The formation of mixed oxides in La2O3/MO–Al2O3 systems (M is a group IIA element: Mg, Ca, Sr, Ba) subjected to a high-temperature treatment and treatment in a water fluid (WF) medium is studied. It is shown that the high-temperature treatment of a group IIA element aluminate with supported lanthanum nitrate leads to the formation of LaAlO3 only in the case of an Mg-containing system. In other cases, original aluminates do not undergo transformations, and lanthanum oxide is formed. The treatment of La/M–Al ternary systems in a WF medium leads to the formation of LaAlO3 in all cases; in addition, in all samples, except for the Ba-containing system, phases of free oxides of group IIA metals appear. The increase in the activity and selectivity of La/M–Al ternary oxide systems in the oxidative coupling of methane compared to the respective parameters of M–Al binary systems is attributed to the presence of an individual La2O3 oxide phase.

The effect of the method used to synthesize Ln–Al (Ln = La, Ce, Pr) mixed oxide systems with an Ln : Al atomic ratio of 1 : 1 on the formation of their phase composition and their catalytic properties in the oxidative coupling of methane (OCM) is studied. The precursors are prepared by impregnating ashless filter paper with mixed solutions of nitrates of the respective metals by the incipient wetness impregnation method and subsequent drying and combustion of the resulting mass in air. Further treatment is conducted by combining calcination at 600 and 900°C with a treatment in a water fluid (WF) or water–ammonia fluid (WAF) medium. The laws governing the transformation of the amorphous precursor of Pr–Al oxides during treatment in WF and WAF media and high-temperature synthesis are similar to those observed for the La–Al system. In both cases, the amorphous precursor in a water-containing fluid is transformed into LnAlO3 with a cubic perovskite structure with an admixture of AlO(OH) (boehmite) and basic REE carbonate phases. The subsequent treatment in air at 900°C leads to the formation of a mixture containing LnAlO3 aluminates and free La2O3 or PrO2 oxides. Single-phase samples containing exclusively lanthanum and praseodymium aluminates are synthesized by heating amorphous precursors in air at 900°C. The treatment of the Ce–Al system in a WF or WAF leads to the formation of a well-crystallized CeO2 oxide instead of aluminate or Ce-containing hydroxides, while the Al-containing component remains X-ray amorphous. Cerium aluminate CeAlO3 is synthesized by treating a mixture of cerium and aluminum oxide precursors in a hydrogen stream. It is found that, due to differences in the 4th ionization potential (IP4) values of the La, Ce, and Pr atoms (49.9, 36.7, and 39.0 eV, respectively), completely different synthesis conditions are required to form LnAlO3 aluminates with a perovskite structure that contain REE in the (3+) oxidation state. The catalytic properties of the synthesized samples in the OCM are studied. The efficiency and stability of isostructural LnAlO3 aluminates in the OCM decreases in the following order: La > Pr > Ce. Despite the fact that PrAlO3 is the most active of these aluminates, LaAlO3 exhibits the highest selectivity for OCM products (ethane + ethylene).

Исследовано образование смешанных оксидов в системах La2O3/MO-Al2O3 (M - элемент IIA группы: Mg, Ca, Sr, Ba) при термообработке и обработке водными флюидами (ВФ). Показано, что высокотемпературная обработка алюмината элемента IIA группы с нанесенным нитратом лантана приводит к образованию LaAlO3 только в случае Mg-содержащей системы. В остальных случаях не происходит превращения исходных алюминатов и образуется оксид лантана. При обработке тройных систем La/M-Al в среде ВФ во всех случаях наблюдается образование LaAlO3; также во всех образцах, кроме Ba-содержащего, появляются фазы свободных оксидов металлов IIA группы. Повышение активности и селективности в процессе окислительной конденсации метана у тройных оксидных систем La/M-Al по сравнению с двойными M-Al системами связано с присутствием отдельной фазы оксида La2O3. The formation of mixed oxides in La2O3/MO—Al2O3 systems (M is a group IIA element: Mg, Ca, Sr or Ba) during high-temperature treatment and treatment with water fluids (WF) has been studied. It has been shown that high-temperature treatment of the corresponding group IIA metal aluminate with supported lanthanum nitrate leads to the formation of LaAlO3 only in the case of the Mg-containing system. In other cases, there is no transformation of the initial aluminates, and lanthanum oxide is formed. When treating La/M—Al ternary systems with WF, the formation of LaAlO3 is observed in all cases. Also, in all samples, except for Ba-containing, phases of free metal oxides of group IIA elements appear. The increase in activity and selectivity in the OCM process in La/M—Al ternary oxide systems compared to double M—Al systems is associated with the presence of a separate La2O3 oxide phase.

