Two component oxide compositions based on TiO2 rutile: ultrasonic treatment, their physicochemical and photocatalytic properties
The creation of oxide two-component systems based on TiO2 rutile was studied. Influence of ultrasound treatment (UST) of these mixtures on their properties was established. The mixtures treatment less influences on the ratio of intensity of (110)/(101) reflexes of TiO2&...
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V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine
2025
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Catalysis and petrochemistry| _version_ | 1872009066315776000 |
|---|---|
| author | Kiziun, Olena V. Sachuk, Olena V. Zazhigalov, Valery O. Zabolotnii, Yevhenii V. Kotynska, Ludmila Y. |
| author_facet | Kiziun, Olena V. Sachuk, Olena V. Zazhigalov, Valery O. Zabolotnii, Yevhenii V. Kotynska, Ludmila Y. |
| author_institution_txt_mv | [
{
"author": "Olena V. Kiziun",
"institution": "Institute for Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine 13 Oleg Mudrak Str., Kyiv, 03164, Ukraine"
},
{
"author": "Olena V. Sachuk",
"institution": "State Research Expert Forensic Center of the Ministry of Internal Affairs of Ukraine 10 Bogomolets Str., Kyiv, 01601, Ukraine"
},
{
"author": "Valery O. Zazhigalov",
"institution": "Institute for Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine 13 Oleg Mudrak Str., Kyiv, 03164, Ukraine"
},
{
"author": "Yevhenii V. Zabolotnii",
"institution": "Institute for Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine 13 Oleg Mudrak Str., Kyiv, 03164, Ukraine"
},
{
"author": "Ludmila Y. Kotynska",
"institution": "Institute for Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine 13 Oleg Mudrak Str., Kyiv, 03164, Ukraine"
}
] |
| author_sort | Kiziun, Olena V. |
| baseUrl_str | https://kataliz.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2025-12-28T17:23:30Z |
| description | The creation of oxide two-component systems based on TiO2 rutile was studied. Influence of ultrasound treatment (UST) of these mixtures on their properties was established. The mixtures treatment less influences on the ratio of intensity of (110)/(101) reflexes of TiO2 what testify any structural change of this oxide but in same time little increase of its particles size was observed. The little increase of the dimension particles for second oxide after UST for the studied mixtures excluding TiO2/MgO and TiO2/ZnO was observed. The partial transformation of MgO to Mg(OH)2 as result of TiO2/MgO composition treatment was shown which accompanied by decrease of MgO particles size. In the case of TiO2/ZnO composition the partial destruction of ZnO was observed. The increase of the pores radius after UST with the change of surface element ratio determined by EDX method can testify that strong interaction between oxides takes place. This fact leads to an increase the band gap for the mixture in comparison with initial TiO2 with its average value between characteristic for TiO2 and other oxide in mixture. The study of photocatalytic properties of the samples in metronidazole (MN) oxidative decomposition in water shows that for all compositions, excluding TiO2/ZnO where the activity is connected with more active ZnO in this reaction but not TiO2, a decrease of initial rate constant Kd was observed. The reduction of rate constant was connected with a decrease of TiO2 content in the mixtures and introduced value of rate constant determined to quantity of TiO2 demonstrate its increase in comparison to individual TiO2.This fact testify the strong interaction in complexes systems between two oxides. Obtained result permits to realize the MN photocatalytic degradation in water with an increase of the complexes catalyst content in reaction mixture what leads to an increase both rate constant and degree of antibiotic transformation. It was established that UST increased the stability of the samples in MN transformation and as result the conversion of MN has more value than in initial mixtures. An increase of degradation degree after UST of the samples correlates with the growth of medium pore radius in result of this treatment what can be connected with an increase of sample surface accessible to UV irradiation.  It was shown that obtained composites demonstrate better properties in MN destruction in water in comparison with data known from the literature. |
| doi_str_mv | 10.15407/kataliz2025.36.044 |
| first_indexed | 2026-03-12T15:50:23Z |
| format | Article |
| fulltext |
44 Каталіз та нафтохімія, 2025, №36
Catalysis and Petrochemistry, 2025, 36
UDC 544.03, 544.4
https://doi.org/10.15407/kataliz2025.36.044
Two component oxide compositions based on TiO2 rutile: ultrasonic treatment,
their physicochemical and photocatalytic properties
Olena V. Kiziun 1, Olena V. Sachuk 2, Valery O. Zazhigalov 1,
Yevhenii V. Zabolotnii 1, Ludmila Y. Kotynska 1
1 Institute for Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine
13 Oleg Mudrak Str., Kyiv, 03164, Ukraine, e-mail: lenakiz25@ukr.net
2 The State Scientific Research Forensic Center of the Ministry of Internal Affairs of Ukraine
10 Bogomolets Str., Kyiv, 01601, Ukraine
The creation of oxide two-component systems based on TiO2 rutile was studied. Influence of ultrasound
treatment (UST) of these mixtures on their properties was established. The mixtures treatment less influences on
the ratio of intensity of (110)/(101) reflexes of TiO2 what testify any structural change of this oxide but in same
time little increase of its particles size was observed. The little increase of the dimension particles for second
oxide after UST for the studied mixtures excluding TiO2/MgO and TiO2/ZnO was observed. The partial
transformation of MgO to Mg(OH)2 as result of TiO2/MgO composition treatment was shown which accompanied
by decrease of MgO particles size. In the case of TiO2/ZnO composition the partial destruction of ZnO was
observed. The increase of the pores radius after UST with the change of surface element ratio determined by EDX
method can testify that strong interaction between oxides takes place. This fact leads to an increase the band gap
for the mixture in comparison with initial TiO2 with its average value between characteristic for TiO2 and other
oxide in mixture. The study of photocatalytic properties of the samples in metronidazole (MN) oxidative
decomposition in water shows that for all compositions, excluding TiO2/ZnO where the activity is connected with
more active ZnO in this reaction but not TiO2, a decrease of initial rate constant Kd was observed. The reduction
of rate constant was connected with a decrease of TiO2 content in the mixtures and introduced value of rate
constant determined to quantity of TiO2 demonstrate its increase in comparison to individual TiO2.This fact testify
the strong interaction in complexes systems between two oxides. Obtained result permits to realize the MN
photocatalytic degradation in water with an increase of the complexes catalyst content in reaction mixture what
leads to an increase both rate constant and degree of antibiotic transformation. It was established that UST
increased the stability of the samples in MN transformation and as result the conversion of MN has more value
than in initial mixtures. An increase of degradation degree after UST of the samples correlates with the growth of
medium pore radius in result of this treatment what can be connected with an increase of sample surface
accessible to UV irradiation. It was shown that obtained composites demonstrate better properties in MN
destruction in water in comparison with data known from the literature.
