UA76794C2 - Photocatalitical active mesoporous titanium dioxide, process and intermediate product for its preparation - Google Patents

Abstract

Mesoporous titanium dioxide contains crystalline phase of anatase in the amount not less than 30 per cent by weight, it has porous structure with average diameter of pores from 2 to 16 nm, specific surface area not less than 70 m2/g. The process for preparation of the mesoporous titanium dioxide includes introduction to water-organic solvent which contains not more than 7 per cent by weight of water of a precursor – titanium tetra-alkoxide and template of organic nature in the form of one of ligands selected from the group of macro-cyclic compounds, comprising oxa- and oxa-substituted compounds which contain not less than four atoms of oxygen, and/or from the complexes of said macro-cyclic compounds with metal ions selected from the group of alkaline or alkaline-earth, or f-metals, including lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium, mixing the mixture of reagents at a temperature not higher than 35 °C up to formation of the ashes, mixture conditioning at the same temperature in open container under conditions of free access of water vapor to it from outside up to final formation of spatial structure, separation of obtained product of reaction and its treatment prior to removal of the template. The obtained product as a catalyst of photochemical reaction of separation of hydrogen from aqueous-alcoholic mixtures provides quantum yield of reaction not less than 0.5 in the presence of palladium or platinum catalyst of dark stage of reaction.

Description

Description of the invention

The invention relates to the composition and structure of mesoporous dispersed materials based on titanium dioxide, to methods and to the composition of intermediate products for obtaining such materials.

Such mesoporous dispersed materials can be used: as catalysts of photochemical reactions at chemical enterprises, in particular, to obtain molecular hydrogen as a fuel for vehicles or as a starting reagent for such technological processes as the synthesis of ammonia, methanol, etc.; as sorbents-photocatalysts, for example, for air purification from harmful organic compounds by means of heterogeneous photocatalytic oxidation of the mentioned compounds in the gas phase with the formation of products safe for human health.

The terms used here and below in relation to the invention mean: photocatalytic reaction - a reaction that does not take place under the influence of light, in which compounds that undergo chemical transformations and photocatalysts as substances that stoichiometrically do not participate in the overall process participate; catalyst of a photochemical reaction (photocatalyst) - a substance that absorbs light, being in individual form or in a complex with one of the reagents, as a result of which it acquires the ability to initiate chemical transformations, transferring the energy of electronic excitation of the substrate or entering into intermediate chemical interactions with it, and, in addition, it regenerates its chemical composition and basic electronic state after each such cycle, the quantum yield is one of the main characteristics of the photocatalytic reaction, which indicates what proportion of the reactant molecules undergo chemical transformations per quantum of light absorbed by the photocatalyst; template - a material that is a structure-directing agent ("template"), on which, in the process of sol-gel synthesis with a defined orientation in space, the initial reagents are fixed and on which the structure of the dispersed porous material is formed; precursor - a starting substance that, as a result of chemical transformations, for example, hydrolysis, becomes a source of material for forming on a template in the process of sol-gel synthesis the framework of a porous dispersed material; sol - a colloidal system with a liquid dispersion medium, the particles of the dispersed phase of which (micelles) freely participate in Brownian motion and which, upon coagulation, turns into a gel; Gee! gel - a structured colloidal system with a liquid dispersion medium, in which the particles of the dispersed phase are connected to each other in a loose spatial grid containing the dispersion medium in its cells; v coordination compound, complex - compound of complex composition, in which ligands are coordinated to the central cation Ge) (complex former) through their donor oxygen and/or nitrogen atoms, and the number of coordinated atoms depends on the nature of the central cation and the nature of the ligand; - macrocyclic compound - a compound in which donor atoms of oxygen and/or nitrogen are connected to each other by carbon bridges of different lengths, which also contain hydrogen atoms and/or different substituents and which form one or more closed cycles; "oxamacrocyclic compound (crown ether) - a macrocyclic compound containing only donor oxygen atoms; C 70 oxaazamacrocyclic compound is a macrocyclic compound containing, along with donor oxygen atoms, also nitrogen atoms; c» hydrothermal treatment - treatment of substances under conditions of high temperatures and pressures, in which water and aqueous solutions are able to dissolve substances that are practically insoluble under normal conditions, and in which the original inorganic substances are transformed into a crystalline product; calcination - calcination of material at high temperatures. and Disperse materials based on titanium dioxide as catalysts for photochemical reactions of separation

Gee! of molecular hydrogen or as sorbents-catalysts of heterogeneous photochemical processes of oxidation of organic compounds in the gas phase should provide: and high quantum yields of product formation reactions; (Te) 20 possibility of preliminary and, preferably, uniform concentration of a pair of organic compounds on its active surface for their subsequent effective decomposition.

T» In turn, methods of obtaining such dispersed materials based on titanium dioxide should ensure stable reproducibility of material properties, and semi-products for obtaining materials should be resistant to changes and decomposition during storage and, at the same time, easily processed into the final product. (porous dispersed titanium dioxide) by removing the template from them when the need arises

HF) materials with a freshly formed and therefore chemically active surface.

Until now, it was possible to fulfill the specified requirements only in some separate combinations. Yes, the Yuedizza R 25 dispersed material of the Yuedizza company, which mainly consists of a crystalline modification of titanium dioxide - anatase, is known (see, for example, the website of the Yuedivva company: lm. bo dedizza.soM/sp/rgodisie. pit). Anatase itself, being, as is known, an OBC-type semiconductor, is capable of simultaneous oxidation and reduction | see, for example, V. Baltsany, F. Scandola, P. MInfelta, and others.

Znergeticheskie resource! through the prism of photochemistry and catalysis: Trans. with English / Ed. M. Gretzel. - M.: Mir, 1986. - P.364.): when photons are absorbed by it, electrons are excited into the conduction band, and holes are generated in the valence band, participating, respectively, in the reduction and oxidation reactions of molecules of substances that are in contact with it a semiconductor At the same time, the crystalline modification of titanium dioxide, having significantly fewer defects compared to its amorphous modification, on the one hand, contributes to the effective movement of photogenerated charges in the mass of the semiconductor, and on the other hand, it reduces the probability of the occurrence of a very undesirable reverse process - the recombination of photogenerated charges. Therefore, the known material-catalyst of photochemical reactions and, in particular, such reactions as the release of molecular hydrogen from water-alcohol mixtures is characterized by rather high values of quantum yields of hydrogen formation (about 0.4) in the presence of a platinum or palladium catalyst of the dark stage of these reactions, which, as you know, see, for example, Baltsany V., Skandola F., Infelta P. and others Znergeticheskie resurs! through the prism of photochemistry and catalysis: Trans. with English / Ed. M. Gretzel. - MA Mir, 1986. - P.365), contribute to the accumulation of atomic hydrogen formed as a result of the reaction and its transformation into molecular hydrogen.

However, the well-known dispersed material of the Yuedizza P 25 brand has an almost dense structure and therefore a very small specific surface (about 50m2/g of substance), formed by finely dispersed particles of the material. Therefore, the efficiency of using this material for preliminary concentration on its active surface of a pair of organic compounds for the purpose of their subsequent heterogeneous photochemical decomposition is very low.

The method of obtaining such a crystalline modification of titanium dioxide is anatase, which is mainly the material

Redizza P 25, well-known (see, for example, Guide to neo-organic synthesis. Edited by G. Brauzra.-

M.: Mir, 1985. - Vol. 4 - pp. 1460-1462). It includes the introduction of titanium tetraalkoxide (ethoxide, isopropoxide or butoxide) during cooling (temperature about 5922) and intensive mixing of a multiple (relatively stoichiometric) amount of water until the formation of a turbid titanium oxide hydrate, stirring the resulting mixture for several hours until complete hydrolysis of titanium tetraalkoxide, filtration obtained sediment, washing it with water, vacuum drying at room temperature, subsequent heating at a temperature of up to 4009 until the formation of a crystalline modification of titanium dioxide - anatase and its grinding.

This method of obtaining titanium dioxide in the form of anatase is relatively simple and, in addition, provides almost a 100965th yield of the finished product, which has photocatalytic properties. Ge

However, this method does not allow to obtain a porous material capable of effectively concentrating the vapor of organic compounds before their photocatalytic decomposition.

It is obvious that the intermediate product for obtaining titanium dioxide is titanium hydroxide, which, as is known, can lose water when stored and, as a result, spontaneously transform into an amorphous modification of titanium dioxide (see ibid.). "AND

Mesoporous titanium dioxide is also known, which has a much larger specific surface compared to the Oedizz material P 25b (see, for example, the US application Mob79029, submitted on 12.06.96). Due to the mesoporous structure and therefore the highly developed specific surface area, the well-known titanium dioxide has a high sorption capacity. Therefore he can Her. to be a good concentrator of a pair of organic compounds subject to subsequent decomposition. with

However, this titanium dioxide consists mainly of an amorphous phase and is therefore ineffective as a catalyst for photochemical reactions of the release of molecular hydrogen and, even more so, as a sorbent-catalyst for heterogeneous photochemical processes of oxidation of organic compounds in the gas phase.

The method of obtaining such mesoporous titanium dioxide by template sol-gel synthesis includes (see ibid.) the introduction into an aqueous-organic solvent of a precursor in the form of titanium tetraalkoxide and a template in the form of an organic compound, preferably selected from among surface-active substances, exposure or processing of the obtained solution under certain conditions and regimes to the formation of a precursor/template mixture, first of a sol, and then of a gel, and - with the removal of the template. a This method makes it possible to obtain sorption-active titanium dioxide with an average pore diameter of about Znm and a specific surface area up to 7t00m2/g.

However, this method does not allow mesoporous titanium dioxide, which has photocatalytic properties, to be obtained.

Accordingly, the semi-product in the form of a spatially organized organic template/titanium dioxide for the preparation of mesoporous titanium dioxide has the same advantages and disadvantages. b Mesoporous titanium dioxide and the method and semi-product for its production, which are known from (articles Zupipeziz oi NekhadopaiPu - Raskey Mezorogoiz TiOo» ru a Moaiei BoI-) are the closest to the group of objects that is claimed, in terms of technical essence and the effect that is achieved beI Meiyod. Oamidy M. Apupeiyi, daskie U. Mipd // Apdem.Spet.Ipi. so 20 EYA.EpaoI.,, 1995, M.34, Moi, R. 2014-2022 and articles by Zupipevziv, SpPagasiegigayop, apa RVRoiosaia| uyk AKiimyu oi

Tiapia apa Mioria Mezvorogoiz MoiieKkshag bZiemev. Mikiog B. Biope, city of Apa Kobregp 9. YuOamiv // Spetivigu oi iz" Maiegia!z, 1998, M.10, Mo5, R.1468-1474)|. In the first of these articles, the texture of the material chosen by us as a prototype is characterized, the process-prototype of obtaining the material is described step by step, indicating the conditions for carrying out each stage of synthesis, and the properties of the semi-product-prototype for obtaining the material are described. In the second, 22 other authors studied the photocatalytic properties of the prototype material (mesoporous titanium dioxide) and explained the nature of its photocatalytic activity.

The known mesoporous titanium dioxide | see Zupipeziz oi Nehadopaiu Raskei Mezorogoiz TiOo Bu a Modiyea de ZoI-Sei! Meiipode Oamid M. Apiopeiii, daskie M. Mipd // Apdem.Spet.Ipi. Ea.Epai., 1995, M.34, Mo1, R.2017| has an average pore diameter of about 3 nanometers and a specific surface area of about 200 m?/g. Therefore, it is effective as a 60 vapor concentrator of organic compounds.

However, this mesoporous titanium dioxide is characterized by a low value of the quantum yield of molecular hydrogen formation - no more than 0.01 in the presence of a platinum or palladium catalyst of the dark stage of the reaction | see Bupipevzi5, SPagasiegigayop, apa Rpoiosaiiauyuyk AKimyu oi Tyapia apa Miorbia Mezorohoiv

Moiiiekshiag Ziemevs. Mikiog B. Biope, the city of Apa Kobregp 9. Yuamiv / Spetivigu oi Maiegiaiv, 1998, M.10, Mo5, R.1470, because table 11, which indicates the superiority of the photocatalytically weak amorphous phase of titanium dioxide in the material

(see ibid., p. 1471, picture 4). In addition, the content of a fragment of the template - phosphorus in its pores contributes to the reduction of the photocatalytic activity of the known material (see ibid.). Therefore, given the set of properties, this mesoporous titanium dioxide is not effective enough as a sorbent-photocatalyst.

The method of obtaining the known mesoporous titanium dioxide includes |see Зупипевзиз ой Нехадопай|у РасКай

Mezorogoiz Ti" Bu a Modyei 5o0I-bSe| Meifioa. Samii M. Apiopeiii, dasKie U.Mipd / Apdem.Spet.Ipi. Ea.Epai., 1995, M.34, Mo1, R.2017| dissolving the template - monododecyl phosphate and pH regulator - potassium hydroxide in water, dissolving the precursor in the form of titanium tetraalkoxide (isopropoxide) in the organic solvent - acetylacetone, mixing the resulting solutions, holding the mixture at a temperature of about 80 9C in a vessel isolated from 70 degrees of the external environment until the final formation from it spatial structure, which, as is known, includes the intermediate stages of the formation of a sol first, and then a gel | see, for example, Chemical encyclopedic dictionary / Ed. I.L. Knunyantsa. - M.: Soviet encyclopedia, 1983. - P.549), separation of sediment, its washing, drying and processing to remove the template from it.

The known method makes it possible to obtain mesoporous titanium dioxide with a well-ordered pore structure and a highly developed surface | see Zupipeziz oi Nekhadopayu RasKked Mezorogoiz Ti» ru a Modyei 5o1-sei!

Meiypoada. Oamid M. Apiopeii, dasKie U. Mipd // Apdem/.Spet.Ipi. Ed. Epai., 1995, M. 34, Mo1, R. 2017).

However, this method does not allow obtaining mesoporous titanium dioxide with a high content of the photocatalytically active crystalline phase - anatase. In addition, the use according to the known method of monododecyl phosphate as a templating reagent prevents the complete removal of fragments of this reagent from the pores of the finished product | see zZupipeviv, "SNagasiegigayop, apa RVNoosayaunk AkKimyu oi Tyapia apa Mioria

Mezorogoiz Moiiekshag Ziemev. Mikog R. Iope, the city of Apa Kobregi 9. YuOamiz // Spetivigu oi Maiegiaiv, 1998, M.10,

Mo5, R.14711.

It is obvious that the semi-product for the implementation of the known method of obtaining mesoporous titanium dioxide is a spatially organized structure of monododecyl phosphate/titanium dioxide (see Zupiyeziz oi Nehadopaiu Raskei su Mezorogoiz Ti» Bu a Moayei 5oI-««Ze| Mefoa. Oamid M. Apiopeiyi, daskie U. Mipud // Apdem.Spet.Ipi.Ea.Epoi., 1995, M.34, Mo1, R.2017). Such a structure is resistant to decomposition during storage and is easily processed into the final product (mesoporous titanium dioxide) by calcination or extraction with alcohol (see ibid.).

