ВПЛИВ ТЕМПЕРАТУРИ КАЛЬЦИНУВАННЯ НА СТРУКТУРНО-РОЗМІРНІ ХАРАКТЕРИСТИКИ C,S-ДОПОВАНИХ TiO2 НАНОСТРУКТУР ТА ЇХНЯ ФОТОКАТАЛІТИЧНА АКТИВНІСТЬ У ПРОЦЕСАХ ФОТОДЕГРАДАЦІЇ ЦЕФТАЗИДИМУ ТА ДОКСИЦИКЛІНУ
Mesoporous C, S-doped TiO2 nanostructures were obtained by solvothermal sol-gel method followed by calcination at different temperatures. It was found that with increasing calcination temperature, the crystallite size remains in the same range of 9–10 nm, while the morphology of TiO2 nanoparticles s...
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| Дата: | 2020 |
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| Автори: | , , , , , , , |
| Формат: | Стаття |
| Мова: | Англійська |
| Опубліковано: |
V.I.Vernadsky Institute of General and Inorganic Chemistry
2020
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Репозитарії
Ukrainian Chemistry Journal| _version_ | 1871465641856204800 |
|---|---|
| author | Romanovska, Natalia Manoryk, Petro Selyshchev, Oleksandr Yaremov, Pavlo Shylzshenko, Olexander Terebilenko, Anastasia Shcherbakov, Sergiy Dietrich R.T. Zahn |
| author_facet | Romanovska, Natalia Manoryk, Petro Selyshchev, Oleksandr Yaremov, Pavlo Shylzshenko, Olexander Terebilenko, Anastasia Shcherbakov, Sergiy Dietrich R.T. Zahn |
| author_institution_txt_mv | [
{
"author": "Natalia Romanovska",
"institution": "L.V. Pisarzevsky Institute of Physical Chemistry, NAS of Ukraine"
},
{
"author": "Petro Manoryk",
"institution": "L.V. Pisarzevsky Institute of Physical Chemistry, NAS of Ukraine"
},
{
"author": "Oleksandr Selyshchev",
"institution": "Semiconductor Physics, Chemnitz University of Technology"
},
{
"author": "Pavlo Yaremov",
"institution": "L.V. Pisarzevsky Institute of Physical Chemistry, NAS of Ukraine"
},
{
"author": "Olexander Shylzshenko",
"institution": "L.V. Pisarzevsky Institute of Physical Chemistry, NAS of Ukraine"
},
{
"author": "Anastasia Terebilenko",
"institution": "M.G. Kholodnyy Institute of Botany, NAS of Ukraine"
},
{
"author": "Sergiy Shcherbakov",
"institution": "M.G. Kholodnyy Institute of Botany, NAS of Ukraine"
},
{
"author": "Dietrich R.T. Zahn ",
"institution": "Semiconductor Physics, Chemnitz University of Technology"
}
] |
| author_sort | Romanovska, Natalia |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:44Z |
| description | Mesoporous C, S-doped TiO2 nanostructures were obtained by solvothermal sol-gel method followed by calcination at different temperatures. It was found that with increasing calcination temperature, the crystallite size remains in the same range of 9–10 nm, while the morphology of TiO2 nanoparticles significantly changes, and the anatase content increases from 42% to 95%. At the same time the nanoparticle size (from 85 to 45 nm), the specific surface area (200–130 m2/g), the mesoporous area (from 170 to 70 m2/g), and the carbon (0.80–0.41%) and sulfur (1.39–0.89%) contents decrease. Varying the calcination temperature allows TiO2 nanostructures to be obtained with a certain balance of these structural-dimensional characteristics that provides high photocatalytic activity in the processes of ceftazidime and doxycycline photodegradation. |
| doi_str_mv | 10.33609/2708-129X.86.10.2020.95-119 |
| first_indexed | 2025-09-24T17:43:35Z |
| format | Article |
| fulltext |
95
UDC 541.145. doi: 10.33609/2708-129X.86.10.2020.95-119
INFLUENCE OF CALCINATION TEMPERATURE ON STRUCTURAL-DIMENSIONAL
CHARACTERISTICS OF C,S-DOPED TiO2 NANOSTRUCTURES AND THEIR
PHOTOCATALYTIC ACTIVITY IN THE CEFTAZIDIME AND DOXYCYCLINE
PHOTODEGRADATION PROCESSES
N. I. Romanovska1*, P. A. Manoryk1, O. V. Selyshchev2, P. S. Yaremov1, O. V. Shylzshenko1,
A.V. Terebilenko3, S. M. Shcherbakov3, D. R. T. Zahn2
1 L.V. Pisarzevsky Institute of Physical Chemistry, NAS of Ukraine Nauky av. 31, Kyiv 03028, Ukraine
2 Semiconductor Physics, Chemnitz University of Technology, D-09127 Chemnitz, Germany
3 M. G. Kholodnyy Institute of Botany, NAS of Ukraine, Tereshchenkivska str. 2, Kyiv 01601, Ukraine
*е-mail: nat.romanovska@gmail.com
Mesoporous C, S-doped TiO2 nanostructures were obtained by solvothermal sol-gel meth-
od followed by calcination at different temperatures. It was found that with increasing cal-
cination temperature, the crystallite size remains in the same range of 9–10 nm, while the
morphology of TiO2 nanoparticles significantly changes, and the anatase content increases
from 42% to 95%. At the same time the nanoparticle size (from 85 to 45 nm), the specific
surface area (200–130 m2/g), the mesoporous area (from 170 to 70 m2/g), and the carbon
(0.80–0.41%) and sulfur (1.39–0.89%) contents decrease. Varying the calcination temperature
allows TiO2 nanostructures to be obtained with a certain balance of these structural-dimen-
sional characteristics that provides high photocatalytic activity in the processes of ceftazidime
and doxycycline photodegradation.
Key words: mesoporous C, S- doped TiO2, thiourea, calcination, photocatalytic activity,
antibiotics.
INTRODUCTION. Titanium dioxide (TiO2)
is one of the most promising materials for solv-
ing a number of modern technical and tech-
nological problems, ensuring the sustainable
development of society, including harvesting
of solar energy, more efficient mineral fuel con-
sumption, environmental protection, air puri-
fication and sterilization [1, 2, 3, 4, 5]. This is
caused by low cost, high availability, chemical
and photocorrosion resistance of the TiO2 (ana-
tase) semiconductor, the properties of which
allow separated charges (electrons and holes,
e-/h+) to be generated under UV-light irradi-
ation, which are involved in redox processes
[1, 2]. Doping and co-doping of TiO2 by non-
metals (NM=B, C, N, F, S, etc.) for obtaining
INFLUENCE OF CALCINATION TEMPERATURE ON STRUCTURAL-DIMENSIONAL CHARACTERISTICS OF C,S-DOPED TiO2 NANO
STRUCTURES AND THEIR PHOTOCATALYTIC ACTIVITY IN THE CEFTAZIDIME AND DOXYCYCLINE PHOTODEGRADATION PROCESSES
96 ISSN 2708-129X. Укр. хім. журн., 2020
PHISICAL CHEMISTRY
NM-doped TiO2 materials is one of the most
promising ways to eliminate the inherent
TiO2 shortcomings, such as the wide bandgap
(Eg = 3.2 eV for anatase), low efficiency to sun-
light (~4%), fast recombination of photogen-
erated e-/h+ pairs, low sorption capacity, etc.
[1, 2]. In addition, doping also makes it possible
to increase the photocatalytic activity (PCA) of
TiO2. According to existing notions, nonmetal
(C and/or S) doping can occur in three ways [1,
6]: substitutional doping (when dopant atoms
(C [7–9] and/or S [10, 11]) substitute oxygen
in the crystal lattice); interstitial doping (when
the additive atom (C [7–9] and/or S [10–12]) is
in the interplanar space of the crystal lattice and
is associated with one or several oxygen atoms
in the lattice, which leads to its distortion); and
mixed (when both types of doping are realized
simultaneously) [8]. At the same time, some
dopant atoms may also be included in differ-
ent functional groups, for example, sulfate [7,
10, 11] or carbonate [8, 9, 13], on the material
surface. The implementation of these options
depends on the nature of the dopant, the con-
ditions of the doping process, the precursor of
the dopant, and the conditions of post-syn-
thetic processing [1, 2, 4, 5]. N>С>S are con-
sidered as the strongest dopants, for which all
the above types of doping can be realized [1,
4, 5, 6, 12, 14, 15]. Even though the numerous
calculations of the energy and electronic states
of O 2p, Ti 3d and NM (N 2p, S 3p, etc.) of
doped anatase (NM-doped TiO2) using differ-
ent models and approximations [1, 4, 5, 6, 14–
16], as well as the interpretation of experimen-
tal results are rather controversial, this makes
it possible to assess the state and role of dopant
in NM-doped TiO2 and NM-codoped TiO2.
In particular, it was shown that the replace-
ment of titanium by sulfur in the crystal lat-
tice of anatase for S-doped and N, S-codoped
TiO2 is more energetically favorable [15] and
leads to bandgap narrowing [16]. At the same
time, from the thermodynamic stability point
of view, S atoms can be localized in both O and
Ti sites in S-doped anatase [17]. As a result
of the mixing of O 2p, N 2p, S 3p, and Ti 3d
states, the bandgap (Eg) decreases and the ab-
sorption band edge shifts to higher wavelength
(>400 nm). In turn, the PCA (VIS) is higher
for N, S-coped TiO2 than for S-doped TiO2 or
N-doped TiO2 [15]. Among C-, N-, S - doped
TiO2 [5], C-doped TiO2 in which carbon enters
the crystal lattice in the form of an anion or
cation [5] is the most promising photocatalyst
due to the overlap of the O 2p and C 1s states
near the valence band edge and its redshift in
C-doped TiO2. Other authors [5] disagreed
with a decrease in Eg and believe that such a
decrease may be very modest. At the same
time, an increase for visible light response and
PCA (VIS) is associated with the appearance of
isolated localized states in the gap, rather than
with narrowing it [1, 5, 6]. Carbon states can
also overlap with the TiO2 conduction band
due to the rather deep location in the bandgap
[15]. For N-doped TiO2, both substitutional
and interstitial localized occupied states are
generated in the bandgap, which provides a
visible light sensitivity and PCA (VIS) [6].
Simultaneous co-doping often gives more
positive results compared to mono-doping due
to the manifestation of synergistic effects [1, 4,
5]. From this point of view, thiourea (TU) is of
particular interest as a precursor that contains
simultaneously C, N, and S. TU and various
titanium (IV) compounds can be used as pre-
cursors for the synthesis of (NM)-doped TiO2
materials by “dry” (calcination of mechani-
cal or mechano-chemically treated mixtures)
УХЖ № 10 / Том 86N. I. Romanovska, P. A. Manoryk, O. V. Selyshchev, P. S. Yaremov, O. V. Shylzshenko, A.V. Terebilenko, S. M. Shcherbakov, D. R. T. Zahn
97https://ucj.org.ua
or “wet” (sol-gel synthesis followed by calci-
nation) methods. It was shown that TiO2 ob-
tained by NM doping, where NM = (С, N, S)
[7], (N, S), [7, 11, 18, 19], (N) [19], (S) [12,
20–22], (С) [8, 9], demonstrate increased
PCA (VIS) in various redox processes.
However, according to the calculation results
and experimental data, the positive doping
effect on the visible light sensitivity and PCA
does not always lead to a change in the band-
gap and the shift of the band edge [1, 5]. So
far, intensive discussions are underway on the
mechanism of doped TiO2 photocatalytic re-
sponse to visible light, and theoretical studies
and experimental results are often contradic-
tory. This can be attributed to the variety of
synthesis methods for these materials and dif-
ferent calculation methods [5]. Because each
factor affecting PCA is difficult to investigate
individually, and because photocatalysis is a
complex process influenced by many factors,
attempts to determine a universal law of the
doping effect on PCA have so far been unsuc-
cessful [5].