Keywords: complex oxide compositions, ultrasonic treatment, photocatalysis, metronidazole destruction
Introduction
Due to increase of the use of pharmaceuticals and drugs, the problem of effective wastewater
purification is becoming more and more urgent. Their pollutions in water are the main problem that must
be constantly solved. For the present time, several different types of emerging contaminants in water
systems are known as new environmental hazards those need to be neutralized by appropriate methods
[1-3]. One from such dangerous pollutants is metronidazole (2-methyl-5-nitroimidazole-1-ethanol, MN)
which has been widely used to treat infections caused by anaerobic bacteria, bacteroides and protozoa.
Since MN is non biodegradable and highly soluble in water, it can be accumulate in the aquatic
environment [4]. Elimination of MN from water system is an important issue considering its toxicity,
potential mutagenicity and carcinogenity [5, 6]. Decontamination of harmful substances in the water
environment by the method of photocatalysis is the most promising means at present [7-10]. Successful
use of this method is connected with availability and creation of highly efficient photocatalysts, which
Каталіз та нафтохімія, 2025, №36 45
Catalysis and Petrochemistry, 2025, 36
can be nanosized oxides of transition metals and systems based on them. From the point of view of
practical application, the well-known best photocatalysts based on ZnO and TiO2, last is one of the most
widely studied semiconductors (n-type) due to its low cost, abundant resource, high photocatalytic
activity, chemically and mechanically stable under ultraviolet (UV) irradiation, is not a toxic substance,
and has industrial availability. Titanium dioxide can exist in eight crystalline polymorphs, of which only
three, i.e. rutile (tetragonal), anatase (tetragonal) and brookite (orthorhombic), are naturally occurring
[11]. In the most cases rutile phase as photocatalyst shows lower photocatalytic activity than anatase
phase [12-14], but also it was shown, that TiO2 rutile demonstrates high photoactivity in such processes
as water splitting, destruction of dyes, various organic and pharmaceutical substances [13-16]. The
preparation of this oxide by various methods and introduction of different additions permits to increase
its catalytic performance.
Methods of synthesis of complexes catalysts on the TiO2 base such as homogeneous co-
precipitation, pyrolysis of salt solutions, compatible hydrolysis of salts, hydrothermal method, etc., do
not always guarantee obtaining the final material with the necessary physicochemical and photocatalytic
characteristics. So perspective to obtain the photocatalysts with improved characteristics is connected
with alternative synthesis use [17, 18]. One of alternative method with influence on the properties of
synthesized photocatalysts can be ultrasonic treatment or sonochemistry (UST) [19-24]. With minimal
energy consumption, low emissions and intensification of the process, this synthesis method allows
obtaining composite nanomaterials with high catalytic activity in various reactions [25-27].
In this study was examined the influence of UST on the physical-chemical and photocatalytic
properties of semiconductor mixtures based on TiO2 rutile with the addition of other oxide (ZnO, ZrO2,
MgO, SnO2, Nb2O5). Photocatalytic properties of the samples were determined in the photodestruction
of metronidazole.
Experiment
Equimolar mixtures of TiO2/ZnO, TiO2/ZrO2, TiO2/MgO, TiO2/SnO2, TiO2/Nb2O5 with a ratio of
1:1 were prepared from oxides TiO2 (pfa), ZnO (p), ZrO2 (p), MgO (pfa), SnO2 (p), Nb2O5 (p). UST of
oxide mixture composites was carried out on an ultrasonic generator “Titan ultrasonic” (Made in
Ukraine) with a power of 80 W, a frequency of 20 kHz and a processed volume of 50 ml. For the
synthesis, 5 g of the mixture and 40 ml of water were taken. Time of treatment was 1 h, only in case of
TiO2/ZnO mixture it was 0.5 h. After UST, the samples were dried in an air atmosphere at 120 °C, 1 h.
Physical-chemical properties of the initial and obtained samples were investigated by the
following methods. Textural parameters, namely the specific surface area and sizes of pores were
determined in the course of low-temperature adsorption-desorption of nitrogen by using a Quantachrome
NOVA-2200e Gas Sorption Analyzer. Structural analysis was carried out by the method of powder
X-ray (XRD) on a DRON-3M diffractometer using CuKα radiation with a wavelength of 1.5418 Ǻ with
scanning in the range of 2θ angles 15-90o. Calculation of the distances (d, nm) between the planes from
the obtained X-ray patterns of the samples was carried out according to the Wolf-Bragg formula:
d = n/2sin, the crystallite size (L, nm) was calculated using the X-ray line width method, which is
based on the Debye-Scherrer formula: L = kλ/βcos. The obtained diffractograms were analyzed by
using the JCPDS electronic database. The surface morphology of samples was investigated by scanning
electron microscopy (SEM) on a Tescan Vega 3 LMU electron microscope with two detectors SE
(“secondary electron” mode). Determination of the quantitative integral composition of the sample and
46 Каталіз та нафтохімія, 2025, №36
Catalysis and Petrochemistry, 2025, 36
distribution of elements on the surface was investigated using an Oxford Instruments Aztec energy
dispersive X-ray microanalyzer with a ONE X-MaxN20 detector.
The photocatalytic properties of the samples were investigated in the destruction of
metronidazole (АC “Lubnyfarm”, NUA/6538/01/01, code ATX J01XD01) with its concentration in
water equal to 0.015 g/l under ultraviolet irradiation (UV irradiation) using Optima high-pressure
mercury lamp with a power of 125 W, which emits only in the UV part of the spectrum with λ = 365 nm.