However, the monododecyl phosphate contained in this semi-product does not allow it to be used to obtain the final product (mesoporous titanium dioxide) with the required sorbent-photocatalyst "I Complex of properties | see Zupipeviv, SNagasiegigayop, apa RIoiosaiiaunik AkKgmyu oi Tiyapia apa Miobia

Mezorogoiz Moiiekshag Ziemev. Mikog R. iope, g. apa Kobregi 9. YuOamiz // Spetivigu oi Maiegiaiv, 1998, M.10, b"

Mo5, R.1470-14711. uh-

The group of inventions is based on the task of creating a sorbent-photocatalyst with high sorption and photocatalytic performance by improving the composition and texture of mesoporous titanium dioxide, by selecting reagents for the method of obtaining mesoporous titanium dioxide and synthesis conditions to ensure the reproducibility of the complex properties of such a sorbent-catalyst and , finally, by improving the composition of the intermediate product to obtain mesoporous dioxide, ensure the resistance of the intermediate product to changes and decomposition during the storage period and, at the same time, its easy processing (by removing the template) into the final product - a sorbent-photocatalyst with freshly formed, which does not contain unwanted impurities, and therefore an active surface. "

The problem is solved by the fact that the mesoporous titanium dioxide according to the invention contains (also) a crystalline phase of anatase in an amount of at least 3095 mass, has a porous structure with an average pore diameter from 2 cm to 1 nm, a specific surface area of at least 7 Ω/g and how the catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures provides a quantum yield of the reaction of at least 0.5 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

The first additional difference is that it additionally contains lanthanum in an amount of no more than 0.019 grams per gram of substance.

The problem is also solved by the fact that in the method of obtaining mesoporous titanium dioxide, which

F includes the introduction of a precursor - titanium tetraalkoxide and a template of an organic - I nature into an aqueous-organic solvent, holding the mixture of reagents until the final formation of a spatial structure from it through successive stages of the formation of a sol and then a gel, separation of the resulting reaction product and its processing until removal and template , according to the invention, the process is carried out in a water-alcohol solvent containing no more than 790 t» wt. water, as a template, at least one of the ligands selected from the group of macrocyclic compounds, which includes oxa- and oxaazamacrocyclic compounds containing at least four oxygen atoms, and/or from complexes of the specified macrocyclic compounds with metal ions selected from the group alkaline, or alkaline earth, or y-metals, which includes lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, and cerium, the mixture of reagents is stirred until the formation of sol, maintaining its temperature no higher than 359, and until the final formation of the spatial structure from the mixture of reagents, the mixture is kept at the same temperature in an open vessel under conditions of free access to the mixture of water vapor.

The first additional difference is that the template is removed from the resulting reaction product 60 by calcination at a temperature from 3002 to 6002C. The use of such firing modes contributes to the almost complete removal of the template from the reaction product, a deep directed process of crystallization of the material with the predominant formation of the anatase phase, and, as a result, obtaining a photocatalytically active sorbent material.

A second additional difference is that the template is removed from the reaction product by alcohol extraction. 65 This method, alternative to the previous one, also allows almost complete removal of the organic template from the reaction product.

The third additional difference to the first and second is that before removing the template, the reaction product is hydrothermally treated at a temperature from 1002 to 2002C. The combination of hydrothermal treatment of the product with the given methods of its de-templating allows to almost completely complete the hydrolysis of titanium tetraalkoxide, to form a photocatalytically active phase of anatase, and to preserve the parameters of the formed mesoporous structure after almost complete removal of the organic template from the reaction product.

The fourth additional difference is that a lanthanum salt is additionally introduced into the water-alcohol solvent. This makes it possible to additionally increase the thermal stability of the inorganic component of the titanium dioxide/organic template spatial structure during its subsequent heat treatment and, as a result, additionally stabilize the 7/0 mesoporous structure of the obtained final product without changing its photocatalytic properties.

The given task is also solved by the fact that the intermediate product for obtaining mesoporous titanium dioxide, containing titanium dioxide and an organic compound, according to the invention, contains as an organic compound at least one of the ligands selected from the group of macrocyclic compounds, which includes oxa- and oxaazamacrocyclic compounds , containing at least four oxygen atoms, and/or from complexes of the specified macrocyclic compounds with 7/5 metal ions selected from the group of alkaline, or alkaline earth, or y-metals, which includes lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium, and one mole of titanium dioxide in the intermediate product contains from 0.001 mol to 0.2 mol of ligand.

The first additional difference is that it additionally contains a lanthanum salt in an amount of no more than 0.006 moles per one mole of titanium dioxide.

The best options for implementing inventions

Next, the essence of the group of inventions is explained by generalized examples of the method of obtaining mesoporous titanium dioxide through the intermediate stage of obtaining an intermediate product of the composition titanium dioxide/organic template, methods for determining the parameters of the porous structure of the final product (mesoporous titanium dioxide), methods for determining the phase composition of the final product, and methods for evaluating the photocatalytic properties of the finished product of the product on the example of its use as a catalyst for the photochemical reaction of the release of molecular hydrogen from water-alcohol mixtures, as well as the method of determining the quantitative composition of the intermediate product. at

The essence of the group of inventions is also explained by specific examples of the method of obtaining mesoporous titanium dioxide (including the stage of obtaining the corresponding intermediate product), in which the parameters of the porous structure determined by these methods (without repeated reference to them), the phase composition and the photocatalytic "I

From the properties of the obtained mesoporous titanium dioxide, as well as the composition of each specific intermediate product.

Example 1. A generalized method of obtaining mesoporous titanium dioxide through the stage of obtaining an intermediate product of the titanium dioxide/organic template composition, generalized methods of determining the parameters of the porous p. structure, phase composition and photocatalytic properties of mesoporous titanium dioxide, as well as a method of determining the composition of the intermediate product. eh

As an organic template for the synthesis of mesoporous titanium dioxide, at least one of the cheoxa- or oxaazamacrocyclic compounds containing at least four oxygen atoms (mostly no more than ten) and/or one of the complexes of the named macrocyclic compounds with an alkali ion (lithium, sodium, potassium) was used , rubidium, cesium), or alkaline earth (magnesium, calcium, strontium, barium), or i-metal (lanthanum, cerium). It should be noted that organic templates in the form of oxa- and oxaazamacrocyclic compounds, as well as complexes of these compounds with the mentioned "0" metals containing less than four oxygen atoms, have not been described in the literature. The use of oxa- and shshc oxaazamacrocyclic compounds, as well as their complexes with these metals containing more than ten oxygen atoms, is not excluded, but, as the results of our research show, the probability of the occurrence of "" heterogeneous structure of the mesoporous material increases and is disturbed stability of its texture parameters.

Titanium tetraethoxide, titanium tetraisopropoxide, titanium tetraisobutoxide, titanium tetrapropoxide or titanium -I tetrabutoxide were used as a titanium tetraalkyoxide precursor for the synthesis of mesoporous titanium dioxide.

As a water-alcohol solvent for the synthesis of mesoporous titanium dioxide, methyl, ethyl, propyl, butyl, hexyl or amyl alcohols were used, the water content of which did not exceed 795 wt. -I As our experiments have shown, it is possible to use other alcohols with the number of carbon atoms from two to nine, the water content of which does not exceed 795 wt. The use of such water-alcohol solvents with a higher water content is impractical, because it leads to a significant acceleration of the process of hydrolysis of tetraalkoxide

Ta" of titanium and, as a result, to the violation of the homogeneity of the mesoporous structure of the final product - titanium dioxide.

Before the synthesis of mesoporous titanium dioxide, portions of one of the named precursor substances and one of arbitrarily chosen (from among the named) template substances were prepared. At the same time, from 0.001 mol to 0.2 mol of organic template was taken for one mol of titanium tetraalkoxide (precursor). As it was found out, the relative decrease in the number of templates below the lower limit leads to the fact that the specific surface of the final synthesis product becomes

IF) poorly developed (less than 70m2/g), which affects the sorption properties of the product. Relatively increasing the number of templates above the upper limit is impractical, because at the same time the template remains in excess, only partially participating in the synthesis. because one of the water-alcohol solvents was poured into a glass beaker in an amount sufficient to dissolve a portion of the template substance in it at room temperature. The same solvent was poured into another glass in an amount sufficient to dissolve a portion of the precursor substance in it at the same temperature. In a number of cases, when the template used for the synthesis of titanium dioxide was one of the oxa- or oxaazamacrocyclic compounds or a complex of one of these macrocyclic compounds that does not contain the lanthanum ion, 65 in a water-alcohol solvent, in addition to the template, a lanthanum salt was introduced into amount of no more than 0.006 mol per one mol of titanium tetraalkoxide (precursor). After preparing a solution of the template substance or a mixture of the template substance with lanthanum salt in the first glass, and a solution of the precursor substance in the second glass, the solution of the precursor substance was added dropwise to the first glass with intensive stirring. After the entire portion of the precursor substance solution was introduced into the template substance solution, the resulting mixture was continued to be stirred for several hours until a sol was formed from the mixture. Since ash formation is accompanied by a sharp increase in the viscosity of the mixture, the completion of this stage of the synthesis process was easily recorded, for example, by a sharp decrease in the speed of rotation of the electric stirrer. The temperature of the mixture at this entire stage of synthesis, starting from the mixing of solutions and ending with ash formation, was maintained no higher than 3520. After ash formation, without stopping to maintain the temperature of the mixture no higher than 35 2C, its stirring was stopped. 70 The mixture was left in an open vessel under conditions of free access to water vapor from the environment (if the relative humidity of the environment was not less than 6095) or the vessel with the reaction mixture was placed in a chamber where the relative humidity was not less than bObo was specially created using saturated solutions of the appropriate salts according to the generally accepted method | see, for example, the Chemist's Handbook / Ed.

B.P. Nikolskyi. M.: Goshimizdat, 1963. Vol. 1, P. 1047)Y. Contact of the mixture with water vapor was provided for 75 several weeks until the final formation of the titanium dioxide/hemplate spatial structure from the reaction mixture.

The criterion for completing this stage of synthesis was the syneresis effect, which is clearly visible visually | see, for example, the Chemical Encyclopedia. M.: Soviet encyclopedia, 1988, Vol. 1, P. 513), - spontaneous final compaction of the titanium dioxide/template spatial structure and, as a result, - cessation of displacement of the liquid phase from it.

For each mixture of specific reagents (precursor, organic template (including one containing a lanthanum salt) and water-alcohol solvent) taken separately for the synthesis of mesoporous titanium dioxide, the time of the final formation of the spatial structure of the titanium dioxide/organic template composition from it under different regimes synthesis was determined experimentally.

As it was established, an increase in the temperature of the reaction mixture above the specified limit (35 C) at such stages of the synthesis of mesoporous titanium dioxide as sol formation and the formation of a spatial structure with the composition titanium dioxide/organic template leads to a deterioration of the textural characteristics of the final product (titanium dioxide) and, first of all, contributes to the formation of a product with a small specific surface. The lower, experimentally established temperature limit at which these stages of synthesis of mesoporous titanium dioxide should be carried out is 109С. At lower temperatures, there is a steady tendency to decrease the number of mesopores in the samples of the final product and, accordingly, to increase the number of micropores in them. F

Depending on the chosen method of removing the template (calcination or alcohol extraction) from the spatial structure finally formed from the mixture of reagents and the method of obtaining the required amount of photocatalytically active anatase in titanium dioxide, the obtained spatial structure was subjected to different pretreatments.

In the case when calcination was used to remove the template from the (finally formed) spatial structure of titanium dioxide/template and the formation of the necessary amount of photocatalytically active anatase in titanium dioxide, the structure was previously separated by filtration from the mother solution, dried in air until the solvent was almost completely removed from it, and then crushed in a disperser. "

The dried, crushed mixture was poured into a crucible and weighed together with the crucible on analytical balances. Then the crucible with the mixture was placed in a muffle furnace, where the mixture was calcined at a temperature from 30092 to 6002 for 4-7 hours until the organic template was completely removed from it. The criterion for complete removal of the template from the structure and obtaining the final product - mesoporous titanium dioxide - was the achievement of a constant mass by the contents of the crucible after its reduction in the detemplating process, which was easily determined by successive weighing on analytical scales of the crucible with the material after cooling. As shown by the results of the X-ray phase analysis of the finished product (mesoporous titanium dioxide), the time allotted for de-templating - the titanium dioxide/template structure by calcination according to the above-described method was quite sufficient for

FO formation in titanium dioxide is not less than 3090 wt. photocatalytically active anatase phase.

It should be noted that practically all organic templates mentioned in the claims of the invention are removed from the spatial structure of titanium dioxide/template already at a calcination temperature of 300 C. However, the duration of the process of calcination of the structure at such a temperature is 20 minutes until the template is completely removed from it and the process of crystallization of the dioxide is completed of titanium with the predominant formation of the anatase phase is about 7 hours. Therefore, in order to accelerate the process of complete de-templating and the formation of a sufficient amount of the photocatalytically active phase of anatase, the calcination of the titanium dioxide/template structure was carried out at temperatures much higher, but not exceeding 6002С. At this upper temperature limit, the specific surface area of the final product (mesoporous titanium dioxide) significantly decreased, and mesoporous titanium dioxide with

GF) with a specific surface area of 70m2/g did not succeed. In addition, calcination of the structure at temperatures above 6002 7 contributed to an undesirable increase in the diameter of mesopores to the size of micropores.

In a number of cases, before calcination, the spatial structure of titanium dioxide/hemplat was subjected to hydrothermal treatment at a temperature from 1002C to 2002C. For this, the spatial structure together with the mother solution was placed in a hermetic autoclave, where at a temperature of 10020-2009C and increased pressure, occurring at these temperatures, it was hydrothermally treated for about two days until complete hydrolysis of the titanium tetraalkoxide and the formation of the photocatalytically active anatase phase. After that, the structure with the mother solution was removed from the autoclave. The structure was separated from the mother solution by filtration, dried in air until almost complete removal of the solvent, crushed in a disperser, and then calcined according to the above-described method. As a result, the template was almost completely removed from the structure and the process of formation of the required amount of photocatalytically active anatase in titanium dioxide, which began during hydrothermal treatment, was completed.

Note that combining the process of calcination of the titanium dioxide/template structure with. process (Its preliminary hydrothermal treatment is highly desirable, but not necessary, because the calcination of the structure even without its preliminary preparation contributes to the formation of mesoporous titanium dioxide with the required amount of photocatalytically active anatase.

In the same case, when the template is finally formed spatial structure of titanium dioxide/template was removed by alcohol extraction, the structure, without separating it from the mother solution, was necessarily subjected to hydrothermal treatment in an autoclave for about four days at a temperature from 10090 to 20020. Such modes of preliminary hydrothermal preparation contributed not only to the complete completion hydrolysis of tetraapoxide, but also the formation of the required amount of photocatalytically active anatase in titanium dioxide.

After this preliminary hydrothermal treatment, the structure with the mother solution was removed from the autoclave.

The structure was separated from the mother liquor by filtration, dried in air until almost complete removal of the solvent, and then crushed in a disperser. The resulting powder structure was placed in a glass beaker. With intense stirring, preheated to boiling temperature alcohol, preferably ethyl, was added to the beaker (at the same time, about 30 ml of alcohol was taken per gram of structure powder) and the titanium dioxide/template organic template was removed from the formed spatial structure by extraction. Without allowing strong cooling of the suspension, the solid phase was separated from it by filtration. Using new portions of hot alcohol, the solid phase separated by filtration was successively processed two more times according to the same method. As a result, mesoporous titanium dioxide was obtained, which practically does not contain an organic template. It was dried until the solvent was almost completely removed, crushed in a disperser and stored in a closed glass container before use as a sorbent-photocatalyst.

