Optical Materials 110 (2020) 110472

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Optical Materials
journal homepage: http://www.elsevier.com/locate/optmat

Enhanced photocatalytic activity of Co doped SnO2 nanoparticles by

controlling the oxygen vacancy states
Dana Toloman, Adriana Popa *, Maria Stefan, Teofil Danut Silipas, Ramona Crina Suciu,
Lucian Barbu-Tudoran, Ovidiu Pana
National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103 Donat, 400293, Cluj-Napoca, Romania

A R T I C L E I N F O A B S T R A C T

Keywords: Co doped SnO2 nanoparticles were synthesized by chemical precipitation. Excess Co ions as doping element were
Tin dioxide used to compensate the deficit of oxygen from SnO2 lattice. The crystalline structure of all samples corresponds to
Co ions tetragonal rutile crystalline phases of tin oxide and the crystallinity increases by doping. The nanoparticles shape
Oxygen vacancies
is polyhedral with narrow distribution. The presence of Co ions in SnO2 lattice results in decreasing the oxygen
Photocatalysis
Reactive oxygen species
deficiency. All the doped samples show the red shift in optical response. Photoluminescence emission spectra
show peaks in UV and visible region. Visible emissions decrease by doping which indicate lower recombination
rate of photogenerated electron-hole pairs. All the samples show photocatalytic activity against RhB synthetic
solution under visible light irradiation, the best performance was obtained using 1.0%Co–SnO2. The mechanism
of photocatalytic activity was explained based on the reactive oxygen species generated by nanoparticles under
visible irradiation in correlation with structural and optical information obtained in this study.

1. Introduction visible quantum efficiency and a high recombination rate for

In the last decades, photocatalysis has a continuous development and
is involved in different processes such as solar energy harvesting [1],
carbon dioxide reduction [2], removal of organic pollutants [3, 4.] and
self-cleaning surfaces [5]. Photocatalysis belongs to the advanced
oxidation processes, through which organic pollutants are mineralized
into carbon dioxide and water. Visible light represents cheap and
abundant energy source able to generate charge carriers implicated in
photocatalysis process.
SnO2, a n-type wide band gap semiconductor have been explored due
to their properties such as excellent chemical stability, optical trans­
parency, and electrical conductivity. Due to these properties, SnO2 is
used for transparent conducting electrodes and chemical sensors [6–9],
production of batteries in conjunction with carbon based materials [10],
solar cells and photocatalysis [11,12].
The similar crystal structure of SnO2 with that of TiO2 represents a
premise for a high photocatalytic activity since a crystal network of
corner-sharing octahedral units increases the mobility of electrons and
holes and therefore influences the recombination probability of elec­
trons and holes [13]. Because the band gap energy of SnO2 range be­
tween 3.5 and 3.8 eV it is necessary UV irradiation resulting in low
electron-hole pairs, so limits its practical utility [14].
Doping of SnO2 nanomaterials with metal cations was demonstrated
to be a successful strategy to extend the response towards visible light
region and hinder charge carrier recombination. Various metal ions such
as Mn, Bi, Cu, V have been used to improve the photocatalytic activity of
the SnO2 [15–18].
The synthesis of nanoparticles with sizes less than 10 nm, shape and
doping controllable still remains a major challenge. The above charac­
teristics of the nanoparticles influence their properties and the large
scale industrial application, to control these properties most often are
required complex synthesis procedures. One of the simplest synthesis
methods is chemical precipitation from aqueous solutions of inorganic
salts. The chemical precipitation method is flexible and enables pro­
ducing nanoparticles with a homogeneous distribution of the doping
element at the molecular level.
We chose to use excess Co ions as doping element to compensate the
deficit of oxygen from SnO2 lattice because the valence of Co2+ is
smaller than that of Sn4+. Consequently, it can be expected that the
oxygen vacancy to decrease by doping, which would lead to reorgani­
zation of SnO2 lattice. In this work was study the influence of doping
degree on crystal growth, morphology, optical and photocatalytic

* Corresponding author.
E-mail address: adriana.popa@itim-cj.ro (A. Popa).