The study of photodegradation of the antibiotic was carried out under ambient conditions in a glass
beaker with a working solution of 300 ml and a weight of catalyst 0.15 g (concentration of catalyst was
equal 0.5 g/l). To achieve equilibrium, the MN adsorption the solution was stirred without UV
irradiation during 1 h. The total duration of the photocatalytic destruction process was 5 h with constant
stirring. To determine the photocatalytic activity of the synthesized composites, the optical density (D)
of the solutions was measured over a certain time (each 1 h of the process) using a Shimadzu UV-2450
UV-Vis spectrometer in the wavelength range of 200-500 nm. From the obtained data the degradation
rate constant (Kd) was calculated for each studied catalyst samples from the curves of dependence of
ln(D/D0) on time according to the formula: Кd = ln(D/D0)/Δt. The degree of photocatalytic efficiency (G)
was determined according to the formula: G = (C0-C)/C0×100 = (D0-D)/D0×100, where C0 is the initial
concentration of MN in the solution, C is the concentration of MN in the solution at a certain time, D0 is
the initial absorbance of MN in the solution (when t = 0 min) and D is the absorbance after certain time
of MN photodegradation at the corresponding λmax. Band gap energy values were determined using the
Kubelka-Munk phenomenological theory under the assumption of an indirect band gap. Using the
method of electron spectroscopy (ES), the band gap energy (Eg) was determined, which was calculated
from the absorption band using the formula: Eg = hc/λ0, where h is Planck’s constant (4.135·10–15 eVs);
c is the speed of light (3·108 m/s); λ0 is the wavelength corresponding to the value of the absorption
edge.
Results and discussion
The structural characteristics of the synthesized composites were analyzed by X-ray diffraction.
The diffractograms of initial mixtures (Fig. 1) show that the samples have a crystalline structure and
their main reflections correspond to the phases of oxides that included in their composition (TiO2
JCPDS 88-1175, ZrO2 JCPDS 37- 1484, MgO JCPDS 45-946, SnO2 JCPDS 41-1445, ZnO JCPDS 36-1451,
Nb2O5 JCPDS 30-0873). On the diffractograms of all oxide mixtures, titanium dioxide has two main
reflections from (110) and (101) planes at 2θ = 27.4o and 36.17o, which correspond to the rutile phase
[12, 16, 28]. It was established that UST of the initial mixtures leads to an increases their reflexes
intensity practically for all compositions excluding TiO2/MgO. In same time for all samples, the ratio
intensity of reflexes of TiO2 (110)/(101) planes less changed after UST and is equal to 2.0-2.1. The
exception is the TiO2/ZnO samples (Fig. 1 d) where the ratio intensity reflexes (110)/(101) for initial
mixture is equal to 0.42 which is connected with superposition of two reflexes of (101) plane at
2θ = 36.17 (TiO2) and 36.29º (ZnO). In result of UST, this ratio increases up to 0.66 which can be
connected with partial destruction of ZnO. Evidence in favor of ZnO destruction is two facts: i) the
intensity of (110) TiO2 reflection after UST increases in 1.2 times but the intensity of (100) ZnO
(2θ = 31.82º) decreases in 1.3 times, ii) all other individual reflexes of TiO2 increase their intensity but
ZnO vise versa decreases. For the other compositions, UST leads to the intensity increase of the reflexes
for both oxides, not only TiO2 but other introduced oxide (Fig. 1 a, b, c).
Каталіз та нафтохімія, 2025, №36 47
Catalysis and Petrochemistry, 2025, 36
The TiO2/MgO composition in a manner stands alone. For TiO2, therefore, as other cases, the
intensity of its reflexes increases after UST and the ratio of intensity (110)/(101) planes rests without
change (equal to 2.1). In same case the appearance of some new reflexes (Fig. 1 e) at 2θ = 18.81, 38.17
and 50.98o which correspond to (001), (101), (102) planes of Mg(OH)2 [31] (JCPDS 84-2163) and a
decrease of MgO reflexes intensity can be observed. So, as result of water presence in UST, the partial
transformation of MgO to Mg(OH)2 proceeds.
The calculation of TiO2 particles sizes shown in full correspondence with an intensity increase of
its reflexes for all studied samples some increase of the particles dimension (Table 1) after UST. Also
for the ZrO2, Nb2O5 and SnO2 can be observed a little increase of the particles dimensions after UST
(Table 1). In the case of ZnO and MgO in accordance with analysis presented above, a decrease of
particles size was observed.
10 20 30 40 50 60 70 80
0
100
200
300
4000
100
200
300
400
−
−
TiO
2
/ZrO
2
2
* r-TiO
2
m-ZrO
2
TiO
2
/ZrO
2
UST 1 h
10 20 30 40 50 60 70 80
0
720
1440
2160
2880
36000
720
1440
2160
2880
3600
•
0
0
1
•
1
0
2
•
1
1
0
•
1
0
1
•
1
0
0
•
0
0
1
TiO
2
/Nb
2
O
5
•
1
0
2
•
1
1
0
•
1
0
1
•
1
0
0
r- TiO
2
• - Nb
2
O
5
2
TiO
2
/Nb
2
O
5
UST 1 h
10 20 30 40 50 60 70 80
0
230
460
690
0
230
460
690
*
3
1
0
*
2
1
1
*
1
0
1*
1
1
0
•
3
2
1
•
2
0
2
•
3
0
1
•
3
1
0
•
0
0
2
•
2
1
1
•
2
0
0
•
1
0
1
•
1
1
0
TiO
2
/SnO
2
2
•
3
2
1
•
2
0
2
•
3
0
1
*
3
1
0
•
3
1
0
•
0
0
2*
2
1
1
•
2
1
1
•
2
0
0
*
1
0
1
•
1
0
1
*
1
1
0
•
1
1
0
r- TiO
2
• r- SnO
2
TiO
2
/SnO
2
UST 1 h
a b c
20 30 40 50 60 70 80 90
0
310
620
930
12400
310
620
930
1240
TiO
2
/ZnO
* r- TiO
2
- ZnO
TiO
2
/ZnO
UST 0,5 h
20 30 40 50 60 70 80 90
0
120
240
360
4800
120
240
360
480
4
2
2
4
2
2
4
0
0
2
2
2
3
1
1
2
2
0
*
0
1
3
2
0
0
*
1
1
1
1
1
1
*
1
0
1
*
1
1
0
TiO
2
/MgO
•
1
0
2•
1
0
1
•
0
0
1
4
0
0
2
2
0
*
0
1
3
*
1
1
1
*
1
0
1
*
1
1
0
- TiO
2
- MgO
• - Mg(OH)
2
TiO
2
/MgO
UST 1 h
2
d e
Fig. 1. Diffractograms of initial oxide mixtures and after UST
Analysis of nitrogen sorption-desorption isotherms shows that all composites are low porous, for
example, two compositions and initial TiO2 presented in Fig. 2 and UST less influence on the type of
isotherms. According to Brunauer’s classification, adsorption isotherms belong to type III, when the
energy released during the formation of a monolayer is little different from the energy of multilayer
48 Каталіз та нафтохімія, 2025, №36
Catalysis and Petrochemistry, 2025, 36
adsorption and the force of attraction between adsorbed molecules and the adsorbent surface is less than
the force of interaction between adsorbed molecules. By the type of hysteresis loops, it can be assumed
that the pores have a wedge-shaped shape with open ends.