Besides, doping can take place both inside
the TiO2 lattice and at the photocatalyst surface
[5], which is in direct contact with the organic
substrate. Therefore, the amount and nature of
dopant in the surface layer may significantly
affect PCA (VIS). However, the questions of
the effect of the precursor concentration (in
particular TU) in the sol-gel system on the
number and nature of dopant atoms in (NM)-
doped TiO2, their distribution in volume and
on the surface, structural and dimensional
characteristics and morphology of the obtained
material have hardly been addressed. With re-
spect to available experimental results (relative
to S2- [10, 11, 19], S4+ [12, 19, 20], S6+ [21, 23])
the interpretation is not unambiguous.
It is known [25] that the hydrothermal
method allows different classes of inorgan-
ic materials in the nanocrystalline state to be
obtained. The calcination temperature signif-
icantly affects the phase composition, mor-
phology, crystallite and particle size, texture,
dopant content, and their chemical state under
doping of the TiO2 nanostructures by carbon,
nitrogen, and sulfur (NM) [12]. The phase
content ratio in (S)-doped TiO2 critically de-
pends on the calcination temperature [12, 23],
the sulfur precursor nature, the amount used
in the reaction mixture [12, 21], and the calci-
nation time [23].
In some cases, doped mixed phases show
higher photocatalytic activity compared to the
corresponding single-phase materials. The op-
timal anatase/rutile phase ratio for the mixed
phases is 75%:25% - 85%:15% [12, 26]. Despite
the fact that anatase has a higher photocatalytic
activity than rutile, in some cases, doped rutile
[27] is more active. Incorporation of dopants,
such as sulfate, in TiO2 stabilizes anatase be-
fore transformation into rutile [21] that begins
at higher temperatures - 800oC [12, 28], 950 oC
[12], and does not end even at 1100oC (48% A
+ 52 % R) [12].
High calcination temperature in air leads to
the formation of sulfuric acid in the structure
of TiO2, in which S atoms are embedded inter-
stitially [12]. There is a certain optimum sulfur
content in (S)-doped TiO2 (0.1-0.3 wt. % S),
which provides a reduction of the bandgap
(3.15-2.75 eV) and provides a sufficient life-
time of photogenerated charge carriers [24].
The decrease of dopant content with increasing
calcination temperature leads to an increase of
crystallite and particle sizes (for example, the
temperature increase from 200 to 600 oC in-
duces a crystallite size growth from 9 nm to
INFLUENCE OF CALCINATION TEMPERATURE ON STRUCTURAL-DIMENSIONAL CHARACTERISTICS OF C,S-DOPED TiO2 NANO
STRUCTURES AND THEIR PHOTOCATALYTIC ACTIVITY IN THE CEFTAZIDIME AND DOXYCYCLINE PHOTODEGRADATION PROCESSES
98 ISSN 2708-129X. Укр. хім. журн., 2020
PHISICAL CHEMISTRY
24.9 nm [21]), resulting in deteriorating the
texture characteristics, first of all, a decrease in
the surface area [12, 29]. Since a larger particle
size and a smaller surface area are known to re-
duce the number of photogenerated electrons
[30, 31], such changes lead to a decrease in
photocatalytic activity [1, 2, 30, 31]. Therefore,
in order to obtain effective photocatalysts, it
is important to choose such a composition of
the reaction mixture and a calcination tem-
perature that would provide non-metal-doped
fine-crystalline (9-10 nm) anatase, character-
ized by an optimal balance of nanoparticles of a
certain morphology, and a mesoporous struc-
ture with a developed surface, which improves
the photocatalytic activity of such materials.
The rapid increase in antibiotic consump-
tion in the last decade has led to intensive
pollution of natural waters, which contributes
to the development of resistance in microor-
ganisms and, consequently, possess a threat to
human health and requires high costs for the
development of new antibiotics as well as ma-
terials and technologies for water purification
[31, 32]. Photocatalytic processes that use the
energy of sunlight [31, 32] and NM- doped
TiO2 materials as catalysts [1, 5, 6] are promis-
ing in this aspect.
The aim of this study was to elucidate the
effect of the calcination temperature on the
chemical and phase composition, texture, and
morphology of TiO2 nanostructures, obtained
from thiourea containing sol-gel systems, and
their photocatalytic activity in the doxycycline
and ceftazidime antibiotics photooxidation re-
actions.
EXPERIMENT AND DISCUSSION OF
THE RESULTS
Titanium tetrabutoxide (Sigma Aldrich),
thiourea (ch.p) (Reachim), acetic acid (ch.p),
ethanol (96%), (UKRORGSYNTEZ Ltd.), doxy
cycline, and ceftazidime (BCPP) were used.
Sulfur and carbon-doped TiO2 nanostruc-
tures were obtained by a modified method [33]
by mixing titanium tetrabutoxide with etha-
nol and thiourea solutions, that were prepared
by dissolving 3.4 ml titanium tetrabutoxide
in 30 ml anhydrous ethanol and 0.253 g of
thiourea in 20 ml of absolute ethanol, followed
by addition of 1 ml glacial acetic acid and 1
ml distilled water and stirring vigorously on a
magnetic stirrer during 30 minutes. The result-
ing sol was transferred into a Teflon beaker and
subjected to solvothermal treatment (STT) at
120 oC for 24 hours. The resulting precipitate
was separated from the mother liquor by cen-
trifugation and washed twice by distilled water
and then dried at 100 °C for 12 hours. The ob-
tained powder was calcined at 200, 300, 400,
and 450 °C for 3 hours. The samples were la-
beled as (X) TiO2 (T1/T2), where X is the molar
ratio TU/Ti(OBu)4, T1 is the STT temperature,
T2 is the calcination temperature. The nitrogen
and carbon content in the samples was deter-
mined using a C, H, N-analyzer “Carlo Erba
1106”. The sulfur content was determined us-
ing an X-ray fluorescence spectrometer ElvaX.
Diffractograms of the samples were record-
ed on a Bruker D8 Advance diffractometer
using CuKα radiation. Transmission (TEM)
and scanning (SEM) electron micrographs
were obtained on microscopes JEM 1230 and
JSM-6060 LA (JEOL) at accelerating voltages
of 200 kV and 30 kV, respectively. Diffuse re-
flection spectra were recorded on an Evolution
600 spectrophotometer (Thermo Scientific).
FTIR spectra were recorded on a spectrome-
ter Perkin Elmer Spectrum One in KBr pellets
with a sample/KBr ratio of 1/100. Nitrogen ad-
sorption/desorption isotherms were measured
УХЖ № 10 / Том 86N. I. Romanovska, P. A. Manoryk, O. V. Selyshchev, P. S. Yaremov, O. V. Shylzshenko, A.V. Terebilenko, S. M. Shcherbakov, D. R. T. Zahn
99https://ucj.org.ua
by the volumetric method at 77 K on a Sorpto
matic 1990 instrument. Before measure-
ments, the samples were degassed for 5 hours
at 330 °C. The external specific surface area
(Sext) was calculated according to the method
described in [34]. Thermoprogrammed deso-
rption with mass spectrometric control (TPD-
MS) was performed in a quartz tube connected
to a quadrupole mass spectrometer MX7304A
(Selmi) with ionization by electrons of 70 eV.
The sample in the tube was heated linearly at
a rate of 14 °C/min from room temperature
to 800 °C. Mass spectra of the gas phase were
recorded continuously during heating. X-ray
photoelectron spectroscopy (XPS) spectra
were recorded using an ESCALAB 250Xi spec-
trometer (Thermo Scientific) equipped with
a monochromatic Al Kα X-ray source (hν =
1486.68 eV). The samples were pumped out in
a vacuum for at least 24 hours until the base
pressure in the chamber reaches 5-8×10-10
mbar. High-resolution spectra were recorded
at an analyzer pass energy of 20 eV, providing a
spectral resolution of 0.5 eV.
The photocatalytic activity (PCA) of sam-
ples calcined at different temperature were in-
vestigated under UV and visible light irradia-
tion (respectively PCA (UV) and PCA (VIS))
for the colorless cephalosporin (ceftazidime)
and doxycycline antibiotics photodegradation
processes. In the absence of a photocatalyst,
solutions of ceftazidime and doxycycline re-
main stable for a long time. PCA (UV) and
PCA (VIS) were determined by the conversion
degree (R60) for 60 minutes. A portion of the
sample was suspended in aqueous solutions
of doxycycline (or ceftazidime) with a con-
centration of 6.5×10-5 M at a sample/solution
ratio of 1 g/L and left overnight to establish
sorption equilibrium. The suspension was ir-
radiated with ultraviolet (l=365 nm, UV lamp
Delux 26W) and visible light (Maxus 8 W
lamp, equipped with a light filter that trans-
mits light with l > 400 nm), with a radiation
intensity near the surface of the suspension of
0.05 mW/cm2 and 2.0 mW/cm2
, respective-
ly. The light intensity was measured with a
91150V Reference Cell and Meter (Newport)
at the distance of 40 cm that corresponds to
the distance from the lamp to the surface of
the suspension. An aliquot of the suspension
was taken at regular intervals, centrifuged for
15 minutes, and absorption spectra were re-
corded on a spectrophotometer Specord 210
(Analytic Jena). The absence of doxycycline
and ceftazidime in the photocatalyst after the
photocatalytic experiment was controlled
by UV-vis spectra (Evolution 600 (Thermo
Scientific)). The content of doxycycline, cef-
tazidime, and its photodegradation products
in the solutions after photocatalysis was moni-
tored by HPLC (liquid chromatograph Waters
Alliance E 2695 with UV detector), according
to the European Pharmacopoeia (EUROPEAN
PHARMACOPOEIA 10.0) and 1H-NMR.
The sol obtained from the reaction mix-
ture containing thiourea after solvothermal
treatment contains about 43% (table 1) of the
anatase crystalline phase (sample (0.33) TiO2
(120/0)). Thus, in the diffraction pattern of
the obtained samples (fig. 1, curve 1), a set
of reflexes at 2q = 25.2, 37.8, 48.1, 54.0, 54.9,
62.6, 68.9, 70.4, 75.2° can be attributed to the
characteristic reflexes of the anatase crystalline
phase (JCPDS № 21-1272). As the calcination
temperature increased (fig. 1, table 1), the ana-
tase content calculated from the diffraction
data gradually increases from 43% for (0.33)
TiO2 (120/0) to 90% for (0.33) TiO2 (120/450)
(Table 1) with a slight increase in the crystallite
INFLUENCE OF CALCINATION TEMPERATURE ON STRUCTURAL-DIMENSIONAL CHARACTERISTICS OF C,S-DOPED TiO2 NANO
STRUCTURES AND THEIR PHOTOCATALYTIC ACTIVITY IN THE CEFTAZIDIME AND DOXYCYCLINE PHOTODEGRADATION PROCESSES
100 ISSN 2708-129X. Укр. хім. журн., 2020
PHISICAL CHEMISTRY
size, calculated by the Scherrer equation from
9 nm (for (0.33) TiO2 (120/0)) to 10 nm (for
(0.33) TiO2 (120/450)). The small narrowing
in the characteristic anatase reflexes with in-
creasing calcination temperature (fig. 1) can be
explained by the small increase in the anatase
crystallite size.
Changes in the chemical composition and
nature of the groups that occur with increasing
calcination temperature were determined us-
ing elemental and thermogravimetric analysis,
FTIR, XPS and UV-vis spectroscopy, and TPD
MS. According to elemental analysis (table 1),
with calcination temperature increase, the car-
bon content in the samples studied decreases
from 0.80% to 0.41% and the sulfur content
decreases from 1.39% to 0.89%. No nitrogen is
detected in the samples.