The specific surface area of the obtained mesoporous titanium dioxide was calculated by the BOI su (Brunauer-Emmett-Teller) method from the methanol adsorption isotherm, using a known technique | see, for example,

Greg S, Singh K. Adsorption, specific surface, porosity. - M.: Mir, 1970. - P.73 or Brunauzr S. i)

Adsorption of gases and vapors. - M.: Foreign. lit., 1948, T.1. - P.784). Adsorption and desorption isotherms of methyl alcohol were recorded at a temperature of 202C by the gravimetric adsorption method, using a vacuum unit with Mac Bena-Bakra spring quartz scales with a sensitivity of 0.25-0.35 mm/mg | see, for example, M.M. Dubinin. Che Physico-chemical basics of sorption technology. - 2nd ed., revised. and additional - L.. ONTI, 1935. -346p. or

Experimental methods in the adsorption of immolecular chromatography // Ed. A.V.Kyseleva and V.P.Dreving. F - Moscow: Moscow State University, 1973. - 448p. or N.V. Keltsev. Basics of adsorption technique. 2nd ed., revised. and additional - M.: h-

Chemistry, 1948, Volume 1. - 592s/4. A weight of an air-dry sample of mesoporous titanium dioxide weighing about 0.1 g was placed in a glass cup, which was suspended on spring quartz scales in the tube of the vacuum installation. oh

The cavity of the vacuum unit with the sample was vacuumed for 3 hours, maintaining the value of residual pressure in the cavity, equal to 10 mm Hg. At the same time, the sample of mesoporous titanium dioxide was additionally thermostated at a temperature of about 1002C throughout this time. After that, without changing the value of the residual pressure in the cavity of the installation, the temperature of the sample in it was reduced to 2020. With the help of a cathometer with a price of 0.0 mm, the initial amount of stretching of the spring of the scales with the sample suspended on it was recorded, and the initial mass of the sample was determined from the calibration table. which corresponds to this amount of stretching. The cavity of the installation was hermetically connected to a vessel partially filled with liquid methanol through a vacuum valve. » The tap was opened and the methanol vapor above this liquid adsorbent entered the cavity of the installation. The change in the pressure value in the installation cavity as methanol vapor enters it was recorded with a mercury manometer. After establishing equilibrium in the system (achieving a pressure value in the installation cavity equal to the pressure value of saturated methanol vapor), the pressure stabilized. With the help of a scathetometer, the final amount of stretching of the spring of scales with a sample suspended on it was recorded and determined

Ge» the final mass of the sample corresponding to this amount of stretching. The amount of methanol (in mmol) adsorbed by the sample was calculated from the difference between the final and initial masses of the sample, taking into account the molecular weight of methanol

Ш- upon reaching equilibrium in the system and determined the amount of adsorption a (mmol/g) of methanol by one gram of the sample.

Ge) 20 Using the obtained value of a, the BET equation (which satisfactorily describes the initial section of the adsorption isotherm of methyl alcohol vapor) determined the capacity of the monolayer of methanol ag. As a result, specific

T" surface of 5ud (U m2/g) of a sample of mesoporous titanium dioxide was calculated using the formula:

Zud at Mao, where at - calculated according to the BET equation (for the initial region of the methanol adsorption isotherm), the capacity of the methanol monolayer, mmol/g, Md - the Avagadro number, mmol", o - the size of the molecular landing site

F) of methanol, which is equal to 0.251078m2 according to generally accepted ideas | see, for example, A.P. Karnaukhov. ka Adsorption method! measurements of the specific surface and structures! pore catalysts // Kinetics and catalysis. - 1962.- T.3, Mo3. - P.583-5981. 60 Based on the model of non-intersecting cylindrical pores, the average diameter of the pores OSR, (unm) formed in a sample of mesoporous titanium dioxide was determined from the ratio (see ibid.):

Osr.--4.109M5/Zud de Zud - the previously obtained value of the specific surface area of a sample of mesoporous titanium dioxide, mg/g, Metam - the limiting sorption volume of pores, m3/g, determined by the weight adsorption method using the above-described vacuum installation at temperature 202 and pressure in its cavity, equal to the pressure of saturated methanol vapor, a - previously obtained under the same conditions of the experiment, the limiting value of adsorption a (mmol/g) of methanol, Mo - molar volume of liquid methanol, equal to 4.05.10СmZ /mmol

X-ray phase analysis of mesoporous titanium dioxide samples for the content of the anatase crystalline phase in them was performed on a DRON-ZM diffractometer, using nickel-filtered copper radiation at a voltage of ЗОкВ and a current of 20 mA, a slit when shooting in the small-angle range of 1.0-1.0-0 ,5, in the middle and far range of angles - 2.0-2.0-1.0 | see, for example, L.M. Mirkin. Handbook of X-ray structural analysis of polycrystals. - M. Gos. izd-vo fiz. and physics and mathematics literature), 1961. - 86bZs. or V.I. Mikheev.

Roentgenometric determiner of minerals. - M.: Gosgeoltekhizdat, 1957. - 868 p.|. The content of anatase in 70 mesoporous titanium dioxide was determined by the relative intensity of the characteristic reflexes at 20-25.49 in comparison with a sample of dispersed material of the YuOedizza brand R 25 of the YuOedizza company, the anatase content of which is known.

The photocatalytic activity of the obtained samples of the mesoporous material based on titanium dioxide was evaluated according to the known method |(|see, for example, Kryukov A.I., Korzhak A.V. Kuchmiy S.Ya. Photocatalytic 75 formation of hydrogen in alcohol solutions of titanium tetrachloride // Theory and experimental chemistry.-1984.- vol.20,

Mo2.- P.169-177|. For this, a suspension consisting of 0.05 g of mesoporous material based on titanium dioxide and 10 ml of ethyl alcohol containing 2 mol/l of water was placed in a glass reactor. With constant stirring of the suspension at a temperature of 409C, it was irradiated with the light of a high-pressure mercury lamp of the type

DRSH-1000, isolating quanta with a wavelength of about Zbonm with the help of a glass light filter UFOS-2.

The total number of quanta absorbed by the reaction system per unit time (I, einstein/min or mole-quantum/min) was determined by a ferrioxalate chemical actinometer using the following relationship:

Iepee (in Fa, where pre) - the number of iron ions (II) formed during the irradiation of the ferrioxalate solution, Fd - the tabular value of the quantum yield of iron (II) formation for a given wavelength of irradiation. Ge

Using the obtained value of |, we calculated the quantum yields Ф for the photocatalytic reaction (5) of molecular hydrogen release from water-alcohol mixtures in the presence of the obtained samples of mesoporous titanium dioxide and a dark-stage palladium catalyst:

Phno-2 tnoi, where tno is the rate of formation of molecular hydrogen in mol/min, which was determined by the chromatographic method. "AND

In order not to repeatedly repeat the rather lengthy process that requires control of individual stages, the process of forming a spatial structure of the titanium dioxide/organic template from a mixture of reagents, a sufficiently large amount of such a structure was specially synthesized once. After separation of the resulting structure - by filtration from the mother liquor, then drying in air until almost complete removal of the solvent and grinding in a disperser, it was stored in a glass container as a semi-finished product. As the results of the tests showed, such an intermediate product consisting of titanium dioxide and one of the oxa- or oxaazamacrocyclic compounds containing at least four oxygen atoms (mostly no more than ten) and/or one of the complexes of the named macrocyclic compounds with an alkaline ion (lithium , sodium, potassium, rubidium, cesium), or alkaline earth (magnesium, calcium, strontium, barium), or y-metal (lanthanum, cerium), resistant to changes and decomposition during long-term storage (at least a year) To prepare the required amount of the mesoporous titanium dioxide photocatalyst with a freshly formed and therefore chemically active surface, an appropriate portion was taken - from the intermediate product, which was calcined according to the above-described method until the template was removed and the necessary amount of photocatalytically active anatase was formed in the dioxide and titanium. is" In order for the intermediate product to be suitable for obtaining mesoporous titanium dioxide - a photocatalyst by extracting the template with alcohol, before separating the resulting structure from the mother liquor by filtration, drying and grinding it together with the mother liquor, it was previously subjected to hydrothermal treatment according to the above-described method until the formation of titanium dioxide of the required amount of photocatalytically active anatase.

The content of the organic template in the intermediate product was determined according to the following method. A small (about 0.5 g) portion of the semi-finished product was poured into a crucible and weighed together with the crucible on analytical scales. Then the crucible with the 50 semi-product was placed in a muffle furnace and what was contained in the crucible was calcined (baked) at a temperature of 6002C for the time required to remove the template. The criterion for complete removal of the template from the semi-product and obtaining the final product - mesoporous titanium dioxide was the achievement of a constant mass by the crucible with the material after its reduction in the detemplating process, which was easily determined by successive weighing on analytical scales of the crucible with the material after cooling. Based on the difference in the mass of the crucible with the intermediate product and the crucible with the final product, the weight amount of the organic template contained in the intermediate product was determined and the molar content of the titanium dioxide and organic template in the intermediate product was calculated.

Example 2 where the oxamacrocyclic compound tetramethyl-12-crown-4 of the general formula С42Н24О54 was used as an organic template for the synthesis of mesoporous titanium dioxide, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)АТи, as a water-alcohol solvent - n-butanol, containing water in the amount of 790 wt. 170 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.141 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture during this entire stage of synthesis was maintained at about 252C. After ash formation, mixing of the mixture was stopped.

The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 2590 with the help of a thermostat, and the relative humidity at 6595 - with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 48 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining 70 mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 3890 mass, had a porous structure with an average pore diameter of Osr-9.inm and a specific surface area of Zud-8BM7/g. As a catalyst 12 of the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.52 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.01 mole of the organic template - tetramethyl-12-crown-4 was required for one mole of titanium dioxide.

Example C

As an organic template for the synthesis of mesoporous titanium dioxide, the oxamacrocyclic compound dibenzo-18-crown-6 of the general formula SooNolOvb was used, as a precursor - titanium tetrabutoxide of the general formula (S.NeO)uTi, as a water-alcohol solvent - n-butanol, which contains water in amount of 6.595 wt. 175 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.135 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture was maintained at about 202C throughout this stage of the synthesis. After ash formation, mixing of the mixture was stopped. "

The glass with the mixture was placed in a chamber, the temperature in which was maintained with the help of a thermostat at about 202C, and the relative humidity at 6590 - with the help of a saturated solution of ammonium nitrate. Contact of the mixture with water vapor at this temperature was ensured for 17 days until the final formation of the spatial structure mixture - titanium dioxide/organic template. Gee)

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 18090 it was hydrothermally treated for 45 hours. After that, the structure together with the mother liquor was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, the appropriate portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at -o temperature of 5002 for 4.5 hours until the template was completely removed. c The mesoporous titanium dioxide obtained in this way contained a crystalline phase of anatase in the amount of 5595 mass, "c" had a porous structure with an average pore diameter of Osr-9.5 nm and a specific surface area of Zud-7.bm7/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фно-0.58 in the presence of a palladium or platinum catalyst of the dark-I stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide per one mole of titanium dioxide

Meh, there was 0.005 mol of organic template - dibenzo-18-crown-6. -1 Example 4

As an organic template for the synthesis of mesoporous titanium dioxide, the oxamacrocyclic CO compound dibenzo-30-crown-10 of the general formula SovNaoOcho was used, and as a precursor - titanium tetrabutoxide of the general formula

Their" formula (С.НеО)АТи, as a water-alcohol solvent - n-butanol, containing water in the amount of 595 wt. 180 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.042 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of precursor were added to it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting (F) mixture was continued to be stirred for 1.5 hours until a sol was formed from the mixture. The temperature of the mixture at this entire stage of the synthesis was maintained at about 302C. After ash formation, mixing of the mixture was stopped.

The glass with the mixture was placed in a chamber, the temperature in which was maintained with the help of a thermostat at about ЗО2С, and the relative humidity of 85905 - with the help of a saturated solution of potassium chloride. Contact of the mixture with water vapor at this temperature was ensured for 12 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 18590 it was hydrothermally treated for 43 hours. After that, the structure together with the mother solution was removed from the 65 autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 4 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 5595 mass, had a porous structure with an average pore diameter Osr-9.3 nm and a specific surface area Zud-7Om/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фно-0.54 in the presence of a palladium or platinum catalyst of the dark stage of the reaction. 70 In the selected semi-product for obtaining mesoporous titanium dioxide, 0.001 mole of the organic template - dibenzo-30-crown-10 was required for one mole of titanium dioxide.

Example 5

As an organic template for the synthesis of mesoporous titanium dioxide, the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 of the general formula С42НовО4М»о was used, as a precursor - titanium tetrabutoxide of the general formula 75 (С.НХО)/ Ti, as a water-alcohol solvent - n- butanol containing water in the amount of 795 wt. 167 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.098 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture during this entire stage of synthesis was maintained at about 252C. After ash formation, mixing of the mixture was stopped.

The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 2520 with the help of a thermostat, and the relative humidity at 6290 - with the help of a saturated solution of ammonium nitrate. Contact of the mixture with water vapor at this temperature was ensured for 15 days until the final formation of the spatial structure mixture with 25 titanium dioxide/organic template. at

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17550.P it was hydrothermally treated for 50 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining - 30 mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, the appropriate Ge! a portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 4.5 hours until the template was completely removed. uh-

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 4796 mass, and had a porous structure with an average pore diameter of 8.5 nm and a specific surface area of 78 m/g. As a catalyst

From the photochemical reaction of the release of hydrogen from water-alcohol mixtures, such mesoporous titanium dioxide - provided the quantum yield of the Fuc»-0O.55 reaction in the presence of a palladium or platinum catalyst of the new stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.005 mol of organic template - 18-coronaase-2-oxa-4 was required for one mol of titanium dioxide. 7

Example 6 c As an organic template for the synthesis of mesoporous titanium dioxide, the oxaazamacrocyclic compound 18-coronaaz-1-oxa-5 of the general formula С42Н25О5ИМ was used as a precursor - titanium tetrapropoxide of the general formula (СзН.7О)/Ти, as a water-alcohol solvent - n -propanol containing water in the amount of 595 wt. 141 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.197 g of the template was dissolved in 75 ml of it. 4O0ml of the same solvent was poured into another glass beaker. Eaten at room temperature. 21 g of the precursor were dissolved in it. The template was introduced dropwise into the solution with intensive stirring

Ge") precursor solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 3 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 15202. After ash formation, mixing of the mixture was stopped. A glass (Ce) 20 with the mixture was placed in a chamber, the temperature of which was maintained at about 152C with the help of a thermostat, and

T" relative humidity 8195 - with the help of a saturated solution of ammonium sulfate. Contact of the mixture with water vapor at this temperature was ensured for 18 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 16590 it was hydrothermally treated for 52 hours. After that, the structure together with the mother solution was removed from (F) the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 4295 wt. of titanium 65 provided the quantum yield of the Fn»-0O.51 reaction in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.01 mole of the organic template -18-coronaase-1-oxa-5 was required for one mole of titanium dioxide.

