RU2291839C2 - Method and the semi-product used for production of the meso-porous titanium dioxide - Google Patents

Abstract

FIELD: chemical industry; methods of production of the catalytic agents of photochemical reaction and sorbents-catalysts of heterogeneous photochemical processes.

SUBSTANCE: the invention is pertaining to the field of chemical industry and may be used in production of the catalytic agents of photochemical reaction and the sorbents-catalysts of heterogeneous photochemical processes of oxidizing of the harmful organic compounds. The precursor in the form of titanium tetraalcoxide and template of the organic nature are introduced into the water-organic dissolvent. The mixture of the reactants is intermixed up to formation of the sol and is kept till the final formation of the special structure. The gained reaction product is separated and treated removal of the template using calcifying or the extraction by the alcohol after preliminary hydrothermal treatment. In preferential version of the invention the water-alcohol dissolvent is additionally introduced with the salt of lanthanum. The invention allows to produce the reproducible sorbent-photocatalyst with the high attributes: the crystal phase of the anatase - no less than 30 mass %, a mean diameter of the pores - 2-16 nanometers, the specific surface - no less than 70 m²/g, does not contain the non-desirable impurities.

EFFECT: the invention ensures production of the reproducible sorbent-photocatalyst with the high attributes of thee crystal phase of the anatase, the effective diameter of the pores, the specific surface at absence of the non-desirable impurities.

7 cl, 68 ex

Description

Technical field

The invention relates to the composition and structure of mesoporous dispersed materials based on titanium dioxide, to methods and compositions of intermediates for producing such materials.

Such mesoporous dispersed materials can be used:

as catalysts for photochemical reactions in chemical plants, in particular for the production of molecular hydrogen as a fuel for vehicles or as a starting reagent for such technological processes as the synthesis of ammonia, methanol, etc .;

as photocatalyst sorbents, for example, for purifying air from harmful organic compounds by heterogeneous photocatalytic oxidation of the compounds in the gas phase to form products that are safe for human health.

The terms used hereinafter in relation to the invention mean:

photocatalytic reaction - a reaction under the influence of light, in which compounds are subjected to chemical transformations, and photocatalysts as substances that are not involved stoichiometrically in the overall process;

a photochemical reaction catalyst (photocatalyst) is a substance that absorbs light, individually or in combination with one of the reagents, as a result of which it acquires the ability to induce chemical transformations, transferring electronic excitation energy to the substrate or entering into intermediate chemical interactions with it, and, in addition, it regenerates its chemical composition and ground electronic state after each such cycle;

quantum yield is one of the main characteristics of the photocatalytic reaction, indicating how much of the reagent molecules undergo chemical conversion per quantum of light absorbed by the photocatalyst;

template - a material that serves as a structural directing agent ("template") on which the initial reagents are fixed in the process of sol-gel synthesis with a certain orientation in space and on which the structure of a dispersed porous material is formed;

precursor - the starting material, which, as a result of chemical transformations, for example, hydrolysis, becomes a source of material for the formation of a framework of a porous dispersed material on a template during sol-gel synthesis;

sol - a colloidal system with a liquid dispersion medium, particles of the dispersed phase of which (micelles) freely participate in Brownian motion and which, when coagulated, turns into a gel;

gel - a structured colloidal system with a liquid dispersion medium in which the particles of the dispersed phase are interconnected into a loose spatial network containing a dispersion medium in its cells;

coordination compound, complex - a compound of complex composition in which ligands are coordinated to the central cation (complexing agent) through their donor oxygen and / or nitrogen atoms, the number of coordinated atoms depending on the nature of the central cation and the nature of the ligand;

macrocyclic compound - a compound in which donor oxygen and / or nitrogen atoms are interconnected by carbon bridges of various lengths containing also hydrogen atoms and / or various substituents and which form one or more closed cycles;

oxamacrocyclic compound (crown ether) - a macrocyclic compound containing only donor oxygen atoms;

oxaazamacrocyclic compound - a macrocyclic compound containing, along with donor oxygen atoms, nitrogen atoms as well;

hydrothermal treatment - treatment of substances at high temperatures and pressures, at which water and aqueous solutions are able to dissolve substances that are practically insoluble in ordinary conditions and in which the original inorganic substances turn into a crystalline product;

calcination - calcination of a material at high temperatures.

State of the art

Dispersed materials based on titanium dioxide as catalysts for the photochemical reactions of molecular hydrogen evolution or as sorbents-catalysts for heterogeneous photochemical processes of oxidation of organic compounds in the gas phase should provide:

high quantum yields of product formation reactions;

the possibility of preliminary and, preferably, uniform concentration of vapors of organic compounds on its active surface for their subsequent effective decomposition.

In turn, the methods for producing such dispersed materials based on titanium dioxide should ensure stable reproducibility of the properties of materials, and intermediates 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 there is a need for materials with a freshly formed and therefore chemically active surface.

Until now, it has been possible to fulfill the indicated requirements only in some partial combinations.

Thus, a dispersed material of the Degussa P 25 brand from Degussa is known, which mainly consists of a crystalline modification of titanium dioxide-anatase (see, for example, the Degussa website: www. Degussa.com/cn/producte.hlml). It is anatase, which is known to be an OR-type semiconductor, capable of oxidation and reduction at the same time (see, for example, Balzani V., Scandola F., Infelt P. et al. Energy resources through the prism of photochemistry and catalysis: Transl. English / Under the editorship of M. Gretzel. - M .: Mir, 1986. - P.364); When photons are absorbed by them, electrons are excited into the conduction band, and holes are generated in the valence band, respectively taking part in the reduction and oxidation reactions of the molecules of substances in contact with this semiconductor. In this case, the crystalline modification of titanium dioxide, having significantly fewer defects in comparison with its amorphous modification, on the one hand, promotes the efficient movement of photogenerated charges in the semiconductor mass, and on the other hand, reduces the likelihood of a very undesirable reverse process - the recombination of photogenerated charges. Therefore, the known catalyst material for photochemical reactions, and in particular, reactions such as the evolution of molecular hydrogen from water-alcohol mixtures, is characterized by rather high 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 is known (see, for example, Balzani V., Scandola F., Infelt P. et al. Energy resources through the prism of photochemistry and catalysis: Transl. from English / Edited by M. Gretzel. - M .: Mir, 1986. - P.365), contributes acc the emulation of atomic hydrogen formed as a result of the reaction and its transformation into molecular hydrogen.

However, the known dispersed material of the Degussa P 25 brand has an almost dense structure and therefore a very small specific surface (about 50 m ² / g of substance) formed by fine particles of material. Therefore, the efficiency of using this material for preliminary concentration of vapors of organic compounds on its active surface for the purpose of their subsequent heterogeneous photochemical decomposition is very low.

The method of obtaining such a crystalline modification of titanium dioxide - anatase, which is mainly Degussa P 25 material, is well known (see, for example, the Guide to neo-organic synthesis. Edited by G. Brauer. - M .: Mir, 1985. - T.4 - S.1460-1462). It includes the introduction of titanium into tetraalkoxide (ethoxide, isopropoxide or butoxide) while cooling (temperature is about 5 ° С) and vigorously stirring multiple (relative to stoichiometric) amounts of water to form titanium oxide turbidity, stirring the mixture for several hours until complete hydrolysis of titanium tetraalkoxide, filtering the precipitate obtained, washing it with water, vacuum drying at room temperature, subsequent heating at temperatures up to 400 ° C until a crystalline modification forms titanium dioxide anatase and its grinding.