Table 1. Some physical-chemical properties of the studied compositions
Sample
L*, nm
SSA, m2/g Vm, cm3/g Rm, nm
TiO2 MeO
TiO2 (initial) 55 - 12.0 0.20 31.3
TiO2/ZrO2 (initial) 52 33 7.0 0.05 13.8
TiO2/ZrO2 (UST) 56 34 7.5 0.09 23.4
TiO2/ZnO (initial) 46 46 8.0 0.10 8.2
TiO2/ZnO (UST) 49 41 6.0 0.06 12.3
TiO2/SnO2 (initial) 52 50 5.0 0.02 19.5
TiO2/SnO2 (UST) 58 55 6.0 0.04 21.2
TiO2/Nb2O5 (initial) 48 50 10.5 0.15 13.8
TiO2/Nb2O5 (UST) 53 55 15.0 0.28 19.7
TiO2/MgO (initial) 50 39 9.0 0.12 28.2
TiO2/MgO (UST) 56 21 (9)** 15.0 0.28 33.7
* L – the average size of crystallites calculated according to Debye-Scherrer’s equation
** The average size of formed MgOH presented in parentheses
0,0 0,2 0,4 0,6 0,8 1,0
0
50
100
150
200
250
300
TiO2
P/Po
V
,
cm
3
/g
0,0 0,2 0,4 0,6 0,8 1,0
0
5
10
15
20
25
30
35
P/Po
V
,
cm
3
/g
TiO2/Nb2O5
TiO2/Nb2O5 UST 1h
0,0 0,2 0,4 0,6 0,8 1,0
0
5
10
15
20
25
P/Po
V
,
cm
3
/g
ZnO/TiO2
ZnO/TiO2 UST 0,5 h
a b c
Fig. 2. Nitrogen adsorption-desorption isotherms obtained at 20 C for TiO2 and some oxides
compositions
The data presented in Table 1 show that the specific surface area (SSA) of the initial mixture is
less than in initial TiO2 what is connected with low values SSA of other oxides introduced in mixtures.
UST little influenced on SSA and its value is increased only in the case of TiO2/Nb2O5 and TiO2/MgO
compositions. Analogous in the case of these compositions, the increase of total pores volume is
observed that can be connected with partial agglomeration and formation of secondary porous systems
[30-32].
The study of the composites by SEM method in full accordance with XRD data show the less
change in surface morphology of the samples and particles dimensions in result of UST (some
characteristic results presented in Fig. 3). In contrary the results of EDX analysis demonstrate the UST
influence on the elements ratio in surface layer of the samples (some results presented in Fig. 4 and full
data in Table 2). From the data presented in Table 2 can be observed that for initial mixtures determined
by EDX ratio of the elements less differs from calculated value at their preparation. Three variants of the
UST influence on the elements ratio in surface layer of the samples were observed (Table 2 and Fig. 4):
practically any influence of treatment on components ratio [TiO2/SnO2 and TiO2/Nb2O5 (EDX spectrum
for the last presented on Fig. 4 a)], a decreases of surface ratio as a result of treatment [TiO2/ZnO and
Каталіз та нафтохімія, 2025, №36 49
Catalysis and Petrochemistry, 2025, 36
TiO2/MgO (EDX spectrum for the last presented on Fig. 4 b)], an increase of the surface ratio as
treatment result (TiO2/ZrO2, EDX spectrum presented on Fig. 4 c).