Исследованы каталитические свойства в процессе окислительной конденсации метана (ОКМ) и особенности структуры ряда образцов смешанных оксидов лантана и алюминия с постоянным атомным соотношением La:Al = 1: 1. Образцы получали на основе предшественников, содержащих нитраты La и Al, а также органический компонент - фильтровальную бумагу или крахмал. После сушки и выжигания органического компонента образцы подвергали дополнительной термообработке и воздействию водного флюида (ВФ) с плотностью 0,2 г/см3 при 415 °С. После прокаливания при 900 °С все полученные образцы содержат фазу алюмината лантана LaAlO3 со структурой кубического перовскита. Варьирование типа органического компонента, а также последовательности процедур и условий обработки приводит к получению образцов, имеющих различную морфологию и каталитические свойства. Минимальную активность, селективность по продуктам ОКМ и стабильность во времени проявляет образец, полученный в условиях, способствующих формированию наиболее упорядоченной структуры - последовательно прокаленный при 900 °С, обработанный в среде ВФ и повторно прокаленный при 900 °С. Наиболее эффективным и стабильным оказался образец, кристаллическая структура которого формировалась, главным образом, в среде ВФ. Отмечено отсутствие корреляции между морфологией частиц и величиной удельной поверхности образцов, с одной стороны, и их каталитическими свойствами - с другой. Сделано предположение о том, что каталитические свойства определяются типом и числом точечных дефектов кристаллической структуры - в первую очередь, катионных вакансий и, как следствие, дырочных центров типа [O¯] в анионной подрешетке. The catalytic properties in the oxidative coupling of methane (OCM) and the structural features of a series of mixed lanthanum-aluminum oxides with a constant atomic ratio La:Al = 1:1 were studied. The samples were prepared from precursors containing La and Al nitrates and organic component - filter paper or starch. After drying and burning the organic component, the samples were subjected to additional heat treatment and exposure to water fluid (WF) with a density of 0.2 g cm-3 at 415 °C. After calcination at 900 °C, all the samples contain a phase of lanthanum aluminate LaAlO3 with a cubic perovskite structure. Varying the type of organic component, as well as the sequence of procedures and processing conditions leads to the production of samples with different morphologies and catalytic properties. The minimum activity, selectivity for OCM products and stability over time is demonstrated by the sample obtained under conditions conducive to the formation of the most ordered structure - successively calcined at 900 °C, treated in a WF medium and re-calcined at 900 °C. The most efficient and stable turned out to be the sample whose crystal structure was formed mainly in the WF medium. It was noted that there is no correlation between the morphology of particles and the specific surface area of the samples, on the one hand, and their catalytic properties, on the other. It was assumed that the catalytic properties are determined by the type and number of point defects in the crystal structure - primarily cation vacancies and, as a consequence, hole centers of the [O¯] type in the anion sublattice.

The synthesis of mixed La–Al oxide systems with the atomic ratio La : Al = 1 : 1 was studied. At the first stage, a dried mass containing starch and La and Al nitrates was burned. Heat treatment of the resulting amorphous product at a temperature of ≥700°C gave LaAlO 3 aluminate with a cubic perovskite structure. The composition and morphology of the product formed by subsequent treatment in a water fluid (WF) medium (density 0.2 g/cm 3 , 415°C) depend on the degree of ordering of the precursor. Crystalline LaAlO 3 (cubic) in the WF medium undergoes additional ordering with a decrease in the specific surface area ( S sp ) while maintaining the crystalline structure; further calcination at 900°C did not lead to a change in either S sp or the structure. Treatment of an amorphous precursor in the WF medium increased S sp and produced a mixture of LaAlO 3 aluminates of cubic and orthorhombic structures and La and Al hydroxides. Further calcination at 900°C gave a mixture of LaAlO 3 (cubic), La 2 O 3 (hexagonal), and, possibly, X-ray amorphous Al 2 O 3 . The synthesized systems were studied as catalysts for methane oxidation. There was no correlation between activity and selectivity for oxidative coupling products (ethane + ethylene) with the S sp value; they were found to depend on the phase composition of the mixed La–Al oxide. The most efficient systems turned out to be those that underwent intermediate treatment in the WF medium and contained the LaAlO 3 (cubic) and La 2 O 3 (hexagonal) phases. The results obtained indicate the high structural sensitivity of the process characteristics.

