Applied Surface Science 448 (2018) 646–654

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Applied Surface Science

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

Full Length Article

Role of defects on the enhancement of the photocatalytic response of

ZnO nanostructures
Marly Montero-Muñoz a,⇑, J.E. Ramos-Ibarra a, Jorge E. Rodríguez-Páez b, Marcio D. Teodoro c,
Gilmar E. Marques c, Alfonso R. Sanabria d, Paola C. Cajas e, Carlos A. Páez f, Benoît Heinrichs f,
Jose A.H. Coaquira a
a
Institute of Physics, University of Brasilia, 70910-900 Brasília - DF, Brazil
b
Department of Physics, University of Cauca, Popayán - Cauca, Colombia
c
Department of Physics, Federal University of São Carlos, 13565-905 São Carlos, SP, Brazil
d
Department of Chemistry, University of Cauca, Popayán - Cauca, Colombia
e
Department of Mechanical Engineering, University of Brasilia, 70910-900 Brasília - DF, Brazil
f
Department of Chemical Engineering, Génie chimique – Nanomatériaux et Interfaces, Université de Liège, Belgium

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

Article history: Zinc oxide (ZnO) nanostructures have been synthesized by a simple controlled precipitation method to
Received 3 January 2018 study the effects of the type solvent – including water, acetic acid and ethylene glycol – on the formation
Revised 18 March 2018 of ZnO and on its photocatalytic activity for the decomposition of H2O2 in aqueous solution. Scanning
Accepted 10 April 2018
electron microscopy (SEM) and synchrotron-based X-ray diffraction (XRD) were used to determine the
Available online 12 April 2018
morphology, crystallinity, and chemical composition of the ZnO structures. Raman spectroscopy and pho-
toluminescence measurements were carried out to determine the nature of the defects present in the dif-
Keywords:
ferent ZnO nanostructures and how they affect the photocatalytic activity. Based on the results, we
ZnO nanostructure
Synthesis solvents
propose plausible growth mechanisms underlying the formation of ZnO with different morphology,
Morphology according to the solvent used during the synthesis. A direct relation between the photocatalytic activity
Defects and the defects type was established, suggesting that defects play a vital role in modulating the photo-
Photocatalytic activity catalytic response.
Ó 2018 Elsevier B.V. All rights reserved.

1. Introduction knowledge, photocatalytic properties of ZnO and their relation

Zinc oxide compound is an excellent material that possesses
interesting properties for multifunctional applications in many
technological fields, such as electronics, magnetic devices, photo-
voltaic (solar cells), sensors and photocatalysts [1–4]. In addition,
ZnO can also be used for lasing in the ultraviolet region because
of its large band gap (3.44 eV at low temperature) and high exciton
binding energy (60 meV) [5].
The optical and electronic properties of ZnO nanocrystals can be
modulated by changing their size and morphology in order to fit
them to some specific applications; therefore, it represents a great
challenge to realize novel functional devices based on ZnO
nanocrystals. So far, many different-shaped ZnO structures have
been prepared (i.e., prismatic, belt-like, flower-like, tubular,
tower-like, needle-like, and propeller-like) using various physical
[1] and chemical [6–14] methods, although to the best of our
⇑ Corresponding author.
E-mail address: marlymontero@gmail.com (M. Montero-Muñoz).
with the size and morphology has not been well understood up
to now. Specifically, Morales et al. [15], fabricated ZnO nanostruc-
tures with different morphologies using the ultrasound-assisted
hydrolysis of zinc acetate at room temperature. They studied the
effects of the morphology and other parameters like specific
surface area, defect content, and surface contamination on the
photocatalytic activity of ZnO for the degradation of methylene
blue (MB) using UV light. The results evidenced that all
the above-mentioned parameters seen to affect the photocatalytic
performance of ZnO nanostructures. Xu et al. [16] synthesized ZnO
materials with different morphologies via the solvothermal
method using different solvents and the results indicated that
the ZnO nanostructures exhibited different activities to the degra-
dation of phenol. The authors found that there was no correlation
between the surface areas and the catalytic activity, suggesting
that there are other more important factors those determine the
photocatalytic activity –such as crystal habits.
In this work, we report the study of ZnO structures synthesized
at room temperature using a controlled precipitation method. We