a b c d
Fig. 3. SEM micrographs of the samples TiO2/ZnO (a, b) and TiO2/Nb2O5 (c, d). Initial mixtures (a, c),
samples after UST (b, d)
a b c
Fig. 4. EDX analysis of the samples after UST: a – TiO2/Nb2O5, b – TiO2/MgO, c – TiO2/ZrO2
Table 2. Surface and photocatalytic properties of the studied compositions
Sample
EDX Ti/Me
weight ratio*
Eg, eV Kd 103, s–1 Kd(TiO2)** 103, s–1 G***, %
TiO2 (initial) - 3.00 0.12 0.12 56.0
TiO2/ZrO2 (initial) 0.54 (0.53) 3.18 0.06 0.15 55.8
TiO2/ZrO2 (UST) 0.63 3.19 0.09 0.23 76.8
TiO2/ZnO (initial) 0.69 (0.73) 3.20 0.23 0.46 98.0
TiO2/ZnO (UST) 0.41 3.16 0.25 0.51 98.5
TiO2/SnO2 (initial) 0.40 (0.38) 3.20 0.05 0.14 77.1
TiO2/SnO2 (UST) 0.42 3.20 0.05 0.14 80.4
TiO2/Nb2O5 (initial) 0.29 (0.25) 3.32 0.04 0.22 65.0
TiO2/Nb2O5 (UST) 0.32 3.31 0.04 0.22 68.7
TiO2/MgO (initial) 1.87 (1,98) 3.04 0.07 0.11 84.0
TiO2/MgO (UST) 0.76 3.04 0.08 0.12 89.7
* ratio of the elements according preparation is in parentheses
** rate constant determined on quantity of TiO2 in the sample
*** degradation degree of MN after 5 h photocatalytic reaction
Hence, the results obtained by EDX analysis show that UST of oxide mixtures in the most cases
leads to migration of the elements from surface layer in the bulk of oxide without change their phase
composition (the formation of new phases don’t take place according XRD data). Analogous effect of
the elements migration was observed early [18, 25, 33-34] at UST and mechanochemical treatment of
the other oxides mixtures. It is necessary to note that the decrease of the titanium surface content as
result of treatment was observed in cases of TiO2/MgO and TiO2/ZnO oxides mixtures use. This fact can
50 Каталіз та нафтохімія, 2025, №36
Catalysis and Petrochemistry, 2025, 36
be explained by partial dissolving of MgO with formation (see XRD data) of Mg(OH)2 and for ZnO was
proposed its partial solution with formation of Zn(OH)2, also, for example the formation of zinc
molybdates by UST and by hydrothermal method from ZnO/MoO3 mixture [33, 35]. In our case, the
formation of Zn(OH)2 compound was not determined that permits to proposed its little quantity which
cannot be detected by XRD method. These hydroxide compounds cover the surface of TiO2 that
accompanied by the decrease of Ti/Me surface ratio and in the case of XRD fixed Mg(OH)2 this decline
is more senses than for ZnO (Table 2). In other cases, UST leads to the mixing of the oxides with any
effect on surface ratio of oxides or with little increase of TiO2 surface content.
It is well known that band gap energy (Eg) is an important parameter of semiconductor materials
especially at their use as photocatalysts in different processes. The data presented in Table 2 demonstrate
that only in the case of TiO2/MgO composition, where TiO2 was mixing with photo catalytically inert
oxide (MgO) [36], the Eg value rests equal to rutile. In case of other mixtures, an increase of Eg was
observed. For TiO2/ZnO and TiO2/Nb2O5 composites, Eg value is equal to second oxide but not TiO2
(Table 2). For TiO2/ZrO2 and TiO2/SnO2 mixtures, Eg exhibits the intermediate value between TiO2 and
second oxide. The presented in Table 2 data demonstrate that UST less influences on Eg values. The last
fact can be connected with minor changes in dimension particles after UST. At same time, the first step
of the mixtures preparation connected with their mixing in agate mortar influences on the properties of
obtained compositions as result of strong contact between different oxides particles creation [36].
The observed values of Eg predicts that the prepared samples will exhibit low photocatalytic
activity in MN photodestruction under visible light irradiation and obtained data show that in reality
photodestruction rate constant (Kd) in best case (TiO2/ZnO) has value equal to 4·10–6 s–1 and
photodestruction degree (G) is 12 % after 5 h of reaction. As result, the photocatalytic activity of
synthesized samples in MN decomposition in water was determined at UV-light irradiation and all
obtained data are presented in Table 2. It can be seen that the rate constant and photo destruction degree
at UV- light irradiation have larger values than at Vis-irradiation for all samples.
In the other hand, an increase of rate constant value in comparison to individual TiO2 was
observed in the case of the TiO2/ZnO compositions use. This fact can be connected with higher activity
of ZnO in MN photocatalytic degradation determined previously [37-39]. It was shown that this process
in the equal conditions in the presence of ZnO different modifications proceeds with rate constant
Kd = 0.16-0.27·10–3 s–1 and this value is in 1.6-3.4 times higher that obtained for TiO2 [37, 38]. UST has
less influence on the value of rate constant of MN photocatalytic degradation in the presence of the
synthesized samples: it some increase observed in case of TiO2/ZrO2, TiO2/ZnO and TiO2/MgO
compositions, this value is unchanged in case of TiO2/SnO2 and TiO2/Nb2O5 composition.
In same time, it is necessary to note that preparation of the mixtures containing two oxides leads
to decrease of the photocatalytic active TiO2 content in the samples. This fact demonstrates the data
EDX presented in Table 2. So, the quantity of active catalyst (TiO2) at use the same content of
composition (0.5 g/l) as catalyst in reaction mixture decreases. In this sense there is an exception,
TiO2/ZnO mixture where the more photoactive in this process oxide (ZnO) [37, 38] was introduced in
composition. It is known [37, 38] that a decrease of TiO2 quantity in reaction MN photocatalytic
degradation accompanied by a decrease of the value rate constant in 1.6-2.0 times. The realized in this
work investigation with decreases of TiO2 content from 0.5 up to 0.25 g/l shows the decrease of rate
constant from 0.12 up to 0.07·10–3 s–1 also. From this point of view, it was interesting to determine what
the dilution of photoactive oxide TiO2 by introduction of second oxide (a decrease of TiO2 quantity)
Каталіз та нафтохімія, 2025, №36 51
Catalysis and Petrochemistry, 2025, 36
influences on catalytic activity of the composition. The calculation of the value of rate constant refers to
quantity of TiO2 in the compositions (Kd(TiO2)) was realized and the obtained data presented in Table 2.
The presented in Table 2 results demonstrate that for the all compositions excluding TiO2/MgO the
values Kd(TiO2) are more than for individual TiO2. In case of the TiO2/MgO composition, Kd(TiO2) is equal
the value obtained for TiO2 what permits concludes that the photo catalytically inert oxide MgO [36] only
dilute active titania without other influence on its properties. For the other compositions including
TiO2/ZnO, an increase of Kd(TiO2) values in comparison to data of TiO2 is observed that can testify the
presence of strong interaction between two oxides. This conception confirmed by an increase of band gap
width in these compositions (Table 2) in contrary to TiO2/MgO. As result of the possibility of separation of
electrons and holes expands [36] which accompanied by an increase of Kd(TiO2). The system stands apart is
TiO2/ZnO where the growth of activity is connected with the presence of ZnO in composition (see above).