Исследован синтез смешанных La-Al-оксидных систем с атомным соотношением La : Al 1 : 1. На первом этапе проводилось сжигание высушенной массы, содержащей крахмал и нитраты La и Al. Термообработка образующегося аморфного продукта при температуре ≥ 700°С приводит к образованию алюмината LaAlO3 со структурой кубического перовскита. Состав и морфология продукта, образующегося при последующей обработке в среде водного флюида (ВФ, плотность 0,2 г/ см3 , 415°С), зависит от степени упорядоченности предшественника. Кристаллический LaAlO3 (куб.) в среде ВФ претерпевает дополнительное упорядочивание со снижением величины удельной поверхности (Sуд.) при сохранении кристаллической структуры; дальнейшее прокаливание при 900°С не приводит к изменению величины Sуд. и структуры. При обработке в среде ВФ аморфного предшественника величина Sуд. возрастает и образуется смесь алюминатов LaAlO3 кубической и орторомбической структуры и гидроксидов La и Al. Дальнейшее прокаливание при 900°С приводит к образованию смеси LaAlO3 (куб.), La2O3 (гекс.) и, возможно, рентгеноаморфного Al2O3. Синтезированные системы исследованы в качестве катализаторов окисления метана. Отмечено отсутствие корреляции активности и селективности по продуктам окислительной конденсации (этан этилен) с величиной Sуд., и их зависимость от фазового состава смешанного La-Al-оксида. Наиболее эффективными оказались системы, прошедшие промежуточную обработку в среде ВФ и содержащие фазы LaAlO3 (куб.) и La2O3 (гекс.). Полученные результаты свидетельствуют о высокой структурной чувствительности показателей процесса. The synthesis of mixed La—Al-oxide systems with the atomic ratio La : Al 1 : 1 was studied. At the first stage, the dried mass containing La and Al nitrates and starch was burned. Heat treatment of the resulting amorphous product at a temperature of 700°C leads to the formation of LaAlO3 aluminate with a cubic perovskite structure. The composition and morphology of the product formed during subsequent processing in a water fluid (WF, density 0.2 g/cm3, 415°C) medium depends on the degree of ordering of the precursor. Crystalline LaAlO3 (cubic) in a WF medium undergoes additional ordering with a decrease in the specific surface area (Ssp.) while maintaining the crystalline structure; further calcination at 900°C does not lead to a change in the value of Ssp. and structure. When processing an amorphous precursor in a WF medium, the value of Ssp. increases and a mixture of LaAlO3 aluminates of cubic and orthorhombic structure and La and Al hydroxides is formed. Further calcination at 900°C leads to the formation of a mixture of LaAlO3 (cub.), La2O3 (hex.) and, possibly, X-ray amorphous Al2O3. The synthesized systems were studied as catalysts for methane oxidation. There was no correlation between activity and selectivity for oxidative coupling products (ethane ethylene) with the value of Ssp., but their dependence on the phase composition of the mixed La—Al-oxide was established. The systems that underwent intermediate treatment in a WF environment and contained the LaAlO3 (cub.) and La2O3 (hex.) phases turned out to be the most efficient. The results obtained indicate the high structural sensitivity of the catalytic process parameters.

The formation of mixed oxides in the Al2O3–MO (M = Mg, Ca, Sr, Ba) systems by heat treatment and treatment with water fluids (WFs) is studied. It is shown that during the high-temperature treatment of mixtures of aluminum hydroxide Al(OH)3 with group 2 metal nitrates, mainly MAl2O4 aluminates are formed, sometimes with an admixture of aluminates of a different composition. If the same mixtures are pretreated in WF (400°C, fluid density 0.2 g/cm3), the composition of the sample is more complex because of dehydration and partial structuring of the Al-containing component during the treatment in the WF medium. It is demonstrated that the addition of ammonia to WF has a stimulating effect on the formation of double oxides, primarily due to the alkaline hydrolysis of the Group II metal salts and the formation of their hydroxides; and the reduction of nitrates and nitrites with ammonia is likely to be a secondary process.