https://doi.org/10.1016/j.optmat.2020.110472
Received 14 August 2020; Received in revised form 23 September 2020; Accepted 24 September 2020
Available online 10 October 2020
0925-3467/© 2020 Elsevier B.V. All rights reserved.
D. Toloman et al.
properties of Co doped SnO2 nanoparticles obtained by chemical pre­
cipitation. The correlation between achieved structural information and
generated reactive oxygen species by Co doped SnO2 nanoparticles
under visible irradiation allow to elucidate photocatalytic mechanism.
2. Experimental part
2.1. Materials
Materials and reagents used for the preparation of Co doped SnO2
nanoparticles are: tin chloride SnCl2 x 2H2O (for synthesis, Merck),
cobalt chloride hexahidrate-CoCl.26H2O(for synthesis, Alpha Aesar),
sodium hydroxide (98% Alpha Aesar), ethanol C2H5OH–EtOH (p.a.,
Alpha Aesar). All chemicals are analytical grade without further puri­
fication and were used as received.
2.2. Samples preparation
The Co doped SnO2 nanoparticles were synthesized by chemical
precipitation method starting from aqueous solution of tin chloride
dihydrate -SnCl.22H2O and sodium hydroxide-NaOH precursors in the
presence of various amount of cobalt chloride hexahidrate-CoCl.26H2O.
The doping method was realized by adding excess Co ions in SnO2 lat­
tice. In the typical synthesis procedure, 3.2 mM of SnCl.22H2O and
different amount of CoCl.26H2O (0.016 ÷ 0.08 mM) were dissolved in
100 ml water and then 100 ml NaOH solution (3.2 mM) was added by
dripping in the solution. To establish the complete reaction of the pre­
cursors, the reaction was kept 4 h under vigorous stirring. To remove the
excess of reactants, the as prepared SnO2:xCo (x = 0, 1, 3 and 5 mol%)
nanoparticles were separated by centrifugation and washed with water
and ethanol (1:1 v/v) for several times and then, dried at 65 ◦ C, in air.
Finally, the dried samples were thermally treated for 2h at 500 ◦ C in
furnace, at a rate of 5 ◦ C/min, in order to get the crystallized
nanoparticles.
2.3. Characterization techniques
X-ray diffraction (XRD) experiments were achieved using a Riga­
ku—SmartLab automated multipurpose X-ray Diffractometer with Cu-
Kα radiation, operating at 45 kV, 200 mA. The X-ray diffraction patterns
were recorded in the 2θ range 20◦ –80◦ in a step-scanning mode with
steps of Δθ = 0.02◦ . PDXL2: Integrated X-ray powder diffraction soft­
ware was used to analyzed the diffraction patterns.
EPR measurements of powder samples were performed using a
Bruker E− 500 ELEXSYS X-band (9.52 GHz) spectrometer at room tem­
perature under identical conditions: microwave frequency of 9.5248
GHz, microwave power 2 mW, modulation frequency of 100 kHz and
modulation amplitude 10 G.
The morphology of the nanoparticles was determined by scanning
electron microscopy (SEM), scanning transmission electron microscopy
(STEM) and high-resolution TEM (HRTEM). SEM measurements were
performed with Hitachi SU-8230 microscope equipped with a cold field
emission gun able to accelerate the electron at 30 kV. The STEM and
HRTEM analysis was achieved using a Hitachi SU8230 microscope
provided with a cold field emission gun able to accelerate the electron at
200 kV.
The diffuse reflectance spectra were recorded using JASCO V570
UV– VIS-NIR, supplied with absolute reflectivity accessory JASCO ARN-
475. The reflectance spectra have been transformed in absorbance
spectra by spectrometer soft and analyzed.
Room temperature photoluminescence (PL) measurements were
recorded using a JASCO FP-6500 spectrophotometer having a DC-
powered 150W Xenon lamp. The excitation wavelength was 270 nm.
The photocatalytic experiments were performed in a Laboratory-
Visible-Reactor system using a 400 W halogen lamp (Osram) [19]. An
aqueous solution of RhB (1.0 × 10− 5 mol L− 1) was used as model
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Optical Materials 110 (2020) 110472
pollutant. To achieve the adsorption equilibrium on the catalyst surface,