This method of producing titanium dioxide in the form of anatase is relatively simple and, in addition, provides almost 100% yield of the finished product with photocatalytic properties.

However, this method does not allow to obtain a porous material that is able to effectively concentrate pairs of organic compounds before their photocatalytic decomposition.

Obviously, the intermediate for the production of titanium dioxide is titanium hydroxide, which, as you know, is capable of losing water during storage and, as a result, spontaneously transform into an amorphous modification of titanium dioxide (see ibid.).

Also known is mesoporous titanium dioxide, which has a much larger specific surface area compared to Degussa P 25 (see, for example, US application No. 6,79029, filed June 12, 1996). Due to the mesoporous structure and therefore the highly developed specific surface, the known titanium dioxide has a high sorption ability. Therefore, it can be a good concentrator of vapors of organic compounds that are subject to subsequent decomposition.

However, this titanium dioxide consists predominantly of the amorphous phase and is therefore ineffective as a catalyst for the photochemical reactions of molecular hydrogen evolution and, moreover, as a sorbent catalyst for heterogeneous photochemical processes of oxidation of organic compounds in the gas phase.

A method for producing such mesoporous titanium dioxide by template sol-gel synthesis includes (see ibid.) Introducing into the aqueous organic solvent a precursor in the form of titanium tetraalkoxide and a template in the form of an organic compound, mainly selected from among surfactants, holding or processing the obtained a solution under certain conditions and conditions until a precursor / template is formed from the mixture, first a sol, and then a gel and the template is removed.

This method allows to obtain sorption active titanium dioxide with an average pore diameter of about 3 nm and with a specific surface area of up to 700 m ² / g.

However, this method does not allow to obtain mesoporous titanium dioxide having photocatalytic properties.

Accordingly, the intermediate product in the form of a spatially organized structure of an organic template / titanium dioxide for producing mesoporous titanium dioxide has the same advantages and disadvantages.

The closest in technical essence and the achieved effect to the claimed group of objects are mesoporous titanium dioxide and the method and intermediate for its preparation, which are known from Synthesis of Hexagonally Packed Mesoporous TiO ₂ by a Modified Sol-Gel Method. David M. Antonelli, Jackie Y. Ying // Angew.Chem.lnt. Ed.Engl., 1995, V.34, No. 1, P.2014-2022 and articles Synthesis, Characterization, and Photocatalytik Aktivity of Titania and Niobia Mesoporous Molekular Sieves. Viktor F. Stone, Jr. and Robert J. Davis // Chemistry of Materials, 1998, V.10, No. 5, P.1468-1474. In the first of these articles, the texture of the material that we selected as a prototype is described, the prototype process of obtaining the material is described in stages, indicating the conditions for each stage of the synthesis, and the properties of the prototype intermediate for obtaining the material are described. In the second, other authors studied the photocatalytic properties of the prototype material (mesoporous titanium dioxide) and gave an explanation of the nature of its photocatalytic activity.

Known Mesoporous Titanium Dioxide (see Synthesis of Hexagonally Packed Mesoporous TiO ₂ by a Modified Sol-Gel Method. David M. Antonelli, Jackie Y. Ying // Angew.Chem.lnt. Ed.Engl., 1995, V.34, No. 1, P.2017) has an average pore diameter of about 3 nanometers and has a specific surface area of about 200 m ² / g. Therefore, it is effective as a concentrator of vapors of organic compounds.

However, this mesoporous titanium dioxide is characterized by a low quantum yield of molecular hydrogen production — not more than 0.01 in the presence of a dark-stage platinum or palladium catalyst (see Synthesis, Characterization, and Photocatalytik Aktivity of Titania and Niobia Mesoporous Molekular Sieves. Viktor F. Stone , Jr. and Robert J. Davis // Chemistry of Materials, 1998, V.10, No. 5, P.1470, table 1), which indicates the predominance of the photocatalytically inactive amorphous phase of titanium dioxide in the material (see ibid., .1471, figure 4). In addition, the content of a template-phosphorus fragment in its pores also contributes to a decrease in the photocatalytic activity of the known material (see ibid.). Therefore, this mesoporous titanium dioxide is not effective enough as a sorbent photocatalyst in terms of its complex of properties.

A method for producing known mesoporous titanium dioxide includes (see Synthesis of Hexagonally Packed Mesoporous Ti02 by a Modified Sol-Gel Method. David M. Antonelli, Jackie Y. Ying // Angew.Chem.lnt. Ed.Engl., 1995, V. 34, No. 1, P.2017) dissolution in water of a template-monododecyl phosphate and a pH regulator — potassium hydroxide, dissolution in a organic solvent — acetylacetone — of a precursor in the form of tetraalkoxide (isopropoxide) titanium, mixing the resulting solutions, holding the mixture at a temperature of about 80 ° С in a vessel isolated from the external environment until the final formation of a spatial structure from it , which, as you know, includes the intermediate stages of the formation of a sol at first, and then a gel (see, for example, the Chemical Encyclopedic Dictionary. / Ed. by I.L. Knunyants. - M .: Soviet Encyclopedia, 1983. - P. 549) , separation of the precipitate, washing, drying and processing until the template is removed from it.

The known method allows to obtain mesoporous titanium dioxide with a well-ordered pore structure and a highly developed surface (see Synthesis of Hexagonally Packed Mesoporous TiO ₂ by a Modified Sol-Gel Method. David M. Antonelli, Jackie Y. Ying // Angew.Chem.lnt. Ed.Engl., 1995, V.34, No. 1, P.2017).

However, this method does not allow to obtain mesoporous titanium dioxide with a high content of photocatalytically active crystalline phase - anatase. In addition, the use of monododecyl phosphate as a templating reagent in accordance with the known method prevents the complete removal of fragments of this reagent from the pores of the finished product (see Synthesis, Characterization, and Photocatalytik Aktivity of Titania and Niobia Mesoporous Molekular Sieves. Viktor F. Stone, Jr. and Robert J. Davis // Chemistry of Materials, 1998, V.10, No. 5, P.1471).

Obviously, a semi-product for implementing the known method for producing mesoporous titanium dioxide is a spatially organized monododecyl phosphate / titanium dioxide structure (see Synthesis of Hexagonally Packed Mesoporous TiO ₂ by a Modified Sol-Gel Method. David M. Antonelli, Jackie Y. Ying // Angew .Chem.lnt. Ed.Engl., 1995, V.34, No. 1, P.2017). This 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 intermediate does not allow it to be used to produce the final product (mesoporous titanium dioxide) with the set of properties necessary for the sorbent-photocatalyst (see Synthesis, Characterization, and Photocatalytik Aktivity of Titania and Niobia Mesoporous Molekular Sieves. Viktor F. Stone, Jr. and Robert J. Davis // Chemistry of Materials, 1998, V.10, No. 5, p. 1470-1471).