Example 7

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaamacrocyclic compound tetramethyl-12-crown-4 with a lithium ion of the general formula |-(С42Но24О4)|СИ-3НоО was used, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)уTi, as a water - alcohol solvent - n-butanol, containing water in the amount of 495 wt. 16 bbml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.426 g of the template was dissolved in it. 45 ml of the same 7/0 solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 25 20. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 252C with the help of a thermostat, and the relative humidity at 6295 - with the help of a saturated solution of ammonium nitrate. Contact of the mixture with water vapor at this temperature was ensured for 13 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 10090 it was hydrothermally treated for 56 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 3502 for 7.5 hours until the template was completely removed. Ge

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 5095 mass, and had a porous structure with an average pore diameter of 6b. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.62 in the presence of a palladium or platinum catalyst of the dark stage of the reaction. -

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide would require 0.02 moles of an organic template - a complex of the oxaamacrocyclic compound tetramethyl-12-crown-4 with a lithium ion. -

Example 8 Ge

A complex was used as an organic template for the synthesis of mesoporous titanium dioxide

From the oxaamacrocyclic compound tetramethyl-12-crown-4 with a potassium ion of the general formula |К(С42Н»404))13-2Н.О, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)уTi, as a water-alcohol solvent - n-butanol containing water in the amount of 69% by weight. 171 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 1.375 g of the template was dissolved in it. 45 ml of the same "solvent" was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 20 20. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 202C using a thermostat, and the relative humidity at 6595 using a saturated solution of -1,395 sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 16 days until the final formation of the titanium dioxide/organic template spatial structure mixture. (o) The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 10090 it was hydrothermally treated for 57 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until almost complete removal of the solvent from it. The dried mixture was stored in a glass container as an intermediate product for preparation

I" of mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 4502 for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 5695 mass, had a porous structure with an average pore diameter of 8.5 nm and a specific surface area of 94 m g. As a catalyst

Ф) of the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided the quantum yield of the reaction Фн»-0.71 in the presence of a palladium or platinum catalyst of the dark stage of the reaction. 60 In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of an organic template - a complex of the oxaamacrocyclic compound tetramethyl-12-crown-4 with a potassium ion.

Example 9

As an organic template for the synthesis of mesoporous titanium dioxide, complex 65 of the oxamacrocyclic compound tetramethyl-12-crown-4 with a potassium ion of the general formula |К(С.42Н24О04))1уУ-2Н20 was used, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)уТи , as a water-alcohol solvent - n-butanol, containing water in the amount of 69% by weight. 171 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 1.375 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 20 20. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 202C with the help of a thermostat, and the relative humidity at 6595 - with the help of a saturated solution of 70% sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 16 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 10090 it was hydrothermally treated for four days. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until almost 75% of the solvent was completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the crushed dry mixture was poured into a glass beaker. With intensive stirring, the required quantity of ethyl alcohol preheated to the boiling point, specified in example 1, was added to the beaker and, according to the method given in example 1, the organic template was removed from the structure by extraction. After de-templating the structure, the solid phase was separated from the suspension by filtration. it was dried until almost complete removal of the solvent, and then ground.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 3290 mass, had a porous structure with an average pore diameter of 5.8 nm and a specific surface area of 71 m g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, this mesoporous dioxide of titanium provided the quantum yield of the Фно-0О.52 reaction in the presence of a palladium or platinum catalyst in the dark stage of the reaction.

About 0.1 mol of the organic template - a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a potassium ion was required for one mol of titanium dioxide in the selected semi-product for obtaining mesoporous titanium dioxide. "

Example 10 Photo

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a potassium ion of the general formula |К(С.42Н24О04))1уУ-2Н20 was used, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)уТи , as a water-alcohol solvent - n-butanol, which contains water in the amount of 69% by weight. 171 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 1.375 g of the template was dissolved in it. 45 ml of the same amount was poured into another glass beaker. solvent At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol mixture was formed. The temperature of the mixture throughout this stage of the synthesis was maintained at about 20 20. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 202C with the help of a thermostat, and the relative humidity at 6595 - with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 16 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 4502 for 5.5 hours until the organic template was completely removed. and The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 5390 (Ce) 20 wt. had a porous structure with an average pore diameter of Osr-/,Znm and a specific surface area of Zud91Mm. Yak

HT" catalyst of the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction of Фн"-0.67 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide 59 contained about 0.11 moles of the organic template complex of the oxamacrocyclic compound

HF) tetramethyl-12-crown-4 with potassium ion.

GF Example 11

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a sodium ion of the general formula (Ma(С412Н245404)|СИ-ЗН2О) was used, 60 as a precursor - titanium tetrabutoxide of the general formula (С.НеО)АТи, as water-alcohol solvent - n-butanol, containing water in the amount of 6.595 wt. 175 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 2.195 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. at room temperature, 25 g of the precursor was dissolved in it. The precursor solution was introduced dropwise into the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 3 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis, about 1520 was maintained. After ash formation, mixing of the mixture was stopped. A beaker with a mixture of were placed in a chamber, the temperature in which was maintained at about 152C with the help of a thermostat, and the relative humidity at 7695 - with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was ensured for 19 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 48 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until almost 70% of the solvent was completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 6490 75 wt. had a porous structure with an average pore diameter of 12.5 nm and a specific surface area of 115 m2/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.73 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.1 mole of the organic template - a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with sodium ion - was required for one mole of titanium dioxide.

Example 12

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a rubidium ion of the general formula IKB(С42Н24О,)|Вг-ЗНоОЙ, с 29 was used as a precursor - titanium tetrapropoxide of the general formula (С зНО)4Ti , as a water-alcohol solvent - d) n-propanol containing water in the amount of 5,590 wt. 145 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.612 g of the template was dissolved in it. 40 ml of the same solvent was poured into another glass beaker. At room temperature, 21 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 302. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, in which the temperature was maintained at about 30 2C with the help of a thermostat, and the relative humidity was 6095 with the help of a saturated ammonium nitrate solution. Contact of the mixture with water vapor at this temperature was maintained for 14 days until the final formation from a mixture of spatial structure titanium dioxide/organic template.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 15090 it was hydrothermally treated for 54 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was practically completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 50°C for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 6190 mass,

It had a porous structure with an average pore diameter of 12.1 nm and a specific surface area of 110 m2/g. As a catalyst -1 of the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фно-0.69 in the presence of a palladium or platinum catalyst of dark

Me, reaction stages. -I In the selected semi-product for obtaining mesoporous titanium dioxide, 0.02 mol of organic template - a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with rubidium ion - was required for one mole of titanium dioxide.

Their" Example 13

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a cesium ion of the general formula |Св(С42Н2404)|Моз.ЗН2О was used, and as a precursor - titanium tetrapropoxide of the general formula (С зН7О)АТи, as in water - alcohol solvent - n-propanol, containing water in the amount of 4,590 wt. 133 bml of this was poured into one glass beaker

F) water-alcohol solvent. At room temperature, 0.656 g of the template was dissolved in it. 40 ml of the same solvent was poured into another glass beaker. At room temperature, 21 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture was maintained at about 252C throughout this stage of the synthesis. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 252 with the help of a thermostat, and the relative humidity at 7595 - with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was provided 65 for 17 days until the final formation from the mixture of spatial structure of titanium dioxide/organic template.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 10090 it was hydrothermally treated for 58 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 55023 for 5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 4590 wt. had a porous structure with an average pore diameter of 11.3 nm and a specific surface area of 87 Mm7/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction of Фно-0.56 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.02 moles of an organic template - a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with 75 cesium ions.

Example 14

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a magnesium ion of the general formula was used

IMa(С412Н2404)|50,.4Н2О, as a precursor - titanium tetrabutoxide of the general formula (С /НеО)АТи, as a water-alcohol solvent - n-butanol, containing water in the amount of 6.595 wt. 180 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.570 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 3.5 hours until a sol was formed from the mixture. The temperature of the mixture during this entire stage of the synthesis was maintained at about 142 °C. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 14 2C with the help of a thermostat, and the relative humidity at 6995 - with the help of a saturated solution of ammonium nitrate. Contact of the mixture with water vapor at this temperature was ensured for 20 days until the final formation of the spatial structure mixture of titanium dioxide/organic tempat. Fo

The formed structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for the preparation of mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at

From a temperature of 4502C for 5.5 hours until the organic template is completely removed. uh-

The mesoporous titanium dioxide contained in this way contained the crystalline phase of anatase in the amount of 5595 mass, had a porous structure with an average pore diameter of Osr-9.inm and a specific surface area of Zud-77m/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction of Фн»о-0.70 in the presence of a palladium or platinum catalyst of the dark 7th stage of the reaction. c In the selected semi-product for obtaining mesoporous titanium dioxide, 0.02 moles of the organic template - a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a magnesium ion - were present per one mole of titanium dioxide.

Example 15 -I 395 As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a calcium ion of the general formula (o) ICa(С12Н2404)|СИ»-3НО was used, as an oprecursor - titanium tetrabutoxide of the general formula ( С No) Those, such as - water-alcohol solvent - n-butanol, containing water in the amount of 5.595 wt. 16 bml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.530 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g was dissolved in it

T" precursor. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 302. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained with the help of a thermostat at about 302C, and the relative temperature (F, humidity 8096 - with the help of a saturated solution of ammonium sulfate. Contact of the mixture with water vapor at this temperature was ensured for 12 days until the final formation of mixtures of spatial structure titanium dioxide/organic template. The formed structure together with the mother liquor was placed in an autoclave, where it was hydrothermally treated at a temperature of 17090 for 49 hours. After that, the structure together with the mother liquor was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in the air until the solvent is almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate b5 portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it calcined at a temperature of 500 2 for 4.5 hours until the template is completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 5290 mass, had a porous structure with an average pore diameter of 9.3 nm and a specific surface area of 77 m/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фно-0.61 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for the production of mesoporous titanium dioxide, 0.02 moles of the organic template - a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a calcium ion - was required for one mole of titanium dioxide. 70 Example 16

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a strontium ion of the general formula was used

ИЗ(С412Н2404)|СИ»ЗН2О, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)уTi, as a water-alcohol solvent - n-butanol, containing water in the amount of 796 wt. 181 ml of this 75 water-alcohol solvent was poured into one glass beaker. At room temperature, 0.601 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture was maintained at about 302C throughout this stage of the synthesis. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 302 with the help of a thermostat, and the relative humidity at 6395 - with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 1009C it was treated hydrothermally for 55 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002C for 4.5 hours until the template was completely removed. Gee!

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 5290 mass, had a porous structure with an average pore diameter of 9.7 nm and a specific surface area of 94 m g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, mesoporous titanium dioxide (Ce) provided a quantum yield of the reaction Фно-0.68 in the presence of a palladium or platinum catalyst of dark

From the reaction stage. -

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.02 moles of an organic template - a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a strontium ion. "

Example 17 7 70 As an organic template for the synthesis of mesoporous titanium dioxide, the complex c of the oxamacrocyclic compound tetramethyl-12-crown-4 with a barium ion of the general formula (Ba(С42Н2404)|СИ»ЗНоО, :з» was used as a precursor - titanium tetrabutoxide of the general formula (С.НеО)АТи, as a water-alcohol solvent - n-butanol, containing water in the amount of 790 wt. 174 ml of this water-alcohol solvent was poured into one glass beaker.

At room temperature, 0.338 g of the template was dissolved in it. 45 ml of the same - 15 solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was (22) introduced into the template solution, the resulting mixture was continued to be stirred for 1.5 hours until a sol mixture was formed. The temperature of the mixture throughout this stage of the synthesis was maintained at about 35 20. After 5 years of ash formation, the mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 352C with the help of a thermostat, and the relative humidity at 6295 with the help of a saturated solution

Their" sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 12 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 10090 it was hydrothermally treated for 54 hours. After that, the structure together with the mother liquor was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until practically

F) complete removal of the solvent from it. The dried mixture was stored in a glass container as an intermediate product for the preparation of mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 3590 mass, had a porous structure with an average pore diameter of 10.8 nm and a specific surface area of 89 m/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction of Фно-0.59 in the presence of a palladium or platinum catalyst of the dark 65 stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.01 mole of an organic template - a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a barium ion.

Example 18

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a lanthanum ion of the general formula was used

And a(С412Н2404)|СИ5.ЗНоС, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)АТи, as a water-alcohol solvent - n-butanol, containing water in the amount of 695 wt. 184 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.708 g of the template was dissolved in it. 45 ml of the same solvent was poured into another 70 glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture was maintained at about 252C throughout this stage of the synthesis. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 252 with the help of a thermostat, and the relative humidity at 7595 - with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 10090 it was hydrothermally treated for 53 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 5 hours until the template was completely removed. p 25 The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 5190 mass, g) had a porous structure with an average pore diameter of 12.8 nm and a specific surface area of 119 m g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction of Фн»-0.62 in the presence of a palladium or platinum catalyst of the dark stage of the reaction. in 30 In the selected semi-product for obtaining mesoporous titanium dioxide per one mole of titanium dioxide, He»! there was 0.02 mol of an organic template - a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a lanthanum ion. -

Example 19 Ge)

As an organic template for the synthesis of mesoporous titanium dioxide, complex 35 of the oxamacrocyclic compound tetramethyl-12-crown-4 with a cerium ion of the general formula (Се(С42Н24О4)|СИ-ЗНоО), - as a precursor - titanium tetrabutoxide of the general formula (С.НеО)АТи, as a water-alcohol solvent - n-butanol, which contains water in the amount of 5.595 mass. Into one glass beaker was poured 1.3 ml of this water-alcohol solvent. At room temperature, 0.355 g of the template was dissolved in it. In another glass beaker was poured "45 ml of the same solvent . At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was introduced dropwise into the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours "from to formation from a mixture of sol The temperature of the mixture was maintained at about 20 20 throughout this stage of the synthesis.

After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 202C with the help of a thermostat, and the relative humidity at 7695 - with the help of a saturated -1% solution of sodium chloride. Contact of the mixture with water vapor at this temperature was ensured for 15 days until the final formation of the titanium dioxide/organic template spatial structure mixture. (22) The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 -1 it was hydrothermally treated for 49 hours. After that, the structure together with the mother liquor was removed from Zvtoklav. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for preparation

T» of mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of -5002C for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 6190 wt. had a porous structure with an average pore diameter of 13.3 nm and a specific surface area of 117 m2/g. As a photochemical reaction catalyst for the release of hydrogen from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фно-0.65 in the presence of a palladium or platinum catalyst of the dark stage of the reaction. In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.01 mole of an organic template - a complex of the oxamacrocyclic compound tetramethyl-12-crown-4 with a cerium ion.

Example 20

As an organic template for the synthesis of mesoporous titanium dioxide, complex b5 of the oxamacrocyclic compound dibenzo-18-crown-6 with a lithium ion of the general formula (C(С20Н2Ов6)|СИ-2СоННОН, as a precursor - titanium tetrapropoxide of the general formula (СзН7О)) was used as a precursor. - alcohol solvent - n-amyl alcohol containing water in the amount of 4.596 wt. 210 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 3.609 g of the template was dissolved in it. 5 ml of the same solvent was poured into another glass beaker. At room temperature, 21 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 2520. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 252C with the help of a thermostat, and the relative humidity at 8095 - with the help of a saturated solution of 70% ammonium sulfate. Contact of the mixture with water vapor at this temperature was ensured for 16 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 46 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until almost 75% of the solvent was completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 3502 for 6.5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 4595 wt., had a porous structure with an average pore diameter of 10.9 nm and a specific surface area of 139 m2/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.52 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.1 mole of the organic template - a complex of the oxamacrocyclic compound dibenzo-18-crown-b with a lithium ion - was required for one mole of titanium dioxide.

Example 21

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-18-crown-b with a sodium ion of the general formula (Ma(СооНо«Ов6)|СИ-ЗНоО) was used, as a "precursor - titanium tetrabutoxide of the general formula (С.НеО)4Ti , as a water-alcohol solvent - n-butanol, which contains water in the amount of 795 wt. 17 Oml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 3.451 g of the template was dissolved in it, then 0.115 g of lanthanum chloride. another glass beaker was filled with 45 ml of the same solvent. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the He template and lanthanum salt solution with intensive stirring. After

The entire portion of this solution was introduced into a solution of the template and lanthanum salts, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 252. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 25 2C with the help of a thermostat, and the relative humidity at 6595 - with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this Т0 temperature was ensured for 14 days until the final formation of the mixture of the spatial structure of titanium dioxide/organic template. "z The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 48 hours. After that, the structure together with the mother liquor was removed from the autoclave. The structure was separated from the mother liquor by filtration and air-dried to almost -1 395 full removing the solvent from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, the appropriate

Ge) a portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at -1 temperature of 500s for 5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 9095 mass, so it had a porous structure with an average pore diameter of 13.8 nm and a specific surface area of 130 m g. In addition, it

Their" additionally contained lanthanum in an amount of about 0.011 g per one gram of substance. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such a mesoporous titanium dioxide provided the maximum possible quantum yield of the Fn»-1.0 reaction in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide (F) contained 0.1 mole of the organic template - a complex of the oxamacrocyclic compound dibenzo-18-crown-b with sodium ion and about 0.006 mole of lanthanum chloride.