It is necessary to note that value rate constant of photocatalytic degradation of MN on TiO2/ZnO refers to
quantity of ZnO in mixture is equal to presented data for Kd(TiO2) (0.46 and 0.50·10–3 s–1, respectively, for
initial and after UST mixtures). These data exceed the values of constant rate of MN degradation
characteristic for individual ZnO (see above). So, it can by testify that in this composition the influence of
one oxide on the other has place too.
The data presented in Table 2 demonstrate that for practically all two components catalysts the
degree of MN degradation has more value that for individual TiO2. This data show advantages of the use
these mixtures in the removal of MN from water as result of photocatalytic process. The best results were
obtained at utilization of TiO2/ZnO and TiO2/MgO compositions.
The obtained results let to make an assumption connected with quantity of the catalyst in reaction
mixture at MN photodegradation. Literature data [37, 38] show that an increase of the catalyst content up
to 1 g/l accompanied by decrease of rate constant of MN photocatalytic degradation. In used mixtures the
quantity of photoactive component in the most cases is near 50 % and it was interesting to study what an
increase of the catalyst contain will be influence of rate constant. It was used two compositions after UST:
TiO2/ZrO2 and TiO2/ZnO. The obtained results show that in both cases the value of Kd increases: for the
first composition up to 0.17·10–3 s–1 and for second – up to 0.38·10–3 s–1 but the Kd(TiO2) rests practically
without change – 0.22·10–3 s–1 for first composition and decreases for second – 0.40·10–3 s–1. In same time
the high degree of MN degradation (near 99 %) was obtained after shorter reaction time 3.5 and 2 h,
respectively, for TiO2/ZrO2 and TiO2/ZnO UST compositions. Thus, obtained result shows the perspective
of the two components photocatalysts use and their UST.
The comparison of the photoactivity samples (Kd) in MN decomposition with their specific surface
area and total pores volume data shows any connection between these parameters. In the other hand, the
results presented on Fig. 5 a, demonstrate that rate constant of MN photodecomposition increases with
increase of medium pores diameter. Separately located samples of TiO2/ZnO compositions which activity
was determined as connected with the presence of ZnO but not TiO2, as for other oxide compositions. In
same time it is necessary to note that for these TiO2/ZnO samples an increase of Kd with growth of pores
diameter observed, also. This correlation can be explained by an increase of sample surface area accessible
to UV irradiation with growth of pores diameter analogously to presented in [36]. In same time these data
shown positive effect of UST which leads to an increase of pores diameter (Table 1) and correspondingly
to an increase of the samples photocatalytic activity (Kd) in MN oxidative decomposition.
On the other hand, the data presented on Fig. 5 b shows that photocatalytic activity of the
samples (Kd) in the process of MN destruction is decreased with an increase of band gap energy values
52 Каталіз та нафтохімія, 2025, №36
Catalysis and Petrochemistry, 2025, 36
of the compositions. Analogous relations are traditional in the case of photocatalytic processes. In this
case, also, the sample of TiO2/ZnO compositions located separately for same reason described below.
The data connected with the obtained degree MN decomposition attract attention because they
demonstrate the positive effect of UST. In all cases this treatment permits to obtain the more value G
(Table 2) than for initial oxides mixtures. It can demonstrate more stability of the compositions after
treatment in the process of MN photodestruction and low influence of time reaction and change of MN
concentration on their photocatalytic activity.
0 5 10 15 20 25 30 35 40
0,00
0,05
0,10
0,15
0,20
0,25
0,300.30
0.25
0.20
0.15
0.10
0.05
0
K
d
1
0
3
,
s-1
R
m
, nm
2,9 3,0 3,1 3,2 3,3 3,4
0,00
0,05
0,10
0,15
0,20
0,25
0,30
K
d
1
0
3
,
s-1
Eg, eV
0.3
0.25
0.20
0.15
0.10
0.05
0
2.9 3.0 3.1 3.2 3.3 3.4
a b
Fig. 5. The dependence of rate constant of MN decomposition in its photocatalytic removal in water
from average radius (Rm) of the oxides compositions (a) and determined band gap energy values for
these samples (b)
Conclusions
The creation of oxide two-component systems based on rutile TiO2 was studied. Influence of
ultrasound treatment of these mixtures on their properties was established. It was shown that
introduction of the second oxide accompanied by a decrease of the reflexes TiO2 intensity as a result of
its content decreases in the mixtures. The treatment of the mixtures less influence on the ratio of
intensity of (110)/(101) reflexes of TiO2 what testify any structural change of this oxide but in same time
little increase of its particles size was observed. The partial increase of the dimension particles for
second oxide after UST for the studied mixtures excluding TiO2/MgO and TiO2/ZnO was observed also.
The partial transformation of MgO to Mg(OH)2 as result of TiO2/MgO composition treatment was
shown which accompanied by decreases of MgO particles size. In case of TiO2/ZnO composition
according XRD data as result of UST the partial destruction of ZnO was observed.
The changes in specific surface area and pores volume after preliminary processing in agate
mortar and as result of UST with an increase of medium pores radius after ultrasound treatment with the
change of surface element ratio determined by EDX method can testify that strong interaction between
oxides takes place. This fact leads to an increase the band gap for the mixture in comparison with initial
TiO2 with its average value between characteristic for TiO2 and other oxide in mixture.
The study of photocatalytic properties of the samples in MN oxidative decomposition in water
shows that for all compositions, excluding TiO2/ZnO where the activity is connected with more active
ZnO in this reaction but not TiO2, a decrease of initial rate constant Kd was observed. The rate constant
of MN photodegradation was connected with a decrease of TiO2 content in the mixtures and introduced
value of rate constant determined to quantity of TiO2 demonstrate its increase in comparison to
Каталіз та нафтохімія, 2025, №36 53
Catalysis and Petrochemistry, 2025, 36
individual TiO2. This fact is a consequence of strong interaction in complexes systems between two
oxides. Obtained results permit to predict and realized the MN photocatalytic degradation in water with
an increase of the complexes catalyst content in reaction mixture what leads to an increase both rate
constant and degree of MN transformation. It was established that UST increased the stability of the
samples in MN transformation and as result the conversion of MN has more value than in initial
mixtures.