SUMMARY OF THE INVENTION

The basis of the group of inventions is the task, by improving the composition and texture of mesoporous titanium dioxide, to create a sorbent photocatalyst with high sorption and photocatalytic characteristics, by selecting reagents for implementing the method for producing mesoporous titanium dioxide and synthesis conditions, to ensure reproducibility of the complex of properties of such a sorbent-catalyst and, finally, by improving the composition of the intermediate to obtain mesoporous dioxide to ensure the stability of the intermediate to changes and decomposition during storage and, at the same time, its easy processing (by removing the template) into the final product - a sorbent-photocatalyst with a freshly formed, free of undesirable impurities and therefore active surface.

The problem is solved in that the mesoporous titanium dioxide according to the invention contains a crystalline anatase phase in an amount of at least 30 wt.%, Has a porous structure with an average pore diameter of 2 to 16 nm, a specific surface area of at least 70 m ² / g and as a photochemical catalyst the reaction of hydrogen evolution 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 reaction stage.

The first additional difference is that it additionally contains lanthanum in an amount of not more than 0.019 grams per gram of substance.

The problem is also solved by the fact that in the method for producing mesoporous titanium dioxide, which includes introducing a precursor of titanium tetraalkoxide and an organic template into an aqueous organic solvent, holding the mixture of reagents until the final formation of the spatial structure from it through successive stages of formation of a sol and then a gel, separation of the obtained reaction product and its processing to remove the template, according to the invention, the process is carried out in a water-alcohol solvent containing not more than 7 m c.% of water, at least one of the ligands selected from the group of macrocyclic compounds consisting of oxo and oxazamacrocyclic compounds containing at least four oxygen atoms and / or from complexes of these macrocyclic compounds with metal ions is introduced into the solvent as a template selected from the group of alkaline, or alkaline earth, or f-metals, consisting of lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium, the mixture of reagents is mixed while maintaining its temperature is not higher than 35 ° C, and until the final formation of the spatial structure of the mixture of reagents, the mixture is kept at the same temperature in an open vessel under free access to a mixture of water vapor.

The first additional difference is that the template is removed from the resulting reaction product by calcination at a temperature of from 300 ° C to 600 ° C. The use of such calcination modes promotes 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, the production of a photocatalytically active sorbent material.

The second additional difference is that the template is removed from the reaction product by extraction with alcohol. This alternative to the previous one also allows one to almost completely remove the organic template from the reaction product.

The third additional to the first and second differences is that before removing the template, the reaction product is hydrothermally treated at a temperature of from 100 ° C to 200 ° C. The combination of the hydrothermal treatment of the product with the above methods of its depamping allows one to almost completely complete the hydrolysis of titanium tetraalkoxide, form the photocatalytically active phase of anatase and preserve the parameters of the formed mesoporous structure after almost completely removing the organic template from the reaction product.

A fourth additional difference is that an additional salt of lanthanum is added to the water-alcohol solvent. This allows us to further increase the thermal stability of the inorganic component of the spatial structure of titanium dioxide / organic template during its subsequent heat treatment and, as a result, to further stabilize the mesoporous structure of the resulting final product without changing its photocatalytic properties.

The problem is solved also by the fact that the intermediate for the production of 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 consisting of oxo and oxazamacrocyclic compounds, containing at least four oxygen atoms and / or from complexes of these macrocyclic compounds with metal ions selected from the group of alkaline, or alkaline earth, or f metals, consisting of lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium, and from one mole of titanium dioxide in the intermediate is from 0.001 mol to 0.2 mol of ligand.

The first additional difference is that the intermediate product additionally contains a lanthanum salt in an amount of not more than 0.006 mol per one mol of titanium dioxide.

BEST EMBODIMENTS

Further, the essence of the group of inventions is illustrated by generalized examples of a method for producing mesoporous titanium dioxide through an intermediate stage of obtaining an intermediate 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 assessing the photocatalytic properties of the finished product on the example of its use as a catalyst for the photochemical reaction of molecular evolution hydrogen from water-alcohol mixtures, as well as the method for determining the quantitative composition of the intermediate.

The essence of the group of inventions is also illustrated by specific examples of a method for producing mesoporous titanium dioxide (including the stage of obtaining the corresponding intermediate), which shows the parameters of the porous structure, phase composition and photocatalytic properties of the obtained mesoporous titanium dioxide determined by these methods (without repeated reference to them), as well as the composition of each specific intermediate.

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

At least one of the oxo- or oxaazamacrocyclic compounds containing at least four oxygen atoms (preferably not more than ten) and / or one of the complexes of these macrocyclic compounds with an alkaline ion (lithium, sodium, potassium, rubidium, cesium), or alkaline earth (magnesium, calcium, strontium, barium), or f-metal (lanthanum, cerium). Note that organic templates in the form of oxa and oxaazamacrocyclic compounds, as well as complexes of these compounds with these metals, which contain less than four oxygen atoms, are not described in the literature. The use of oxa- and oxazamacrocyclic compounds, as well as their complexes with these metals, which contain more than ten oxygen atoms, is not ruled out, but, according to the results of our studies, this increases the likelihood of an inhomogeneous structure of the mesoporous material and violates the stability of its texture parameters.

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

Methyl, ethyl, propyl, butyl, hexyl or amyl alcohols, the water content of which did not exceed 7 wt.%, Were used as a water-alcohol solvent for the synthesis of mesoporous titanium dioxide. As our experiments have shown, you can use other alcohols with the number of carbon atoms from two to nine, the water content of which does not exceed 7 wt.%. The use of such water-alcohol solvents with a high water content is impractical, since this leads to a significant acceleration of the process of hydrolysis of titanium tetraalkoxide and, as a result, to a violation of the uniformity 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 the randomly selected (from among the named) template substances were prepared. In this case, from one mole of titanium tetraalkoxide (precursor) was taken from 0.001 mol to 0.2 mol of the organic template. As it was found out, a relative decrease in the amount of the template below the lower limit leads to the fact that the specific surface of the final synthesis product is underdeveloped (less than 70 m ² / g), which affects the sorption properties of the product. A relative increase in the amount of the template above the upper limit is impractical, since the template remains in excess, only partially taking part in the synthesis.

One of the water-alcohol solvents was poured into a glass beaker in an amount sufficient to dissolve a portion of the template substance therein at room temperature. The same solvent was poured into another glass beaker in an amount sufficient to dissolve a portion of the precursor substance therein at the same temperature. In some cases, when the template used for the synthesis of titanium dioxide was one of the oxo- or oxaazamacrocyclic compounds or a complex of one of these macrocyclic compounds that did not contain a lanthanum ion in a water-alcohol solvent, in addition to the template, a lanthanum salt was added in an amount not more than 0.006 moles per mole of titanium tetraalkoxide (precursor). After preparing a solution of a template substance or a mixture of a template substance with a lanthanum salt in the first glass and a solution of a precursor substance in a second glass, a solution of a precursor substance was introduced dropwise into the contents of the first glass with vigorous stirring. After the entire portion of the solution of the precursor substance was introduced into the solution of the template substance, the resulting mixture was continued to mix 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 fixed, for example, by a sharp decrease in the speed of rotation of the electric mixer. The temperature of the mixture at this stage of synthesis, starting from mixing solutions and ending with ash formation, was maintained no higher than 35 ° C. After ash formation, without stopping to maintain the temperature of the mixture no higher than 35 ° C, its stirring was stopped. The mixture was left in an open vessel with free access to water vapor from the environment (if the relative humidity of the medium was not less than 60%) or a vessel with the reaction mixture was placed in a chamber where the relative humidity of at least 60% was specially created using saturated solutions of the corresponding salts according to the generally accepted methodology (see, for example, Chemistry Handbook. / Ed. by B.P. Nikolsky. - M.: Goskhimizdat, 1963. V.1, S.1047). The mixture was contacted with water vapor for several weeks until the final formation of the spatial structure of titanium dioxide / template from the reaction mixture. The criterion for completing this stage of the synthesis was the clearly visible visual effect of syneresis (see, for example, Chemical Encyclopedia. - M .: Soviet Encyclopedia, 1988, T.1, P.513) - spontaneous final compaction of the spatial structure of titanium dioxide / template and, as consequence, the cessation of the displacement of the liquid phase from it.