https://doi.org/10.1016/j.apsusc.2018.04.105
0169-4332/Ó 2018 Elsevier B.V. All rights reserved.
 M. Montero-Muñoz et al. / Applied Surface Science 448 (2018) 646–654
obtain ZnO structures with various distinct morphologies, particle
size and surface area, which are obtained by simply changing the
synthesis-solvent and the pH of the solution. The control of the
growth parameters allowed us to improve the photocatalytic activ-
ity of ZnO structures. The effect of the synthesis parameters on the
structural and optical properties of the synthesized powders was
also studied to determine their relation with the photocatalytic
activity improvement.
2. Experimental section
2.1. Materials
Zinc acetate dihydrate (Zn(CH3COOH)2), Acetic acid (CH3COOH),
Ethylene glycol (C2H6O2), Nitric acid (HNO3), and Ammonium
hydroxide solution (NH4OH) were purchased from Sigma–Aldrich
and used without further treatment. Distilled-deionized water
(18.2 MX.cm) was obtained from a Milli-Q water purification sys-
tem (Millipore, Billerica, MA, USA) and used as the solvent in some
ZnO synthesis reactions.
2.2. Synthesis
The ZnO nanoparticles were prepared by the controlled precip-
itation method [13]. An amount of 3.0 mmol of Zn(Ac)2
2H2O were
dissolved in 200 mL of a specific solvent; water for sample ZnO-1;
acetic acid for sample ZnO-2 and ethylene glycol acidified with
nitric acid for sample ZnO-3. The mixture was steady stirred at
room temperature for 20 min until reach a completely homoge-
neous and transparent solution. Then the NH4OH solution was
added to the above solutions at a rate of 1 ml/min until getting a
pH of 8.8, 7.0 or 9.0 for samples ZnO-1, ZnO-2 or ZnO-3, respec-
tively. The pH values were previously established from the titra-
tion curves. The obtained precipitates were washed in a 100 mL
of deionized water and re-dispersed using high shear equipment
(Ultraturrax-T50) at 10000 rpm for 10 min. Then, the obtained pro-
duct was left to rest for 24 h and after that, the liquid of the solu-
tion was removed by decanting. This process was repeated four
times. After the fourth washing, the liquid of the solution was
removed and the wet sample was dried at 100 °C in air atmosphere
for 4 h. Finally, the resulting product was macerated and heated at
300 °C in a commercial furnace for 2 h.
2.3. Characterization
The crystalline structure of the synthesized ZnO samples was
characterized using a synchrotron-based X-ray diffraction (XRD)
carried out at the Brazilian Synchrotron Light Laboratory (LNLS).
The XRD measurements were performed by fixing the sample on
borosilicate glass capillaries – with outer diameters of 0.7 mm –
using a fine layer of commercial Vaseline. The sample was spun
during data collection to minimize preferred orientation and sam-
pling effects (for further information see the references) [17]. The
XRD patterns were obtained at room temperature in a transmis-
sion mode using the MYTHEN 24 K systems (Dectris Ò) and col-
lected from 2 to 120°, with a step size fixed at 0.004°. Twenty-
five scans of 60 s each were taken to reduce the signal-to-noise
ratio. The NIST SRM640d standard Si and NIST SRM660b standard
LaB6 powders were used to determine the X-ray wavelength with a
good precision and the instrumental parameters, respectively. The
mean wavelength used was 1.0328(1) Å. The profile peak shape
was described using a Thompson-Cox-Hastings (TCH) pseudo-
Voigt function: convolution of a Gaussian (HG ) and a Lorentzian
(HL ) [18], with an additional term to allow for anisotropic particle
size broadening effects. The FWHM (H) was easily obtained using
647
the numerical approximation provided by TCH relation (Eq. (1))
and the integral breath (b) of the Voigt function is then calculated
using the expression (3) of the pseudo-Voigt approximation,
through the previous calculation of H and g using the expressions
(1) and (2).
H5 ¼ ðH5G þ 2:69269H4G HL þ 2:42843H3G H2L þ 4:47163H2G H3L
þ 0:07842HG H4L þ H5L Þ ð1Þ

2
3
HL HL HL
g ¼ 1:36603  0:47719 þ 0:11116 ð2Þ
H H H
pH=2
b¼ pffiffiffiffiffiffiffiffiffiffiffiffi ð3Þ
g þ ð1  gÞ p ln 2
The Rietveld refinement was performed using the fourth func-
tion of GSAS package [19]. The crystallite size was estimated using
the Scherrer’s relation: Dp ¼ kk=b cos h, where Dp is the average
crystallite size in Å, k is the Scherrer constant (typically  1), k is
the mean wavelength, b is the integral breadth of a peak, and h is
the diffraction angle.
Fourier-transform infrared spectroscopy (FT-IR) spectra were
recorded on a Thermo Scientific TM Nicolet TM iS TM 10 spectrometer.
BET surface area analysis was performed on an automated surface
area analyzer (ASAP 2020, U.S.A.) by means of nitrogen adsorp-
tion–desorption curves. The morphology of the samples was deter-
mined by scanning electron microscopy (SEM, JSM 7001-F
microscope, JEOL). In order to know more about the structure of
the synthesized samples and about their vibrational properties,
Raman spectra were obtained using an argon laser excitation
source coupled to a Jobin-Yvon (model T6400) spectrometer with
grids of 1800 lines/mm and a CCD of 2048512 pixels cooled by
liquid nitrogen.
The optical properties of the ZnO materials were determined
using a commercial spectrophotometer (Shimadzu, UV–vis NIR)
in the range of 200 and 900 nm with the samples placed inside
quartz cuvettes of 1 cm of lengths. Photoluminescence measure-
ments were performed by using a Helium closed cycle cryostat
(Attocube – Attodry 1000) at 10 K. The powders samples were
placed on top of a home build holder, and excited by a 355 nm
Argon laser line (Coherent Enterprise) launched into an optical
fiber, and focused on a 200 um spot by an achromatic lens. The
backscattered luminescence was collected by the same lens, and
demagnified into a 100 um optical fiber, dispersed by a 75 cm spec-
trometer and detected by a back-illuminated Silicon Charged Cou-
ple Device (Andor).
The catalytic and photocatalytic activities of the ZnO synthe-
sized samples were determined from the rate of decomposition
of H2O2 solved in aqueous solution. The adapted O2-monitored
method was used to carried out the experiments as described in
Ref. [20].
3. Results and discussion
3.1. Structural and morphological characterizations
The diffraction patterns, calculated and difference profile plots
of ZnO samples are shown in Fig. 1; and the final lattice parameters
and crystallite sizes are given in Table 1. The diffraction patterns
are in good agreement with those of standard ZnO (ICDD 36-
1451) and reveal the formation of the hexagonal Wurtzite struc-
ture (P63mc space group). The refined lattice parameters are close
to standard ZnO as shown in Table 1. The ZnO samples synthesized
using water (ZnO-1) and acetic acid (ZnO-2) as solvents are well
648 M. Montero-Muñoz et al. / Applied Surface Science 448 (2018) 646–654

Fig. 1. XRD patterns of the ZnO samples.