the catalyst (10 mg) was mixing in aqueous solution of RhB (10 mL) in
the dark. The degradation experiment for all the samples was continued
for 240 min. At every 60 min, 3.5 mL from mixture was analyzed after
separating the catalyst from the suspensions by centrifugation. The
maximum absorbance of resulting solution at 554 nm was monitored
using a T90+ UV–Vis spectrophotometer (PG Instruments). Photo­
catalytic activity was estimated from the following equation:
A0 − At
Photocatalytic activity (%) = X 100 (1)
A0
where Ao and At represent the initial and the absorbance of RhB at time
t, respectively (at 553 nm wavelength).
To identify the reactive oxygen species (ROS) generated by the
nanoparticles under visible irradiation, EPR coupled with the spin
trapping method was used. 5,5-dimethyl-1-pyrroline N-oxide (DMPO,
Sigma-Aldrich) was used as spin trapping reagent and DMSO as solvent.
Immediate after irradiation, the obtained solution were transferred into
the quartz flat cell and the EPR spectra were measured.
3. Results and discussion
Crystalline phases were identified using XRD diffraction. The
diffraction patterns are presented in Fig. 1. All the samples are poly­
crystalline with diffraction lines assigned to the tetragonal rutile crys­
talline phases of tin oxide, space group 136: P42/mnm, ICDD 01-088-
0287. No characteristic peaks of impurities, such as cobalt oxide or
other tin oxides, were observed. Based on the obtained diffraction pat­
terns, lattice parameters, lattice distortion, unit cell volumes, crystallite
size and strain were obtained and the values are summarized in Table 1.
By doping with Co ions an expansion along the a direction accom­
panied by contraction along the c direction could be observed. Also, the
tetragonal distortion (c/a) is decreasing by Co doping, but it is
increasing comparing with bare SnO2, however the change in unit cell
volume is insignificant. Besides, from the careful examination of the
diffraction pattern position results a slight shift toward higher 2θ values
of (101) reflection plane with increasing doping degree as shown in
Fig. 1b. This variation can be explained due to ionic radius size effect by
replacing Sn4+ ions (r = 0.69 Å) with Co2+ (r = 0.745 Å) into the SnO6
octahedra [20].
The mean crystallite size dimension is increasing by doping from
6.76 nm in case of SnO2 to 8.8 nm for 5% Co doped SnO2. Therefore, the
crystallinity increases for Co doped samples. This physical process can
be explain that a part of the Co2+ ions formed stable solid solutions with
SnO2 and occupy the regular lattice site in SnO2 [20].
The morphology of the samples was analyzed using SEM, TEM and
HRTEM. Some illustrative images of the samples are presented in Fig. 2.
SEM, TEM and HRTEM images show particles with polyhedral shape and
narrow particles size distribution of about 7–10 nm with a slight ten­
dency of agglomeration. By doping with Co ions, the nanoparticles shape
is similar with that of SnO2 and a slight decrease of the nanoparticles size
can be observed with values between 5 and 10 nm. The results obtained
are in concordance with that from XRD.
The presence of defects in the synthesized nanoparticles can be
probed using EPR spectroscopy. Fig. 3 shows the EPR spectra of the
samples at (a) room temperature, RT and (b) 110K.
EPR spectrum of SnO2 nanoparticles shows an intense and narrow
signal centered at g = 1.89 which is due to oxygen vacancy center arising
under moist air at high temperature treatment [21]. VO0 , VO+ and VO2+ are
the three charge states of the oxygen vacancies, which could appear in
the tin oxide. The EPR signal is assigned to VO+ because it is the only one
in paramagnetic state [22]. From the presence of this signal results that
in SnO2 lattice there is an oxygen deficiency. By doping with Co2+ ions,
this signal is decreasing and almost disappears at higher concentration.
The surface states of SnO2 are represented by fivefold coordinated Sn4+
D. Toloman et al. Optical Materials 110 (2020) 110472

