
perature for undoped ZnO and ZnO-Al x%. Undoped ZnO exhibits a
broad absorption between 250 and 370 nm [57,58], due to the
electronic transitions from the valence to the conduction band,
which can be assigned to the intrinsic band gap absorption of ZnO
[59]. The Al-doped ZnO NPs demonstrated similar behavior, but,
their absorption curves appear slightly displaced to the visible re-
gion when compared to the absorption curve of undoped ZnO. The
red-shift showed by the ZnO-Al x% oxides indicates that the
incorporation of Al3þ into the ZnO crystal lattice cause changes in
their optical properties, enhancing the ZnO absorption in the visible
region. Ahmad et al. also observed this effect with Al-doped ZnO Fig. 4. TEM images obtained for (a) undoped ZnO and (b) ZnO-Al 10% NPs.
synthesized by a combustion method [34].
The band gap energy values estimated by Tauc equation
(Table 1) reveal that this parameter of the oxides decreased with Al for the ZnO-Al x%, which can be associated to superficial defects
doping. Undoped ZnO exhibited an Eg of 3.12 eV and the lowest Eg such as a greater amount of negatively charged oxygen species [62],
value of 2.95 eV was found for ZnO-Al 3%. This result indicates that which may decrease mobility, and therefore decrease the carrier
the insertion of Al3þ dopant ions changes the electronic and optical concentrations.
characteristics of ZnO, reducing the energy between their valence The influence of Al3þ content on the optical properties of ZnO
and conduction bands, due to the creation of additional electronic was also investigated from the PL spectra obtained for the ZnO-Al x
sub-levels. % samples, which are shown in Fig. 6. It can be clearly seen in these
Some authors report that Al doping ZnO may increase its band PL spectra that the undoped ZnO showed an intense emission
gap energy, due to observed blue-shift caused by the Burstein-Moss above 430 nm, which was considerably decreased with the inser-
effect [60,61]. This effect is related to the increase of the carrier tion of Al3þ ions.
concentrations, that induces an increase of the band gap, due to the ZnO-Al x% NPs showed a broad emission band at the visible
displacement of the Fermi level. However, in this work we observed region, between 430 and 650 nm, with a maximum in the green
a red-shift and consequently the decrease in the band gap energy region at 550 nm. This intense emission at 550 nm may be assigned
 J.L. Andrade et al. / Journal of Alloys and Compounds 729 (2017) 978e987
Fig. 5. PA spectra of undoped ZnO and ZnO-Al x% oxides synthesized with different
Al3þ contents.
Fig. 6. PL spectra obtained at room temperature for the undoped ZnO and ZnO-Al x%
with different Al3þ contents.
to intrinsic defects, such as oxygen vacancies (VO), interstitials Zn
(Zni) and zinc vacancies (VZn) [63,64], or to the recombination of
electrons trapped in singly ionized vacancies with photogenerated
holes [64,65]. The undoped ZnO also shows emission at longer
wavelengths in the yellow and orange region, which can be asso-
ciated with lattice defects, such as Zni [63]. The changes observed in
the PL intensity of ZnO with the insertion of Al3þ dopant suggest
that the doping can considerably influence the recombination rate
between photogenerated electron-hole pairs [31].
The specific surface areas determined from BET isotherms for
ZnO-Al x% are listed in Table 2. The surface area of the samples
increased with Al3þ insertion from 21.9 (for undoped ZnO) to
45.8 m2 g1 (for ZnO-Al 10%). Doping prevents grain growth, and
thus, higher Al contents lead to smaller crystallite sizes, resulting in
higher surface areas [31], in agreement with our XRD results
(Table 1). The higher surface area of the Al-doped ZnO is indicative
that the doping may enhance the efficiency of these semi-
conductors when they are applied in photocatalysis heterogeneous
983
Table 2
Specific surface area (SBET) and pHpzc estimated for undoped ZnO and ZnO-Al x%
with different Al3þ contents.
Nanoparticles Surface area (m2 g1) pHpzc
ZnO 21.9 11.8
ZnO-Al 1% 32.2 10.6
ZnO-Al 3% 41.0 10.5
ZnO-Al 5% 38.0 12.0
ZnO-Al 10% 45.8 12.0
reactions, once the adsorption is the first step involved in these
reactions, Generally, for all catalyst materials, a high surface area is
an advantage in terms of a greater quantity of active sites per square
meter and this generally leads to higher reactivity.