The effect of the synthesis method on the formation of the structure and composition of composites produced by the deposition of lanthanum oxide compounds on porous alumina is studied. The effect of the morphology of porous alumina (α-modification) on the formation of various compounds (La 2 O 3 oxide, as well as LaAlO 3 and La 10 Al 4 O 21 aluminates) during the thermal treatment of a support impregnated with a solution of lanthanum nitrate is shown. It is found that when systems are treated in a water fluid (WF), the processes of structuring and phase formation proceed at a much lower temperature and more intensely than during the thermal treatment, which is due to the mobility of the structural elements in the hydrated state. It is shown that the formation of LaAlO 3 aluminate is limited by the hydration of the initial aluminum oxide, which proceeds more intensely in the case of its γ-modification. Varying the sequence and conditions of the stages of the treatment in a WF and the thermal treatment makes it possible to obtain composites that have different morphologies and contain various oxide compounds and phases.

The catalytic properties in the oxidative coupling of methane (OCM) and the structural features of a series of lanthanum aluminum mixed oxides with a constant La : Al atomic ratio of 1 : 1 were studied. Samples were prepared from precursors containing lanthanum and aluminum nitrates and an organic component: filter paper or starch. After drying and burning of the organic component, the samples were subjected to additional heat treatment and treatment with water fluid (WF) with a density of 0.2 g/cm 3 at 415°C. After calcination at 900°C, all the samples contained a phase of lanthanum aluminate LaAlO 3 with a cubic perovskite structure. Varying the type of organic component and the sequence of procedures and treatment conditions gave samples with different morphologies and catalytic properties. The minimum activity, selectivity for OCM products, and stability over time was demonstrated by the sample obtained under conditions conducive to the formation of the most ordered structure, namely, the sample sequentially calcined at 900°C, treated in a WF medium, and recalcined at 900°C. The most efficient and stable sample turned out to be the one whose crystal structure was formed mainly in the WF medium. It was noted that there is no correlation between the morphology of the particles and the specific surface area of the samples, on the one hand, and their catalytic properties, on the other. It was assumed that the catalytic properties are determined by the type and number of point defects in the crystal structure—primarily cation vacancies and, as a consequence, hole sites of the [O – ] type in the anion sublattice.

Metal–hypercrosslinked polystyrene (HCP) composites active in the hydrogenation of unsaturated hydrocarbons are obtained by impregnation of HCP with palladium and rhodium compounds in a supercritical carbon dioxide (SC-CO2) medium followed by their reduction to the metallic state with molecular hydrogen. The influence of the conditions of preparation of the composites on their activity and selectivity in the hydrogenation of diphenylacetylene (DPA) is evaluated. The adsorption of palladium hexafluoroacetylacetonate on HCP from an SC-CO2 medium is studied for the first time using supercritical fluid chromatography; it is shown that the adsorption equilibrium is described by the Langmuir equation.

Исследовано образование смешанных оксидов в системах AlO-MO (M - Mg, Ca, Sr, Ba) при термообработке и обработке водными флюидами (ВФ). Показано, что при высокотермпературной обработке смесей гидроксида алюминия Al(OH) нитратами металлов II группы образуются в основном алюминаты состава MAlO, иногда - с примесью алюминатов иного состава. Если те же смеси проходят предварительную обработку в водном флюиде (400 °С, плотность флюида 0,2 г/см), то состав образца более сложный, что связано с дегидратацией и частичным структурированием Al-содержащего компонента в процессе обработки в среде ВФ. Показано, что добавление аммиака к ВФ оказывает стимулирующее влияние на образование двойных оксидов, в первую очередь в связи с протеканием щелочного гидролиза солей металлов II группы и образованием их гидроксидов; восстановление нитратов и нитритов аммиаком является, по-видимому, вторичным процессом. The formation of mixed oxides in the AlO-MO (M - Mg, Ca, Sr, Ba) system during heat treatment and treatment with water fluids (WF) has been studied. It is shown that during high-temperature treatment of mixtures of aluminum hydroxide Al(OH) with nitrates of metals of group II, aluminates of the composition MalO are formed mainly, sometimes with an admixture of aluminates of a different composition. If the same mixtures undergo preliminary treatment in a water fluid (400 °C, fluid density 0,2 g/cm), then the sample is more complex, which is associated with dehydration and partial structuring of the Al-containing component during processing in a WF medium. It is shown that the addition of ammonia to WF has a stimulating effect on the formation of double oxides, first of all, due to the alkaline hydrolysis of salts of II group metals and the formation of corresponding hydroxides; the reduction of nitrates and nitrites with ammonia is apparently a secondary process.