Fig. 3. FTIR spectra of the ZnO samples.

Table 1
Lattice parameters and crystallite sizes obtained from Rietveld refinement.
1628 cm1 is attributed to the bending modes of the adsorbed
a (Å) c (Å) Dp (nm) H2O molecules [23]. The weak peaks at 1577 cm1 and
ZnO-1 3.25061 (2) 5.20811 (4) 103 (3) 1384 cm1 were related to the asymmetric and symmetric stretch-
ZnO-2 3.25000 (2) 5.20745 (3) 121 (3) ing modes of COO which likely indicate the presence of a small
ZnO-3 3.2515 (3) 5.2094 (6) 10.3 (2) amount of organic residues remaining at the surface of the
Standard ZnO 3.249865 (5) 5.20674 (3) —— nanoparticles, in special for the sample synthesized using ethylene
glycol with nitric acid (ZnO-3). Thermal treatments at high tem-
peratures (500 °C) were done to completely remove the organic
crystallized (Fig. 1(a) and (b)) but this does not happen with the residues. The strong peaks at 523, 463 and 448 cm1 can be
sample using ethylene glycol (ZnO-3) (Fig. 1(c)). ascribed to the vibrational modes of the Zn–O bonds as reported
The formation of the hexagonal Wurtzite phase was confirmed in the literature [13].
by Raman spectroscopy. Room-temperature Raman spectra of the Experimental data show that the variation of synthesis condi-
ZnO samples are shown in Fig. 2. The peak at 439 cm1 has been tions affects significantly the specific surface area (BET) and pore
assigned to the E2 (high) phonon mode, whereas the peaks at size distribution, as shown in Fig. 4. According to the IUPAC classi-
410 and 379 cm1 were assigned to the E1(TO) and A1(TO) phonons fication, the hysteresis loops observed in the samples synthesized
modes.The band at 538 cm1 may be attributed to the 2B(low) or with ethylene glycol acidified with nitric acid (ZnO-3) and acetic
2LA mode. The observed E1(LO) at 577 cm1 peak is associated acid (ZnO-2) can be attributed to H3-type mesoporous material
with the presence of oxygen vacancies and interstitial zinc and and the isotherm of the sample synthesized with water (ZnO-1)
their complexes [21,22]. corresponds to a solid microporous [24]. The sample which shows
The FTIR spectra of the ZnO samples are shown in Fig. 3. The the highest specific surface was the ZnO-3 synthesized using ethy-
peak observed at 3432 cm1 was assigned to the stretching lene glycol acidified with nitric acid as the solvent (38 m2/g);
vibrational mode of the OAH groups; meanwhile, the peak at meanwhile, the sample which shows the lowest specific surface

Fig. 2. Raman spectra of ZnO samples taken at room temperature. Fig. 4. Typical N2 adsorption–desorption isotherms for ZnO nanostructures.
 M. Montero-Muñoz et al. / Applied Surface Science 448 (2018) 646–654 649

area was the ZnO-1 synthesized with water as the solvent dissolved in water, it dissociates into zinc ions (Zn2+) and acetate
(1.5 m2/g). ions (CH3COO), as show in Eq. (4). Then, CH3COO ions are hydro-
Scanning electron microscopy (SEM) images of the thermally lyzed to release OH ions as described by Eq. (5).
treated samples at 300 °C are shown in Fig. 5. The image of the
sample synthesized with water (ZnO-1) is shown in Fig. 5(a). As ZnðCH3 COOÞ2 $ 2CH3 COO þ Zn2þ ð4Þ
can be observed, a needle-like morphology has been obtained after
the annealing process, where the needles are 3 lm longer with CH3 COO þ H2 O $ OH þ CH3 COOH ð5Þ
hexagonal cross sections in the range from 100 to 200 nm, which
The Zn2+ ion must hydrolyze producing species whose nature
leads to the pencil shape grown along the c axis. Fig. 5(b) displays
depends on the pH of the suspension, generating Zn hydroxide spe-
the SEM image of the sample synthesized using acetic acid (ZnO-2).
cies, mainly the (Zn(OH)4)2, or chemical complexes of zinc. When
As can be seen, agglomerated particles with more than 10 lm in
the pH is increased by adding ammonia, NH4OH is dissolved in the
size and without any defined morphology are obtained. In Fig. 5
water and it is hydrolyzed to ammonium ions (NH+4) and hydroxide
(c), we show the SEM image of the sample synthesized using ethy-
ion (OH) resulting in the increase of the solution concentration of
lene glycol acidified with nitric acid (ZnO-3), where large agglom-
OH. The following chemical reactions are expected to rule the
erates with sponge-like morphology are observed. The interaction
growth process:
between the solvent used in the synthesis and the ZnO precursors
can be the responsible to explain the particular morphology NH3 þ H2 O $ NHþ4 þ OH ð6Þ
obtained. It is known that the crystal morphology is determined
by the relative growth rates along a certain crystallographic direc-
Zn2þ þ 2OH $ ZnðOHÞ2 ð7Þ
tion, which can differ greatly due to differences in surface energy
[25].
ZnðOHÞ2 $ ZnO þ H2 O ð8Þ