An increase of MN degradation degree after UST correlates with the growth of medium pore
radius in result of UST what can be connected with an increase of sample surface accessible to UV
irradiation. It was shown that obtained samples demonstrate better properties in MN destruction in water
in comparison with data known from the literature. So, the perspective of complex oxide compositions
creation on the base of one known photocatalyst and use of UST were shown.
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Надійшла до редакції 30 .11 .2025
56 Каталіз та нафтохімія, 2025, №36
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Двокомпонентні оксидні композити на базі ТіО2 рутилу: ультразвукова
обробка, їх фізико-хімічні та фото каталітичні властивості
Олена В. Кізюн 1, Oлена В. Сачук 2, Валерій O. Зажигалов 1,
Євгеній В. Заболотній 1, Людмила Й. Котинська 1
1 Інститут сорбції та проблем ендоекології Національної академії наук України
вул. Олега Мудрака, 13, Київ, 03164, Україна, e-mail: lenakiz25@ukr.net
2 Державний науково-дослідний експертно-криміналістичний центр Міністерства внутрішніх справ України
вул. Богомольця, 10, Київ, 01601,Україна
Вивчено створення оксидних двокомпонентних систем на основі рутилу ТіО2. Встановлено вплив
ультразвукової обробки (УЗО) на властивості даних композитів. Показано, що дана обробка сумішей мало
впливає на їхні структурні характеристики, а саме, на співвідношення інтенсивності (110)/(101) рефлексів
ТіО2, але в той же час спостерігається незначне збільшення розміру його частинок. Для другого оксиду
також відбувається невелике зростання розміру його частинок в результаті УЗО, виключенням є TiO2/MgO
та TiO2/ZnO зразки. Показано, що в результаті обробки TiO2/MgO суміші відбувається часткове
перетворення MgO у Mg(OH)2, яке супроводжується зменшенням розміру MgO частинок. У випадку
TiO2/ZnO суміші спостерігається часткове руйнування ZnO як результат УЗО.
Встановлено, що УЗО сприяє збільшенню середнього радіусу пор композицій одночасно зі зміною
поверхневого співвідношення елементів, визначеного ЕДА методом, що може свідчити про сильну
взаємодію між оксидами в суміші. Даний факт веде до зростання значення енергії ширини забороненої зони
(Еg) оксидної системи у порівнянні з вихідним ТіО2. При цьому, у більшості випадків значення Еg має
середню величину між показником характерним для діоксиду титану та іншого оксиду в зразку.
Дослідження фотокаталітичних властивостей зразків в процесі окислювальної деградації
метронідазолу (МН) у воді показують, що для всіх композитів спостерігається зниження значень константи
швидкості Kd. Виключенням є TiO2/ZnO система, фотоактивність якої пов’язана з більш активним ZnO в
даній реакції, але не з TiO2. Падіння значень Kd можна пояснити зниженням вмісту TiO2 у сумішах і даний
показник визначається кількістю рутилу в них, а введене значення Kd(ТіО2), яке визначене для кількості TiO2,
демонструє її підвищення у порівнянні з індивідуальним TiO2. Даний факт свідчить про сильну взаємодію в
складних системах. Одержаний результат (підвищене значення Kd(ТіО2) для композитів, у порівнянні з ТіО2)
дозволив реалізувати фотодеструкцію МН у водному середовищі із більшим вмістом складного каталізатора
в реакційній суміші, що веде до зростання значень константи швидкості та ступеню деструкції антибіотику.
Встановлено, що УЗО метод підвищив стабільність зразків у процесі перетворення МН і, як результат,
конверсія антибіотика має більші значення, ніж для вихідних сумішей.
Підвищення значень ступеню деградації МН для УЗО зразків корелюється із зростанням середнього
радіусу пор в них, що може бути пов’язано із збільшенням їхньої поверхні, яка доступна для
УФ-опромінення. Показано, що одержані композити демонструють кращі властивості в деструкції МН у
воді у порівнянні з відомими зразками в літературі.
Ключові слова: складні оксидні композити, ультразвукова обробка, фотокаталіз, деструкція
метронідазолу
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| id | oai:katalizorgua:article-127 |
| institution | Catalysis and petrochemistry |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-03-12T15:50:23Z |
| publishDate | 2025 |
| publisher | V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | katalizorgua/e0/fd9291f3999ca506f53b4f145af5d1e0.pdf |
| spelling | oai:katalizorgua:article-1272025-12-28T17:23:30Z Two component oxide compositions based on TiO2 rutile: ultrasonic treatment, their physicochemical and photocatalytic properties Two component oxide compositions based on TiO2 rutile: ultrasonic treatment, their physicochemical and photocatalytic properties Kiziun, Olena V. Sachuk, Olena V. Zazhigalov, Valery O. Zabolotnii, Yevhenii V. Kotynska, Ludmila Y. complex oxide compositions, ultrasonic treatment, photocatalysis, metronidazole destruction складні оксидні композити, ультразвукова обробка, фотокаталіз, деструкція метронідазолу The creation of oxide two-component systems based on TiO2 rutile was studied. Influence of ultrasound treatment (UST) of these mixtures on their properties was established. The mixtures treatment less influences on the ratio of intensity of (110)/(101) reflexes of TiO2 what testify any structural change of this oxide but in same time little increase of its particles size was observed. The little increase of the dimension particles for second oxide after UST for the studied mixtures excluding TiO2/MgO and TiO2/ZnO was observed. The partial transformation of MgO to Mg(OH)2 as result of TiO2/MgO composition treatment was shown which accompanied by decrease of MgO particles size. In the case of TiO2/ZnO composition the partial destruction of ZnO was observed. The increase of the pores radius after UST with the change of surface element ratio determined by EDX method can testify that strong interaction between oxides takes place. This fact leads to an increase the band gap for the mixture in comparison with initial TiO2 with its average value between characteristic for TiO2 and other oxide in mixture. The study of photocatalytic properties of the samples in metronidazole (MN) oxidative decomposition in water shows that for all compositions, excluding