For each mixture of specific reagents (precursor, organic template (including 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 titanium dioxide / organic template from it under different synthesis conditions was determined experimentally .

It was found that increasing the temperature of the reaction mixture above the specified limit (35 ° C) at stages of synthesis of mesoporous titanium dioxide, such as ash formation and the formation of the spatial structure of the composition of titanium dioxide / organic template, leads to a deterioration in the texture characteristics of the final product (titanium dioxide) and, First of all, it promotes the formation of a product with a small specific surface. The lower experimentally established temperature limit at which these stages of the synthesis of mesoporous titanium dioxide should be carried out is 10 ° C. 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.

Depending on the chosen method of removing the template (by calcination or extraction with alcohol) from the spatial structure finally formed from the reagent mixture and the method for obtaining the required amount of photocatalytically active anatase in titanium dioxide, the obtained spatial structure was subjected to various preliminary processing.

In the case when, to remove the template from the finally formed spatial structure, titanium dioxide / template and the formation of the required amount of photocatalytically active anatase in titanium dioxide, calcination was used, the structure was preliminarily separated by filtration from the mother liquor, dried in air until the solvent was almost completely removed from it, and then crushed in a dispersant. The dried ground mixture was poured into a crucible and weighed together with the crucible on an analytical balance. Then the crucible with the mixture was placed in a muffle furnace, where the mixture was calcined at a temperature of 300 ° C to 600 ° C for 4-7 hours until the organic template was completely removed from it. The criterion for the complete removal of the template from the structure and the preparation of the final product, mesoporous titanium dioxide, was the achievement by the contents of the crucible of constant mass after its loss in the process of detection, which was easily determined by sequential weighing on the analytical balance 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 the sampling of the titanium dioxide / template structure by calcination by the above method is quite sufficient for the formation of at least 30 wt.% Photocatalytically active anatase phase in titanium dioxide.

Note that almost all of the organic templates listed in the claims are removed from the spatial structure of titanium dioxide / template even at a calcination temperature of 300 ° C. However, the duration of the calcination of the structure at this temperature until the template is completely removed from it and the crystallization of titanium dioxide is completed with the predominant formation of the anatase phase is about 7 hours. Therefore, in order to accelerate the process of complete detampling and the formation of a sufficient amount of the photocatalytically active anatase phase, the titanium dioxide / template structure was calcined at temperatures much higher, but not exceeding 600 ° С. Beyond this upper temperature limit, the specific surface area of the final product (mesoporous titanium dioxide) decreased markedly and it was not possible to obtain mesoporous titanium dioxide with a specific surface of ≥70 m ² / g. In addition, calcination of the structure at temperatures above 600 ° C contributed to an undesirable increase in the diameter of mesopores to the size of micropores.

In some cases, before calcining the finally formed spatial structure, titanium dioxide / template was subjected to hydrothermal treatment at temperatures from 100 ° C to 200 ° C. For this, the spatial structure together with the mother liquor was placed in a sealed autoclave, where at a temperature of 100 ° С-200 ° С and increased pressure that arose at these temperatures, it was hydrothermally treated for about two days until the hydrolysis of titanium tetraalkoxide was completely completed and photocatalytic formation started active phase of anatase. After that, the structure with the mother liquor was removed from the autoclave. The structure was separated from the mother liquor by filtration, dried in air until the solvent was almost completely removed, crushed in a dispersant, and then calcined according to the method described above. 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 was started during hydrothermal treatment, was completed.

Note that combining the process of calcining the titanium dioxide / template structure with the process of its preliminary hydrothermal treatment is very desirable, but not necessary, since calcining the structure even without its preliminary preparation promotes the formation of mesoporous titanium dioxide with the required amount of photocatalytically active anatase.

In the case when the template was removed from the finally formed spatial structure by titanium dioxide / template by extraction with alcohol, the structure, without being separated from the mother liquor, must be preliminarily subjected to hydrothermal treatment in an autoclave for about four days at a temperature from 100 ° C to 200 ° C. Such modes of preliminary hydrothermal preparation contributed not only to the complete completion of the hydrolysis of tetraalkoxide, but also to the formation of the required amount of photocatalytically active anatase in titanium dioxide.

After this preliminary hydrothermal treatment, the mother liquor structure was removed from the autoclave. The structure was separated from the mother liquor by filtration, dried in air until the solvent was almost completely removed, and then ground in a dispersant. The resulting structure powder was placed in a glass beaker. With vigorous stirring, alcohol pre-heated to boiling point was added, mainly ethyl alcohol (about 300 g of alcohol was taken per gram of structure powder) and the organic template was removed from the formed spatial structure by titanium dioxide / template. Preventing strong cooling of the suspension, the solid phase was separated by filtration from it. Using new portions of hot alcohol, the solid phase separated by filtration was further processed twice successively by the same procedure. As a result, mesoporous titanium dioxide was obtained that practically did not contain an organic template. It was dried until the solvent was almost completely removed, crushed in a dispersant, and stored in a sealed glass container until used as a sorbent-photocatalyst.