Specific area surface, the pHpzc is also important information
about whether the surface oxide becomes either positively or
negatively charged as a function of pH medium. The pH of the so-
lution affects the photocatalytic activity of a semiconductor, mak-
ing the interaction between an organic pollutant and the catalyst
easier or more difficult. The pHpzc data shown in Table 2 demon-
strate that the surfaces of all Al-doped ZnO are positively charged at
pH < 10.0, which could favor the adsorption of negatively charged
molecules of CR due to interactions with their sulfonate groups (see
Fig. 1). However, preliminary experiments showed that a strong and
irreversible adsorption occurs between the molecules of CR and the
catalysts at pH < 10.0. Contrary, at pH  12.0 the surface of Al-
doped ZnO are negatively charged, with a weakening of the in-
teractions between the pollutant molecules and the surface of the
NPs, consequently resulting in less intense adsorption between
these species in solution.
3.2. Photocatalytic performance of synthesized ZnO-Al x% NPs
The investigation of the effect of Al3þ content on the photo-
catalytic activity of the ZnO-Al x% was performed using the best
experimental conditions found in the preliminary tests for CR
photodegradation. Such conditions correspond to pH 12.0 and a
catalyst concentration of 1.00 g L1. Fig. 7(a) shows that the Al3þ
dopant content does not affect the kinetic profile of the CR pho-
todegradation, and that the reaction is in agreement with Lang-
muireHinshelwood first-order kinetic behavior [66,67]. A
nonlinear decrease was observed in the photocatalytic activity of
ZnO with the insertion of Al3þ dopant ions. The kapp value
decreased from 1.00  102 min1 (for undoped ZnO) to
0.25  102 min1 (for ZnO-Al 3%), which exhibited the lowest
photocatalytic efficiency among all tested Al-doped ZnO samples.
Despite of the insertion of Al3þ into the crystal structure of ZnO
decreased the band gap energy (Table 1) and increased the specific
areas estimated (Table 2). Contrary, the insertion of dopant ions in
specific conditions can increase the recombination rate between
photogenerated charges, decreasing the photocatalytic activity of
the ZnO-Al x% in relation to undoped ZnO. This effect could be
related to a possible increase of the quantity of structural defects
promoted by the doping, as suggested by the Raman and PL results.
Fig. 7(b) shows the variations in the percentage of photo-
degradation of CR after 300 min of irradiation under UVeVis light,
using ZnO-Al x% NPs as catalysts. It is clear that the undoped ZnO
NPs exhibited a better photocatalytic activity than Al-doped ZnO, it
degraded 96% of the CR while the ZnO-Al x% degraded between 42
and 82%. CR is an organic pollutant with a more complex chemical
structure than other dyes studied as model pollutants, such as MO,
for example [31,34]. CR with more aromatic rings is a more stable
molecule and needs a greater quantity of photogenerated charges
for its degradation. The results obtained for the photodegradation
984 J.L. Andrade et al. / Journal of Alloys and Compounds 729 (2017) 978e987
Fig. 7. (a) Effect of Al3þ content on the photocatalytic performance of ZnO-Al x%
(1.00 g L1) for the photodegradation of CR at an initial pH adjusted to 12.0. (b) Rate
photodegradation of CR using ZnO-Al x% as catalysts after 300 min of irradiation under
visible light.
under UVeVis light of CR using the semiconductors synthesized in
the current work can be considered satisfactory when compared
with results that report the photodegradation of this dye using
other oxides NPs.
Has been reported that the photodegradation of CR using CuO
NPs with different morphologies as catalyst, for example, showed
that almost 67%, 48% and 12% of CR was photodegraded with CuO
with morphologies of nanorods, nanoleaves and nanosheets,
respectively, after 210 min of UV light irradiation [68]. Mohammad
et al. studied the photocatalytic degradation of CR using nano-
structured ZnO-CdS core-shell structures as catalyst, and reached
88% of degradation after 100 min under UV irradiation [69]. Guy
et al. reported the photodegradation of CR using Pd-doped ZnO as
catalyst. The best doping content was 5 wt% Pd, which degraded
98% of the CR dye, after 60 min of irradiation under UV light [15].
Although there are several reports on the photodegradation of CR
using different metal oxides as catalysts, until now, there have been
no reports on the specific use of Al-doped ZnO NPs, nor the use of
irradiation with visible light.
3.3. In-vitro cytotoxicity of synthesized ZnO-Al x% NPs
The results of in-vitro studies of the cytotoxicity of the ZnO-Al x%
NPs after 24 h of incubation with different concentrations of oxide,
in the range of 0e800 mg/mL, with L929 fibroblast cells, are shown
in Fig. 8. The samples employed were undoped ZnO, ZnO-Al 1% and
ZnO-Al 5% NPs. The cytotoxicity was measured by enzymatic assays
of MTT. Since the results for all tested concentrations of the
undoped ZnO NPs demonstrated that the viability of the L929
fibroblast cells decreased, even for small concentrations of oxide
(10 mg/mL), the cell viability was only 10% compared to the negative
control (100% cell viability). The ZnO-Al 1% and ZnO-Al 5% oxides
exhibited viability similar to undoped ZnO. These results demon-
strated that both undoped ZnO and Al-doped ZnO NPs inhibit the
cells viability, due to its elevated cytotoxic effect. Pandurangan et al.