3.2. Possible mechanisms of the formation of ZnO nanostructures ZnðOHÞ2 þ 2OH $ ½ZnðOHÞ4 2 ð9Þ

Considering the nature of the synthesis processes, as well as the
type of solvent, possible mechanisms favoring the formation of a
specific morphology are proposed below:
a. Sample synthesized with water as the solvent (ZnO-1).
The chemical reaction during the crystal growth has already
been discussed by G. Amin et al. and J. Gupta et al. [26,27]. Accord-
ingly to them, when zinc acetate dehydrate (Zn(CH3COO)2) is
½ZnðOHÞ4 2 $ ZnðOHÞ2 þ 2OH ð10Þ
ZnðOHÞ2 $ ZnO þ H2 O ð11Þ
After the complete addition of ammonia, a precipitate is
obtained which is subsequently aged. During this aging process
and redispersion in water, different chemical reactions and struc-
tural changes occur. ‘‘Sheet-like” seeds containing Zn(OH)2 crystals
are expected to be formed. According to Dietrich and Johnston [28],

Fig. 5. SEM images of the ZnO samples synthesized using (a) water (ZnO-1), (b) acetic acid (ZnO-2) and (c) ethylene glycol acidified with nitric acid (ZnO-3).
650 M. Montero-Muñoz et al. / Applied Surface Science 448 (2018) 646–654
this system has suitable features to the formation of Zn(OH)2
whose representative morphology is orthorhombic bipyramidal,
as shown in Fig. 6.
According to the internal structure, the growth habit of ZnO
crystals is preferred along the c-axis. Since anionic zinc species
such as Zn(OH)24 dominantly exist under a basic condition (pH =
8.8), the growth along the c direction could be initiated with a pref-
erential adsorption of the anionic precursor on the positively
charged (0 0 1) facet. In some cases, depending on the pH value,
the Zn(OH)2 phase dissolves and forms the Zn(OH)2 4 ions, which
can react with the OH ions present in the solution by re-
forming the zinc hydroxide [29]. Finally, by subjecting the sample
to a drying process and subsequent heat treatment at 300 °C, the
Zn(OH)2 precursor transforms into ZnO phase via dehydration
reaction. This sample displays nanoneedles morphologies as seen
in Fig. 5(a).
b. Sample synthesized with acetic acid as the solvent (ZnO-2).
We started adding ammonia into the initial solution to neutral-
ize the acetic acid which comes from the 200 mL of the initial
synthesis-solvent and the acetic acid generated by ligand exchange
between CH3COO and OH. When the zinc acetate is dissolved in
acetic acid, the chemical stability of zinc precursor becomes dis-
turbed by the addition of ammonia. The main reaction, during
the incorporation of ammonium hydroxide, is the formation of
basic zinc acetate as follow [30]:
ZnðCH3 COOÞ2 þ NH4 OH þ CH3 COOH
! ZnðCH3 COOÞðOHÞ þ NH4 CH3 COO
and leading to the ammonium acetate as the by-product. This basic
salt is formed in a controlled manner according to the amount of
CH3COO present in the system. This is the reason why the solution
is always transparent and no precipitate is formed, because the
nucleation process does not reach the supersaturated condition,
which is necessary to form a bulk solid (only embryos that would
not reach its critical size are formed). Therefore, this condition
favors the formation of a nanoparticulated system when the sample
is subjected to a drying process at 150 °C during 24 h. The formed
Fig. 6. SEM image showing a typical morphology of Zn(OH)2 blocks obtained for the sample synthesized using water (ZnO-1) as the solvent.
nuclei would be very small –on the order of tenths of nanometers.
In the synthesis of ZnO using acetic acid as a solvent, an undefined
morphology is obtained as shown in Fig. 5(b). This is because when
the drying process is carried out to obtain the powder, the nucle-
ation process is broken, i. e., no crystalline growth is observed and
the reaction reaches the equilibrium.
c. Sample synthesized with ethylene glycol acidified with
nitric acid as the solvent (ZnO-3)
In order to increase the concentration of Zn2+ in the solution, we
added dilute HNO3 to control the pH of the growth solution in the
range from 6.2 to 4. It must favor the dissociation of Zn(CH3COO)2.
During the addition of HNO3 other chemical species must appear
including an acid ion according to the following reaction:
Zn2þ þ 2NO3 þ Hþ þ H2 O $ ZnðNO3 Þ2 þ H3 Oþ ð13Þ
Zinc nitrate which can also be formed via a ligand exchange
reaction with the release of CH3COO groups, favors the existence
of this species in the medium.
Within the dissolution of zinc acetate with nitric acid by the
addition of ammonia, an organic matrix consisting of carboxylic
groups and ammonia is mainly formed. This organic matrix could
act as substrate for the Zn2+ and Zn+AOACH2CH3 ions nuclei for-
mation. The presence of the organic matrix favors the decrease of
the interface energy and, thus, the activation energy for the nucle-
ation. The present ethylene glycol could act as a surfactant, pre-
venting the agglomeration of the nanoparticles or as a complex
of both Zn(CH3COO)2 and Zn(NO3)2 present in the system [31]. It
can be inferred that ‘‘lamellae‘‘ crystallites, crystallite group or
nanometric zinc alkoxide form zinc - acetate/nitrate- ethylene gly-
ð12Þ col complexes that are supported by the organic matrix, inhibiting
the crystal growth, and favoring the final particle size (10.3 nm).