Исследовано влияние метода синтеза на формирование структуры и состава композитов, представляющих собой оксидные соединения лантана, нанесенные на пористый оксид алюминия. Показано влияние морфологии пористого оксида алюминия (α-модификация) на образование различных соединений (оксида LaO и алюминатов LaAlO и LaAlO) при термической обработке носителя, пропитанного раствором нитрата лантана. Установлено, что при обработке систем в водном флюиде процессы структурирования и фазообразования протекают при гораздо более низкой температуре и более интенсивно, чем при термическом воздействии, что обусловлено высокой подвижностью элементов структуры в гидратированном состоянии. Показано, что процесс образования алюмината LaAlO лимитируется гидратацией исходного оксида алюминия, которая более интенсивно протекает в случае его y-модификации. Варьирование последовательности и условий проведения стадий обработки в водном флюиде и термического воздействия позволяет получать композиты различной морфологии и содержащие различные оксидные соединения и фазы. The effect of the synthesis method on the formation of the structure and composition of materials composed of porous alumina supported lanthanum oxide, has been studied. The effect of the morphology of porous aluminum oxide (α-modification) on the formation of various compounds (oxide LaO and aluminates LaAlO and LaAlO) during thermal treatment of a support impregnated with a solution of lanthanum nitrate is shown. It was found that when systems are treated in a water fluid, the processes of structuring and phase formation proceed at a much lower temperature and more intensively than under thermal action, which is due to the high mobility of structural elements in a hydrated state. It is shown that the formation of LaAlO aluminate is limited by the hydration of the initial aluminum oxide, which proceeds more intensively in the case of its y-modification. Varying the sequence and conditions of the stages of treatment in a water fluid and thermal action makes it possible to obtain composites of various morphologies and containing various single and complex oxide compounds and phases.

The effect of the density of water fluid in the range of ~10–3–0.25 g cm–3 on the structuring of amorphous silica gel was studied at 380°C that exceeds the temperature of critical point of water. It was shown that a decrease in the specific surface area (Ssp) is observed already at the lowest density. As the latter increases, Ssp decreases further, and starting from the density of ~0.01 g cm–3, the formation of crystalline silica phases (cristobalite, keatit) was observed in the sample. Based on the observed regularities in the change in the morphology and crystallinity of SiO2, as well as on the data on the variations in the properties of the water fluid with temperature and pressure below and above the critical point, it was concluded that the increase in the structuring rate with an increase in the density of the water fluid is more likely due to the kinetic factor (mass action law) than with a change in the physical state of water (intermolecular interaction forces action). Using the obtained samples of treated silica gel as a support for the NaWMn/SiO2 catalysts it was shown that their efficiency in the oxidative coupling of methane decreases with increasing degree of crystallinity of the support. However, when supports that have undergone processing in the water fluid of relatively low densities (<0.05 g cm3) were used, the catalysts were more active and selective than the one prepared using the untreated silica gel.

Strontium and barium titanates deposited on a porous support (α-Al2O3) are synthesized by the treatment of previously deposited precursors (titanium oxide, strontium nitrate, or barium nitrite) in a water fluid medium at 400°C. The obtained samples are characterized by X-ray powder diffraction (XRD) analysis and scanning electron microscopy (SEM) with energy-dispersive X-ray (EDX) spectroscopy. It is found that, in the presence of titanium oxide, α-Al2O3 is partially hydrated to form basic aluminum hydroxide AlO(OH) (boehmite), which is not detected by XRD after the treatment of α-Al2O3 in a water fluid. SEM with EDX spectroscopy demonstrates that strontium ions under the conditions of the treatment in a water fluid preferably interact with titanium oxide to form SrTiO3, although the aluminum oxide content in the samples is much higher. The conditions are determined for obtaining systems with different spatial distributions of the supported component inside the granules of the support by varying the procedure of its preliminary impregnation with the titanium oxide precursor.