Example 22 in As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-18-crown-b with a potassium ion of the general formula (К(С2оНогОв6)19У-2Н20) was used, as a precursor - titanium tetrapropoxide of the general formula (СзНО)уТи, as a water-alcohol solvent - methanol containing water in the amount of 6.595 wt. 100 ml of this water-alcohol solvent was poured into one glass beaker.

At room temperature, 8.205 g of template was dissolved in it, then 0.798 mg of lanthanum chloride. In another 65 glass beaker, 1 ml of the same solvent was poured. At room temperature, 21 g of the precursor was dissolved in it. A solution of precursor and lanthanum salt was added dropwise to the template solution with intensive stirring. After the entire portion of this solution was introduced into the template solution, the resulting mixture was continued to be stirred for 3 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 152. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 1529 with the help of a thermostat, and the relative humidity at 6990 - with the help of a saturated solution of ammonium nitrate. Contact of the mixture with water vapor at this temperature was ensured for 16 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 50 hours. After that, the structure together with the mother solution was removed from the 70 autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 4502 for 5.5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7190 wt., had a porous structure with an average pore diameter of 11.3 nm and a specific surface area of 119 m2/g. In addition, it additionally contained lanthanum in an amount of about 0.018 g per one gram of substance. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided the quantum yield of the Фно-0О.87 reaction in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.2 moles of an organic template - a complex of the oxamacrocyclic compound dibenzo-18-crown-b with a potassium ion and about 0.038 g of lanthanum chloride per one gram of titanium dioxide.

Example 23

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-18-crown-b6 with a rubidium ion of the general formula (КБ(СооН2Ов)ИВг.ЗНоО, as a precursor - titanium tetrabutoxide of the general formula (0,НеО))Ti, was used as an organic template for the synthesis of mesoporous titanium dioxide. as a water-alcohol solvent - n-butanol, containing water in the amount of 69% by weight. 180 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 8.467 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was introduced dropwise into the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 25 20. After the formation of the isole, the mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 252C with the help of a thermostat, and the relative humidity at 7595 - with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was ensured for 15 days until the final formation of the spatial structure mixture of titanium dioxide/organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 49 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 5 hours until the template was completely removed. 15 The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7590 -1 by mass, had a porous structure with an average pore diameter of 12.00 nm and a specific surface area of 121 m g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures such mesoporous titanium dioxide

Me, provided a quantum yield of the reaction of Фн»-0.85 in the presence of a palladium or platinum catalyst of the dark -1 stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.2 moles of the organic template - a complex of the oxamacrocyclic compound dibenzo-18-crown-b with

Their" rubidium ion.

Example 24

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-18-crown-b with a cesium ion of the general formula |Св(СгоНоггОв6)|МОз.2НО was used, as a precursor - titanium tetraethoxide of the general formula (СоНьО)уТи, as a water-alcohol the solvent is ethanol, which (F) contains water in the amount of 595 wt. 120 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 4.317 g of the template was dissolved in it. 32 ml of the same solvent was poured into another glass beaker. temperature, 18 g of the precursor was dissolved in it. The precursor solution was introduced dropwise into the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 4 hours until a sol was formed from the mixture. The temperature of the mixture at throughout this stage of the synthesis, about 10 20 was maintained. After ash formation, mixing of the mixture was stopped. The beaker with the mixture was placed and into the chamber, the temperature of which was maintained at about 102C with the help of a thermostat, and the relative humidity at 7395 - with the help of a saturated solution of 65% ammonium nitrate. Contact of the mixture with water vapor at this temperature was ensured for 19 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 10090 it was hydrothermally treated for 53 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 55023 for 5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7290 mass, 70 had a porous structure with an average pore diameter of 9.2 nm and a specific surface area of 90 m7/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.82 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide 75 contained 0.1 mole of an organic template - a complex of the oxamacrocyclic compound dibenzo-18-crown-b with a cesium ion.

Example 25

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-18-crown-b6 with a magnesium ion of the general formula |IMa(С2оНогОв)|504-4Н20 was used, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)уTi, as a water - alcohol solvent - n-butanol, containing water in the amount of 6.595 wt. 177/ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 4.040 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture was maintained at about 25 26 throughout this stage of synthesis.

After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 252C with the help of a thermostat, and the relative humidity at 7595 - with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was ensured for 16 days until the final formation of the spatial structure mixture of titanium dioxide/organic template. Gee!

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 20090 it was hydrothermally treated for 51 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until almost complete removal of the solvent from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a suitable portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7790 mass, it had a porous structure with an average pore diameter of 12.9 nm and a specific surface area of 115 M g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol of mixtures, such mesoporous titanium dioxide c provided a quantum yield of the reaction of Фно-0.80 in the presence of a palladium or platinum catalyst of the dark "c" stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of the organic template - a complex of the oxamacrocyclic compound dibenzo-18-crown-b with -35 magnesium ions.

Example 26 (22) As an organic template for the synthesis of mesoporous titanium dioxide, a complex was used - the oxamacrocyclic compound dibenzo-18-crown-6 with a calcium ion of the general formula (Са(СооН24Ов)|СИ»ЗН.О), as a precursor - titanium tetrabutoxide of the general formula of the formula (САНеО)4Ti, as a water-alcohol solvent - n-butanol, which is), contains water in the amount of 795 wt. 183 ml of this water-alcohol solvent was poured into one glass beaker. At

3.834 g of template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was

The template was introduced into the solution, the resulting mixture was continued to be stirred for 2 hours until the formation of a sol from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 30 2. After (F) sol formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 302С with the help of a thermostat, and the relative humidity at 8095 - with the help of a saturated solution of ammonium sulfate. Contact of the mixture with water vapor at this temperature was ensured for 13 days until the final formation from the mixture of spatial structure titanium dioxide/organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 49 hours. After that, the structure together with the mother liquor was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining 65 mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide of titanium dioxide, the corresponding portion of the dry mixture was poured into a crucible.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 5890 wt. had a porous structure with an average pore diameter of 10.6 nm and a specific surface area of 157 mm/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.63 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of the organic template - a complex of the oxamacrocyclic compound dibenzo-18-crown-b with 70 calcium ions.

Example 27

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-18-crown-b6 with a strontium ion of the general formula |Zg(С2оН24Ов)|СИ».ЗНоО was used as a precursor - titanium tetrabutoxide of the general formula (САнес)АТти, as a water- alcohol solvent - n-butanol, 75 containing water in the amount of 59% by weight. 172 ml of this water-alcohol solvent was poured into one glass beaker.

At room temperature, 0.859 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol mixture was formed. The temperature of the mixture throughout this stage of the synthesis was maintained at about 30 2. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained with the help of a thermostat at about 302С, and the relative humidity at 7595 - with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the titanium dioxide/organic template spatial structure mixture. c 25 The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 17590 o it was hydrothermally treated for 47 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. In order to obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at Ge! at a temperature of 4002 for 5.5 hours until the template is completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 6290 by mass. had a porous structure with an average pore diameter of 12.2 nm and a specific surface area of 127 m2/g. such mesoporous titanium dioxide as a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures

Zo provided the quantum yield of the Fn»o-0.70 reaction in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.02 mol of organic template - a complex of the oxamacrocyclic compound dibenzo-18-crown-b with strontium ion was required for one mol of titanium dioxide.

Example 28 not with As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-18-crown-b6 with a barium ion of the general formula |Ba(СооН24Ов)|СИ».ЗН.О was used as a precursor - titanium tetrabutoxide of the general formula ( C.NeO)uTi, as a water-alcohol solvent - n-butanol, containing water in the amount of 5.595 wt. 1b2ml of this water-alcohol solvent was poured into one glass beaker. - At room temperature, 0.934 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was introduced dropwise into the template solution with intensive (22) stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 3 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 20 20. After 20 seconds of ash formation, the mixing of the mixture was stopped. The glass with the mixture was placed in a chamber with a temperature of

T" was maintained at about 302C with the help of a thermostat, and the relative humidity was maintained at 7595 with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was ensured for 17 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 46 hours. After that, the structure together with the mother liquor was removed from

F) autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was practically completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a suitable portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7390 wt., had a porous structure with an average pore diameter of 14.3 nm and a specific surface area of 107 m/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide 65 provided a quantum yield of Фно-0.75 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.02 moles of an organic template - a complex of the oxamacrocyclic compound dibenzo-18-crown-b with a barium ion.

Example 29

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-18-crown-6 with a lanthanum ion of the general formula | a(С2оН2Ов)|СИз-3Н2О, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)уTi, as a water-alcohol solvent - n-butanol, containing water in the amount of 4.595 wt. 175 ml of this water-alcohol solvent was poured into one glass beaker. 7/0 At room temperature, 4.703 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 3.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 17 20. After 75 sol formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 172C with the help of a thermostat, and the relative humidity at 6595 - with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 20 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 48 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 4702 °C for 5 hours until the template was completely removed. (5)

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 6190 wt. had a porous structure with an average pore diameter of 13/nm and a specific surface area of 125 m2/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction of Фн»о-0.79 in the presence of a palladium or platinum catalyst in the dark stage of the reaction. Fo

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of the organic template - a complex of the oxamacrocyclic compound dibenzo-18-crown-b with the lanthanum ion. Ge

Example 30 3o As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-18-crown-6 with a cerium ion of the general formula |Се(С2оНа2лов)|СИ3-3Н.Ю was used, as a precursor - titanium tetrabutoxide of the general formula (S. NiO)ATi, as a water-alcohol solvent - n-butanol, containing water in the amount of 695 wt. 185 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 2.35 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 3 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 202. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 209C with the help of a thermostat, and their relative humidity at 7695 - with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this (o) temperature was ensured for 17 days until the final formation of the spatial structure mixture of titanium dioxide -1/organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 (se) 50 of it was hydrothermally treated for 46 hours. After that, the structure together with the mother liquor was removed from

I" autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 4.5 hours until the template was completely removed. (F) The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7090 ka by mass. had a porous structure with an average pore diameter of Osr-14.0 nm and a specific surface area of Zud-122 m g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Fn»-0.74 in the presence of palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.05 mol of the organic template - a complex of the oxamacrocyclic compound dibenzo-18-crown-b with a cerium ion - was required for one mole of titanium dioxide. 65 Example 31

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-30-crown-10 with a lithium ion of the general formula (C(СовНаоОч0)ИВг-ЗНоО) was used, as a precursor - titanium tetrabutoxide of the general formula (САНед)АТти, as a water-alcohol solvent - n-butanol containing water in the amount of 795 wt. 193 ml of this water-alcohol solvent was poured into one glass beaker.

4.941 g of template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 30 C. After 70 minutes of sol formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained with the help of a thermostat at about 302С, and the relative humidity at 7595 - with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 10090 it was hydrothermally treated for 56 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 3502 for 5.5 hours until the template was completely removed.

The mesoporous titanium dioxide contained in this way contained the crystalline phase of anatase in the amount of 4095 mass, had a porous structure with an average pore diameter of 10.8 nm and a specific surface area of 118 m2g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction of Фно-0.50 in the presence of a palladium or platinum catalyst of the dark stage of the reaction. at

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of an organic template - a complex of the oxamacrocyclic compound dibenzo-30-crown-10 with a lithium ion.

Example 32 « 30 As an organic template for the synthesis of mesoporous titanium dioxide, complex b of the oxamacrocyclic compound dibenzo-30-crown-10 with a potassium ion of the general formula |(К(СовНа0О10)19У-2Н20) was used, as a precursor - titanium tetrabutoxide of the general formula (С.НеО )uTi, as a water-alcohol solvent - n-butanol, which contains water in the amount of 5.795 wt. 175 ml of this water-alcohol solvent was poured into one glass beaker. Ge)

At room temperature, 5.392 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was introduced dropwise into the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 30 2. After sol formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 302C with the help of a thermostat, and the relative humidity at 8095 - with the help of a saturated solution of ammonium sulfate. Contact of the mixture with water vapor at this temperature was provided for 13 days until final formation from the mixture of spatial structure titanium dioxide/organic template.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 18090 it was hydrothermally treated for 52 hours. After that, the structure together with the mother solution was removed from -1 autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining (e)) mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, the corresponding -1 portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 5 hours until the template was completely removed. is), the mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 5290 wt. mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction of Фно-0.65 in the presence of a palladium or platinum catalyst in the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide per one mole of titanium dioxide

F) accounted for 0.1 mol of the organic template - a complex of the oxamacrocyclic compound dibenzo-30-crown-10 with a potassium cation.

Example 33 60 As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-30-crown-10 with a sodium ion of the general formula (Ma(SovNaoOcho)1СИ.2Н.О0) was used, as a precursor - titanium tetrabutoxide of the general formula (С.НеО )ATi, as a water-alcohol solvent - n-butanol, containing water in the amount of 5.796 mass. 1b8ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 4.606g of the template was dissolved in it. 45ml 65 was poured into another glass beaker of the same solvent. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was introduced dropwise into the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until formation from the mixture ash. The temperature of the mixture throughout this stage of the synthesis was maintained at about 2520. After ash formation, mixing of the mixture was stopped. A glass of the mixture was placed in a chamber, the temperature in which was maintained at about 252C with the help of a thermostat, and the relative humidity at 8095 - with the help of a saturated solution of ammonium sulfate. Contact of the mixture with water vapor at this temperature was ensured for 16 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 10090 it was hydrothermally treated for 57 hours. After that, the structure together with the mother solution was removed from the 70 autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 4002 for 6 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7090 wt. had a porous structure with an average pore diameter of 10.6 nm and a specific surface area of 112 m2/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фно-0.71 in the presence of a palladium or platinum catalyst of the reaction stage.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of an organic template - a complex of the oxamacrocyclic compound dibenzo-30-crown-10 with a sodium ion.

Example 34

As an organic template for the synthesis of mesoporous titanium dioxide, complex c 259 of the oxamacrocyclic compound dibenzo-30-crown-10 with a rubidium ion of the general formula (КБ(СовНаоОч10)Вг-ЗН.О) was used, and as a precursor - titanium tetrabutoxide of the general formula (С.НеО) ATi, as a water-alcohol solvent - n-butanol, containing water in the amount of 69% by mass. 14 bml of this water-alcohol solvent was poured into one glass beaker.

At room temperature, 1.134 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was introduced dropwise into the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to stir for 4 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 15 20. After the formation of the isole, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 152C with the help of a thermostat, and the relative humidity at 6995 - with the help of a saturated solution of ammonium nitrate. Contact of the mixture with water vapor at this temperature was ensured for 19 days until the final formation of the titanium dioxide/organic template spatial structure from the mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 17090 it was hydrothermally treated for 56 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 3502 for 6.5 hours until the template was completely removed. 15 The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 6690 -1 by mass, had a porous structure with an average pore diameter of 11.4 nm and a specific surface area of 142 m g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures such mesoporous titanium dioxide

Me, provided a quantum yield of the Fn»o-0.70 reaction in the presence of a palladium or platinum catalyst of the dark -1 stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.02 mol of the organic template - a complex of the oxamacrocyclic compound dibenzo-30-crown-10 with

Their" rubidium ion.