During the drying process to which the sample is subjected the
organic matrix acts as a sort of ‘bag’ that covers the crystals and
prevents its dissolution. The final thermal treatment eliminates
the organic matrix and releases zinc oxide nanoparticles. The
SEM images show a sponge-like morphology for this sample syn-
thesized with ethylene glycol acidified with nitric acid as the sol-
vent (see Fig. 5(c)). The system is composed of nano-sized
particles as the primary group that make up the sponge-like parti-
cles as secondary group.
 M. Montero-Muñoz et al. / Applied Surface Science 448 (2018) 646–654
3.3. Optical characterization
The optical characterizations of the samples were carried out
using an UV–Vis absorption spectrophotometer. Fig. 7(a) shows
the UV–Visible absorption spectra of the ZnO samples as a function
of wavelength. As observed in these spectra, it is evident that the
synthesis conditions strongly affect the behavior of the ZnO com-
pounds against the incidence of radiation. It is clearly observed
that the absorbance decreases with the increase of the wavelength.
The sharp decrease in absorbance near the band edge (390 nm)
indicates the better crystallinity of samples synthesized with water
(ZnO-1) and acetic acid (ZnO-2) which show single-sloped curves,
and thus, suggesting the formation of samples with a direct band-
to-band allowed transition of the hexagonal Wurtzite ZnO
compound.
In order to estimate the band gap energy, the Tauc plot has been
used. In Fig. 7(b) is shown the plots for the three samples. The
intrinsic band gap is obtained from the linear fit of the (ahm)2 vs.
hm curve using the energy interval above the band gap. An illustra-
tion of this procedure is shown in Fig. 7(b). The obtained band gap
values are 3.16 and 3.18 eV for samples (ZnO-1) and (ZnO-2) and
2.72 eV for sample (ZnO-3). The presence of organic phases or
the diffusion of carbon atoms into the ZnO matrix, as determined
from the IR measurements (see Fig. 3(c)) in sample ZnO-3 synthe-
sized with ethylene glycol acidified with nitric acid, could partially
justify the appreciable difference in the band-gap energy value
with respect to the other two samples. It is worth mentioning that
according to the results, the incorporation of coal, for instance, in a
controlled manner drives to the possibility of closing the band-gap
energy.
Fig. 8 shows the photoluminescence (PL) spectra of the ZnO
samples. In Fig. 8(a) is shown the low-temperature (10 K) PL spec-
tra of the sample synthesized with water (ZnO-1). The data analy-
sis in the high-energy region (Fig. 8(b)) revealed the presence of at
least five emissions for this sample. The strong and narrow peak
(FWHM = 10.93 meV) centered at 3.39 eV has been assigned to
the to the near band edge (NBE) emission of the ZnO originated
from the direct recombination of free exciton [32,33]. The peak
centered at 3.35 eV has been assigned to donor bound exciton
[34]. Such clearly defined peaks are also the fingerprints of the high
crystalline quality of the sample, as also demonstrated by the
structural studies.
The weak peak centered at 3.27 eV, which likely correspond to
an LO phonon replica of the bound exciton peaks (80 meV below
the exciton peak) [35]. The broad peak at 3.17 eV (violet emission)
is attributed to the transitions from interstitial zinc (Zni) states to
the valance band [36,37]. Moreover, the peak at 3.06 eV (blue
emission) might be related to the direct recombination of electrons
from the conduction band to the Zn vacancy (VZn) level [38].
Fig. 7. (a) UV-visible spectra of the ZnO samples. (b) Tauc plot used to determine the band gap energy.
651
Moreover, in the intermediate energy region, the sample ZnO-1
shows a broad emission (see Fig. 8(a)), which can be decomposed
into three emissions. According to the literature, the green emis-
sion centered at 2.26 eV is related to the Zn vacancies, which act
as acceptors [39]. It is worth mentioning that the hydrogen passi-
vation of the green luminescence is possible whether the green
luminescence is originated from zinc vacancies and resulting in
the formation of strong OAH chemical bonds [39]. The broad peak
centered at 2.1 eV (yellow emission) can be related to a deep level
or trap state emission attributed to the singly ionized oxygen
vacancy. However, this yellow emission can also be attributed to
the presence of Zn(OH)2 that is attached to the surface of the
needle-like grains likely because of different water adsorption
properties of the ZnO compound. It seems that the yellow emission
is more related to the presence of hydroxyl groups or Zn(OH)2
instead of being related to interstitial oxygen or singly ionized oxy-
gen vacancies, in agreement with the Raman spectroscopy results
(see Fig. 2(c)), as reports in the literature [40,41]. The red emission
centered at 1.84 eV has been attributed to the transition from the
oxygen vacancies (Vo) level to the valence band and/or a transition
related to interstitial oxygen (Oi) and Vo which energy emission
range from 1.65 to 1.99 eV [42].
The low-temperature PL spectrum of sample ZnO-2 (see Fig. 8
(b)) exhibit a multimode broad emission band, the deconvolution
leads one to obtain the PL bands centered at 3.35, 3.32, 3.26,