The specific surface area of the obtained mesoporous titanium dioxide was calculated by the BET method (Brunauer-Emmett-Teller) from methanol adsorption isotherms using a known method (see, for example, Greg S., Sing K. Adsorption, specific surface area, porosity. - M .: Mir , 1970. - P.73 or Brunauer S. Adsorption of gases and vapors. - M .: Foreign Literature., 1948, T.1. - P.784). Methyl adsorption and desorption isotherms were registered at a temperature of 20 ° С by the adsorption gravimetric method using a Mac Ben-Bakr spring quartz balance with a sensitivity of 0.25-0.35 mm / mg (see, for example, M.M.Dubinin Physicochemical principles of sorption technology. - 2nd ed., Revised and supplemented - L .: ONTI, 1935. - 346 pp. Or Experimental methods in adsorption and molecular chromatography // edited by A.V. Kiselev and V.P. Dreving. - M.: Moscow State University, 1973. - 448 pp. or N. V. Keltsev. Fundamentals of adsorption technology. 2nd ed., revised and enlarged. - M.: Chemistry, 1948, T. 1. - 592 p.). A sample of an air-dry sample of mesoporous titanium dioxide weighing about 0.1 g was placed in a glass cup, which was suspended on a spring quartz balance in a vacuum installation tube. The cavity of the vacuum unit with the sample was evacuated for 3 hours, maintaining the value of the residual pressure in the cavity equal to 10 ^-3 mm Hg At the same time, a sample of mesoporous titanium dioxide was additionally thermostated at a temperature of about 100 ° C 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 lowered to 20 ° C. Using a catheter with a division value of 0.01 mm, the initial tensile value of the spring of the balance with the sample suspended on it was recorded and the initial mass of the sample corresponding to this tensile value was determined from the calibration table. Through the vacuum valve, the installation cavity was hermetically connected to a vessel partially filled with liquid methanol. The faucet was opened and methanol vapor above this liquid adsorbent entered the cavity of the unit. The change in the pressure in the cavity of the installation as methanol vapor was introduced into it was recorded with a mercury manometer. After the equilibrium was established in the system (reaching a pressure value in the cavity of the apparatus equal to the pressure value of saturated methanol vapor), the pressure stabilized. Using a catheter, the final tensile value of the spring of the balance with the sample suspended on it was recorded and the final mass of the sample corresponding to this tensile value was determined. The difference in the final and initial masses of the sample, taking into account the molecular weight of methanol, was used to calculate the amount of methanol (in mmol) adsorbed by the sample upon reaching equilibrium in the system and the adsorption value a (mmol / g) of methanol with one gram of the sample was determined. Using the obtained value of a, the value of the methanol monolayer capacity a _{m was} determined using the BET equation (which satisfactorily describes the initial portion of the adsorption isotherm of methyl alcohol vapor). As a result, the specific surface S _beats (in m ² / g) of the sample of mesoporous titanium dioxide was calculated by the formula:

S _beats = a _m · N _A ·,

where a _m is the BET equation calculated (for the initial region of the methanol adsorption isotherm) the methanol monolayer capacity, mmol / g, N _A is the Avagadro number, mmol ^-1 , is the size of the landing site of the methanol molecule, equal to 0.25 · 10 ^-18 m ² according to generally accepted notions (see, for example, A.P. Karnaukhov. Adsorption methods for measuring the specific surface and pore structure of catalysts // Kinetics and Catalysis. - 1962. - T.3, No. 3. - S.583-598).

Based on the model of disjoint cylindrical pores, the average pore diameter D _cp (in nm) formed in the sample of mesoporous titanium dioxide was determined from the ratio (see ibid.):

D _cp = 4 · 10 ⁹ V _s / S _beats ,

where S _beats - the previously obtained value of the specific surface of the sample of mesoporous titanium dioxide, m ² / g, V _s = a · V _o is the maximum sorption volume of pores, m ² / g, determined by the adsorption weight method using the above-described vacuum installation at a temperature of 20 ° C and the pressure in its cavity, equal to the pressure value of the saturated vapors of methanol, and a is the adsorption limit a (mmol / g) of methanol previously obtained under the same experimental conditions, V _o is the molar volume of liquid methanol equal to 4.05 · 10 ^-8 m ³ / mmol.

X-ray phase analysis of samples of mesoporous titanium dioxide for the content of the crystalline phase of anatase in them was carried out on a DRON-3M diffractometer using copper, nickel-filtered, radiation at a voltage of 30 kV and a current strength of 20 mA, the gap when shooting in the small-angle region of 1.0-1.0 -0.5, in the middle and far regions of the corners - 2.0-2.0-1.0 (see, for example, L.I. Mirkin. Handbook of X-ray structural analysis of polycrystals. - M.: State ed. - in physical and physical-mathematical literature, 1961. - 863 p. or V.I. Mikheev, X-ray determinant of minerals. - M .: Gosgeoltekhizdat, 195 7 .-- 868 p.). The anatase content in mesoporous titanium dioxide was determined by the relative intensity of characteristic reflexes at 2θ = 25.4 ° in comparison with a sample of dispersed material of the Degussa P25 brand from Degussa, in which the anatase content is known.

The photocatalytic activity of the obtained samples of mesoporous titanium dioxide was evaluated by a known method (see, for example, Kryukov A.I., Korzhak A.V., Kuchmiy S.Ya. Photocatalytic formation of hydrogen in alcohol solutions of titanium tetrachloride // Theoretical and experimental chemistry . - 1984.- t.20, No. 2. - S.169-177). For this, a suspension consisting of 0.05 g of titanium dioxide and 0.02 g of the dark reaction stage catalyst — palladium silica gel (0.2 wt% palladium of the total catalyst mass) in 10 ml of ethanol containing 2 mol, was placed in a glass reactor. / l of water. With constant stirring of the suspension at a temperature of 40 ° C, it was irradiated with the light of a high-pressure mercury lamp type DRSh-1000, highlighting quanta with a wavelength of about 360 nm using a UFS-2 glass sphytofilter. The total number of quanta absorbed by the reaction system per unit time (I, Einstein / min or mol-quantum / min) was determined by a ferrioxalate chemical actinometer using the following relationship:

I = n _{Fe (II)} / Ф _e ,

where n _{Fe (II)} is the number of iron (II) ions formed during irradiation of a ferrioxalate solution, Ф _e is the tabular value of the quantum yield of iron (II) formation for a given irradiation wavelength.

Using the obtained value of I, the quantum yields Φ _{H2 of the} photocatalytic reaction for the liberation of molecular hydrogen from water-alcohol mixtures were calculated in the presence of the obtained samples of mesoporous titanium dioxide and a palladium catalyst of the dark reaction stage:

Ф _H2 = 2m _Н2 / I,

where m _H2 is the rate of formation of molecular hydrogen in mol / min, which was determined by chromatographic method.

In order not to repeatedly repeat a sufficiently long, requiring separate stages control, the process of forming a titanium dioxide / organic template composition of a spatial structure of a reagent mixture specially synthesized a sufficiently large amount of such a structure. After separating the resulting structure by filtration from the mother liquor, then drying in air until the solvent was almost completely removed and crushed in a dispersant, it was stored in a glass container as an intermediate. As the test results showed, such an intermediate product consisting of titanium dioxide and one of the oxo- or oxaazamacrocyclic compounds containing at least four oxygen atoms (preferably not more than ten) and / or one of the complexes of these macrocyclic compounds with an alkaline ion (lithium, sodium, potassium, rubidium, cesium), or alkaline earth (magnesium, calcium, strontium, barium), or f-metal (lanthanum, cerium), is resistant to changes and decomposition during long-term storage (at least a year). To prepare the required amount of mesoporous titanium dioxide photocatalyst with a freshly formed and therefore chemically active surface, we took the corresponding portion of the intermediate product, which was calcined according to the above procedure until the template was removed and the necessary amount of photocatalytically active anatase was formed in titanium dioxide.

In order for the intermediate to be suitable for the production of mesoporous titanium dioxide - a photocatalyst by extraction of the template with alcohol, it was preliminarily subjected to hydrothermal treatment using the above-described method until the necessary amount of photocatalytic formation was obtained in titanium dioxide by filtering from the mother liquor, drying and grinding it with the mother liquor active anatase.