Table 1
Structural and dimensional characteristics of samples and the dopants content
Sample %А
d, nm
% С % S Eg, eV
XRD TEM SEM
(0,33) TiO2 (120/0) 43 9 8 85 0.80 1.39 3.05
(0,33) TiO2 (120/200) 77 9 95 0,62 1.24 3.07
(0,33) TiO2(120/300) 80 9 64 0,53 1.12 3.07
(0,33) TiO2 (120/400) 85 9 52 0,47 0.98 3.07
(0,33) TiO2 (120/450)* 90 10 9 45 0.41 0,89 3.07
(0) TiO2 (120/450)* 85 9 0.45 - 3.09
(0,17) TiO2 (120/450)* 95 10 0.51 0,48 3.07
*data from [36]
Fig.1 Diffraction patterns of synthesized sam-
ples: 1 – (0.33) TiO2 (120/0); 2 – (0.33) TiO2
(120/200); 3 - (0.33) TiO2 (120/300); 4 – (0.33)
TiO2 (120/400); 5 – (0.33) TiO2 (120/450).
The evolution in the content of anatase in
the samples (Table 1) as well as the appearance
of carbon and sulfur (Table 1) with calcination
temperature increase indicates the presence of
an amorphous phase. The amorphous phase
can be a modified amorphous titanium inor-
ganic polymer (MATІP), similar to the one
described in [35], stabilized with organic (ace
tate, alcohol, etc.) and inorganic (carbonate,
sulfate, ОН) groups.
The above-mentioned groups, which are
present in MATIP, probably, prevent its de-
struction and anatase crystallization, as well as
block the anatase crystallite growth (Table 1)
and the anatase to rutile phase transforma-
tion.
УХЖ № 10 / Том 86N. I. Romanovska, P. A. Manoryk, O. V. Selyshchev, P. S. Yaremov, O. V. Shylzshenko, A.V. Terebilenko, S. M. Shcherbakov, D. R. T. Zahn
101https://ucj.org.ua
This trend maintains [36] for the other cal-
cined at 450 °C samples. For example, for (0.17)
TiO2 (120/450) with a crystallite size of 10 nm,
the anatase content is 95%. It was previously
shown [37] that anatase nanoparticles, which
are formed mainly in an acidic medium, are
stabilized by the surface adsorbates containing
a lot of hydrogen (hydrogenated, hydrogen-rich
and hydrated surfaces), which prevent the phase
transformation to rutile, and the size and shape
of anatase nanoparticles vary only slightly and
depends on the surface chemistry (only minor
changes in the particles ratio occur). However,
both polymorph (anatase and rutile) nano-
crystals become elongated in the case of hy-
drogen-depleted and oxygenated surfaces [37].
Taking into account the fact that the Ti-O-
SO3H groups on the TiO2 surface are stable up
to 600 oC [38], the results of elemental analysis
(table 1), TPD MS (fig.4 a, b), and FTIR spec-
troscopy (fig. 2), allow to assume that the Ti-O-
SO3H and Ti-OH groups are also responsible
for maintaining the anatase crystallites size and
shape during calcination (200-450 oC).
In the FTIR spectra of (0) TiO2 (120/0)
(fig. 2, curve 1), the bands 1588 and 1440 cm-1
(with Dv = 144 cm-1) are observed, which can
be attributed to the valence vs and vas oscilla-
tions of acetate groups bridged by CO bonds
[35] (or to n1 and n5 of bidentate and mono-
dentate carbonate [39]). The band at 1630 cm-1
is characteristic for deformation oscillations of
OH groups in H2O [39] and/or Ti-OH [18]. The
low-intensity bands at 1115, 1090, 1020 cm-1 can
be attributed to group oscillations of interstitial
Ti-O-C bonds [35, 40] and/or oscillations of Ti-
O-C butoxyl groups directly associated with ti-
tanium [35]. The broad band between 900 - 400
cm-1 can be attributed to Ti-O-Ti vibrations of
the frame [35, 40, 41]. The broadening of this
band is assigned to the amorphous phase. In
the FTIR spectra of (0.33) TiO2 (120/0), (fig. 2,
curve 2), these bands are preserved (with a
slight shift in their position), and new low-in-
tensity bands appear, which can be attributed
to oscillations of C-O bonds n1 (1393 cm-1), n5
(1598 cm-1) for monodentate and n1 (1463 cm-
1), n5 (1285 cm-1) for bidentate carbonate. The
valence symmetric and asymmetric oscillations
of S-O bonds n3 (1120,1045 cm-1), n1 (985 cm-
1),n2 (469 cm-1) of bidentate sulfate, caused by a
decrease in the symmetry of the sulfate ion with
high-symmetric Td to low-symmetric C2v, indi-
cate the formation of bridge bonds with titani-
um ions. The band n3 (1046 cm-1) of monoden-
tate sulfate [39] is identified in similar samples
as Ti-O-SO3H groups [38]. Since the content
of the incorporated nonmetals in the obtained
samples is quite low, the corresponding bands
are low intense and/or manifested themselves
as shoulders to the more intense bands in the
FTIR spectrum. Because of this, it is difficult to
quantify the changes in their intensity during
calcination. Nevertheless, a number of trends in
their change should be noted.
Fig.2 FTIR spectra of the samples: 1 – (0) TiO2
(120/0); 2 – (0.33) TiO2 (120/0); 3 - (0.33) TiO2
(120/200); 4 – (0.33) TiO2 (120/300); 5 – (0.33)
TiO2 (120/400); 6 – (0.33) TiO2 (120/450).
INFLUENCE OF CALCINATION TEMPERATURE ON STRUCTURAL-DIMENSIONAL CHARACTERISTICS OF C,S-DOPED TiO2 NANO
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PHISICAL CHEMISTRY
As can be seen from fig. 2 (curves 3–6),
with calcination temperature increase, there is
a tendency to a decrease in the intensity of the
valence vibrations band of acetate C-O groups
that are associated with a decreasing content of
the amorphous phase.
Starting from 300oC, there is also a tenden-
cy of a decrease in the intensity of the bands re-
lated to monodentate and bidentate carbonate
(interstitial carbon).
However, the intensity of the bands, which
belong to the bridge (interstitial) sulfate, re-
mains practically unchanged. The intensity
of the bands related to the oscillations of OH
groups slightly decreases but remains quite
high even after calcination at 450oC (fig. 2,
curve 6). This may indicate the presence of
a large number of OH groups in the sample
(0.33) TiO2 (120/450). The latter fact is impor-
tant for photocatalysis.
As can be seen in the thermogram (fig. 3a),
for (0.33) TiO2 (120/0) three endoeffects are
observed (Textr at 50, 110, 190oC). The two first
extrema in the DTG and weight loss in the TG
curve can be attributed to the loss of physi-
cally and chemically bound water at 50 and
110 oC, respectively. The third effect (190 oC)
can be attributed to the loss of residues of or-
ganic substances (solvents) that is confirmed
by the absence of this effect in the thermogram
of the calcined sample (fig. 3 b). An exoeffect
with Textr at 370 oC is also observed in the DTA
curve that corresponds to the extremum in the
DTG and the mass loss in the TG curves. This
effect can be associated with the combustion
of acetic acid residues and other organic com-
pounds in the modified amorphous titanium
oxide inorganic polymer. The course of the
DTA curve in the range of 250–650 oC with
several extrema that have no correspondence
in the DTG curve, may indicate the melting
processes. According to the TG this process
is accompanied by a slight weight loss in the
temperature range 400-650 oC. The extremum
in the DTA curve (about 580 °C) can be attrib-
uted to the destruction of titanyl sulfate groups
on the surface. The similar peak was observed
by us previously for samples of doped TiO2,
which were obtained using H2SO4 as a sulfur
precursor (unpublished results).
In the thermogram of the calcined sam-
ple (0.33) TiO2 (120/450) (fig. 3 b), similarly
to (0.33) TiO2 (120/0) (fig. 3 a), the two en-
doeffects (Textr. 50, 110 oC) in the DTA curve
are observed. They correspond to the extrema
on the DTG curve and the weight loss on the
TG curve due to desorption of physically and
chemically bound water. At higher temper-
atures, in the thermogram (Fig. 3 b) signifi-
cant changes in comparison with (0.33) TiO2
(120/0) (fig. 3 a) are observed. The mass loss in
the TG curve in the range of 150–250 °С cor-
responds to the extremum on the DTG curve
(~200 °С), and the exoeffect (Textr. ~215 °С) can
be attributed to the combustion of residues of
organic compounds that are a part of MATIP.
In the temperature range 300–700 °C accord-
ing to the DTG and TG curves, a barely no-
ticeable monotonic weight loss is observed. In
this case, the course of the DTA curve, which
has a number of indistinct extrema, indicates
the presence of several phase transitions in the
temperature range of 300–700 °C. An extrem-
um at Textr. about 730 oC in the DTG and the
DTA corresponds to a significant mass loss on
the TG curve. Similarly to the peak at 710 oC in
the sample (0.33) TiO2 (120/0) (Fig. 3 a), this
effect сan be associated with the destruction
of the surface Ti-O-SO3H groups [38] that are
formed due to Ti-SH groups oxidation.
УХЖ № 10 / Том 86N. I. Romanovska, P. A. Manoryk, O. V. Selyshchev, P. S. Yaremov, O. V. Shylzshenko, A.V. Terebilenko, S. M. Shcherbakov, D. R. T. Zahn
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a
b
Fig. 3 Thermograms of the samples: a – (0.33)
TiO2 (120/0); b – (0.33) TiO2 (120/450).
In TPD-MS of freshly obtained (0.33) TiO2
(120/0) (fig. 4 a), maxima of TPD-MS pro-
files with m/z=28, m/z=34, m/z=44 can be
associated with the desorption of CO+, H2S
+,
and CO2
+, respectively. As a result of sol-gel
synthesis and STT in (0.33) TiO2 (120/0), the
MATIP structure is formed, in which sulfide,
carbonate, and, possibly, acetate groups stabi-
lize its structure. The close values of temper-
atures at which the maxima are observed in
the TPD MS profiles m/z=28, m/z=34, m/z=44
in the temperature range 150–500 °C indicate
that desorption and destruction processes in
MATIP begins with the carbonate bridges de-
struction (at Textr ~175 °C). The process occurs
in two stages. On the first, the CO2
+, H2S
+, CO+,
(Textr 203, 216, 230°C, respectively), and at the
second, H2S
+, CO+, CO2
+ (Textr 309, 309, 317 °C,
respectively) are desorbed. In the temperature
range of 500-800°C, extrema in TPD-MS pro-
files with m/z=44, m/z=34, m/z=28 (at Textr
639, 653, 688 °C) correspond to CO2
+, H2S
+,
CO+, respectively. It should be noted that in
the TPD MS, the profiles with m/z=18 (H2О
+)
correspond to these three groups of extrema,
at Textr 200, 315, and 680°C, indicating the in-
terconnection of desorption processes of CO+,
H2S
+, CO2
+, and H2О
+.
a
b
Fig.4 TPD-MS spectra of the samples: a – (0.33)
TiO2 (120/0); b – (0.33) TiO2 (120/450).
Desorption of the lion’s share of products in
the uncalcined sample (fig. 4 a) occurs in the
temperature range of 150-500°C in two sta
ges – at Textr 203, 216, 230 °C (CO2
+, H2S
+, CO+,
INFLUENCE OF CALCINATION TEMPERATURE ON STRUCTURAL-DIMENSIONAL CHARACTERISTICS OF C,S-DOPED TiO2 NANO
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PHISICAL CHEMISTRY
respectively) and at Textr ~309, 309, 317 °C
(H2S
+, CO+, CO2
+, respectively), probably due
to the gradual destruction of monodentate and
bridged acetate and sulfide groups.