3.18, 3.06 eV. The peak at 3.35 eV has been assigned to the donor
bound exciton, similarly to that determined for sample ZnO-1.
The peak at 3.26 eV has been assigned to the first order longitudi-
nal optical phonon replica of the bound exciton. The peaks at 3.18
and 3.05 eV have the same origin as the peak at 3.17 and 3.06 eV
determined for the sample ZnO-1. Contrary to that observed for
sample ZnO-1, no distinguishable peaks are determined in the
intermediate energy region. For sample ZnO-3, which shows a
sponge-like morphology (see Fig. 8(c)), a convolution of two emis-
sions are determined in the high-energy region. The peak at 3.35
eV is also observed in samples ZnO-1 and ZnO-2 and it has been
assigned to the bound exciton emission. The peak at 3.31 eV is
exclusively emitted from distinct lines on sample surfaces and
cross sections representing intersections with basal planes of the
Wurtzite hexagons [43].
As can clearly be observed from Fig. 8, samples ZnO-2 and ZnO-
3 does not present the characteristic green band emission coming
from the oxygen vacancies, unlikely demonstrated by the sample
ZnO-1. Since the measurements were taken at 10 K, the low tem-
perature is enough to freeze-out the carriers responsible for the
green emission in samples ZnO-2 and ZnO-3. At the same time,
for sample ZnO-1, the great number of oxygen incorporated inside
the lattice are responsible for such pronounced emission, even at
such low temperature.
652 M. Montero-Muñoz et al. / Applied Surface Science 448 (2018) 646–654
Fig. 8. 10 K-photoluminescence spectra of the ZnO nanostructures. In (a) are shown the emissions obtained in the whole range of the measurements. In (b) is shown the
amplification of the near-band-edge emissions.
It is well known that defect types and their concentrations, as
well as the nanostructure morphology are determined by the
synthesis conditions. Similarly, as the results obtained from the
UV–Vis absorption measurements, the photoluminescence spectra
also indicate that the luminescent response of the samples is
affected by the synthesis conditions (nature of the solvent).
According to SEM, IR, Raman and PL, all results suggest that the
defects formed in our samples are strongly related to the synthesis
conditions. Specifically, the nucleation process was broken down
during the synthesis of samples ZnO-2 and ZnO-3; meanwhile in
sample ZnO-1 the nucleation process was carried to completion
of all stages of the nanoparticles crystalline growth process.
3.4. Photocatalytic activity of ZnO nanoparticles
The catalytic and photocatalytic activities of the ZnO samples
were studied via the decomposition of H2O2 (initial rate) in aque-
ous solution (see Fig. 9). The kinetic study was followed by the pro-
duction of O2 via gas pressure monitoring (O2 – monitored
Fig. 9. Photodecomposition of H2O2 catalyzed by the ZnO samples.
method) [20], at 20 °C and using the UV–visible light irradiation
(k  400 nm). Experimental data showed that the rate of H2O2
decomposition, under UV–visible light irradiation, obeys a first
order kinetic law [44]. Under light irradiation, the H2O2 decompo-
sition rate achieved a maximum value of 9.5 mmol g1 s1 for the
sample synthesized with water (ZnO-1) at 25 min. Almost the half
value (5.8 mmol g1s1) is obtained for the sample synthesized
with acetic acid (ZnO-2) and 3.74 mmol g1s1 for the sample syn-
thesized with ethylene glycol acidified with nitric acid (ZnO-3).
These results show that the nanoparticles with well-defined
morphology (ZnO-1) (Fig. 5(a)) exhibit a large photocatalytic activ-
ity to decompose H2O2 (see Fig. 9), regardless the specific surface
area (see Fig. 4). This result indicates that the high photo-
reactivity of the ZnO samples is not necessarily related to the sur-
face area. It seems that the type of some specific sites and their
abundance, which strongly depend on the preparation route, are
the most important parameters which determine the photocat-
alytic active of the ZnO compound. Our results indicated that nano-
needles of the ZnO compound show significantly higher
photocatalytic activity than the others ZnO morphologies. The pho-
tocatalytic activity was found to be associated with the presence of
oxygen vacancy and Zn located in interstitial sites according to the
PL spectroscopy results (see Fig. 8). We suppose either the forma-
tion of OH groups or the formation of oxygen vacancies would be
the energetically favorable process for stabilization of top and
down surface of ZnO nanoneedles. These oxygen vacancies on
the surface of polar ZnO are expected to play a vital role in OAO
bond cleavage of atmospheric O2. These results suggest that the
oxygen vacancies can favor the adsorption of O2, which interact
with the photo-induced electrons and producing O2 radical
groups. These radical groups are chemically active and promote
the oxidation of nearby organic substances [45].
O2  + H2 O2 ! OH + OH + O2 ð14Þ
At the same time, this reaction also happens
1
Znþi þ O2 ðadsÞ þ e $ Zn2þ
i þO
2
ð15Þ
2
Therefore, the photocatalytic activity is related to the type of
defects present in the synthesized ZnO samples. The population
 M. Montero-Muñoz et al. / Applied Surface Science 448 (2018) 646–654