The content of the organic product in the intermediate was determined by the following method. A small (about 0.5 g) portion of the intermediate was poured into the crucible and weighed together with the crucible on an analytical balance. Then the crucible with the intermediate product was placed in a muffle furnace and the contents of the crucible were calcined (calcined) at a temperature of 600 ° C for the time required to remove the template. The criterion for the complete removal of the template from the intermediate product and the preparation of the final product of mesoporous titanium dioxide was the achievement by the contents of the crucible of constant mass after its loss in the process of detection, which was easily determined by sequential weighing on an analytical balance of the crucible with the material after cooling. By the mass difference 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 was determined and the molar content of the titanium dioxide and the organic template in the intermediate was calculated.

Example 2

An oxamacrocyclic tetramethyl-12-corona-4 compound of the general formula C ₁₂ H ₂₄ O _{4 was} used as an organic template for the synthesis of mesoporous titanium dioxide, titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti was used as a precursor, and alcohol solvent - n-butanol containing water in an amount of 7 wt.%. 170 ml of this aqueous-alcoholic solvent were poured into one glass beaker. 0.141 g of template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 25 ° C with a thermostat, and the relative humidity was 65% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 38 wt.%, Had a porous structure with an average pore diameter D _cp. = 9.1 nm and specific surface area S _beats. = 85 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.52 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide accounted for 0.01 moles of organic template-tetramethyl-12-corona-4.

Example 3

An oxamacrocyclic compound dibenzo-18-corona-6 of the general formula C ₂₀ H ₂₄ O _{6 was} used as an organic template for the synthesis of mesoporous titanium dioxide, titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti was used as a precursor, and alcohol solvent - n-butanol containing water in an amount of 6.5 wt.%. 175 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 0.135 g of template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 20 ° C with a thermostat, and the relative humidity was 65% using a saturated solution of ammonium nitrate. The mixture was contacted with water vapor at this temperature for 17 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 180 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 55 wt.%, Had a porous structure with an average pore diameter D _cp. = 9.5 nm and specific surface S _beats. = 76 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.58 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide accounted for 0.005 mol of the organic template-dibenzo-18-corona-6.

Example 4

An oxamacrocyclic dibenzo-30-corona-10 compound of the general formula C ₂₈ H ₄₀ O _{10 was} used as an organic template for the synthesis of mesoporous titanium dioxide, titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti was used as a precursor, and alcohol solvent - n-butanol containing 5 wt.% water. 180 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.042 g of template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 1.5 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 30 ° C using a thermostat and 85% relative humidity was saturated with a saturated solution of potassium chloride. The mixture was contacted with water vapor at this temperature for 12 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 185 ° C it was hydrothermally treated for 43 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 55 wt.%, Had a porous structure with an average pore diameter D _cp. = 9.3 nm and specific surface S _beats. = 70 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.54 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide accounted for 0.001 mol of the organic template-dibenzo-30-corona-10.

Example 5

Oxaazamacrocyclic compound 18-Coronaase-2-oxa-4 of the general formula C ₁₂ H ₂₆ O ₄ N _{2 was} used as an organic template for the synthesis of mesoporous titanium dioxide, titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti was used as a precursor as a water-alcohol solvent, n-butanol containing 7 wt.% water was poured into one glass beaker 167 ml of this water-alcohol solvent. 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. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A beaker with the mixture was placed in a chamber where the temperature was maintained at about 25 ° C with a thermostat, and the relative humidity was 62% with a saturated solution of ammonium nitrate. The mixture was contacted with water vapor at this temperature for 15 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C it was hydrothermally treated for 50 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 47 wt.%, Had a porous structure with an average pore diameter D _cp. = 8.5 nm and specific surface area S _beats. = 78 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.55 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide accounted for 0.005 moles of organic template-18-Coronaase-2-oxa-4.

Example 6

Oxaazamacrocyclic compound 18-Coronaase-1-oxa-5 of the general formula C ₁₂ H ₂₅ O ₅ N was used as an organic template for the synthesis of mesoporous titanium dioxide, titanium tetrapropoxide of the general formula (C ₃ H ₇ O) ₄ Ti, in as a water-alcohol solvent, n-propanol containing 5 wt.% water was poured into a glass beaker into 141 ml of this water-alcohol solvent. 0.197 g of template was dissolved in it at room temperature. 40 ml of the same solvent was poured into another glass beaker. At room temperature, 21 g of the precursor was dissolved in it. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 3 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 15 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 15 ° C with a thermostat, and the relative humidity was 81% using a saturated solution of ammonium sulfate. The mixture was contacted with water vapor at this temperature for 18 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 165 ° C it was hydrothermally treated for 52 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 42 wt.%, Had a porous structure with an average pore diameter D _cp. = 8.9 nm and specific surface area S _beats. = 72 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.51 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide accounted for 0.01 moles of organic template-18-Coronaase-1-oxa-5.

Example 7

A complex of oxamacrocyclic tetramethyl-12-corona-4 compounds with a lithium ion of the general formula [Li (C ₁₂ H ₂₄ O ₄ ] Cl · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide of the general formula ( C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent — n-butanol containing 4 wt.% Water. 166 ml of this water-alcohol solvent was poured into a glass beaker, 0.426 g of template was dissolved in it at room temperature. In another glass beaker, 45 ml of such e of the solvent. 25 g of the precursor was dissolved in it at room temperature. The precursor solution was added dropwise into the template solution with vigorous stirring. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until the mixture formed sol.

The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A beaker with the mixture was placed in a chamber where the temperature was maintained at about 25 ° C with a thermostat, and the relative humidity was 62% with a saturated solution of ammonium nitrate. The mixture was contacted with water vapor at this temperature for 13 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 100 ° C it was hydrothermally treated for 56 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 350 ° C for 7.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 50 wt.%, Had a porous structure with an average pore diameter D _cp. = 6.8 nm and specific surface area S _beats. = 104 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.62 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide accounted for 0.02 moles of an organic template — a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a lithium ion.

Example 8

A complex of oxamacrocyclic tetramethyl-12-corona-4 compound with potassium ion of the general formula [K (C ₁₂ H ₂₄ O ₄ )] J · 2H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide of the general formula was used as a precursor (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 6 wt.% Water. 171 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 1.375 g of template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 20 ° C with a thermostat, and the relative humidity was 65% with a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 16 days until the final formation of the mixture of the 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 100 ° C it was hydrothermally treated for 57 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 450 ° C for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 56 wt.%, Had a porous structure with an average pore diameter D _cp. = 8.5 nm and specific surface area S _beats. = 94 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.71 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide was 0.1 mole of an organic template — a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with potassium ion.

Example 9

A complex of oxamacrocyclic tetramethyl-12-corona-4 compound with potassium ion of the general formula [K (C ₁₂ H ₂₄ O ₄ )] J · 2H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide of the general formula was used as a precursor (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent — n-butanol containing 6 wt.% Water. 171 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 1.375 g of template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 20 ° C with a thermostat, and the relative humidity was 65% with a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 16 days until the final formation of the mixture of the 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 100 ° C it was hydrothermally treated for four days. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the crushed dry mixture was poured into a glass beaker. With vigorous stirring, the required amount of ethyl alcohol, preliminarily heated to the boiling point, was added to the glass, and the organic template was removed from the structure by the method described in example 1. After the de-sampling of the structure, the solid phase was separated by filtration from the suspension. It was dried until the solvent was almost completely removed, and then ground.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 32 wt.%, Had a porous structure with an average pore diameter D _cp. = 5.8 nm and specific surface area S _beats. = 71 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.52 in the presence of a palladium or platinum catalyst of the dark reaction stage.