[70] found a high cytotoxicity for ZnO NPs towards HeLa (Human
cervical carcinoma cells). The significant cytotoxic activity of ZnO
on the HeLa and innumerous others reports on the enhanced
cytotoxicity and high selectivity of ZnO NPs make this material a
promising anticancer agent [1].
The changes in the morphology of the L929 fibroblast cells
clearly confirm the high cytotoxicity of ZnO-Al x% oxides, as can be
seen in Fig. 9. Fig. 9(a) shows the typical stellar morphology of the
fibroblast cells [71] in the control cells. In Fig. 9(b), (c) and (d), the
spread morphology characteristic of the fibroblast cells was
completely changed after contact with the ZnO NPs in all tested
concentrations, exhibiting a spherical morphology, characteristic of
death cells. The fibroblast cell morphology after addition of the
ZnO-Al 1% and ZnO-Al 5% oxides also exhibited a spherical
morphology (Fig. 9(e)-(j)), confirming the cytotoxic effects of the
Al-doped ZnO synthesized oxides in this work.
The high cytotoxicity observed for undoped ZnO and Al-doped
ZnO NPs can be mostly related to two factors: particle dissolution
and hence the release of toxic Zn2þ ions into the cells [72,73], and
the increase in the generated reactive oxygen species (ROS),
resulting in an imbalance of the antioxidant systems and severe
oxidative stress responses [74] inducing cell death by apoptosis
[75]. Buerki-Thurnherr et al. [41] investigated the role of different
cell death pathways, when the human Jurkat T cells were exposed
to various ZnO NPs. ROS formation, particle dissolution and the
contribution of soluble Zn2þ ions were investigated in their
research. They suggest that Zn2þ ions released from ZnO NPs is
mainly responsible for apoptotic cell death.
In our work, we also observed that the insertion of Al3þ dopant
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-
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
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-
tical and morphological properties of the ZnO NPs, possibly
increasing the quantity of structural defects and the recombination
rate between photogenerated electron-hole pairs. We believe that
such changes significantly affected the photocatalytic efficiency of
each oxide tested as a catalyst for the CR photodegradation. How-
ever, in relation to cytotoxic effects, both systems, undoped ZnO
and Al-doped ZnO, exhibited high cytotoxicity towards L929
fibroblast cells. This effect is likely to be related to the toxic Zn2þ
ions released into the cells, since complementary studies revealed
that Al3þ ions from undoped Al2O3 was not cytotoxic towards L929
fibroblast cells. With the increase of Zn2þ released into the cells, the
ROS generation is also increased, leading to cytotoxicity of cells
through oxidative stress. An interesting aspect is that the cytotox-
icity of these NPs can be molded by chemical modification on its
surface or immobilization into biocompatible polymers, or in core-
shell type nanostructure, aiming biomedical applications such as
drug delivery system. The selective cytotoxicity of the ZnO-Al x NPs
against cancerous cells in vitro, compared to others NPs [1], is
another interesting aspect to be investigated in future studies.
4. Conclusions
In summary, ZnO-Al x% NPs, with x ¼ 0, 1, 3, 5 and 10 mol% of
Al3þ dopant ions, were successfully synthesized by a modified sol-
gel method. From the XRD data, secondary phase formation was not
detected. The average crystallite size of the oxides decreased from
25 (for undoped ZnO) to 7 nm (for ZnO-Al 10%). Raman spectra
indicated that the doping promoted changes in the structural or-
ganization of the ZnO host, indicating an increase in the quantity of
intrinsic defects, such as oxygen vacancies. The ZnO-Al x% NPs
exhibited a broad absorption band slightly shifted to the visible
region, leading to reduction in the band gap energy from 3.12 (for
undoped ZnO) to 2.95 eV (for ZnO-Al 3%). Undoped ZnO exhibited
intense PL above 430 nm associated with lattice defects, such as Zn
985
interstitials, which was considerably decreased with the insertion
of Al. The ZnO-Al x% oxides showed a broad and less intense
emission band at the visible region, with maximum in the green
region (at 550 nm) that may be assigned to intrinsic defects, such as
oxygen vacancies and Zn interstitials and vacancies. The insertion
of Al3þ ions into the crystalline structure of the ZnO NPs decreased
their photocatalytic activity, probably due to the increase of the
recombination rate between photogenerated electron-hole pairs.
With respect to cytotoxicity, both undoped ZnO and Al-doped ZnO
oxides inhibited the fibroblast cell viability and affected the cell
morphology.
Acknowledgments
The authors are grateful to Department of Physics/UEM, to
COMCAP/UEM for providing the equipment used in this work, to
CAPES and to CNPq (Process n. 405381/2016-6) for financial
support.
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