of these defects, oxygen vacancies, affects the electron-hole pair
recombination process.
The sample ZnO-3, shows a semiconducting deactivation phe-
nomenon which reduces the photocatalytic activity and it might
be related to the blocking of the active sites provoked by the pres-
ence of carbon species (carboxyl group especially), as evidenced by
IR spectra. These observations point out to the formation of depos-
its of organic species and whose kinetics of degradation is remark-
ably slower.
4. Conclusions
ZnO structures with different sizes and morphologies were syn-
thesized by a controlled precipitation method using three different
solvents and modifying the washing processes. According to the
photochemical tests, morphological characterization, surface area
and PL results, it seems that the abundance of specific sites is
strongly dependent on the preparation route and directly related
to the morphological conformation of ZnO structures. Our results
indicate that the needle-like morphology is established due to
the crystal growth direction and the occurrence of crystalline
defects such as oxygen vacancies and interstitial Zn located at
the surface which is necessary to stabilize that morphology. It is
found that those defects can absorb OH ions and atmospheric
O2 and are important to improve the photocatalytic activity as they
act as the active centers at the interface between catalyst surface
and organic pollutants. Those specific sites and its abundance are
the most important features, which determine the photocatalytic
activity of the ZnO compound.
Acknowledgments
This work was financially supported by the Brazilian agencies
CAPES, CNPq, FAPDF and FAPESP (grants # 2013/18719-1,
2014/07375-2, 2014/19142-2, and 2015/13771-0). The authors
thank LNLS - Brazilian Synchrotron Light Laboratory (CNPEM/
MCTIC) for granting the beamtime (proposals # 20150157 and
20170018) and to XRD1 beamline staff for technical assistance
during the measurements.
References
[1] A. Kołodziejczak-Radzimska, T. Jesionowski, Zinc oxide—from synthesis to
application: a review, Materials 7 (2014) 2833–2881.
[2] R. Ameta, S.C. Ameta, Photocatalysis: Principles and Applications, CRC Press,
2016.
[3] J.E. Ramos, M. Montero-Muñoz, J.A.H. Coaquira, J.E. Rodríguez-Páez, Evidence
of a cluster glass-like behavior in Fe-doped ZnO nanoparticles, J. Appl. Phys.
115 (2014) 17E123.
[4] J.E. Ramos, M. Montero-Muñoz, J.A.H. Coaquira, J.E. Rodríguez-Páez, Mn-
doping effects on structure and magnetic properties of ZnO nanoparticles, J.
Low Temp. Phys. 179 (2015) 42–47.
[5] M. Hadis, Ö. Ümit, Zinc Oxide: Fundamentals, Materials and Device
Technology, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2009.
[6] Y.M. Wang, J.H. Li, R.Y. Hong, Large scale synthesis of ZnO nanoparticles via
homogeneous precipitation, J. Central South Univ. 19 (2012) 863–868.
[7] J. Guo, C. Peng, Synthesis of ZnO nanoparticles with a novel combustion
method and their C 2 H 5 OH gas sensing properties, Ceram. Int. 41 (2015)
2180–2186.
[8] R.M. Alwan, Q.A. Kadhim, K.M. Sahan, R.A. Ali, R.J. Mahdi, N.A. Kassim, A.N.
Jassim, Synthesis of zinc oxide nanoparticles via sol–gel route and their
characterization, Nanosci. Nanotechnol. 5 (2015) 1–6.
[9] K. Elen, H. Van den Rul, A. Hardy, M.K. Van Bael, J. D’Haen, R. Peeters, D. Franco,
J. Mullens, Hydrothermal synthesis of ZnO nanorods: a statistical
determination of the significant parameters in view of reducing the
diameter, Nanotechnology 20 (2009) 055608.
[10] K. Anand, S. Varghese, T. Kurian, Synthesis of ZnO nano rods through mechano-
chemical route: a solvent free approach, Int. J. Theor. Appl. Sci. 6 (2014) 87.
[11] A. Dakhlaoui, M. Jendoubi, L.S. Smiri, A. Kanaev, N. Jouini, Synthesis,
characterization and optical properties of ZnO nanoparticles with controlled
size and morphology, J. Cryst. Growth 311 (2009) 3989–3996.
653
[12] H. Avila, M. Cruz, M. Villegas, C. Caballero, J.E. Rodríguez-Páez, Estudio
comparativo de dos métodos de síntesis para la obtención de polvos cerámicos
de ZnO-Pr, Bol. Soc. Esp Ceram. 43 (2004) 740–744.
[13] J.E. Rodríguez-Páez, A. Caballero, M. Villegas, C. Moure, P. Duran, J. Fernandez,
Controlled precipitation methods: formation mechanism of ZnO nanoparticles,
J. Eur. Ceram. Soc. 21 (2001) 925–930.
[14] A. Moharram, S. Mansour, M. Hussein, M. Rashad, Direct precipitation and
characterization of ZnO nanoparticles, J. Nanomater. 2014 (2014) 20.
[15] N.M. Flores, U. Pal, R. Galeazzi, A. Sandoval, Effects of morphology, surface
area, and defect content on the photocatalytic dye degradation performance of
ZnO nanostructures, RSC Adv. 4 (2014) 41099–41110.
[16] L. Xu, Y.L. Hu, C. Pelligra, C.H. Chen, L. Jin, H. Huang, S. Sithambaram, M.
Aindow, R. Joesten, S.L. Suib, ZnO with different morphologies synthesized by
solvothermal methods for enhanced photocatalytic activity, Chem. Mater. 21
(2009) 2875–2885.
[17] A. Carvalho, D. Araújo, H. Canova, C. Rodella, D. Barrett, S. Cuffini, R. Costa, R.
Nunes, X-ray powder diffraction at the XRD1 beamline at LNLS, J. Synchrotron
Radiat. 23 (2016) 1501–1506.
[18] P. Thompson, D. Cox, J. Hastings, Rietveld refinement of Debye-Scherrer
synchrotron X-ray data from Al2O3, J. Appl. Crystallogr. 20 (1987) 79–83.