In TPD-MS of calcined (0.33) TiO2 (120/450)
(Fig. 4 b) in comparison with (0.33) (fig. 4 a),
the extrema intensity on TPD MS profiles with
m/z=18 (H2О
+), m/z=28 (CO+), m/z=44 (CO2
+)
is significantly lower due to the fact that in the
process of calcination at 450 oC a significant
part of the respective groups is removed from
the sample. According to the thermogram of
(0.33) TiO2 (120/0) (fig. 3 a), ~90% of the mass
is lost when the sample is heated to 450 oC. Of
the five extrema observed on the profile with
m/z=28 (CO+), the first two (at Textr ~110, 254 oC)
are probably due to the decomposition of ace-
tate residues. The remaining three (at Textr ~352,
444, 615оС), coinciding with the extrema in the
TPD MS profiles with m/z=44 (CO2
+) at a Textr
of about 444, 617 oC, are probably due to the
destruction of surface and interstitial carbonate.
Next to these three extrema, the peaks in the
TPD MS profile with m/z=64 at Textr about 435,
645 oC correspond to the desorption of SO2
+.
Taking into account the fact that the sample
(0.33) TiO2 (120/450) (fig. 3 b) according to
X-ray phase analysis contains 95% anatase, the
desorption of CO+, CO2
+, SO2
+ at T>300oC can
be attributed as to the interstitial also to the sur-
face adhering carbonate and sulfate groups.
Earlier, in the study of TPD of adsorbed
H2S and SO2 on the surface of TiO2 [42], it was
shown that H2S and elemental sulfur can be ox-
idized by titanium dioxide and that the desorp-
tion of SO2 occurs at Textr ~350 oC. According
to this, the presence of (0.33) TiO2 (120/450)
in the TPD MS profile (fig. 4 b) with m/z = 64
three extrema (at Textr about ~429, 461, 645 oC)
corresponding to the desorption of SO2
+, may
indicate that the main source of SO2 here are
sulfate groups rather than adsorbed SO2. The
sulfate groups are a part of MATIP and stabilize
its structure. Because of SO4
2- groups, as well as
due to the presence in the TPD MS profiles with
m/z=34 (fig. 4 a) for (0.33) TiO2 (120/0) extrema
at Textr ~216oC and 309 oC, we can assume that
sulfur, which is the source of H2S
+, is not phys-
ically adsorbed but chemically bound. This fact
is consistent with the XPS analysis.
The chemical composition and chemical
(oxidation) states of the elements in TiO2 sam-
ples are investigated by means of X-ray photo
emission spectroscopy (XPS). The results on
the calcined (0.33) TiO2 (120/450) were re-
ported by us previously [36]. The uncalcined
sample (0.33) TiO2 (120/0) is discussed in de-
tail in this work (fig.5).
As determined from the fragment of the
survey XPS spectrum, the surface of the (0.33)
TiO2 (120/0) is composed of titanium and ox-
ygen atoms (30.0 at.% Ti and 52.2 at.% O) and
also contains C (17.1 at.%), S (0.36 at.%), and
N (0.31 at.%). The atomic Ti/O ratio calculat-
ed for the TiO2 lattice oxygen (the O1s peak
at 530.2 eV, fig. 5) is 1:1.74 (± 0.05). Such an
oxygen deficiency is mostly caused by the co-
ordination of Ti4+ to other functional groups
detected in the surface layer, SO4
2-, CO3
2-, OH,
etc. Fig. 5 shows the high-resolution spectra
fitted with Voigt profiles. The peaks at (459.1 ±
0.1) eV and (464.8 ± 0.1) eV correspond to the
Ti2p3/2 and Ti2p1/2 components of the spin-or-
bit doublet. The separated doublet of lower
intensity at (472.3 ± 0.1) and (478.4 ± 0.1) eV
stems from plasmon satellites. Thus, the sam-
ple contains titanium in a single chemical state,
which due to the synthesis conditions, can be
unambiguously attributed to Ti4+. It should be
noted that the lower oxidation states Ti3+, Ti2+
УХЖ № 10 / Том 86N. I. Romanovska, P. A. Manoryk, O. V. Selyshchev, P. S. Yaremov, O. V. Shylzshenko, A.V. Terebilenko, S. M. Shcherbakov, D. R. T. Zahn
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that usually manifest themselves at lower bind-
ing energies to the main Ti4+ peak, are not ob-
served in our samples.
Fig. 5. XPS spectra of the sample (0.33) TiO2 (120/0).
In the high-resolution O1s XPS spectrum
(fig. 5), the intense peak at (530.2 ± 0.1) eV
stems from the lattice oxygen of TiO2 (530.2 eV
[9]). The second broader peak at (531.7 ± 0.1)
eV can be referred to carbonate (533.0 eV [8])
and sulfate oxygen (531.6 [12]), as well as to
oxygen in surface OH (532.0 eV [9], 532.1 eV
[21]) and C-O (532.1 eV [8, 21]) groups.
Despite the fact that according to the elemen-
tal analysis (Table 1), the (0.33) TiO2 (120/0)
does not contain nitrogen (within the sensi-
tivity of the gas chromatography detection), a
low intense N1s core-level XPS peak at 400.3
eV is observed. Since XPS is a surface-sensitive
method with an information depth less than
10 nm, one can assume that the nitrogen orig-
inates from the adsorption of gaseous N2, NH3
from the atmosphere by the near-surface layer
of the nanostructured sample [7]. Moreover,
the surface sensitivity causes the abnormal in-
flation of the carbon atoms content compared
to the CHN analysis data. In the C1s high-res-
olution XPS spectrum, the most intense peak
at (284.8 ± 0.1) eV is mainly formed by the
so-called adventitious carbon (typical range
284.5 - 285.0 eV). The latter comes from vol-
atile organic compounds adsorbed on the sur-
face from the atmosphere [8, 9]. Since the total
(bulk) carbon content, determined by the el-
emental CHN analysis for this sample (Table
1), is 0.80%, one can assume that the main
share of carbon (fig. 5) is adventitious and
does not belong to the volume of the analyzed
sample. Two other peaks of approximately the
same intensity at (286.3 ± 0.1) eV and (288.8
± 0.1) eV may correspond to the interstitially
incorporated or surface adsorbed carbonate
species [8, 9].
It should be noted that the binding energies
of Ti2p, O1s, C1s, and N1s peaks detected for
(0.33) TiO2 (120/0) with an accuracy of 0.1 eV
coincide with the XPS results on (0.33) TiO2
(120/450) [36], indicating the proximity of the
chemical states of these elements in the sam-
ples.
The peaks at (169.0 ± 0.2) eV and (170.4 ±
0.2) eV, revealed in the S2p XPS spectrum (fig.
5), correspond to the S2р3/2 and S2р1/2 spin-or-
bit components, respectively. According to the
chemical shift, the XPS analysis confirms the
S6+ oxidation state of sulfur [21].
According to the authors [12], who ob-
served similar results, this indicates the forma-
tion of sulfuric acid residues in the structure
INFLUENCE OF CALCINATION TEMPERATURE ON STRUCTURAL-DIMENSIONAL CHARACTERISTICS OF C,S-DOPED TiO2 NANO
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PHISICAL CHEMISTRY
of TiO2 during calcination and the incorpora-
tion of S6+ sulfur in the structure of TiO2 (in-
terstitially and on the surface). This is consist-
ent with the FTIR spectroscopy results for the
samples (0.33) TiO2 (120/T2) (fig. 2), according
to which the intensity of the bands attributed
to S-O and S=O modes decreases with increas-
ing calcination temperature. This is also con-
firmed by the results of TPD MS (fig. 4 a, b),
where profiles with m/z 64 (SO2
+) are observed
not only for (0.33) TiO2 (120/450) but also
for (0.33) TiO2 (120/0). In addition, for (0.33)
TiO2 (120/450) (fig. 4 b) in the profile with m/z
64 (SO2
+), two peaks (Textr ~429 and 652°C) of
approximately the same intensity are detected
and can be attributed to surface and interstitial
sulfate, respectively. The S2p spectrum of the
sample after calcination is very close to the un-
calcined one. However, the S2p1/2 component
(170.4 eV) for the (0.33) TiO2 (120/0) becomes
more distinct and exhibits a small shift towards
higher binding energies (for comparison, the
S2p1/2 for the calcined (0.33) TiO2 (120/450) is
at (169.9 ± 0.2) eV [36]). In our opinion, this
may be caused by Ti-O-SO3H groups in the un-
calcined sample, revealed by the results of the
TGA analysis (fig. 3 a). A low-intense signal
about 160.9 eV corresponds to S2- [10, 11, 19]
that is consistent with the results of TPD MS
(fig. 4a). The intensity of the peak is extremely
low, probably, due to the oxidation of the S2-
at the surface. Thus, in addition to the CHN
analysis, XPS gives reason to believe that the
sample (0.33) TiO2 (120/450) is supplemented
with carbon and sulfur.
According to the results of elemental and
thermogravimetric analysis, IR, XPS, and
TPD MS investigations, the final structure of
the calcined samples, in particular (0.33) TiO2
(120/450), is formed due to the MATIP struc-
ture destruction during calcination, which is
formed at STT and stabilized by groups (wa-
ter molecules, carbonate, acetate, sulfate and,
possibly, alcohol, which also contains sulfide).
According to the XPS and the results of ele-
mental analysis and TPD MS a small number
of the permeable nonmetals (C, S), which are
part of the interstitial and surface carbonate
and sulfate groups, remains in the calcined
sample. The MATIP calcination is accompa-
nied by a gradual loss of modifying groups,
including sulfate (bridge and surface), which
are formed due to sulfide oxidation under cal-
cination that creates the preconditions for the
anatase crystallization.
According to the SEM image (fig. 6a) the
sample (0.33) TiO2 (120/0) is in the form of na-
noparticles with an average size of 85 nm, con-
sisting of an amorphous phase (58%, table 1)
and anatase crystalline sheets (42%, table 1).
According to the TEM study (fig. 6 b), the aver-
age size of the sheets, is of about 8x7 nm. These
sheets also form rectangular units (fig. 6 b, in-
set) with an average size of 30x8 nm. As the
result of calcination at 200 °C, according to the
SEM image (fig. 6 c), the average particle size
in the sample (0.33) TiO2 (120/200) increas-
es (up to 95 nm) and their compaction oc-
curs. The size of the anatase crystalline sheets
(fig. 6 d) increases from 8x7 nm to 10x8 nm.
The anatase sheets aggregate in the rectangu-
lar rods with an average size of 200x50 nm
(fig. 6 d, inset). After calcination at 300 oC
in (0.33) TiO2 (120/300) the average particle
size decreases (up to 64 nm) and their further
compaction occur. At the same time, the ana-
tase sheet size decreases from 10x8 nm to 9x8
nm (fig. 6 e), forming aggregates in a shape of
rectangular rods (fig. 6 e, inset) with an av-
erage size of 20x10 nm. In the SEM image of
УХЖ № 10 / Том 86N. I. Romanovska, P. A. Manoryk, O. V. Selyshchev, P. S. Yaremov, O. V. Shylzshenko, A.V. Terebilenko, S. M. Shcherbakov, D. R. T. Zahn
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Fig. 6 SEM and TEM images of the sam-
ples: a, b – (0.33) TiO2 (120/0); c, d – (0.33) TiO2
(120/200); e, f – (0.33) TiO2 (120/300); g, h – (0.33)
TiO2 (120/400); i, j – (0.33) TiO2 (120/450).
the sample (0.33) TiO2 (120/400), calcined at
400°C (fig. 6 g), the particle size decreases to
52 nm, and the particle compactness increas-
es. In the TEM image of this sample (fig. 6 h),
the sheets with an average size of 10x9 nm,
forming aggregates (fig. 6h, inset) of rectangu-
lar (110x170 nm) and hexagonal (65x65 nm)
shape, are observed. Calcination at 450 °C en-
sures a particle size decrease in the SEM im-
age (fig. 6 i) of (0.33) TiO2 (120/450) to 45 nm
and compaction of the material. In the TEM
image (fig. 6 j), these anatase crystals are rep-
resented by rectangular particles with fused
edges of medium size of 10x9 nm, as well as
the anatase crystal sheet aggregates in the
form of rectangular rods with an average size
of 20x14 nm.