Fig. 1. (a) XRD diffraction patterns of the samples; (b) change in (101) peak position with cobalt doping.

of the samples were calculated extrapolating the linear portion of Tauc’s

Table 1
plots and the values obtained are presented in the inset of Fig. 4b. As
Lattice parameters, tetragonal distortion, unit cell volume, crystallite size and
expected, based on the absorption spectra, all the samples show lower
band gap energy.
optical band gap energy except 1.0% Co doped SnO2 sample. The
Sample a = b(Å) c(Å) c/a V(Å3) Dcryst(nm) Eg(eV)
reduction of band gap energy was explain based on the sp-d exchange
SnO2 4.746(9) 3.181(8) 0.6703 71.7 6.7(6) 3.52 interactions between the band electrons and the localized d electrons of
(3) the Co2+ ions substituting Sn4+ ions. The s-d and p-d exchange in­
1.0% 4.760(7) 3.167 0.6653 71.7 8.1(9) 3.35
teractions lead to negative and positive corrections of the conduction-
Co–SnO2 (10) (3)
3.0% 4.754 3.177 0.6683 71.8 6.9(8) 3.46 band and valence band edges, respectively, resulting in band gap nar­
Co–SnO2 (16) (12) (4) rowing [26].
5.0% 4.752 3.175 0.6681 71.7 8.8(14) 3.40 The photoluminescence (PL) emissions give information about the
Co–SnO2 (15) (13) (4)
structure and the presence of defects or impurities of the material. The
PL spectra of the obtained samples are shown in Fig. 5. All the samples
ions and twofold coordinated O2− ions. Thus, by substitutional doping of present the following peaks of different intensities centered at 330, 420,
Sn4+ with Co2+ ions appear redundant negative charges in the lattice, 467, 510 and 654 nm. The emission peak at 330 nm is due to direct
resulting in un-balance in the total charge. To keep charge equilibrium, recombination of electron from Sn 4p conduction band to hole in O 2p
an amount of O2− ions need to get out from the lattice and form the valance band [27].
oxygen vacancies [23]. In our case, a dramatic decrease of oxygen va­ The emissions at 420, 467 and 510 nm correspond to violet, blue and
cancy resonance signal occurs by excess Co2+ doping. This excess of green colors. Emission band centered at 420 nm originates from the
Co2+ seems to compensate the oxygen deficiency from the lattice. In intrinsic states localized on SnO6 octahedra [28]. Blue and green emis­
literature, the decrease of oxygen vacancy by doping Co ions in SnO2 sions were originated from the surface states such as oxygen vacancy.
lattice was explain by incorporation of Co2+ ions in interstitial position The band centered at 467 nm was attributed to oxygen vacancy with two
of SnO2 lattice [24]. trapped electrons, VO++ , which lead to blue spectral emission and the
In samples with Co content, besides, the above resonance signal band at 510 nm was assigned to oxygen vacancy with one trapped
appears another signal at lower magnetic field. To solve the origin of this electron, VO+ [28,29].
signal, EPR measurements at 110 K were done. The resonance signals In visible range, the emission intensity decreases for doped samples,
obtained at low temperature are better resolved; these signals are higher 1.0% Co–SnO2 sample shows the lowest intensity. The reduction of the
and broader and the resonance signal is shifted to lower magnetic field emissions indicates reduced electron-hole pair recombination rate,
compared with the signal obtained at room temperature. The behavior which drive to higher photocatalytic activity in visible region [30].
of this signal is specific to ferromagnetic phase. The assignments of the The photocatalytic activity of the sample was evaluated against RhB
above resonance signals were done based on the simulation of EPR model solution pollutant, under visible irradiation. To achieve
spectrum. The simulation of the spectra have been achieved assuming adsorption-desorption equilibrium, the samples were kept 60 min in
possible contribution due to (i) ferromagnetically coupled Co2+ spins RhB solution in the dark. All the doped samples show enhanced
and (ii) oxygen vacancy center, VO+ . As an example, Fig. 3c shows EPR adsorption capacity and the adsorption is well correlated with the mean
spectra for 1% Co doped SnO2 sample recorded at RT and 110 K, and a crystallite size obtained from XRD results. 3.0% Co doped SnO2 sample
simulation of the spectrum recorded at 110 K. possess the highest adsorption capacity and this sample has the lowest
For the simulation were used the following Hamiltonian spin pa­ crystallite size dimension among the doped samples, therefore the
rameters (i) S = 1/2, g = 2.48336, dH = 1400G - ferromagnetic biggest specific surface. Interestingly, the undoped sample shows the
component and (ii) S = 1/2, g = 1.89049, dH = 47 G - paramagnetic lowest adsorption capacity even if this sample has the lowest crystallite
component. dimensions. The enhanced adsorption capacity of the doped samples can
Optical properties of the samples were investigated by recording be explained by appearance of surface states by doping with Co ions
their diffuse reflectance, R, at room temperature. R can be related to the where the dye molecules are adsorbed. The photocatalytic activity was
absorption Kubelka-Munk function FKM, by the equation FKM (R)= (1- monitored by measuring the solution absorbance at different irradiation
R)2/2R, which is proportional to the absorption coefficient [25]. Fig. 4a time intervals. As an example, Fig. 6a shows the absorbance of RhB
shows the obtained absorption spectra for all the samples. solution in the presence of 3%Co–SnO2 sample. It could be observed that
All the doped samples show the red shift in optical response, which the RhB absorbance is decreasing with irradiation time. The photo­
results in the narrowing of optical band gap. Optical band gap energies degradation of the sample is shown in Fig. 6b.
The photocatalytic process can be evaluated by a first order kinetic