[19] B.H. Toby, R.B. Von Dreele, GSAS-II: the genesis of a modern open-source all
purpose crystallography software package, J. Appl. Crystallogr. 46 (2013) 544–
549.
[20] C.A. Páez, D.Y. Liquet, C. Calberg, S.D. Lambert, I. Willems, A. Germeau, J.P.
Pirard, B. Heinrichs, Study of photocatalytic decomposition of hydrogen
peroxide over ramsdellite-MnO 2 by O 2-pressure monitoring, Catal.
Commun. 15 (2011) 132–136.
[21] S. Kumar, P. Sahare, Effects of annealing on the surface defects of zinc oxide
nanoparticles, Nano 7 (2012) 1250022.
[22] F. Ahmed, N. Arshi, M. Anwar, R. Danish, B.H. Koo, Morphological evolution of
ZnO nanostructures and their aspect ratio-induced enhancement in
photocatalytic properties, RSC Adv. 4 (2014) 29249–29263.
[23] D. Scarano, S. Bertarione, G. Spoto, A. Zecchina, C.O. Arean, FTIR spectroscopy
of hydrogen, carbon monoxide, and methane adsorbed and co-adsorbed on
zinc oxide, Thin Solid Films 400 (2001) 50–55.
[24] Z.A. ALOthman, A review: fundamental aspects of silicate mesoporous
materials, Materials 5 (2012) 2874–2902.
[25] X. Zhang, J. Qin, Y. Xue, P. Yu, B. Zhang, L. Wang, R. Liu, Effect of aspect ratio
and surface defects on the photocatalytic activity of ZnO nanorods, Sci. Rep. 4
(2014).
[26] G. Amin, M. Asif, A. Zainelabdin, S. Zaman, O. Nur, M. Willander, Influence of
pH, precursor concentration, growth time, and temperature on the
morphology of ZnO nanostructures grown by the hydrothermal method, J.
Nanomater. 2011 (2011) 5.
[27] J. Gupta, P. Bhargava, D. Bahadur, Morphology dependent photocatalytic and
magnetic properties of ZnO nanostructures, Physica B 448 (2014) 16–19.
[28] H.G. Dietrich, J. Johnston, Equilibrium between crystalline zinc hydroxide and
aqueous solutions of ammonium hydroxide and of sodium hydroxide, J. Am.
Chem. Soc. 49 (1927) 1419–1431.
[29] R. Pawar, J. Shaikh, A. Babar, P. Dhere, P. Patil, Aqueous chemical growth of ZnO
disks, rods, spindles and flowers: pH dependency and photoelectrochemical
properties, Sol. Energy 85 (2011) 1119–1127.
[30] T. Kawano, H. Imai, A simple preparation technique for shape-controlled zinc
oxide nanoparticles: Formation of narrow size-distributed nanorods using
seeds in aqueous solutions, Colloids Surf., A 319 (2008) 130–135.
[31] J.E. Rodríguez-Páez, A. Caballero, M. Ocana, C. Moure, P. Durán, J. Fernández,
Synthesis of nanoparticle ZnO powders by controlled precipitation, Ceram.
Trans 83 (1997) 19–26.
[32] M.R. Wagner, Fundamental properties of excitons and phonons in ZnO: A
spectroscopic study of the dynamics, polarity, and effects of external fields, in,
Technische Universität Berlin, 2010.
[33] W. Park, Y. Jun, S. Jung, G.C. Yi, Excitonic emissions observed in ZnO single
crystal nanorods, Appl. Phys. Lett. 82 (2003) 964–966.
[34] A. Djurišić, Y. Leung, K. Tam, Y. Hsu, L. Ding, W. Ge, Y. Zhong, K. Wong, W. Chan,
H. Tam, Defect emissions in ZnO nanostructures, Nanotechnology 18 (2007)
095702.
[35] M.T. Htay, M. Itoh, Y. Hashimoto, K. Ito, Photoluminescence properties and
morphologies of submicron-sized ZnO crystals prepared by ultrasonic spray
pyrolysis , Jpn. J. Appl. Phys. 47 (2008) 541.
[36] S. Prucnal, J. Wu, Y. Berencén, M. Liedke, A. Wagner, F. Liu, M. Wang, L. Rebohle,
S. Zhou, H. Cai, Engineering of optical and electrical properties of ZnO by non-
equilibrium thermal processing: The role of zinc interstitials and zinc
vacancies, J. Appl. Phys. 122 (2017) 035303.
[37] Z. Huang, C. Chai, B. Cao, Temperature-dependent emission shifts of peanutlike
ZnO microrods synthesized by a hydrothermal method, Cryst. Growth Des. 7
(2007) 1686–1689.
[38] M. Willander, O. Nur, J.R. Sadaf, M.I. Qadir, S. Zaman, A. Zainelabdin, N. Bano, I.
Hussain, Luminescence from zinc oxide nanostructures and polymers and
their hybrid devices, Materials 3 (2010) 2643–2667.
[39] A. Janotti, C.G. Van de Walle, Native point defects in ZnO, Phys. Rev. B 76
(2007) 165202.
[40] A. Djurišić, Y. Leung, K. Tam, L. Ding, W. Ge, H. Chen, S. Gwo, Green, yellow, and
orange defect emission from ZnO nanostructures: Influence of excitation
wavelength, Appl. Phys. Lett. 88 (2006) 103107.
654 M. Montero-Muñoz et al. / Applied Surface Science 448 (2018) 646–654
[41] K. Tam, C. Cheung, Y. Leung, A. Djurišić, C. Ling, C. Beling, S. Fung, W. Kwok, W.
Chan, D. Phillips, Defects in ZnO nanorods prepared by a hydrothermal
method, J. Phys. Chem. B 110 (2006) 20865–20871.
[42] N. Alvi, K. Ul Hasan, O. Nur, M. Willander, The origin of the red emission in n-
ZnO nanotubes/p-GaN white light emitting diodes, Nanoscale Res. Lett. 6
(2011) 130.
[43] M. Schirra, R. Schneider, A. Reiser, G. Prinz, M. Feneberg, J. Biskupek, U. Kaiser,
C. Krill, K. Thonke, R. Sauer, Stacking fault related 3.31 eV luminescence at
130 meV acceptors in zinc oxide, Physical Review B 77 (2008) 125215.
[44] J.M. Herrmann, Heterogeneous photocatalysis: state of the art and present
applications In honor of Pr. RL Burwell Jr. (1912–2003), Former Head of Ipatieff
Laboratories, Northwestern University, Evanston (Ill), Top. Catal. 34 (2005)
49–65.
[45] R. Muñoz-Espí, G. Jeschke, I. Lieberwirth, C.M. Gómez, G. Wegner, ZnO latex
hybrids obtained by polymer-controlled crystallization: a spectroscopic
investigation, J. Phys. Chem. B 111 (2007) 697–707.