The sizes of crystallites (table 1), calculated
from diffractograms (fig. 1) and TEM imag-
es (fig. 6), are slightly different. According to
the calculations from the diffraction patterns
(fig. 1), the average particle size in the uncal-
cined sample (0.33) TiO2 (120/0) is 8 nm and
increases to 9–10 nm in the calcined ones (ta-
ble 1). According to the TEM images (fig. 6),
the size of anatase crystallites of the rectangu-
lar sheet shape changes from 8x7nm to 10x8,
9x8, 10x9, and 10x9 nm, depending on the cal-
cination temperature (table 1). The elevating
of the crystals results in the formation of the
particles of an elliptical shape, probably due
to melting of their edges. The differences be-
tween the calculation results of X-ray diffrac-
tion data and TEM (table 1) may be related to
the sheet formation, since the Debye-Scherrer
equation is better fitted for the spherical par-
ticles. Lamellar morphology is characteristic
for facet structures formed in the presence of
a dopant such as fluorine [43], which binds to
high-energy {001} faces and blocks the anatase
crystal growth along the {001} axis. The forma-
tion of lamellar anatase crystals in the case of
(0.33) TiO2 (120/T2) samples can be explained
due to the presence of carbonate and sulfate
groups on the anatase crystals surface, which,
like fluorine, promote the formation of plates
INFLUENCE OF CALCINATION TEMPERATURE ON STRUCTURAL-DIMENSIONAL CHARACTERISTICS OF C,S-DOPED TiO2 NANO
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PHISICAL CHEMISTRY
with open faces {001}. Due to the simultaneous
presence of the amorphous phase and the ana-
tase crystalline phase in the samples studied
(table 1), which according to TEM images is
of the sheet shape (fig. 6), we can assume that
the nanoparticles, observed in the SEM image
(fig. 6) are anatase sheets or sheet agglomerates,
covered by amorphous MATIP, i.e., particles of
the type “core-shell”.
a
b
Fig. 7 a – Isotherms of samples (0.33) TiO2
(120/T2): 1 – (0.33) TiO2 (120/0); 2 – (0.33) TiO2
(120/450); b – mesopore size distribution of the
sample: 1 – (0.33) TiO2 (120/0); 2 – (0.33) TiO2
(120/450).
After the sol-gel synthesis of TiO2 in the
presence of thiourea, followed by solvothermal
treatment, mesoporous materials are formed.
Isotherms of samples (0.33) TiO2 (120/0)
(fig. 7 a, curve 1) and (0.33) TiO2 (120/450)
(fig. 7 a, curve 2) can be attributed to type IV,
which is characteristic for micro-mesoporo-
us materials. The specific surface area (SBET)
for the sample (0.33) TiO2 (120/0) is 190 m2/g
with a mesopore diameter of 5.4 nm, Smeso of
170 m2/g and a total adsorption volume of
0.25 cm3/g. Nanoparticles form a mesoporous
structure, which is formed already at the stage
of STT [36]. After calcination at 450°C, the SBET
decreases to 130 m2/g, the total pore volume to
0.22 cm2/g, the Smeso to 70 m2/g, and the meso
pore diameter increases to 6.4 nm. For (0.33)
TiO2 (120/0) on the mesopore distribution
curve (fig. 7 b, curve 1) two extrema with max-
ima at 5.5 and 6.4 nm are observed, and the
mesopore average size is 5.4 nm, that indicate
the presence of two types of mesopores.
Probably, mesopores of smaller diameter
are cavities between spheroidal nanoparticles,
which consist of anatase sheets (45%), covered
with an amorphous phase, and mesopores of
larger diameter are cavities between sheet ag-
gregates (fig. 6 b, inset), in particular, in the
form of rods. For the calcined sample (0.33)
TiO2 (120/450), only one extremum (6.4 nm) is
observed (fig. 7 b, curve 2) and the average size
of mesopores is 6.4 nm. It is possible that the
mesopores here are cavities between spheroi-
dal nanoparticles, which consist mainly of ana-
tase crystal sheets (90%) with fused edges (fig.
6, inset), which are tightly adjacent to each oth-
er. As a result of calcination, according to TEM
images (Fig. 6 d, f, h. j), the 2D anatase crystal-
lite sizes increase, and rectangular (fig. 6 d, f)
and hexagonal (fig. 6 h ) sheet aggregates, as a
result of calcination at 450ºC, are compacted
and transformed into spheroidal particles. The
УХЖ № 10 / Том 86N. I. Romanovska, P. A. Manoryk, O. V. Selyshchev, P. S. Yaremov, O. V. Shylzshenko, A.V. Terebilenko, S. M. Shcherbakov, D. R. T. Zahn
109https://ucj.org.ua
specific surface area for (0.33)TiO2 (120/450)
is reduced to 130 m2/g compared to 190 m2/g
for (0.33)TiO2 (120/0), which is probably due
to a slight increase in the size of the crystallites
and the compaction of particles in the volume
of the material due to the destruction of the
amorphous phase and sintering. A significant
increase in the size of the crystallites (table 1)
and drastic changes in the texture prevent car-
bon and sulfur-containing groups. Thus, the
calcination temperature is a factor controlling
the anatase content, the crystallite and nano-
particle sizes, as well as the textural character-
istics of the obtained materials.
For non-calcined sample (0.33) TiO2 (120/0)
(table 1), the bandgap (Eg) value, calculated
from the UV-Vis spectra (fig. 8 a, curve 1),
is slightly smaller (3.05 eV) compared to Eg
(3.2 eV) for bulk anatase. In the UV-vis spectra
of samples (0.33) TiO2 (120/T2) (fig. 8 b, curves
1-5), the increasing calcination temperature
(T2) induces the bathochromic shift of the ab-
sorption band resulting to the slight absorp-
tion in the visible region.
In particular, for sample (0.33) TiO2
(120/450) in the UV-vis spectrum (fig. 8 a,
curve 2) the absorption maximum at 320 nm
is shifted in comparison with the sample (0.33)
TiO2 (120/0) (fig. 8 a, curve 1). The latter may
be due caused by an increase of the amount of
titanium ions in an octahedral surrounding,
which is characteristic for the anatase crystal-
line phase [44]. This is consistent with an in-
crease in the anatase content in these samples
with calcination temperature increase (table 1).
Besides, for uncalcined sample the absorb-
ance at l ≥ 400 nm is greater than for the cal-
cined sample (table 1), that is probably due to
the presence of more interstitial Ti-O-C groups
in (0.33) TiO2 (120/0), consistent with the el-
emental analysis results (table 1). According
to the latter, the total carbon and sulfur con-
tents decrease with calcination temperature
increase.
a
b
Fig. 8. Electronic spectra: а – absorbance spec-
tra of samples: 1 – (0.33) TiO2 (120/0); 2 – (0.33)
TiO2 (120/450); b - diffusion reflectance spectra
of samples (0.33) TiO2 (120/Т2): 1 – (0.33) TiO2
(120/0); 2 – (0.33) TiO2 (120/200); 3 – (0.33) TiO2
(120/300); 4 – (0.33) TiO2 (120/400); 5 – (0.33)
TiO2 (120/450);
As can be seen from the evolution of the
UV-vis reflectance spectra (fig. 8 b), for the
samples (0.33) TiO2 (120/T2), an additional
absorption in the visible region at l ≥ 400 nm
INFLUENCE OF CALCINATION TEMPERATURE ON STRUCTURAL-DIMENSIONAL CHARACTERISTICS OF C,S-DOPED TiO2 NANO
STRUCTURES AND THEIR PHOTOCATALYTIC ACTIVITY IN THE CEFTAZIDIME AND DOXYCYCLINE PHOTODEGRADATION PROCESSES
110 ISSN 2708-129X. Укр. хім. журн., 2020
PHISICAL CHEMISTRY
is observed after calcination at 200oC (fig. 8 b,
curve 2). This may be caused by the intersti-
tial carbonate groups formed in (0.33) TiO2
(120/200). The intensity of absorption decreas-
es (fig. 8 b, curves 3–5) with calcination tem-
perature increase. At the same time, the nature
of the bands changes, which may be associated
with the formation of interstitial sulfate groups
under these conditions. This is consistent with
the results of TPD MS (fig. 4), ХРS (fig. 5),
FTIR (fig. 2), and TG (fig. 3).
Thus, based on the obtained results (FTIR,
XPS, TPD MS, XRD, SEM, TEM, nitrogen ad-
sorption/desorption, elemental analysis), it
can be concluded that in the samples (0.33)
TiO2 (120/T2) the calcination temperature in-
crease (200-450oC) induces an anatase content
increase, while amorphous phase content de-
crease. At that time, the crystallite (of lamellar
morphology) size (8–10 nm) slightly increas-
es. The average size of nanoparticles formed
by such crystallites together with the amor-
phous phase decreases (95–45 nm), so as the
SBET, Smeso, the total adsorption volume, and the
interstitial and surface carbonate and sulfate
groups content decrease. The bandgap insig-
nificantly narrowed, reaching 3.05–3.07 еV. All
these changes lead to a significant effect on the
photocatalytic activity of (0.33) TiO2 (120/T2)
samples.
The effect of calcination temperature on
PCA (UV/VIS) of the samples was investigat-
ed in the photodegradation reactions of cef-
tazidime (fig. 9 a) and doxycycline (fig. 9 b).
The results are presented in Table 2. As can be
seen in fig. 9 a, b, the calcination temperature
significantly affects the photocatalytic activi-
ty of the obtained samples in the ceftazidime
and doxycycline photodegradation processes.
The dependence of PCA (VIS) changes on the
increasee in calcination temperature, in con-
trast to the dependence for PCA (UV), shows
a dome-shape behaviour (fig. 9 a, b). The
conversion of ceftazidime, as well as doxycy-
cline, in the presence of (0.33) TiO2 (120/T2)
photocatalysts under UV light irradiation in-
crease with calcination temperature increasee
and reaches a maximum on the sample (0.33)
TiO2 (120/450) (fig. 9 a, b). The last sample
contains the largest amount of anatase (about
a b
Fig. 9 Conversion degree of: a – ceftazidime; b – doxycycline on the obtained sample under UV (black)
and visible (grey) light irradiation
УХЖ № 10 / Том 86N. I. Romanovska, P. A. Manoryk, O. V. Selyshchev, P. S. Yaremov, O. V. Shylzshenko, A.V. Terebilenko, S. M. Shcherbakov, D. R. T. Zahn
111https://ucj.org.ua
90%) among the studied samples. At the same
time, when exposed to visible light, the maxi-
mum ceftazidime and doxycycline conversion
(fig. 9 a, b) is observed on the sample (0.33)
TiO2 (120/300) with a lower content of ana-
tase (80%) than 90% for (0.33) TiO2 (120/450).
Possibly, the higher photocatalytic activity of
the first sample is due to the optimal nanopar-
ticles size (64 nm) and larger number of inter-
stitial Ti-O-C groups, the amount of which in-
creases with an increase in the calcination tem-
perature from 200 to 450oC. It should be noted
that a similar trend in PCA (UV/VIS) changes
is observed for both stained (doxycycline) and
colorless (ceftazidime) antibiotics. Based on
this, we can assume that the key positive effect
on PCA (UV) is an increasing anatase content
in the samples. This effect is also present in the
case of PCA (VIS) but taking into account the
non-substantial bandgap narrowing (to 3,05–
3,07 eV, table 1). This effect is also present in
the case of FCA (VIS). However, considering
the slight narrowing of the bandgap (table 1)
to 3.05–3.07 eV, it is difficult to explain this
effect only by the bathochromic shift. Taking
into account that the positive doping effect
on the visible light sensitivity and PCA does
not always lead to a change in the bandgap
and shift of the band edge [1, 5] but is a result
of interstitial doping and localized states
formed in the mid-gap [1, 5, 6], it can be con-
sidered that the interstitial carbonate and sul-
fate groups may play a key role. The ratio be-
tween the latter groups changes (increases in
favor of the latter) with increasing calcination
temperature. Higher PCA (VIS) compared
to PCA (UV) of the samples for doxycycline
(fig. 9 b) in contrast to ceftazidime (fig. 9 a)
photodegradation processes is probably as-
sociated with a higher adsorption capacity of
these samples relative to doxycycline compa-
rable to ceftazidime (table, 2), as well as the
doxycycline photosensitizing effect.