TiO2/ZnO where the activity is connected with more active ZnO in this reaction but not TiO2, a decrease of initial rate constant Kd was observed. The reduction of rate constant was connected with a decrease of TiO2 content in the mixtures and introduced value of rate constant determined to quantity of TiO2 demonstrate its increase in comparison to individual TiO2.This fact testify the strong interaction in complexes systems between two oxides. Obtained result permits to realize the MN photocatalytic degradation in water with an increase of the complexes catalyst content in reaction mixture what leads to an increase both rate constant and degree of antibiotic transformation. It was established that UST increased the stability of the samples in MN transformation and as result the conversion of MN has more value than in initial mixtures. An increase of degradation degree after UST of the samples correlates with the growth of medium pore radius in result of this treatment what can be connected with an increase of sample surface accessible to UV irradiation.  It was shown that obtained composites demonstrate better properties in MN destruction in water in comparison with data known from the literature. Вивчено створення оксидних двокомпонентних систем на основі рутилу ТіО2. Встановлено вплив ультразвукової обробки (УЗО) на властивості даних композитів. Показано, що дана обробка сумішей мало впливає на їхні структурні характеристики, а саме, на співвідношення інтенсивності (110)/(101) рефлексів ТіО2, але в той же час спостерігається незначне збільшення розміру його частинок. Для другого оксиду також відбувається невелике зростання розміру його частинок в результаті УЗО, виключенням є TiO2/MgO та TiO2/ZnO зразки. Показано, що в результаті обробки TiO2/MgO суміші відбувається часткове перетворення MgO у Mg(OH)2, яке супроводжується зменшенням розміру MgO частинок. У випадку TiO2/ZnO суміші спостерігається часткове руйнування ZnO як результат УЗО. Встановлено, що УЗО сприяє збільшенню середнього радіусу пор композицій одночасно зі зміною поверхневого співвідношення елементів, визначеного ЕДА методом, що може свідчити про сильну взаємодію між оксидами в суміші. Даний факт веде до зростання значення енергії ширини забороненої зони (Еg) оксидної системи у порівнянні з вихідним ТіО2. При цьому, у більшості випадків значення Еg має середню величину між показником характерним для діоксиду титану та іншого оксиду в зразку. Дослідження фотокаталітичних властивостей зразків в процесі окислювальної деградації метронідазолу (МН) у воді показують, що для всіх композитів спостерігається зниження значень константи швидкості Kd. Виключенням є TiO2/ZnO система, фотоактивність якої пов’язана з більш активним ZnO в даній реакції, але не з TiO2. Падіння значень Kd можна пояснити зниженням вмісту TiO2 у сумішах і даний показник визначається кількістю рутилу в них, а введене значення Kd(ТіО2), яке визначене для кількості TiO2, демонструє її підвищення у порівнянні з індивідуальним TiO2. Даний факт свідчить про сильну взаємодію в складних системах. Одержаний результат (підвищене значення Kd(ТіО2)  для композитів, у порівнянні з ТіО2) дозволив реалізувати фотодеструкцію МН у водному середовищі із більшим вмістом складного каталізатора в реакційній суміші, що веде до зростання значень константи швидкості та ступеню деструкції антибіотику. Встановлено, що УЗО метод підвищив стабільність зразків у процесі перетворення МН і, як результат, конверсія антибіотика має більші значення, ніж для вихідних сумішей. Підвищення значень ступеню деградації МН для УЗО зразків корелюється із зростанням середнього радіусу пор в них, що може бути пов’язано із збільшенням їхньої поверхні, яка доступна для УФ-опромінення. Показано, що одержані композити демонструють кращі властивості в деструкції МН у воді у порівнянні з відомими зразками в літературі. V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2025-12-08 Article Article application/pdf https://kataliz.org.ua/index.php/journal/article/view/127 10.15407/kataliz2025.36.044 Catalysis and petrochemistry; No. 36 (2025): Catalysis and petrochemistry; 44-56 Каталіз та нафтохімія; № 36 (2025): Каталіз та нафтохімія; 44-56 2707-5796 2412-4176 10.15407/kataliz2025.36 en https://kataliz.org.ua/index.php/journal/article/view/127/111 Copyright (c) 2025 Catalysis and petrochemistry |
| spellingShingle | складні оксидні композити ультразвукова обробка фотокаталіз деструкція метронідазолу Kiziun, Olena V. Sachuk, Olena V. Zazhigalov, Valery O. Zabolotnii, Yevhenii V. Kotynska, Ludmila Y. Two component oxide compositions based on TiO2 rutile: ultrasonic treatment, their physicochemical and photocatalytic properties |
| title | Two component oxide compositions based on TiO2 rutile: ultrasonic treatment, their physicochemical and photocatalytic properties |
| title_alt | Two component oxide compositions based on TiO2 rutile: ultrasonic treatment, their physicochemical and photocatalytic properties |
| title_full | Two component oxide compositions based on TiO2 rutile: ultrasonic treatment, their physicochemical and photocatalytic properties |
| title_fullStr | Two component oxide compositions based on TiO2 rutile: ultrasonic treatment, their physicochemical and photocatalytic properties |
| title_full_unstemmed | Two component oxide compositions based on TiO2 rutile: ultrasonic treatment, their physicochemical and photocatalytic properties |
| title_short | Two component oxide compositions based on TiO2 rutile: ultrasonic treatment, their physicochemical and photocatalytic properties |
| title_sort | two component oxide compositions based on tio2 rutile: ultrasonic treatment, their physicochemical and photocatalytic properties |
| topic | складні оксидні композити ультразвукова обробка фотокаталіз деструкція метронідазолу |
| topic_facet | complex oxide compositions ultrasonic treatment photocatalysis metronidazole destruction складні оксидні композити ультразвукова обробка фотокаталіз деструкція метронідазолу |
| url | https://kataliz.org.ua/index.php/journal/article/view/127 |
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