3
D. Toloman et al.
Fig. 2. Illustrative SEM, TEM and HRTEM images of (a, b, c) SnO2 and (d, e, f) 1% Co doped SnO2 samples.
model with respect to the absorbance of RhB:
( )
At
− ln * = ki (2)
A0
where At- absorbance of RhB at t time; A0*- absorbance of RhB after dark
adsorption; t - irradiation time; ki – apparent kinetic constant. The ob­
tained plots show a linear relationship with the irradiation time
(Fig. 6c).The calculated kinetic constants are presented in the inset of
Fig. 6c. Based on the evaluated k values results that the best performance
was obtained for 1.0% Co–SnO2 sample, followed by 3.0% Co–SnO2>
SnO2 > 5.0% Co–SnO2.
In general, photocatalytic mechanism can be explain based on the
generation of electron-hole pairs by Co doped SnO2 nanoparticles under
visible irradiation which interact with the dye molecules adsorbed on
the nanoparticles surface. This interaction conducts to the generation of
reactive oxygen species able to degrade the dye molecules.
As an example, the production of reactive oxygen species upon
visible light irradiation of 1.0% Co doped SnO2 - DMPO - DMSO the
aqueous mixture was investigated using electron spin resonance (ESR)
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Optical Materials 110 (2020) 110472
experiment coupled with spin-trapping technique. A complex multiline
spectrum was obtained and it is shown in Fig. 7. To evaluate the
contribution of the spin adducts generated in these systems a simulation
was performed.
The EPR spectra obtained upon photoexcitation of 1.0% Co–SnO2
nanoparticles (Fig. 7) are compatible with the generation of the
following spin adducts: •DMPO-OCH3 (S1: aN = 13.3G,aβH = 9.5G,aγH =
1.55GaN = 13.3G,aβH = 9.5G,aγH = 1.55GaN = 13.5 G, aβH = 9.4 G, aγH =
1.9 G, g = 2.0097, ΔH = 1.3 G relative concentration 45%), •DMPO-
OOH (S2: aN = 13.23 G, aβH = 9.87 G, aγH = 1.6 G, g = 2.0102, ΔH = 1.4 G
relative concentration 25%), •DMPO-O-2 (S3: aN = 13.4 G, aβH = 11.4 G,
aγH = 1.15 G, g = 2.0087, ΔH = 1 G relative concentration 20%) and
nitroxide–like radical (S4: aN = 13.8 G, g = 2.0097, ΔH = 1 G relative
concentration 10%). The obtained Hamiltonian parameters are in
accordance with literature related date [31,32].
•DMPO–OCH3 spin adducts are obtained by the interaction between
DMSO solvent and photogenerated •OH radicals [33]. The predominant
presence of this radical exhibits a great number of •OH radicals. •OH
radicals are generated from OH− and H2O through the oxidation
D. Toloman et al. Optical Materials 110 (2020) 110472

Fig. 3. EPR spectra of the samples at (a) room temperature, (b) 110K and (c) EPR spectra of 1% Co doped SnO2 sample recorded at RT and 110 K, and a simulation of
the spectrum recorded at 110 K.