Table 2
Sorption capacity of (0.33) TiO2 (120/T2)
samples
Sample
Q, 10-5 mol/g
ceftazidime doxycycline
(0,33) TiO2 (120/0) 2.12 4.05
(0,33) TiO2 (120/200) 1.93 3.64
(0,33) TiO2(120/300) 2.46 4.57
(0,33) TiO2 (120/400) 1.95 3.57
(0,33) TiO2 (120/450)* 1.97 3.78
P-25 Evonik 0.13 0,46
Regardless of the samples calcination tem-
perature, PCA (UV) in the ceftazidime photo-
degradation process on such samples is more
than 3 times higher than the conversion value
for Evonik P-25. Probably, this is due to the
fact that the content of anatase in these sam-
ples is higher than in Evonik P-25 (table 1). In
addition, these samples are characterized by a
more developed surface and a higher adsorp-
tion capacity relative to ceftazidime compared
with P-25 (table 2). When irradiated with vis-
ible light, the conversion on calcined samples
(0.33) TiO2 (120/T2) (T2 = 0, 200, 300oC) is 1.5-2
times higher than the value for Evonik P-25
and is maximum for the sample (0, 33) TiO2
(120/300). This may be due to the slightly high-
er adsorption capacity relative to ceftazidime
compared to the rest of the samples (Table 2),
as well as with the optimal size (~50 nm) of na-
noparticles. In addition, the interstitial carbon
content in this sample is also higher, which
may provide its increased PCA (VIS).
INFLUENCE OF CALCINATION TEMPERATURE ON STRUCTURAL-DIMENSIONAL CHARACTERISTICS OF C,S-DOPED TiO2 NANO
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112 ISSN 2708-129X. Укр. хім. журн., 2020
PHISICAL CHEMISTRY
However, it is noteworthy that the PCA
(UV/VIS) of (0.33) TiO2 (120/T2) samples in
the doxycycline photodegradation processes is
generally higher (1.5-1.7 times) compared with
ceftazidime, which is probably due to the ap-
proximately 2 times higher adsorption capacity
(Q, mol/g) of the corresponding samples re
lative to doxycycline compared to ceftazidime
(Table 2). For example, PCA (UV) for (0.33)
TiO2 (120/450) is 43.09 and 29.29, respectively,
and the average adsorption capacity for doxy
cycline and ceftazidime is 1.97×10-5 mol/g and
4.02×10-5 mol/g, respectively. The approximate-
ly two times greater adsorption capacity may
be the reason for this difference between PCA
(UV) relative to doxycycline and ceftazidime.
In contrast to PCA (UV), the PCA (VIS)
(conversion, R60) ratio values for the doxy-
cycline and ceftazidime photodegradation
processes (R60 (dox)/R60 (cef)) increases from
2.7 to 6.7 as the calcination temperature of
the samples (0.33) TiO2 (120/T2). This may
be associated not only with the greater ad-
sorption capacity of these samples relative to
doxycycline (table 2) but also with changes in
the interstitial carbonate and sulfate groups
amount and their ratios in (0.33) TiO2 (120/T2)
and the photosensitization effect of the sub-
strate (doxycycline). These assumptions are
confirmed by the results of PCA (UV/VIS)
comparison with Evonik P-25 in the doxy-
cycline and ceftazidime photodegradation
processes (table 2). In particular, the adsorp-
tion capacity for Evonik P-25 to doxycycline
(Q=0.49 10-5 mol/g) is 3 times higher than to
ceftazidime (Q=0.13 10-5 mol/g). Noteworthy
that PCA (UV) for Evonik P-25 in the doxy
cycline (R60=21.56%) photodegradation pro-
cess is approximately also about 3 times higher
than in the ceftazidime (R60=7.53%) photode-
gradation process (table 2). At the same time,
the PCA (VIS) is approximately 4.3 times high-
er. For doxycycline and ceftazidime, R60 are
33.12 and 7.66%, respectively. Based on these
comparisons, it can be assumed that the PCA
(VIS) is affected by another additional factor,
namely, the photosensitization effect of the
substrate (antibiotic). Therefore, it can be ex-
pected that for photodegradation processes of
stained antibiotics, like doxycycline, in which
the absorption band edge in the UV region en-
ters the visible region, the studied (0.33) TiO2
(120/T2) nanostructures will be even better
photocatalysts.
From the comparison of the PCA (UV/Vis)
values for the samples (0.33) TiO2 (120/T2) (ta-
ble 2), it is seen that PCA (UV) and, especially
PCA (VIS), of these photocatalysts are signifi-
cantly higher in the doxycycline photodegrad-
ation processes compared to ceftazidime. The
reason for that can be the lower adsorption
capacity of these materials and Evonik P-25 to
ceftazidime (table 2). This may be due to the
ceftazidime’s greater hydrophobicity and its
molecule larger size, compared to doxycycline,
as a result, this substrate is less efficiently ad-
sorbed on the photocatalyst surface. The possi-
ble influence of different donor atoms in these
antibiotic molecules on the efficiency of their
interaction with the surface of the photocata-
lyst is also not excluded.
An additional factor for the superior photo-
catalytic activity can be the photosensitization
effect of the surface-adsorbed doxycycline,
which absorbs in the UV region and contains
two intense bands with maxima lmax = 270 nm
and lmax = 347 nm, the edge of which enters
the visible region. Ceftazidime, in contrast to
doxycycline, absorbs light mainly in the UV
region of < 300 nm.
УХЖ № 10 / Том 86N. I. Romanovska, P. A. Manoryk, O. V. Selyshchev, P. S. Yaremov, O. V. Shylzshenko, A.V. Terebilenko, S. M. Shcherbakov, D. R. T. Zahn
113https://ucj.org.ua
It was previously shown [22], that the
main reason for the three times higher pho-
tocatalytic activity in the methylene blue and
phenol photodegradation reactions of N,
S-doped TiO2 samples obtained from titanyl
sulfate and thiourea, compared to Degussa
P25, is the small anatase crystallite size (5–6
nm). According to the authors [22], this may
be due to the synergism of the interaction of
sulfate and nitrogen with the TiO2 lattice. In
N, S-doped TiO2, N-Ti-O and O-Ti-N-O are
responsible for the redshift, and the sulfate
group acts as a cocatalyst to increase surface
acidity and to maintain a high stability of the
redox cycles [22]. In the case of TiO2 sam-
ples doped with C, S, obtained by us, the av-
erage crystallite size is small (9–10 nm) and
both interstitial and surface sulfate groups are
present. Therefore, the surface sulfate proba-
bly also acts as a cocatalyst and the photoca-
talysis process. According to the mechanism
proposed by the authors [22], it provides for
the participation of surface sulfate in the re-
dox transformations (S6+ ↔ S4+). The visible
light absorption by (0.33) TiO2 (120/T2) na-
nostructures with a small decrease (~0.15 eV)
in the bandgap width (table 1) in comparison
with pure anatase is provided, mainly, by the
interstitial C-O-Ti and S-O-Ti. According to
[1, 5, 6], these groups can form localized states
between VB and CB, helping to increase the
sensitivity to visible light without significantly
narrowing the bandgap. The presence of sul-
fate ions in the (0.33) TiO2 (120/T2) sample
surface structure that are formed during cal-
cinating may promote the migration of pho-
togenerated electrons, thereby improving the
photogenerated charge carriers separation,
and inhibition of recombination processes,
which improves the photocatalytic activity,
as it was observed for N, S-doped [22] and
S-doped [21] TiO2 nanostructures.
As can be seen from the comparison of
the PCA (UV/VIS) for (0.33) TiO2 (120/T2)
samples and (X) TiO2 (120/450) [36], the op-
timal calcination temperature is one of the key
controlling factors for the structural and di-
mensional characteristics of doped TiO2 nano-
structures and their photocatalytic activity in
the doxycycline and ceftazidime photodegrad-
ation processes. Thus, PCA (UV/VIS) for (X)
TiO2 (120/T2) samples, in which the anatase
content increases with increasing calcinating
temperature, gradually increases but is small-
er compared to samples with a high content of
anatase (X) TiO2 (120/450) (X=0; 0.17; 0.33).
At the same time, the PCA (VIS) of the (0.33)
TiO2 (120/300) sample, which is calcined at
300oC, is higher in comparison with all other
samples (Table 2), including the best sample
(0.17) TiO2 (120/450), which was obtained at
the optimal X=TU/TBT=0.17 ratio in the re-
action mixture [36]. Taking into account the
above results and assumptions, we can assume
that one of the reasons for this is changes in the
interstitial dopants content and their ratio, that
are achieved at a calcination temperature of
300 oC. This is also consistent with the results
of elemental analysis (table 1) and XPS (fig.5).
It should be noted that our (0.33) TiO2 (120/
T2) samples, containing interstitial and surface
carbonate and sulfate groups, show a higher
PCA (VIS), compared to those obtained by ti-
tanate nanotube with TU calcinating in vacu-
um at 500 °C encoded by N/S co-doped TiO2
nanotubes, where N and S replace oxygen in
the lattice [11], and which were tested in the
methylene blue photodegradation process un-
der close conditions. The PCA (VIS) of the
(0.33) TiO2 (120/T2) samples is comparable
INFLUENCE OF CALCINATION TEMPERATURE ON STRUCTURAL-DIMENSIONAL CHARACTERISTICS OF C,S-DOPED TiO2 NANO
STRUCTURES AND THEIR PHOTOCATALYTIC ACTIVITY IN THE CEFTAZIDIME AND DOXYCYCLINE PHOTODEGRADATION PROCESSES
114 ISSN 2708-129X. Укр. хім. журн., 2020
PHISICAL CHEMISTRY
to the activity in the same process [45] of F,S-
doped TiO2 lamellar nanostructures with a
nanoparticle size of 10–15 nm, obtained by
solvothermal method (precursors F and S, re-
spectively NH4F and TU), followed by calci-
nating at 450 oC and in which F and S are in-
corporated in the lattice in the oxygen position
and show a synergistic effect, that increases
the concentration of superoxide and, accor
dingly, the growth of PCA (VIS) in the meth-
ylene blue photodegradation process. Thus,
among the (0.33) TiO2 (120/T2) samples, the
best photocatalytic activity under visible light
irradiation in the doxycycline and ceftazidime
photodegradation processes is demonstrated
by the sample (0.33) TiO2 (120/300), which
is characterized by an anatase content (80%),
crystallite size of 9 nm, and spherical nanopar-
ticles (64 nm) and contains interstitial dopants
(C, S), and PCA (UV/VIS), that significantly
outperforms Evonik P-25.
As can be seen (fig. 9 a, b), the conversion
of ceftazidime, as well as doxycycline, under
UV light irradiation increases with increasing
calcination temperature and reaches a maxi
mum for the sample (0.33) TiO2 (120/450)
(fig. 9 b). Regardless of the calcination tem-
perature of the samples, the PCA (UV) in the
photodegradation of ceftazidime is more than
3 times higher than the conversion value for
Evonik P-25. At the same time, under visible
light irradiation, the maximum doxycycline
conversion is observed on the sample (0.33)
TiO2 (120/300) and 1.5-2 times higher than the
value for Evonik P-25. It is noteworthy that the
PCA (UV/VIS) on the corresponding samples
(0.33) C, S doped TiO2 (120/T2) in the doxy-
cycline photodegradation is generally higher
(1.5 - 1.7 times ) in comparison with ceftazi-
dime (Fig. 6 a, b). However, for samples (0.33)
TiO2 (120/T2) the ratio of PCA (VIS) (conver-
sion after 60 min, R60) for the doxycycline and
ceftazidime photodegradation processes (R60
(dox)/R60 (cef)) increases from 2.7 to 6.7 as the
calcination temperature increases (T2 = 200-
450 oC). In contrast, the PCA (UV) for these
samples is remained at the same level.