Исследовано влияние плотности водного флюида в диапазоне ~10- 0,25 г/см на структурирование аморфного силикагеля при 380 °С - температуре выше критической точки воды. Показано, что снижение величины удельной площади поверхности (5у) силикагеля наблюдается уже при наименьшей плотности; при ее возрастании происходит дальнейшее снижение 5у, а начиная с величины плотности ~ 0,01 г/см в образце наблюдается образование кристаллических фаз кремнезема (кристобалит, китит). На основании наблюдаемых закономерностей изменения морфологии и кристалличности SiO, а также анализа данных по изменению свойств водного флюида при варьировании температуры и давления ниже и выше критической точки сделан вывод о том, что возрастание скорости структурирования с ростом плотности водного флюида связано скорее с кинетическим фактором (закон действующих масс), чем с изменением физического состояния воды (действие сил межмолекулярного взаимодействия). Использование полученных образцов обработанного силикагеля в качестве носителя катализатора NaWMn/SiO для реакции окислительной конденсации метана показало, что эффективность катализатора снижается с ростом степени кристалличности носителя. Однако при использовании носителей, прошедших обработку при относительно низких плотностях водного флюида (< 0,05 г/см) катализатор более активен и селективен, чем при использовании исходного силикагеля. The effect of the density of water fluid in the range of ~10-0.25 g/cm on the structuring of amorphous silica gel was studied at 380 °C that exceeds the temperature of critical point of water. It is shown that a decrease in the specific surface area (S) is already observed at the lowest density; as the latter increases, S decreases further, and starting from a density of ~0.01 g/cm, the formation of crystalline silica phases (cristobalite, keatit) is observed in the sample. Based on the observed regularities in the change in the morphology and crystallinity of SiO, as well as the analysis of data on the variations in the properties of the water fluid with temperature and pressure below and above the critical point, it was concluded that the increase in the structuring rate with an increase in the density of the aqueous fluid is more likely due to the kinetic factor (mass action law) than with a change in the physical state of water (intermolecular interaction forces action). Using the obtained samples of treated silica gel as a support for the NaWMn/SiO catalyst for the oxidative coupling of methane it was shown that the efficiency of the catalyst decreases with increasing degree of crystallinity of the support. However, when using supports that have undergone processing at relatively low densities of water fluid (< 0.05 g/cm), the catalysts are more active and selective than the one supported on the initial silica gel.

Синтез титанатов стронция и бария на пористом носителе (α-AlO) проводили обработкой предварительно нанесенных соединений-предшественников (оксида титана, нитрата стронция или нитрита бария) в среде водного флюида при 400 °С. Полученные образцы исследовали методами рентгенофазового анализа (РФА) и сканирующей электронной микроскопии, совмещенной с рентгеновским энергодисперсионным анализом (СЭМ-ЭДА). Установлено, что в присутствии оксида титана происходит частичная гидратация α-AlO с образованием основного гидроксида AlO(OH) (бёмит), который не обнаруживается методом РФА при обработке в водном флюиде чистого α-AlO. Методом СЭМ-ЭДА показано, что, несмотря на значительно более высокое содержание в образцах оксида алюминия, в условиях обработки в водном флюиде ионы стронция преимущественно взаимодействуют с оксидом титана с образованием SrTiO. Определены условия получения систем с различным пространственным распределением нанесенного компонента внутри гранул носителя путем варьирования метода предварительной его импрегнации предшественником оксида титана. The synthesis of strontium and barium titanates supported on the porous carrier (α-AlO) was performed via the treatment of the previously deposited precursors (titanium oxide, strontium nitrate, barium nitrite) in the water fluid medium at 400 °C. The obtained samples were characterized using the X-Ray Powder Diffraction (XRD) and Scanning Electron Microscopy combined with Energy Dispersion X-Ray analysis (SEM-EDX) techniques. It was found that in the presence of titanium oxide α-alumina undergoes a partial hydration with the formation of the basic aluminum hydroxide AlO(OH) (boemite) that was not found using the XRD method after the treatment of the pure α-AlO in the same conditions. Using the SEM-EDX method we demonstrated that in spite of much higher content of alumina in the samples, strontium ions preferably interact with titania forming SrTiO. It was shown that samples with different spatial distribution of the supported component inside the carrier particle can be obtained by varying the method of the preliminary deposition of the titania precursor (titanium tetra-iso-propoxide).