About 0.1 moles of an organic template — a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with potassium ion — accounted for one mole of titanium dioxide in the isolated intermediate to obtain mesoporous titanium dioxide.

Example 10

A complex of oxamacrocyclic tetramethyl-12-corona-4 compound with potassium ion of the general formula [K (C ₁₂ H ₂₄ O ₄ )] J · 2H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide of the general formula was used as a precursor (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 6 wt.% Water. 171 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 1.375 g of template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 20 ° C with a thermostat, and the relative humidity was 65% with a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 16 days until the final formation of the mixture of the spatial structure 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 450 ° C for 5.5 hours until the organic template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 53 wt.%, Had a porous structure with an average pore diameter D _cp. = 7.3 nm and specific surface area S _beats. = 91 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.67 in the presence of a palladium or platinum catalyst of the dark reaction stage.

About 0.11 moles of an organic template — a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with potassium ion — accounted for one mole of titanium dioxide in the isolated intermediate to obtain mesoporous titanium dioxide.

Example 11

A complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a sodium ion of the general formula [Na (C ₁₂ H ₂₄ O ₄ )] Cl · 2H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide of the general formula was used as a precursor (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-butanol containing water in an amount of 6.5 wt.%. 175 ml of this aqueous-alcoholic 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. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 3 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 15 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 15 ° C with a thermostat, and the relative humidity was 76% with a saturated solution of sodium chloride. The mixture was contacted with water vapor at this temperature for 19 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 64 wt.%, Had a porous structure with an average pore diameter of D _cp. = 12.5 nm and specific surface S _beats. = 115 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.73 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 moles of an organic template — a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with sodium ion.

Example 12

A complex of the oxamacrocyclic tetramethyl-12-corona-4 compound with a rubidium ion of the general formula [Rb (C ₁₂ H ₂₄ O ₄ )] Br · 2H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrapropoxide of the general formula was used as a precursor (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-propanol containing 5.5 wt.% Water. 145 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 0.612 g of 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. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 30 ° C with a thermostat, and the relative humidity was 60% using a saturated solution of ammonium nitrate. The contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 150 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 61 wt.%, Had a porous structure with an average pore diameter D _cp. = 12.1 nm and specific surface area S _beats. = 110 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.69 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.02 moles of an organic template — a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a rubidium ion.

Example 13

A complex of oxamacrocyclic tetramethyl-12-corona-4 compounds with a cesium ion of the general formula [Cs (C ₁₂ H ₂₄ O ₄ )] NO ₃ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrapropoxide common of the formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent n-propanol containing water in an amount of 4.5 wt.% 136 ml of this water-alcohol solvent were poured into a glass beaker. 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. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 25 ° C with a thermostat, and the relative humidity was 75% with a saturated solution of sodium chloride. The mixture was contacted with water vapor at this temperature for 17 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 100 ° C it was hydrothermally treated for 58 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 550 ° C for 5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 45 wt.%, Had a porous structure with an average pore diameter D _cp. = 11.3 nm and specific surface S _beats. = 87 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.56 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide accounted for 0.02 moles of an organic template — a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with cesium ion.

Example 14

A complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a magnesium ion of the general formula [Mg (C ₁₂ H ₂₄ O ₄ )] SO ₄ · 4H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 6.5 wt.%. 180 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 0.570 g of template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 3.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 14 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 14 ° C with a thermostat, and a relative humidity of 69% was achieved using a saturated solution of ammonium nitrate. The mixture was contacted with water vapor at this temperature for 20 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 55 wt.%, Had a porous structure with an average pore diameter D _cp. = 9.1 nm and specific surface area S _beats. = 77 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.70 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide accounted for 0.02 moles of an organic template - a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a magnesium ion.

Example 15

A complex of the oxamacrocyclic tetramethyl-12-corona-4 compound with a calcium ion of the general formula [Ca (C ₁₂ H ₂₄ O ₄ )] Cl ₂ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5.5 wt.%. 166 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 0.530 g of template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 30 ° C using a thermostat, and a relative humidity of 80% was saturated with a saturated solution of ammonium sulfate. The mixture was contacted with water vapor at this temperature for 12 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 170 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 52 wt.%, Had a porous structure with an average pore diameter D _cp. = 9.3 nm and specific surface S _beats. = 77 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.61 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.02 moles of an organic template — a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a calcium ion.

Example 16

A complex of the oxamacrocyclic tetramethyl-12-corona-4 compound with a strontium ion of the general formula [Sr (C ₁₂ H ₂₄ O ₄ )] Cl ₂ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent - n-butanol containing water in an amount of 7 wt.%. 181 ml of this aqueous-alcoholic 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. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 30 ° C with a thermostat, and the relative humidity was 63% with a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 100 ° C it was hydrothermally treated for 55 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 52 wt.%, Had a porous structure with an average pore diameter D _cp. = 9.7 nm and specific surface area S _beats. = 94 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.68 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.02 moles of an organic template — a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with strontium ion.

Example 17

A complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a barium ion of the general formula [Ba (C ₁₂ H ₂₄ O ₄ )] Cl ₂ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent - n-butanol containing water in an amount of 7 wt.%. 174 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 0.338 g of the template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 1.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 35 ° C. After ash formation, the stirring of the mixture was stopped. A beaker with the mixture was placed in a chamber where the temperature was maintained at about 35 ° C with a thermostat, and the relative humidity was 62% with a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 12 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 100 ° C 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 the solvent was almost completely removed from it. The dried mixture was stored in a glass container as an intermediate to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 35 wt.%, Had a porous structure with an average pore diameter D _cp. = 10.8 nm and specific surface area S _beats. = 89 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.59 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide accounted for 0.01 moles of an organic template — a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a barium ion.

Example 18

A complex of the oxamacrocyclic tetramethyl-12-corona-4 compound with a lanthanum ion of the general formula [La (C ₁₂ H ₂₄ O ₄ )] Cl ₃ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 6 wt.%. 184 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 0.708 g of template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 25 ° C with a thermostat, and the relative humidity was 75% with a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 100 ° C it was hydrothermally treated for 53 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed.

The thus-obtained mesoporous titanium dioxide comprises a crystalline anatase phase in an amount of 51 wt.%, Had a porous structure with average pore diameter D _cp. = 12.8 nm and specific surface area S _beats. = 119 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.62 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the selected intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide accounted for 0.02 moles of an organic template — a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with lanthanum ion.

Example 19

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a cerium ion of the general formula [Ce (C ₁₂ H ₂₄ O ₄ )] Cl ₃ · 3H ₂ O, and a titanium tetrabutoxide of total formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5.5 wt.%. 163 ml of this aqueous-alcoholic solvent were poured into one glass beaker. 0.355 g of template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 20 ° C with a thermostat, and the relative humidity was 76% using a saturated solution of sodium chloride. The mixture was contacted with water vapor at this temperature for 15 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 61 wt.%, Had a porous structure with an average pore diameter D _cp. = 13.3 nm and specific surface area S _beats. = 117 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.65 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.01 moles of an organic template — a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with cerium ion.