CONCLUSIONS
Interstitially carbon and sulfur-doped TiO2
nanostructures with high photocatalytic activ-
ity in the ceftazidime and doxycycline photo-
degradation processes were synthesized by sol-
gel synthesis followed by solvothermal treat-
ment (120 °C) and calcinating (200–450 °C).
With increasing calcination temperature, the
anatase content and mesopore diameter (from
5.4 to 6.4 nm) increase, while the amorphous
phase content decrease in the obtained sam-
ples. The anatase crystallites of lamellar mor-
phology slightly increase in sizes (from 8x7 nm
to 10x9 nm). The anatase crystallites, together
with the amorphous phase, are arranged in
rectangular and hexagonal stacks that form
nanoparticles. The average size of the nano-
particles decreases (95-45 nm) along with the
decrease in the SBET (190-130 m2/g), the Smeso
(170–70 m2/g), the total adsorption volume
(0.25–0.22 cm3/g), and the carbon and sulfur
content, which are a part of the interstitial and
surface carbonate and sulfate groups.
Varying the calcination temperature allows
TiO2 nanostructures to be obtained with a cer-
tain balance of these characteristics that pro-
vides a high photocatalytic activity for these
structures not only under ultraviolet irradiation
but also under visible light. The key positive ef-
fect on the PCA (UV) of the studied samples
in doxycycline and ceftazidime photodegrada
tion processes is exerted by the high anatase
УХЖ № 10 / Том 86N. I. Romanovska, P. A. Manoryk, O. V. Selyshchev, P. S. Yaremov, O. V. Shylzshenko, A.V. Terebilenko, S. M. Shcherbakov, D. R. T. Zahn
115https://ucj.org.ua
content, the large mesopore surface area, and
the small crystallite and nanoparticle size. This
effect is also present in the case of PCA (VIS),
but here the key role is played by the interstitial
carbonate and sulfate groups. The content and
ratio of these groups decrease with increasing
calcination temperature. The higher PCA (VIS)
compared to the PCA (UV) of the (0.33) TiO2
(120/T2) samples to doxycycline, in contrast to
the ceftazidime photodegradation process, is as-
sociated with the higher adsorption capacity of
these samples, and probably with the photosen-
sitizing effect of doxycycline.
The visible light absorption by (0.33) TiO2
(120/T2) samples is ensured, mainly, by the
presence of interstitial C-O-Ti and S-O-Ti with
a small decrease (~0.15 eV) in the width of the
bandgap compared to pure anatase. The sul-
fate ions formed during calcination, which are
present in the surface structure of C, S-doped
TiO2, promote the photogenerated electron
migration, thereby improving the separation
of photogenerated charge carriers and inhibi-
tion of recombination processes that improves
photocatalytic activity.
Thus, the calcination temperature is a factor
of controlling the anatase content, crystallite
and nanoparticle size, morphology, textur-
al characteristics, and the content of intersti-
tial and surface sulfate and carbonate groups.
The balance of these factors ensures their PCA
(UV/VIS) in the ceftazidime and doxycycline
photodegradation processes. The photocat-
alytic activity (PCA UV/VIS) of the samples
containing carbon and sulfur only in the inter-
stitial and surface groups and not containing
(C, S) dopants incorporated directly into the
lattice significantly outperform Evonik P-25
and can be used for the antibiotic photodeg-
radation processes under sunlight irradiation.
Acknowledgment
This work was supported by National Aca
demy of Science of Ukraine.
ВПЛИВ ТЕМПЕРАТУРИ КАЛЬЦИНУВАННЯ НА
СТРУКТУРНО-РОЗМІРНІ ХАРАКТЕРИСТИКИ
C,S-ДОПОВАНИХ TiO2 НАНОСТРУКТУР ТА
ЇХНЯ ФОТОКАТАЛІТИЧНА АКТИВНІСТЬ
У ПРОЦЕСАХ ФОТОДЕГРАДАЦІЇ
ЦЕФТАЗИДИМУ ТА ДОКСИЦИКЛІНУ
H. І. Романовська1*, П. А. Манорик1,
О. В. Селищев2, П. С. Яремов1, О. В. Шуль
женко1, А. В. Теребіленко3, С. М. Щербаков3,
Д. Р. Т. Цан2
1Інститут фізичної хімії ім. Л. В. Пи
саржевського НАН України, просп. Науки,
31, Київ 03028, Україна
2Фізика напівпровідників, Технічний уні-
верситет міста Кемніц, Кемніц, 09127,
Німеччина
3Інститут ботаніки ім. М. Г. Холодного
НАН України, вул. Терещенківська, 2, Київ
01601, Україна
*е-mail: nat.romanovska@gmail.com
Мезопористі С, S-доповані нанострукту-
ри TiO2 одержано сольвотермальним золь-
гель методом з наступним кальцинуванням
за різних температур. Встановлено, що зі
зростанням температури кальцинування
при незначних змінах розмірів кристалі-
тів (9–10 нм) зростає вміст анатазу (з 42%
до 95%), зменшується розмір наночасти-
нок (з 85 до 45 нм), питома площа поверхні
(200–130 м2/г ) та площа мезопор (з 170 до
70 м2/г), зменшується вміст вуглецю (0,80–
0,41%) та сірки (1,39–0,89%), відбуваються
INFLUENCE OF CALCINATION TEMPERATURE ON STRUCTURAL-DIMENSIONAL CHARACTERISTICS OF C,S-DOPED TiO2 NANO
STRUCTURES AND THEIR PHOTOCATALYTIC ACTIVITY IN THE CEFTAZIDIME AND DOXYCYCLINE PHOTODEGRADATION PROCESSES
116 ISSN 2708-129X. Укр. хім. журн., 2020
PHISICAL CHEMISTRY
кардинальні зміни морфології нанострук-
тур TiO2. Показано, що варіювання темпе-
ратури кальцинування дозволяє одержати
наноструктури TiO2 з певним балансом цих
характеристик, який забезпечує їхню висо-
ку фотокаталітичну активність у процесах
фотодеградації цефтазидиму та доксици-
кліну при опроміненні не лише ультрафіо-
летовим, а й видимим світлом.
Ключові слова: мезопористий C, S-допо
ваний ТіО2, тіосечовина, кальцинування,
фото каталітична активність, антибіотики.
ВЛИЯНИЕ ТЕМПЕРАТУРЫ
КАЛЬЦИНИРОВАНИЯ НА СТРУКТУРНО-
РАЗМЕРНЫЕ ХАРАКТЕРИСТИКИ C,S-ДОПИ
РОВАННЫХ TiO2 НАНОСТРУКТУР И ИХ
ФОТОКАТАЛИТИЧЕСКУЮ АКТИВНОСТЬ
В ПРОЦЕССАХ ФОТОДЕГРАДАЦИИ
ЦЕФТАЗИДИМА И ДОКСИЦИКЛИНА
H. И. Романовская1*, П. А. Манорик1,
А. В. Селищев2, П. С. Яремов1, А. В. Шуль
женко1, А. В. Теребиленко3, С. Н. Щербаков3,
Д. Р. Т. Цан2
1Институт физической химии им.
Л. В. Писаржевского НАН Украины, просп.
Науки, 31, Киев 03028, Украина
2Физика полупроводников, Технический
университет города Кемница, Кемниц
09127, Германия
3Институт ботаники им. М. Г. Холод
ного НАН Украины, ул. Терещенковская, 2,
Киев 01601, Украина
*е-mail: nat.romanovska@gmail.com
Мезопористые С, S-допированные нано-
структуры TiO2 получены сольвотермаль-
ным золь-гель методом с последующим
прокаливанием при различных темпера-
турах. Установлено, что с ростом темпера-
туры кальцинирования при незначитель-
ных изменениях размеров кристаллитов
(9–10 нм) увеличивается содержание ана-
таза (с 42% до 95%), уменьшается размер
наночастиц (с 85 до 45 нм), удельная пло-
щадь поверхности (200–130 м2/г) и пло-
щадь мезопор (с 170 до 70 м2/г), уменьшает-
ся содержание углерода (0,80–0,41%) и серы
(1,39–0,89%), происходят кардинальные из-
менения морфологии наноструктур TiO2.
Показано, что варьирование температуры
кальцинирования позволяет получить на-
ноструктуры TiO2 с определенным балан-
сом этих характеристик, обеспечивающих
их высокую фотокаталитическую актив-
ность в процессах фотодеградации цефта-
зидима и доксициклина при облучении не
только ультрафиолетовым, но и видимым
светом.
Ключевые слова: мезопористый C, S-до
пированный TiO2, тиомочевина, кальцини-
рование, фотокаталитическая активность,
антибиотики.