Example 35

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-24-crown-8 with a cesium ion of the general formula |Св(Со4НазгОв)|МО»з.4Н2О was used, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)у/ Those, as a water-alcohol solvent - n-hexyl (F, an alcohol containing water in the amount of 6.596 wt. 24 bml of this water-alcohol solvent were poured into one glass beaker. At room temperature, 1.073 g of the template was dissolved in it. In another glass beaker 74 ml of the same solvent was poured into a glass. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 4 hours until the formation of a sol from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 2520. After the formation of a sol, the mixing of the mixture was stopped. the mixture was placed in a chamber, the temperature of which was maintained at about 252C with the help of a thermostat, and the relative humidity at 7595 - with the help of a saturated solution of 65% sodium chloride. Contact of the mixture with water vapor at this temperature was ensured for 15 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 15090 it was hydrothermally treated for 58 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7290 70 wt. had a porous structure with an average pore diameter of 12.7 nm and a specific surface area of 90 m7/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.78 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide 75 contained 0.02 moles of an organic template - a complex of the oxamacrocyclic compound dibenzo-24-crown-8 with a cesium ion.

Example 36

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-30-crown-10 with a magnesium ion of the general formula IMa(СовНаоО10)1304-4Н20 was used, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)уTi, as a water-alcohol solvent - n-butanol, containing water in the amount of 5.595 wt. 17/bml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 1.092 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture during this entire stage of synthesis was maintained at about 352C. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 352C with the help of a thermostat, and the relative humidity at 8095 - with the help of a saturated solution of ammonium sulfate. Contact of the mixture with water vapor at this temperature was ensured for 12 days until the final formation of the spatial structure mixture of titanium dioxide/organic template. Gee!

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 57 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until almost complete removal of the solvent from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a suitable portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of -5002C for 5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 6595 mass, it had a porous structure with an average pore diameter of 15.7 nm and a specific surface area of 129 M g. As a catalyst for the photochemical reaction of hydrogen release from aqueous-alcohol of mixtures, such mesoporous titanium dioxide c provided a quantum yield of the reaction of Фн»-0.67 in the presence of a palladium or platinum catalyst of the dark :c» stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.02 moles of the organic template - a complex of the oxamacrocyclic compound dibenzo-30-crown-10 with -35 magnesium ions.

Example 37 (22) As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-30-crown-10 with a calcium ion of the general formula |Са(СовНаоО 10))СИ»С3Н2О, 5р was used as a precursor - titanium tetrabutoxide of the general formula (S.NZO),) Those, as a water-alcohol solvent - n-butanol, is), containing water in the amount of 790 wt. 198 ml of this water-alcohol solvent was poured into one glass beaker.

T» At room temperature, 5.120 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was

The template was introduced into the solution, the resulting mixture was continued to be stirred for 2 hours until the formation of a sol from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 30 2. After (F) sol formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 302C with the help of a thermostat, and the relative humidity at 6395 - with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 14 days before the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 58 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining b5 mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 5295 wt. had a porous structure with an average pore diameter of 15.0 nm and a specific surface area of 120 m/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.61 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of the organic template - a complex of the oxamacrocyclic compound dibenzo-30-crown-10 with 70 calcium ions.

Example 38

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-24-crown-8 with a strontium ion of the general formula |5g((С24НазгОв)|СИ».2Н2О was used, as a precursor - titanium tetraethoxide of the general formula (СоНеО)АТти, as water-alcohol solvent - ethanol, which contains water in the amount of 695 wt. 124 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 4.693 g of the template was dissolved in it. 32 ml of the same solvent was poured into another glass beaker. At room temperature temperature, 18 g of the precursor was dissolved in it. The precursor solution was introduced dropwise into the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for three hours until a sol was formed from the mixture. The temperature of the mixture throughout at this stage of the synthesis, the temperature was maintained at about 202 C. After ash formation, mixing of the mixture was stopped. The beaker with the mixture was placed into the chamber, the temperature in which was maintained at about 2 2C with the help of a thermostat, and the relative humidity at 7596 - with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was ensured for 17 days until the final formation of the spatial structure of the dioxide from the mixture. CM of titanium/organic template. at

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 10090 it was hydrothermally treated for 56 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, the corresponding F portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed. -

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 5096% by mass. had a porous structure with an average pore diameter of Osr-12.0 nm and a specific surface area of Zud-T7MmOt. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.62 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.1 mole of the organic template - a complex of the oxamacrocyclic compound dibenzo-24-crown-8 with a strontium ion was required for one mole of titanium dioxide. с Example 39:z» As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-30-crown-10 with a barium ion of the general formula IVa(СовНаоО40)|СИ»-ЗНоО was used, as a precursor - titanium tetrapropoxide of the general formula (СзН7О) / Those, as a water-alcohol solvent - - n-heptyl alcohol containing water in the amount of 790 wt. 270 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 2.915 g of the template was dissolved in it. 75 ml of the same solvent was poured into another glass (o) beaker. At room temperature, 21 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution under intense stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture was maintained throughout this stage of the synthesis

T" is about 302. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 302 with the help of a thermostat, and the relative humidity at 7595 - with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was provided for 13 days until the final formation of the spatial structure mixture of titanium dioxide/organic template.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 15590 °F) it was hydrothermally treated for 56 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 5490 wt. had a porous structure with an average pore diameter of 11.7 nm and a specific surface area. Wood -89 mm/h. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction of Фно-0.59 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.05 mol of the organic template - a complex of the oxamacrocyclic compound dibenzo-30-crown-10 with / nom of barium was required for one mol of titanium dioxide.

Example 40

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-24-crown-8 with a lanthanum ion of the general formula was used. a(Co/NagOv)|SiIz-3H2O, as a precursor - titanium tetrabutoxide of the general formula (S.NeO)uTi, as a water-alcohol solvent - n-butanol, which 70 contains water in the amount of 69% by weight. 184 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 5.349 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a 7/5 sol mixture was formed. The temperature of the mixture throughout this stage of the synthesis was maintained at about 30 C. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained by a thermostat at about 302С, and the relative humidity at 6395 - by means of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 58 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at (5) temperature 5002 for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7090 wt. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide - provided a quantum yield of the reaction Фно-0.78 in the presence of a palladium or platinum catalyst of dark He! reaction stage.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.1 mole of the organic template - a complex of the oxamacrocyclic compound dibenzo-24-crown-8 with the He ion of lanthanum - was added to one mole of titanium dioxide.

From Example 41 in

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-24-crown-8 with a cerium ion of the general formula |Се(Со4НзгОв)|СИз-ЗНоО was used, as a precursor - titanium tetrabutoxide of the general formula "(САНеФ)4Ti, as a water- alcohol solvent - n-butanol, containing water in the amount of 595 wt. 192 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 5.35 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 202. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 202C with the help of a thermostat, and

Ge) relative humidity 6395 - with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this -1 temperature was ensured for 18 days until the final formation of the spatial structure mixture of titanium dioxide/organic template. (Ce) 50 The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 17590

GT" was treated hydrothermally for 57 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at

HF) at a temperature of 6002C for 4 hours until the template is completely removed.

GI The mesoporous titanium dioxide contained in this way contained the crystalline phase of anatase in the amount of 6595 wt. had a porous structure with an average pore diameter of 16.0 nm and a specific surface area of 123 m/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided the quantum yield of the Фn»-0.73 reaction in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of the organic template - a complex of the oxamacrocyclic compound dibenzo-24-crown-8 with 65 cerium ion.

Example 42

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-24-crown-8 with a cerium ion of the general formula |Се(Со4Наз2Ов)|СИз-ЗНоС was used, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)уTi, as a water - alcohol solvent - n-butanol, which

Contains water in the amount of 59% by mass. 192 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 5.35 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to stir for 2 hours until a 7/0 sol mixture was formed. The temperature of the mixture throughout this stage of the synthesis was maintained at about 20 20. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 202C with the help of a thermostat, and the relative humidity at 6395 - with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 18 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the organic template was completely removed.

The mesoporous titanium dioxide contained in this way contained the crystalline phase of anatase in the amount of 6195 wt. had a porous structure with an average pore diameter of 14.50 nm and a specific surface area of 102 m2/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.63 in the presence of a palladium or platinum catalyst of the dark stage of the reaction. with

In the selected semi-product for the preparation of mesoporous titanium dioxide, 0.11 moles of the organic template - a complex of the oxamacrocyclic compound dibenzo-24-crown-8 with a cerium ion - were added to one mole of titanium dioxide.

Example 43

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxamacrocyclic compound dibenzo-24-crown-8 with a cerium ion of the general formula (Се(С24Наз2Ов)|СИз-ЗНоЙ) was used, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)уTi, as a water-alcohol solvent - n-butanol, containing water in the amount of 595 wt. 192 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 5.35 mg of the template was dissolved in it. 45 ml of this was poured into another glass beaker same He solvent. At room temperature, 25 g of the precursor was dissolved in it. Into the template solution under intensive

The precursor solution was added dropwise with stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 20 20. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 202C with the help of a thermostat, and the relative humidity at 6395 - with the help of a saturated solution of 30% sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 18 days until the final formation of the spatial structure mixture of titanium dioxide/organic template. "z The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 20090 it was hydrothermally treated for three days. After that, the structure together with the mother liquor was removed from the autoclave. The structure was separated from the mother liquor by filtration and air-dried to almost -1 395 full removing the solvent from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, the appropriate

Ge) a portion of the crushed dry mixture was poured into a glass beaker. With intensive stirring, the required amount of ethyl alcohol preheated to the boiling temperature, specified in example 1, was added to the beaker and, according to the method given in example 1, the organic template was removed from the structure by extraction. After (se) 50 de-templating of the structure, the solid phase was separated from the suspension by filtration. it was dried until almost

T» complete removal of the solvent, and then crushed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 3690 wt. had a porous structure with an average pore diameter of 11.5 nm and a specific surface area of 72 m t. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фn»-0.53 in the presence of palladium or platinum catalyst of the dark (F) stage of the reaction.

He In the selected semi-product for obtaining mesoporous titanium dioxide, 0.1 mole of the organic template - a complex of the oxamacrocyclic compound dibenzo-24-crown-8 with cerium bromine - was required for one mole of titanium dioxide.

Example 44

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a lithium ion of the general formula |Ч(С42НовО4М2)|СИ-ЗН2О was used, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)АТи, as a water-alcohol solvent - n-butanol, 65 iso contains water in the amount of 5.595 wt. 184 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 5.232 g of the template was dissolved in it. Poured into another glass

45 ml of the same solvent. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture was maintained at about 25,290 during this entire synthesis stage.

After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 252C with the help of a thermostat, and the relative humidity at 6295 - with the help of a saturated solution of ammonium nitrate. Contact of the mixture with water vapor at this temperature was ensured for 16 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 20090 it was hydrothermally treated for 53 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding 75 portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7690 wt. had a porous structure with an average pore diameter of 12.4 nm and a specific surface area of 100 m/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of Фно-0.73 reaction in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.2 moles of the organic template - a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a lithium ion - was required for one mole of titanium dioxide. with

Example 45 o

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a potassium ion of the general formula ИК(С42НовОдМ2)|уУ-2Н2О was used, as a precursor - titanium tetrabutoxide of the general formula (С.НеО)АТи, as water-alcohol solvent - n-butanol, containing water in the amount of 59% by weight. 194 ml of this water-alcohol solvent was poured into one glass beaker. -

At room temperature, 6.779 g of the template was dissolved in it. 45 ml of the same Ge was poured into another glass beaker! solvent At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 30 C. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which - with the help of a thermostat was maintained at about 302С, and the relative humidity at 6395 - with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 15 days until the final formation of the titanium dioxide/organic template spatial structure mixture. "

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 20090 it was hydrothermally treated with 70 for 50 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was practically completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at -1 395 at a temperature of 6002C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7490

Me, mass had a porous structure with an average pore diameter of 12.7 nm and a specific surface area of 105 m2/g. As a -1 catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide 20 provided a quantum yield of the reaction of Фн»о-0.76 in the presence of a palladium or platinum catalyst in the dark so stage of the reaction.

Their" In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.2 moles of an organic template - a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a potassium ion.

Example 46

As an organic template for the synthesis of mesoporous titanium dioxide, complex (F) of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a sodium ion of the general formula ka IMa(С412НовО4М2)|)СИ-3Н»О was used, as a precursor - titanium tetrabutoxide of the general formula ( C /NeO)ATi, as a water-alcohol solvent - n-butanol, containing water in the amount of 7956 wt. 204 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 5.209 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of synthesis 65 was maintained at about 302C. After the formation of a sol, the mixing of the mixture was stopped. The beaker with the mixture was placed in chamber, the temperature of which was maintained by a thermostat at about 30 2C, and the relative humidity was maintained at 8095 with the help of a saturated solution of ammonium sulfate. The contact of the mixture with water vapor at this temperature was ensured for 13 days until the final formation from the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 20090 it was hydrothermally treated for 52 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding 70 portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7890 wt., had a porous structure with an average pore diameter of Osr-13.inm and a specific surface area of Zud-109m/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide 75 provided the quantum yield of the reaction Фно-0О.71 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.2 moles of an organic template - a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a sodium ion.

Example 47

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a rubidium ion of the general formula was used

IKB(С12НовО4М2)|Вг.ЗНО, as a precursor - titanium tetraethoxide of the general formula (С 2Н5О)ATi, as a water-alcohol solvent - ethanol, containing water in the amount of 79% by weight. 120 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 3.518 g of the template was dissolved in it. ZOml of the same solvent was poured into another glass beaker. At room temperature, 18 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 3.5 hours until a sol was formed from the mixture. The temperature of the mixture during this entire stage of synthesis was maintained at about 102C. After ash formation, mixing of the mixture was stopped. The glass with the mixture would be placed in a chamber, the temperature in which was maintained by a thermostat at about 10 2С, and the relative humidity at 7395 - by means of a saturated solution of ammonium nitrate. Contact of the mixture with water vapor at this temperature was ensured for 18 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 10090 it was hydrothermally treated for 58 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining "mesoporous titanium dioxide." To obtain the required amount of mesoporous titanium dioxide, a portion of the dry mixture corresponding to C t0 was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed. The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 5090 wt. As a 415 catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide -1 provided a quantum yield of the reaction Фн»о-0.51 in the presence of a palladium or platinum catalyst of the dark stage of the reaction. b» In the selected semi-product for obtaining mesoporous titanium dioxide, 0.1 mole of the organic template - a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a rubidium element - was required for one mole of titanium dioxide -1. se) Example 48

T» As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a cesium ion of the general formula was used

ISv(С12НовО4М2))Моз3.3НО, as a precursor - titanium tetrabutoxide of the general formula (С /АНеоО)/Ti, as a water-alcohol solvent - n-butanol, containing water in the amount of 596 wt. 182 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 3.733 g of the template was dissolved in it. IN

F) another glass beaker was filled with 45 ml of the same solvent. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 3 hours until a sol was formed from the mixture.

The temperature of the mixture was maintained at about 159C throughout this stage of the synthesis. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 152C with the help of a thermostat, and the relative humidity at 7695 - with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was provided for 17 days until the final 65 formation from the mixture of spatial structure of titanium dioxide/organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 10090 it was hydrothermally treated for 55 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 5390 wt. had a porous structure with an average pore diameter of Orsr-/,nm and a specific surface area of Zud-71MmOt. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction of Фно-0.68 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of the organic template - a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with 75 cesium ions.