Fig. 4. (a) UV–Vis absorption spectra and (b) Tauc’s plots.

reaction initiated by photogenerated holes. Superoxide radical •O−2 is
obtained by electron reduction of the absorbed molecular oxygen from
the nanoparticles surface. By protonation of superoxide radical •O−2 ,
•OOH radical is created [34]. Nitroxide-like radical is obtained by
breaking the N–C bond and ring opening of DMPO [35].
The enhancement of photocatalytic activity of SnO2 by doping with
Co ions under visible-light irradiation, can be explained based on the
combined effects of enhanced crystallinity, low recombination rates of
photogenerated electron-hole pairs, visible light absorption and high
amounts of •OH and •O−2 radicals.
Co ions and the oxygen vacancy introduced intermediate energy
levels between conduction and valence bands that act as trapping cen­
ters for the photogenerated electrons or holes to delay the recombina­
tion process, resulting in enhancement of photocatalytic activity. When
defects states or doping degree are too high, the doping and oxygen
vacancy states can act as recombination centers. This will hurried the
recombination of photoinduced charge carriers and therefore reduce the
photocatalytic activity. The photocatalytic degradation mechanism
generated by Co doped SnO2 nanoparticles under visible irradiation is
presented schematically in Fig. 8.
When the Co doping concentration was below 3%, intermediate
energy levels act as trapping centers. By increasing the doping concen­
tration to 5%, the additional states are converting in recombination
centers. So, 1% Co doping degree represents the optimal doping
concentration.

5
D. Toloman et al. Optical Materials 110 (2020) 110472

Fig. 5. Photoluminescence spectra of the samples.

Fig. 6. (a) The absorbance of RhB solution in the presence of 3%Co-SnO2 sample, (b) Photodegradation of the samples and (c) Evaluation of photo­
degradation kinetic.

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D. Toloman et al. Optical Materials 110 (2020) 110472

Fig. 7. Experimental EPR spectra of DMPO spin adducts generated in 1.0% Co–SnO2/DMSO/DMPO suspension after 25 min of irradiation.

Fig. 8. Photocatalytic degradation mechanism generated by Co doped SnO2 nanoparticles under visible irradiation.

4. Conclusions
A series of Co doped SnO2 nanoparticles were synthesized by
chemical precipitation. XRD analysis evidenced that all the samples are
polycrystalline with diffraction lines assigned to the tetragonal rutile
crystalline phases of tin oxide. The crystallinity of the samples increases
with the increase of doping degree. The shape of the nanoparticles is
polyhedral with narrow distribution. From EPR spectra results that in
SnO2 lattice there is an oxygen deficiency. By doping with Co ions the
oxygen deficiency is decreasing. Also, from EPR analysis result the
presence of ferromagnetic phase in the samples. All the doped samples
show the red shift in optical response, due to the additional energy levels
introduced in the band gap of the SnO2 by doping ions and oxygen va­
cancy, which results in the narrowing of optical band gap. Photo­
luminescence emission spectra show peaks in UV region due to direct
recombination of electron and hole from conduction and valance band,
respectively and in visible region due to intrinsic and surfaces states
such as oxygen vacancies. In visible range, the emission decrease by
doping which indicate lower recombination rate of photogenerated
charge carriers. The photocatalytic activity of the sample was evaluated
against RhB synthetic solution, under visible light irradiation. All the
samples show photocatalytic activity, the best performance was

7
D. Toloman et al.
obtained using 1.0%Co–SnO2. The enhancement of photocatalytic ac­
tivity of SnO2 by doping with Co ions, could be due to the combined
effects of enhanced crystallinity, low recombination of photogenerated
electron-hole pairs due to the intermediate energy levels introduced in
the band gap of SnO2, increased optical absorption of visible light and
high amounts of radical oxygen species which were evidenced using spin
trapping method.
Data availability statement
The raw/processed data required to reproduce these findings cannot
be shared at this time as the data also forms part of ongoing study.
CRediT authorship contribution statement
Dana Toloman: Conceptualization, Investigation, Writing - review
& editing, preparation. Adriana Popa: Investigation, Writing - review &
editing, Investigation, Validation. Maria Stefan: Investigation, Valida­
tion. Teofil Danut Silipas: Investigation. Ramona Crina Suciu:
Investigation. Lucian Barbu-Tudoran: Investigation. Ovidiu Pana:
Investigation.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was supported by the Romanian Ministry of Education,
Core Programme, Project PN19 35 02 03.
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