УХЖ № 10 / Том 86N. I. Romanovska, P. A. Manoryk, O. V. Selyshchev, P. S. Yaremov, O. V. Shylzshenko, A.V. Terebilenko, S. M. Shcherbakov, D. R. T. Zahn
117https://ucj.org.ua
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Стаття надійшла 21.09.2020.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-247 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:05:16Z |
| publishDate | 2020 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/6a/1465fc211fc25e5d5248e9fc4046996a.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-2472026-07-22T08:23:44Z INFLUENCE OF CALCINATION TEMPERATURE ON STRUCTURAL-DIMENSIONAL CHARACTERISTICS OF C,S-DOPED TiO2 NANOSTRUCTURES AND THEIR PHOTOCATALYTIC ACTIVITY IN THE CEFTAZIDIME AND DOXYCYCLINE PHOTODEGRADATION PROCESSES ВЛИЯНИЕ ТЕМПЕРАТУРЫ КАЛЬЦИНИРОВАНИЯ НА СТРУКТУРНО- РАЗМЕРНЫЕ ХАРАКТЕРИСТИКИ C,S- ДОПИРОВАННЫХ TiO2 НАНОСТРУКТУР И ИХ ФОТОКАТАЛИТИЧЕСКУЮ АКТИВНОСТЬ В ПРОЦЕССАХ ФОТОДЕГРАДАЦИИ ЦЕФТАЗИДИМА И ДОКСИЦИКЛИНА ВПЛИВ ТЕМПЕРАТУРИ КАЛЬЦИНУВАННЯ НА СТРУКТУРНО-РОЗМІРНІ ХАРАКТЕРИСТИКИ C,S-ДОПОВАНИХ TiO2 НАНОСТРУКТУР ТА ЇХНЯ ФОТОКАТАЛІТИЧНА АКТИВНІСТЬ У ПРОЦЕСАХ ФОТОДЕГРАДАЦІЇ ЦЕФТАЗИДИМУ ТА ДОКСИЦИКЛІНУ Romanovska, Natalia Manoryk, Petro Selyshchev, Oleksandr Yaremov, Pavlo Shylzshenko, Olexander Terebilenko, Anastasia Shcherbakov, Sergiy Dietrich R.T. Zahn mesoporous C, S- doped TiO2, thiourea, calcination, photocatalytic activity, antibiotics. Mesoporous C, S-doped TiO2 nanostructures were obtained by solvothermal sol-gel method followed by calcination at different temperatures. It was found that with increasing calcination temperature, the crystallite size remains in the same range of 9–10 nm, while the morphology of TiO2 nanoparticles significantly changes, and the anatase content increases from 42% to 95%. At the same time the nanoparticle size (from 85 to 45 nm), the specific surface area (200–130 m2/g), the mesoporous area (from 170 to 70 m2/g), and the carbon (0.80–0.41%) and sulfur (1.39–0.89%) contents decrease. Varying the calcination temperature allows TiO2 nanostructures to be obtained with a certain balance of these structural-dimensional characteristics that provides high photocatalytic activity in the processes of ceftazidime and doxycycline photodegradation. V.I.Vernadsky Institute of General and Inorganic Chemistry 2020-11-16 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/247 10.33609/2708-129X.86.10.2020.95-119 Ukrainian Chemistry Journal; Vol. 86 No. 10 (2020): Ukrainian Chemistry Journal; 95-119 Украинский химический журнал; ##issue.vol## 86 ##issue.no## 10 (2020): Украинский химический журнал; 95-119 Український хімічний журнал; Том 86 № 10 (2020): Український хімічний журнал; 95-119 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/247/137 Copyright (c) 2020 Natalia Romanovska, Petro Manoryk, Oleksandr Selyshchev, Pavlo Yaremov, Olexander Shylzshenko, Anastasia Terebilenko, Sergiy Shcherbakov, Dietrich R.T. Zahn https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Romanovska, Natalia Manoryk, Petro Selyshchev, Oleksandr Yaremov, Pavlo Shylzshenko, Olexander Terebilenko, Anastasia Shcherbakov, Sergiy Dietrich R.T. Zahn ВПЛИВ ТЕМПЕРАТУРИ КАЛЬЦИНУВАННЯ НА СТРУКТУРНО-РОЗМІРНІ ХАРАКТЕРИСТИКИ C,S-ДОПОВАНИХ TiO2 НАНОСТРУКТУР ТА ЇХНЯ ФОТОКАТАЛІТИЧНА АКТИВНІСТЬ У ПРОЦЕСАХ ФОТОДЕГРАДАЦІЇ ЦЕФТАЗИДИМУ ТА ДОКСИЦИКЛІНУ |
| title | ВПЛИВ ТЕМПЕРАТУРИ КАЛЬЦИНУВАННЯ НА СТРУКТУРНО-РОЗМІРНІ ХАРАКТЕРИСТИКИ C,S-ДОПОВАНИХ TiO2 НАНОСТРУКТУР ТА ЇХНЯ ФОТОКАТАЛІТИЧНА АКТИВНІСТЬ У ПРОЦЕСАХ ФОТОДЕГРАДАЦІЇ ЦЕФТАЗИДИМУ ТА ДОКСИЦИКЛІНУ |
| title_alt | INFLUENCE OF CALCINATION TEMPERATURE ON STRUCTURAL-DIMENSIONAL CHARACTERISTICS OF C,S-DOPED TiO2 NANOSTRUCTURES AND THEIR PHOTOCATALYTIC ACTIVITY IN THE CEFTAZIDIME AND DOXYCYCLINE PHOTODEGRADATION PROCESSES ВЛИЯНИЕ ТЕМПЕРАТУРЫ КАЛЬЦИНИРОВАНИЯ НА СТРУКТУРНО- РАЗМЕРНЫЕ ХАРАКТЕРИСТИКИ C,S- ДОПИРОВАННЫХ TiO2 НАНОСТРУКТУР И ИХ ФОТОКАТАЛИТИЧЕСКУЮ АКТИВНОСТЬ В ПРОЦЕССАХ ФОТОДЕГРАДАЦИИ ЦЕФТАЗИДИМА И ДОКСИЦИКЛИНА |
| title_full | ВПЛИВ ТЕМПЕРАТУРИ КАЛЬЦИНУВАННЯ НА СТРУКТУРНО-РОЗМІРНІ ХАРАКТЕРИСТИКИ C,S-ДОПОВАНИХ TiO2 НАНОСТРУКТУР ТА ЇХНЯ ФОТОКАТАЛІТИЧНА АКТИВНІСТЬ У ПРОЦЕСАХ ФОТОДЕГРАДАЦІЇ ЦЕФТАЗИДИМУ ТА ДОКСИЦИКЛІНУ |
| title_fullStr | ВПЛИВ ТЕМПЕРАТУРИ КАЛЬЦИНУВАННЯ НА СТРУКТУРНО-РОЗМІРНІ ХАРАКТЕРИСТИКИ C,S-ДОПОВАНИХ TiO2 НАНОСТРУКТУР ТА ЇХНЯ ФОТОКАТАЛІТИЧНА АКТИВНІСТЬ У ПРОЦЕСАХ ФОТОДЕГРАДАЦІЇ ЦЕФТАЗИДИМУ ТА ДОКСИЦИКЛІНУ |
| title_full_unstemmed | ВПЛИВ ТЕМПЕРАТУРИ КАЛЬЦИНУВАННЯ НА СТРУКТУРНО-РОЗМІРНІ ХАРАКТЕРИСТИКИ C,S-ДОПОВАНИХ TiO2 НАНОСТРУКТУР ТА ЇХНЯ ФОТОКАТАЛІТИЧНА АКТИВНІСТЬ У ПРОЦЕСАХ ФОТОДЕГРАДАЦІЇ ЦЕФТАЗИДИМУ ТА ДОКСИЦИКЛІНУ |
| title_short | ВПЛИВ ТЕМПЕРАТУРИ КАЛЬЦИНУВАННЯ НА СТРУКТУРНО-РОЗМІРНІ ХАРАКТЕРИСТИКИ C,S-ДОПОВАНИХ TiO2 НАНОСТРУКТУР ТА ЇХНЯ ФОТОКАТАЛІТИЧНА АКТИВНІСТЬ У ПРОЦЕСАХ ФОТОДЕГРАДАЦІЇ ЦЕФТАЗИДИМУ ТА ДОКСИЦИКЛІНУ |
| title_sort | вплив температури кальцинування на структурно-розмірні характеристики c,s-допованих tio2 наноструктур та їхня фотокаталітична активність у процесах фотодеградації цефтазидиму та доксицикліну |
| topic_facet | mesoporous C S- doped TiO2 thiourea calcination photocatalytic activity antibiotics. |
| url | https://ucj.org.ua/index.php/journal/article/view/247 |
| work_keys_str_mv | AT romanovskanatalia influenceofcalcinationtemperatureonstructuraldimensionalcharacteristicsofcsdopedtio2nanostructuresandtheirphotocatalyticactivityintheceftazidimeanddoxycyclinephotodegradationprocesses AT manorykpetro influenceofcalcinationtemperatureonstructuraldimensionalcharacteristicsofcsdopedtio2nanostructuresandtheirphotocatalyticactivityintheceftazidimeanddoxycyclinephotodegradationprocesses AT selyshchevoleksandr influenceofcalcinationtemperatureonstructuraldimensionalcharacteristicsofcsdopedtio2nanostructuresandtheirphotocatalyticactivityintheceftazidimeanddoxycyclinephotodegradationprocesses AT yaremovpavlo influenceofcalcinationtemperatureonstructuraldimensionalcharacteristicsofcsdopedtio2nanostructuresandtheirphotocatalyticactivityintheceftazidimeanddoxycyclinephotodegradationprocesses AT shylzshenkoolexander influenceofcalcinationtemperatureonstructuraldimensionalcharacteristicsofcsdopedtio2nanostructuresandtheirphotocatalyticactivityintheceftazidimeanddoxycyclinephotodegradationprocesses AT terebilenkoanastasia influenceofcalcinationtemperatureonstructuraldimensionalcharacteristicsofcsdopedtio2nanostructuresandtheirphotocatalyticactivityintheceftazidimeanddoxycyclinephotodegradationprocesses AT shcherbakovsergiy influenceofcalcinationtemperatureonstructuraldimensionalcharacteristicsofcsdopedtio2nanostructuresandtheirphotocatalyticactivityintheceftazidimeanddoxycyclinephotodegradationprocesses AT dietrichrtzahn influenceofcalcinationtemperatureonstructuraldimensionalcharacteristicsofcsdopedtio2nanostructuresandtheirphotocatalyticactivityintheceftazidimeanddoxycyclinephotodegradationprocesses AT romanovskanatalia vliânietemperaturykalʹcinirovaniânastrukturnorazmernyeharakteristikicsdopirovannyhtio2nanostrukturiihfotokatalitičeskuûaktivnostʹvprocessahfotodegradaciiceftazidimaidoksiciklina AT manorykpetro vliânietemperaturykalʹcinirovaniânastrukturnorazmernyeharakteristikicsdopirovannyhtio2nanostrukturiihfotokatalitičeskuûaktivnostʹvprocessahfotodegradaciiceftazidimaidoksiciklina AT selyshchevoleksandr vliânietemperaturykalʹcinirovaniânastrukturnorazmernyeharakteristikicsdopirovannyhtio2nanostrukturiihfotokatalitičeskuûaktivnostʹvprocessahfotodegradaciiceftazidimaidoksiciklina AT yaremovpavlo vliânietemperaturykalʹcinirovaniânastrukturnorazmernyeharakteristikicsdopirovannyhtio2nanostrukturiihfotokatalitičeskuûaktivnostʹvprocessahfotodegradaciiceftazidimaidoksiciklina AT shylzshenkoolexander vliânietemperaturykalʹcinirovaniânastrukturnorazmernyeharakteristikicsdopirovannyhtio2nanostrukturiihfotokatalitičeskuûaktivnostʹvprocessahfotodegradaciiceftazidimaidoksiciklina AT terebilenkoanastasia vliânietemperaturykalʹcinirovaniânastrukturnorazmernyeharakteristikicsdopirovannyhtio2nanostrukturiihfotokatalitičeskuûaktivnostʹvprocessahfotodegradaciiceftazidimaidoksiciklina AT shcherbakovsergiy vliânietemperaturykalʹcinirovaniânastrukturnorazmernyeharakteristikicsdopirovannyhtio2nanostrukturiihfotokatalitičeskuûaktivnostʹvprocessahfotodegradaciiceftazidimaidoksiciklina AT dietrichrtzahn vliânietemperaturykalʹcinirovaniânastrukturnorazmernyeharakteristikicsdopirovannyhtio2nanostrukturiihfotokatalitičeskuûaktivnostʹvprocessahfotodegradaciiceftazidimaidoksiciklina AT romanovskanatalia vplivtemperaturikalʹcinuvannânastrukturnorozmírníharakteristikicsdopovanihtio2nanostrukturtaíhnâfotokatalítičnaaktivnístʹuprocesahfotodegradacííceftazidimutadoksiciklínu AT manorykpetro vplivtemperaturikalʹcinuvannânastrukturnorozmírníharakteristikicsdopovanihtio2nanostrukturtaíhnâfotokatalítičnaaktivnístʹuprocesahfotodegradacííceftazidimutadoksiciklínu AT selyshchevoleksandr vplivtemperaturikalʹcinuvannânastrukturnorozmírníharakteristikicsdopovanihtio2nanostrukturtaíhnâfotokatalítičnaaktivnístʹuprocesahfotodegradacííceftazidimutadoksiciklínu AT yaremovpavlo vplivtemperaturikalʹcinuvannânastrukturnorozmírníharakteristikicsdopovanihtio2nanostrukturtaíhnâfotokatalítičnaaktivnístʹuprocesahfotodegradacííceftazidimutadoksiciklínu AT shylzshenkoolexander vplivtemperaturikalʹcinuvannânastrukturnorozmírníharakteristikicsdopovanihtio2nanostrukturtaíhnâfotokatalítičnaaktivnístʹuprocesahfotodegradacííceftazidimutadoksiciklínu AT terebilenkoanastasia vplivtemperaturikalʹcinuvannânastrukturnorozmírníharakteristikicsdopovanihtio2nanostrukturtaíhnâfotokatalítičnaaktivnístʹuprocesahfotodegradacííceftazidimutadoksiciklínu AT shcherbakovsergiy vplivtemperaturikalʹcinuvannânastrukturnorozmírníharakteristikicsdopovanihtio2nanostrukturtaíhnâfotokatalítičnaaktivnístʹuprocesahfotodegradacííceftazidimutadoksiciklínu AT dietrichrtzahn vplivtemperaturikalʹcinuvannânastrukturnorozmírníharakteristikicsdopovanihtio2nanostrukturtaíhnâfotokatalítičnaaktivnístʹuprocesahfotodegradacííceftazidimutadoksiciklínu |