Example 49

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a magnesium ion of the general formula was used

IMa(С12НовО4М2)1504.3Н2О, as a precursor - titanium tetrabutoxide of the general formula (САНеО)АТти, as a water-alcohol solvent - n-butanol, containing water in the amount of 5,595 wt. 16 in 8 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 3.185 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture during this entire stage of the synthesis was maintained at about 252. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 25 2C with the help of a thermostat, and the relative humidity at 6595 - with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 15 days until the final formation of the spatial structure mixture of titanium dioxide/organic template. Fo

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 52 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until almost complete removal of the solvent from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a suitable portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 6190 "du by mass. It had a porous structure with an average pore diameter of Osr.-9.bnm and a specific surface area of Zud-92m. of alcohol mixtures, such a mesoporous titanium dioxide c provided a quantum yield of the Fn»o-0.70 reaction in the presence of a palladium or platinum catalyst of the dark :c» stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of the organic template - a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with -35 magnesium ions.

Example 50 (22) As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a calcium ion of the general formula was used

ИСа(С12НовО4М2)|СИ»-3НО, as an oprecursor - titanium tetrabutoxide of the general formula (С /НеО)Ti, as se) water-alcohol solvent - n-butanol, containing water in the amount of 4.595 wt. They poured into one glass

Their" 17Oml of this water-alcohol solvent. At room temperature, 3.118 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After two hours, after the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage (F) of the synthesis was maintained at about 252C. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 25 2C using a thermostat, and the relative humidity at 6595 - using a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 15 days until the final formation of the spatial structure mixture of titanium dioxide/organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 53 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was practically completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide contained in this way contained the crystalline phase of anatase in the amount of 6495 wt. had a porous structure with an average pore diameter of 10.2 nm and a specific surface area of 89 m/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.67 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide 70 contained 0.1 mole of an organic template - a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a calcium ion.

Example 51

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a calcium ion of the general formula 75 |Са(С12НовО4М2)|СИ»-3ЗНХО was used, as a precursor - titanium tetrabutoxide of the general formula (САНеО) ATti, as a water-alcohol solvent - n-butanol, containing water in the amount of 4.595 mass. 17Oml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 3.118 g of the template was dissolved in it. In another glass beaker was poured 45 ml of the same of the solvent. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was introduced dropwise into the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until formation from the mixture sol. The temperature of the mixture throughout this stage of the synthesis was maintained at about 252. After sol formation, mixing of the mixture was stopped. was placed in a chamber, the temperature of which was maintained at about 25 2C with the help of a thermostat, and the relative humidity of 6596 - with the help of a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this CM temperature was ensured for 15 days until the final formation of the spatial-structure mixture d) titanium dioxide/organic template.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 15090 it was hydrothermally treated for four days. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining F mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the crushed dry mixture was poured into a glass beaker. With intensive stirring, the required quantity of ethyl alcohol preheated to boiling point and He) was added to the glass according to the method given in example 71, and the organic template was removed from the structure by extraction. After de-templating the structure, the solid phase was separated from the suspension by filtration. it was dried until almost complete removal of the solvent, and then it was ground.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 3490 wt. had a porous structure with an average pore diameter of 13.2 nm and a specific surface area of 7 Zm/g. As a "catalyst of the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide 7 70 provided a quantum yield of the reaction of Фн"-0.57 in the presence of a palladium or platinum catalyst of the slow c stage of the reaction. "z In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of an organic template - a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a calcium ion. 35 Example 52 ev. As an organic template for the synthesis of mesoporous of titanium dioxide, a complex (e) of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a calcium ion of the general formula - ИСа(С12НовО4М2)|СИ»-3НО was used as an oprecursor - titanium tetrabutoxide of the general formula (С/НеО)АТи, as water-alcohol solvent - n-butanol, containing water in the amount of 4.595 wt. 17Oml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 3.118 g of the template was dissolved in it. IN

45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 2592. After ash formation, mixing of the mixture was stopped. The glass with the mixture (F) was placed in a chamber, the temperature in which was maintained at about 25 2C with the help of a thermostat, and the relative humidity at 6595 - with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 15 days until the final formation of the spatial structure mixture of titanium dioxide/organic template.

The formed structure was separated by filtration from the mother liquor and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at 65°C for 5 hours until the organic template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 6190 wt. had a porous structure with an average pore diameter of 11.4 nm and a specific surface area of 81 mm7/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.62 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for the preparation of mesoporous titanium dioxide, 0.11 moles of the organic template - a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a calcium ion was required for one mole of titanium dioxide.

Example 53

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a calcium ion of the general formula was used

ИСа(С412НовО4М2)|СИ»-3Н»О, as a precursor - titanium tetrabutoxide of the general formula (С 4НеО)АТти, as a water-alcohol solvent - n-butanol, containing water in the amount of 4.595 wt. 17Oml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 3.118 g of template was dissolved in it, then 75 0.105 g of lanthanum chloride. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the solution of the template and lanthanum salt with intensive stirring. After the entire portion of this solution was introduced into the solution of the template and the lanthanum salt, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture.

The temperature of the mixture was maintained at about 252C throughout this stage of the synthesis. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 2520 with the help of a thermostat, and the relative humidity at 6595 - with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 15 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure was separated by filtration from the mother liquor and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the organic template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 6095 mass - it had a porous structure with an average pore diameter of 12.2 nm and a specific surface area of 75 M/g. In addition, it F) additionally contained lanthanum in an amount of about 0.012 m per one m of substance. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield - reaction Фно-0.59 in the presence of a palladium or platinum catalyst of the dark stage of the reaction. Gee)

In the selected semi-product for obtaining mesoporous titanium dioxide per one mole of titanium dioxide

There were 0.11 moles of the organic template - a complex of the oxaazamacrocyclic compound 18-coronaase-2-oxa-4 - with a calcium ion and about 0.006 moles of lanthanum chloride.

Example 54

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with strontium ion 0, of the general formula - 70 IZ(С42НовО4М2)|СИб.2Н2О, was used as a precursor - titanium tetraisopropoxide of the general formula (С зН7О )u/Ti, as with a water-alcohol solvent - n-propanol, containing water in the amount of 6.595 wt. 142 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 1.667 g of the template was dissolved in it. 41 ml of the same solvent was poured into another glass beaker. At room temperature, 21 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 3 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis (o) was maintained at about 202. After ash formation, mixing of the mixture was stopped. The glass with mixture -1 was placed in the chamber, the temperature in which was maintained at about 20 2C with the help of a thermostat, and the relative humidity at 7696 - with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was ensured for 18 days until the final formation of the spatial structure of the mixture of dioxide

Their" titanium/organic template.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 54 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining (F) mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of -5002C for 4.5 hours until the template was completely removed. The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 69905 mass, had a porous structure with an average pore diameter of 10.9 nm and a specific surface area of 8 bm/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.72 in the presence of a palladium or platinum catalyst of the dark stage of the reaction. 65 In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.05 moles of an organic template - a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a strontium ion.

Example 55

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a barium ion of the general formula was used

IVa(С12НовО4М2)|СИ»-3НО, as a precursor - titanium tetrabutoxide of the general formula (САНеО)АТи, as a water-alcohol solvent - n-butanol, containing water in the amount of 5.595 wt. 177 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 1.914 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of 70 precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 302. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 30 2C with the help of a thermostat, and the relative humidity at 75 6395 - with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 15590 it was hydrothermally treated for 54 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed. c 25 The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7290 g) by mass. had a porous structure with an average pore diameter of Osr-12.3 nm and a specific surface area of Zud-83M7/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.63 in the presence of a palladium or platinum catalyst of the dark stage of the reaction. in 30 In the selected semi-product for obtaining mesoporous titanium dioxide per one mole of titanium dioxide, He»! there was 0.05 mol of an organic template - a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a barium ion. -

Example 56 Ge)

Complex 35 of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with the lanthanum ion of the general formula was used as an organic template for the synthesis of mesoporous titanium dioxide

М(С42НовО4М2)|СИ3-7НХО, as a precursor - titanium tetrabutoxide of the general formula (САНеО)АТи, as a water-alcohol solvent - n-butanol, containing water in the amount of 7956 wt. 167 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.928 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 202. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 20 2C using a thermostat, and the relative humidity - 8195 - using a saturated solution of ammonium sulfate. Contact of the mixture with water vapor at this temperature was ensured for 18 days until the final formation of the titanium dioxide (2)/organic template spatial structure mixture. - The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 55 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and air-dried until practical

T" complete removal of the solvent from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide contained in this way contained the crystalline phase of anatase in the amount of 7095 by mass. had a porous structure with an average pore diameter of 12.80 nm and a specific surface area of 97 Mm7/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, this mesoporous titanium dioxide provided a quantum yield of Фно-0.69 in the presence of a palladium or platinum catalyst of the dark 60 stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.02 moles of the organic template - a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a lanthanum ion - was required for one mole of titanium dioxide.

Example 57 65 As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a cerium ion of the general formula was used

ISe(С12НовО4М2)|СИз-2Н2О, as a precursor - titanium tetrabutoxide of the general formula (САНеО)АТи, as a water-alcohol solvent - n-butanol, containing water in the amount of 4.795 wt. 157 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.794 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 202. After ash formation, mixing of the mixture was stopped. A glass with mixture 70 was placed in a chamber, the temperature of which was maintained at about 202C with the help of a thermostat, and the relative humidity at 7696 with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was ensured for 19 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 54 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 50022 for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 6790 wt. had a porous structure with an average pore diameter of 11.9 nm and a specific surface area of 99 m2/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.71 in the presence of a palladium or platinum catalyst of the dark stage of the reaction. at

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.02 moles of an organic template - a complex of the oxaazamacrocyclic compound 18-coronaaz-2-oxa-4 with a cerium ion.

Example 58 "

As an organic template for the synthesis of mesoporous titanium dioxide, a complex b of the oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-5 with a lithium ion of the general formula was used

IN(СгоН»БО5М)|СИ-ЗН»О, as a precursor - titanium tetrabutoxide of the general formula (С./НеО)уTi, as a water-alcohol solvent - n-butanol, which contains water in the amount of 3,790 wt. 207 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 2.623m of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 3 hours until a sol was formed from the mixture. The temperature of the mixture during this entire stage of synthesis was maintained at about 202C. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 202 with the help of a thermostat, and the relative humidity at 6595 - with the help of a saturated solution of ammonium nitrate. Contact of the mixture with water vapor at this temperature was ensured for 18 days until the final formation of the spatial structure mixture of titanium dioxide/organic template.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 20090 it was hydrothermally treated for 49 hours. After that, the structure together with the mother liquor was removed from the -1 no autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining (e)) mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, the corresponding -1 portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed. is), the mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7,690% by mass, had a porous structure with an average pore diameter of 13.5 nm and a specific surface area of 119 m2/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.77 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide per one mole of titanium dioxide

F) there was 0.1 mol of the organic template - a complex of the oxaazamacrocyclic compound ka dibenzo-18-coronaaz-1-oxa-5 with a lithium ion.

Example 59 60 As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-5 with a potassium ion of the general formula was used

IR("СгоНо5О5М)1У.2Н20, as a precursor - titanium tetrabutoxide of the general formula (С.АНеО)уTi, as a water-alcohol solvent - n-butanol, which dissolves water in the amount of 796 wt. 211 ml of this water-alcohol solvent was poured into one glass beaker. At 65 room temperature, 3.398 g of template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 20 20. After ash formation, the mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 202C with the help of a thermostat, and the relative humidity at 6595 - with the help of a saturated solution of ammonium nitrate. Contact of the mixture with water vapor at this temperature was ensured for 16 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 20090 it was hydrothermally treated for 52 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at 75°C for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 8090 wt., had a porous structure with an average pore diameter of 13.8 nm and a specific surface area of 112 m g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, this mesoporous titanium dioxide provided a quantum yield of the reaction of Fn»-0.77 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of an organic template - a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-5 with a potassium ion.

Example 60 p

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-5 with a sodium ion of the general formula was used

IMa(С2гоНовО5М)|СИ-ЗНоО, as a precursor - titanium tetrabutoxide of the general formula (С /НеО)АТи, as a water-alcohol solvent - n-butanol, containing water in the amount of 596 wt. 191 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 2.611 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of He was dissolved in it! precursor The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 3 hours until a sol was formed from the mixture. The temperature of the mixture during this entire stage of He synthesis was maintained at about 152. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained by a thermostat at about 15 2С, and the relative humidity at 8195 - by means of a saturated solution of ammonium sulfate. Contact of the mixture with water vapor at this temperature was ensured for 21 days until the final formation of the titanium dioxide/organic template spatial structure mixture. "

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 15090 it was hydrothermally treated with 70 for 49 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was practically completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at -1 395 at a temperature of 6002C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7890

Me, mass had a porous structure with an average pore diameter of 13.0 nm and a specific surface area of 117 m2/g. As a -1 catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide 20 provided a quantum yield of the reaction Фn»-0.75 in the presence of a palladium or platinum catalyst of the dark so stage of the reaction.

Their" In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of an organic template - a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-5 with a sodium ion.

Example 61

As an organic template for the synthesis of mesoporous titanium dioxide, complex (F) of the oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-5 with a rubidium ion of the general formula ko IKB(SgoNoBO BM) |Vg.ZNoO was used, as a precursor - titanium tetraethoxide of the general formula ( SoNhO)uTi, as a water-alcohol solvent - ethanol, containing water in the amount of 4956 wt. 120 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 3.525 g of the template was dissolved in it. ZOml of the same solvent was poured into another glass beaker. At room temperature, 18 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 4.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of synthesis was maintained at 65 around 102C. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 1029 with the help of a thermostat, and the relative humidity at 8295 - with the help of a saturated solution of ammonium sulfate. Contact of the mixture with water vapor at this temperature was ensured for 20 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 20090 it was hydrothermally treated for 48 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding 70 portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained a crystalline phase of anatase in the amount of 5290 wt. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide 75 provided a quantum yield of the reaction Фн2-0.55 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of an organic template - a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-5 with a rubidium ion.

Example 62

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-5 with a cesium ion of the general formula was used

ISv(С2оНо5О5М)Моз.3НО, as a precursor - titanium tetrabutoxide of the general formula (САНеО)АТи, as a water-alcohol solvent - n-butanol, containing water in the amount of 4.595 wt. 182 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 3.740 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 102. After the sol was formed, the mixing of the mixture was stopped. The glass with the Fo mixture was placed in a chamber, the temperature in which was maintained at about 10 2C with the help of a thermostat, and the relative humidity at 7395 - with the help of a saturated solution of ammonium nitrate. Contact of the mixture with water vapor at this temperature was ensured for 22 days until the final formation of the He titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 15090 it was hydrothermally treated for 50 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining "mesoporous titanium dioxide." To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 4002 for 6 hours until the template was completely removed. "from Mesoporous titanium dioxide obtained in this way contained a crystalline phase of anatase in the amount of 5890 mass. It had a porous structure with an average pore diameter of Orsr-8, Znm and a specific surface area of Zud-77m/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures such mesoporous titanium dioxide - 15 provided a quantum yield of the reaction Фно-0О.67 in the presence of a palladium or platinum catalyst of the dark stage of the reaction. (22) In the isolated semi-product for obtaining mesoporous titanium dioxide, 0.1 mole of organic template was required for one mole of titanium dioxide - complex of oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-5 with cesium ion (se) 50 Example 63

GT" As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-i-oxa-5 with a magnesium ion of the general formula was used

IMa(СгоНо5О5М)|504.3Н2О, as a precursor - titanium tetrabutoxide of the general formula (САНеО)АТи, as a water-alcohol solvent - n-butanol, containing water in the amount of 495 wt. 174 ml of this water-hydrogen solvent was poured into one glass beaker. At room temperature, 3.193 g of the template was dissolved in it. 45 ml of the same solvent was poured into (F) another glass beaker. At room temperature, 25 g was dissolved in it

Ge precursor. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 2592. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 25 2C with the help of a thermostat, and the relative humidity at 8095 - with the help of a saturated solution of ammonium sulfate. Contact of the mixture with water vapor at this temperature was ensured for 17 days until the final formation of the spatial structure mixture of titanium dioxide 65/organic template.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 15090 it was hydrothermally treated for 48 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 6890 wt. had a porous structure with an average pore diameter of 10.3 nm and a specific surface area of 97 Mm7/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.78 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.1 mole of the organic template - a complex of oxaazamacrocyclic compound 75 dibenzo-18-coronaaz-1-oxa-5 with a magnesium ion was required for one mole of titanium dioxide.

Example 64

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-5 with a calcium ion of the general formula was used

ИСа(СгоНоБО5М)|СИ»-ЗНоО, as a precursor - titanium tetrabutoxide of the general formula (С /НеО)АТи, as a water-alcohol solvent - n-butanol, containing water in the amount of 796 wt. 17Oml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 3.126 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued Ge! stir for 2.5 hours until a sol is formed from the mixture. The temperature of the mixture throughout this stage of synthesis (5) was maintained at about 2592. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 252C with the help of a thermostat, and the relative humidity was 65.95 with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this temperature was ensured for 18 days until the final formation of the titanium dioxide/organic template spatial structure mixture. Fo

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 46 hours. After that, the structure together with the mother liquor was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining

From mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, the corresponding a portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 6690% by mass, had a porous structure with an average pore diameter of 11.3 nm and a specific surface area of 91 m. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, it is mesoporous titanium dioxide c provided the quantum yield of the Fn»o-0.70 reaction in the presence of a palladium or platinum catalyst in the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 mole of an organic template - a complex of oxaazamacrocyclic compound 75 dibenzo-18-coronaaz-1-oxa-5 with a calcium ion.

Example 65

Ge») As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-i-oxa-b with a strontium ion of the general formula IZ((Сг2оНовО5М)|СИ»2Н2О was used, as a precursor - titanium tetrapropoxide of the general formula (C zH7O)/Ti as (Ce) 50 water-alcohol solvent -n-propanol containing water in the amount of 6.595 wt. Poured into one glass beaker

GT» 143 ml of this water-alcohol solvent. At room temperature, 1.671 g of the template was dissolved in it. 5 Oml of the same solvent was poured into another glass beaker. At room temperature, 21 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 3 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of synthesis

HF) was maintained at about 202. After ash formation, mixing of the mixture was stopped. The glass with the mixture g was placed in the chamber, the temperature in which was maintained by a thermostat at about 20 2С, and the relative humidity at 7696 - with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was ensured for 20 days until the final formation of the spatial structure mixture of titanium dioxide/organic template.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 17590 it was hydrothermally treated for 48 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 4002 for 5.5 hours until the template was completely removed.

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 6390 wt. had a porous structure with an average pore diameter of 11.6 nm and a specific surface area of 89 m/g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Фн»-0.72 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide 70 contained 0.05 moles of an organic template - a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-5 with a strontium ion.

Example 66

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-i-oxa-5 with a barium ion of the general formula 75 ИВа(Со2оНоБО5М))СИ»ЗНО was used as an oprecursor - titanium tetrabutoxide of the general formula (0 /НеО) / Those, as a water-alcohol solvent - n-butanol, containing water in the amount of 6.395 wt. 164 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 1.918 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 302. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature of which was maintained at about 30 2C with the help of a thermostat, and the relative humidity at 6395 - with the help of a saturated solution of sodium nitrite. Contact of the mixture with water vapor at this EM temperature was ensured for 16 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 12590 it was hydrothermally treated for 53 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining Ge! of mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed. Ge

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7190

By mass, it had a porous structure with an average pore diameter of 12.1 nm and a specific surface area of 92 m. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction of Фно-0.68 in the presence of palladium or platinum catalyst of the dark stage of the reaction. "

In the selected semi-product for obtaining mesoporous titanium dioxide, one mole of titanium dioxide Z7Z 70 contained 0.05 moles of an organic template - a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-5 with a barium ion. from Example 67

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-b with an o-lanthanum ion of the general formula -1 75 IHa(SgoNovOBM)|Сиз-7НО was used, as a precursor - titanium tetrabutoxide of the general formula (С АНеО)АТи, as a water-alcohol solvent - n-butanol, containing water in the amount of 596 wt. 144 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.929 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of the precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After se) 50 after the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued

HT" to stir for 2.5 hours until a sol is formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 2592. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 25 2C with the help of a thermostat, and the relative humidity at 7596 - with the help of a saturated solution of sodium chloride. Contact of the mixture with water vapor at this temperature was ensured for 18 days until the final formation of the titanium dioxide (F)/organic template spatial structure mixture. The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 18590 it was hydrothermally treated for 49 hours. After that, the structure together with the mother solution was removed from the autoclave. The structure was separated from the mother liquor by filtration and dried in air until the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 5002 for 4.5 hours until the template was completely removed. 65 The mesoporous titanium dioxide contained in this way contained a crystalline phase of anatase in the amount of 7695 wt., had a porous structure with an average pore diameter of 13.9 nm and a specific surface area of 112 g. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, the following mesoporous titanium dioxide provided a quantum yield of the reaction of Фн»-0.73 in the presence of a palladium or platinum catalyst of the dark stage of the reaction.

In the selected semi-product for obtaining mesoporous titanium dioxide, 0.02 moles of the organic template - a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-5 with a lanthanum ion - was required for one mole of titanium dioxide.

Example 68

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-y-oxa-5 with a cerium ion of the general formula was used

ISe(SgoNoBOBM)|СИз-2Н2О, as a precursor - titanium tetrabutoxide of the general formula (САНеО)АТи, as a water-alcohol solvent - n-butanol, containing water in the amount of 4.596 wt. 135 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.796 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. At room temperature, 25 g of 7/5 precursor was dissolved in it. The precursor solution was added dropwise to the template solution with intensive stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to be stirred for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this stage of the synthesis was maintained at about 302. After ash formation, mixing of the mixture was stopped. The glass with the mixture was placed in a chamber, the temperature in which was maintained at about 30 2C with the help of a thermostat, and the relative humidity at 8595 - with the help of a saturated solution of potassium chloride. Contact of the mixture with water vapor at this temperature was ensured for 15 days until the final formation of the titanium dioxide/organic template spatial structure mixture.

The formed structure together with the mother solution was placed in an autoclave, where at a temperature of 15090 it was hydrothermally treated for 51 hours. After that, the structure together with the mother liquor was removed from Ge! autoclave The structure was separated from the mother liquor by filtration and dried in air until almost (5) complete removal of the solvent from it. The dried mixture was stored in a glass container as an intermediate product for obtaining mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, a corresponding portion of the dry mixture was poured into a crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 6002C for 4 hours until the template was completely removed. "AND

The mesoporous titanium dioxide obtained in this way contained the crystalline phase of anatase in the amount of 7290 by mass. had a porous structure with an average pore diameter of 15 nm and a specific surface area of 114 mg. As a catalyst for the photochemical reaction of hydrogen release from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of Фно-0.77 reaction in the presence of a palladium or platinum catalyst of the dark Ge stage of the reaction. 3o In the selected semi-product for the production of mesoporous titanium dioxide, 0.02 moles of the organic template - a complex of the oxaazamacrocyclic compound dibenzo-18-coronaaz-1-oxa-5 with a cerium ion - was per one mole of titanium dioxide.

The given examples do not exhaust all the possibilities of practical implementation of the inventive idea. So. in a more complex form of the implementation of the inventive idea, which does not contradict the main points of the claims, at the stage of synthesis of mesoporous titanium dioxide from sol formation to the final formation from the reaction mixture of spatial structure precursor/organic template, the temperature of the mixture does not exceed the specified upper limit and the lower limit that is recommended can be maintained by another, different from the one at which the mixture is maintained at the previous stage of synthesis (from mixing reagent solutions to ash formation).

In addition, in the case when the temperature of the environment and its humidity during the time required for the synthesis of mesoporous titanium dioxide change little and changes in these parameters of the external environment are predictable, the final product - mesoporous titanium dioxide with the given set of properties could be synthesized according to the above the above methods without the use of a thermostat and saturated solutions of the corresponding salts. - Example 69.

Ge) 20 Testing samples of mesoporous titanium dioxide as catalysts for photochemical heterogeneous oxidation reactions of harmful organic compounds (for example, acetone) to the formation of environmentally safe products.

T» Samples of mesoporous titanium dioxide, which were first obtained according to the methods given in examples 21 and 29, and then fixed in the form of a thin layer on glass plates, were also tested as sorbents-catalysts of the heterogeneous photochemical reaction of acetone oxidation in the gas phase. For comparison, a highly dispersed pyrogen fixed on another glass plate in the form of a layer of the same thickness was used

GF) 10095th anatase, which did not have a porous structure. The masses of the samples of the mesoporous material and the sample of 10095 anatase, which were applied to the plates, were the same and equal to 0.25 g. Photocatalytic oxidation of acetone vapors was carried out at room temperature with air oxygen. A plate with a layer of one of the samples of mesoporous titanium dioxide was placed in a closed glass reactor with a volume of 275 ml. A plate with a layer of pyrogenic 10095 anatase was placed in the second reactor. The introduction of the same starting amounts of acetone vapors into the reactors (up to a concentration of 510 mol/l), as well as sampling for the chromatographic determination of the acetone content and the products of its photocatalytic oxidation, was carried out with the help of a dispenser through elastic rubber membranes hermetically embedded in the walls of the reactors. Through the glass windows in the walls of the reactors, plates with samples were irradiated for 60 minutes with a mercury lamp of the DRSH-1000O type with X»231OnmM b5 light (light intensity - 2.710 Einstein/min). The photocatalytic activity of the samples was evaluated by the degree of conversion (transformation) of acetone K, 95, which was calculated according to the formula

К-А(С4-С2).100/С., where Su is the initial concentration of acetone in each of the reactors (5.10 Zmol/l); Co is the concentration of acetone in each of the reactors after the end of irradiation of plates with samples.

For samples of mesoporous titanium dioxide, which were obtained according to the methods given in examples 21 and 29, the value of K was equal to 46905 and 3895, respectively. For the non-porous 10095 anatase sample

K-1796. Thus, the photocatalytic activity of the proposed mesoporous titanium dioxide is more than 2 times higher than the activity of highly dispersed pyrogenic 10095 anatase, which does not have a porous structure. 70 This, as evidenced by the results of chromatographic analysis, during the photocatalytic oxidation of acetone with air oxygen in the presence of samples of the claimed sorbent-catalyst, no other gaseous reaction products, except carbon dioxide, were recorded.

The given examples do not exhaust all the possibilities of the practical implementation of the inventive idea. Thus, in a more complex form of implementation of the inventive idea, which does not contradict the main clauses of formula 75 of the invention, at the stage of synthesis of mesoporous titanium dioxide from sol formation to the final formation from the reaction mixture of the spatial structure of the precursor/organic template, the temperature of the mixture does not exceed the specified upper and lower limits the recommended limit can be maintained by another, different from the one at which the mixture is maintained at the previous stage of synthesis (from mixing reagent solutions to ash formation).

In addition, in the case when the temperature of the environment and its humidity during the time from the mixing of reagent solutions to the final formation from the reaction mixture of the spatial structure of the precursor / organic template change slightly, moreover, changes in these parameters of the environment are predictable and correspond to the conditions of synthesis, these the stages of synthesis of mesoporous titanium dioxide can be carried out without the use of a thermostat and saturated solutions of the corresponding salts.

Possibilities of industrial application of

The proposed mesoporous titanium dioxide and the intermediate product can be easily obtained industrially according to the proposed method using reagents produced by the chemical industry.

Such mesoporous titanium dioxide can be successfully used in the chemical industry as a sorbent-catalyst for photochemical reactions of the release of molecular hydrogen from water-alcohol mixtures or as a sorbent-catalyst for heterogeneous photochemical processes of oxidation of harmful organic compounds in the gaseous phase with the formation of environmentally safe products. F

Claims (9)

Formula of the invention i- (Se) 1. Photocatalytically active mesoporous titanium dioxide, which is characterized by the fact that it contains a crystalline phase of anatase in the amount from 3% by weight to 90% by weight, has a porous structure with an average pore diameter from 2 to 16 nm and a specific surface area of at least 70 m "/g. 2. Photocatalytically active mesoporous titanium dioxide according to claim 1, which is characterized by the fact that it additionally contains lanthanum in an amount of no more than 0.019 grams per one gram of substance. C. The method of obtaining photocatalytically active mesoporous titanium dioxide, which consists in introducing a precursor - titanium tetraalkoxide and a template of organic nature into an aqueous-organic solvent, and keeping the mixture of reagents until the final formation of a spatial structure from it through successive stages of ""sol formation , and then the gel, separate the resulting semi-product of the reaction and process it to remove the template to obtain the final product, which is distinguished by the fact that the process is carried out in a water-alcohol solvent containing no more than 7 wt.9o of water, as a template, at least one from ligands, -and selected from the group of macrocyclic compounds, which includes oxa- and oxaazamacrocyclic compounds containing at least four oxygen atoms, and/or from complexes of the specified macrocyclic compounds with metal ions selected from the group of alkaline or alkaline earth, or i-metals, which include lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum an and cerium, until the formation of a sol, the mixture of reagents is stirred, maintaining its temperature at 50 °C not higher than 352С, and until the final formation of a spatial structure from the mixture of reagents, the mixture is kept at the same temperature in an open vessel under conditions of free access to the mixture of water vapor. I" 4. The method according to claim 3, which differs in that the template is removed from the resulting semi-product of the reaction by calcination at a temperature from 3002 to 60026. 5. The method according to claim 4, which differs in that before the removal of the template, the intermediate product of the reaction is treated 22 hydrothermally at a temperature from 1002 to 20020. GF! 6. The method according to claim 3, which is characterized by the fact that the template is removed from the intermediate product of the reaction by extraction with alcohol under the conditions of preliminary hydrothermal treatment of the intermediate product at a temperature from 1002 to 20026. where 7. The method according to claim 3, which differs in that a lanthanum salt is additionally introduced into the water-alcohol solvent, if the template does not contain the lanthanum ion. 60 8. Semi-finished product for obtaining photocatalytically active mesoporous titanium dioxide, containing titanium dioxide and an organic compound, which is characterized by the fact that it contains as an organic compound at least one of the ligands selected from the group of macrocyclic compounds, which includes oxa- and oxaazamacrocyclic compounds containing at least four oxygen atoms, and/or from complexes of the specified macrocyclic compounds with metal ions selected from the group of alkaline or alkaline earth metals, or y-metals, which includes lithium, potassium, sodium, bo rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium, and one mole of titanium dioxide in the semi-product accounts for from 0.001 mole to 0.2 mole of the ligand. 9. The semi-finished product according to claim 8, which is characterized by the fact that it additionally contains a lanthanum salt in an amount of no more than 0.006 moles per one mole of titanium dioxide. 5. Kk K-4. . . new Official Bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2006, M 9, 15.09.2006. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. s schi 6) « (22) cha (Se) and - - with . and? -I (22) -I at 50 s» F) ime) bo b5