Example 20

A complex of the oxamacrocyclic compound dibenzo-18-corona-6 with a lithium ion of the general formula [Li (C ₂₀ H ₂₄ O ₆ )] Cl · 2C ₂ H ₅ OH was used as an organic template for the synthesis of mesoporous titanium dioxide, titanium tetrapropoxide was used as a precursor of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-amyl alcohol containing water in an amount of 4.5 wt.%. 210 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 3.609 g of a template were dissolved in it at room temperature. 55 ml of the same solvent was poured into another glass beaker. At room temperature, 21 g of the precursor was dissolved in it. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber in which the temperature was maintained at about 25 ° C with a thermostat, and a relative humidity of 80% with a saturated solution of ammonium sulfate. The mixture was contacted with water vapor at this temperature for 16 days until the final formation of the mixture of the 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 175 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 350 ° C for 6.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 45 wt.%, Had a porous structure with an average pore diameter D _cp. = 10.9 nm and specific surface S _beats. = 139 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.52 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide was 0.1 mole of an organic template — a complex of the oxamacrocyclic compound dibenzo-18-corona-6 with lithium ion.

Example 21

A complex of oxamacrocyclic compound dibenzo-18-corona-6 with a sodium ion of the general formula [Na (C ₂₀ H ₂₄ O ₆ )] Cl · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide of the general formula was used as a precursor (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent - n-butanol containing water in an amount of 7 wt.%. 170 ml of this aqueous-alcoholic solvent were 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. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. Under vigorous stirring, a precursor solution was introduced dropwise into the solution of the template and lanthanum salts. After the entire portion of this solution was introduced into the solution of the template and lanthanum salts, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 25 ° C with a thermostat, and the relative humidity was 65% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 90 wt.%, Had a porous structure with an average pore diameter D _cp. = 13.8 nm and specific surface S _beats. = 130 m ² / g. In addition, it additionally contained lanthanum in an amount of about 0.011 g per g of substance. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided the maximum possible quantum yield of the reaction Ф _H2 = 1.0 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 moles of an organic template — a complex of the oxamacrocyclic compound dibenzo-18-corona-6 with sodium ion and about 0.006 moles of lanthanum chloride.

Example 22

A complex of oxamacrocyclic compound dibenzo-18-corona-6 with potassium ion of the general formula [K (C ₂₀ H ₂₄ O ₆ )] J · 2H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrapropoxide of the general formula was used as a precursor (C ₄ H ₉ O) ₄ Ti, methanol containing water in an amount of 6.5 wt.% As a water-alcohol solvent. 100 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 8.205 g of the template was dissolved in it, then 0.798 g of lanthanum chloride. 50 ml of the same solvent was poured into another glass beaker. At room temperature, 21 g of the precursor was dissolved in it. With vigorous stirring, a solution of the precursor and lanthanum salt was introduced dropwise into the solution of the template. After the entire portion of this solution was introduced into the template solution, the resulting mixture was continued to mix for 3 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 15 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 15 ° C with a thermostat, and a relative humidity of 69% - with a saturated solution of ammonium nitrate. The mixture was contacted with water vapor at this temperature for 16 days until the final formation of the mixture of the 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 175 ° C it was hydrothermally treated for 50 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 450 ° C for 5.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 71 wt.%, Had a porous structure with an average pore diameter D _cp. = 11.3 nm and specific surface S _beats. = 119 m ² / g. In addition, it additionally contained lanthanum in an amount of about 0.018 g per g of substance. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.87 in the presence of a palladium or platinum catalyst of the dark reaction stage.

0.2 mol of an organic template — a complex of the oxamacrocyclic compound dibenzo-18-corona-6 with potassium ion and about 0.038 g of lanthanum chloride per gram of titanium dioxide — was produced per mol of titanium dioxide in the selected intermediate.

Example 23

A complex of oxamacrocyclic compound dibenzo-18-corona-6 with a rubidium ion of the general formula [Rb (C ₂₀ H ₂₄ O ₄ )] Br · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide of the general formula was used as a precursor (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 6 wt.% Water. 180 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 8.467 g of the template were dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 25 ° C with a thermostat, and the relative humidity was 75% with a saturated solution of sodium chloride. The mixture was contacted with water vapor at this temperature for 15 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 75 wt.%, Had a porous structure with an average pore diameter D _cp. = 12.0 nm and specific surface S _beats. = 121 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.85 in the presence of a palladium or platinum catalyst of the dark reaction stage.

0.2 mol of an organic template — a complex of the oxamacrocyclic compound dibenzo-18-corona-6 with a rubidium ion, was accounted for one mole of titanium dioxide in the isolated intermediate to obtain mesoporous titanium dioxide.

Example 24

A complex of the oxamacrocyclic compound dibenzo-18-corona-6 with a cesium ion of the general formula [Cs (C ₂₀ H ₂₄ O ₆ )] NO ₃ · 2H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetraethoxide total formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is ethanol containing water in an amount of 5 wt.%. 120 ml of this aqueous-alcoholic 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. At room temperature, 18 g of the precursor was dissolved in it. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 4 hours until a sol was formed from the mixture. The temperature of the mixture during this synthesis step was maintained at about 10 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was kept at about 10 ° C with a thermostat, and the relative humidity was 73% using a saturated solution of ammonium nitrate. The mixture was contacted with water vapor at this temperature for 19 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 100 ° C it was hydrothermally treated for 53 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 550 ° C for 5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 72 wt.%, Had a porous structure with an average pore diameter D _cp. = 9.2 nm and specific surface S _beats. = 90 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.82 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide was 0.1 mole of an organic template — a complex of the oxamacrocyclic compound dibenzo-18-corona-6 with cesium ion.

Example 25

A complex of oxamacrocyclic compound dibenzo-18-corona-6 with a magnesium ion of the general formula [Mg (C ₂₀ H ₂₄ O ₄ )] SO ₄ · 4H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 6.5 wt.%. 177 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 4.040 g of template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 25 ° C with a thermostat, and the relative humidity was 75% with a saturated solution of sodium chloride. The mixture was contacted with water vapor at this temperature for 16 days until the final formation of the mixture of the 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 200 ° C it was hydrothermally treated for 51 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 77 wt.%, Had a porous structure with an average pore diameter D _cp. = 12.9 nm and specific surface S _beats. = 115 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.80 in the presence of a palladium or platinum catalyst of the dark reaction stage.

0.1 mol of the organic template of the oxamacrocyclic compound of the dibenzo-18-corona-6 compound with the magnesium ion accounted for one mole of titanium dioxide in the isolated intermediate to obtain mesoporous titanium dioxide.

Example 26

A complex of oxamacrocyclic compound dibenzo-18-corona-6 with a calcium ion of the general formula [Ca (C ₂₀ H ₂₄ O ₆ )] Cl ₂ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 7 wt.%. 183 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 3.834 g of template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 30 ° C using a thermostat, and a relative humidity of 80% was saturated with a saturated solution of ammonium sulfate. The mixture was contacted with water vapor at this temperature for 13 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 58 wt.%, Had a porous structure with an average pore diameter of D _cp. = 10.6 nm and specific surface area S _beats. = 157 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.63 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide there was 0.1 mole of an organic template — a complex of the oxamacrocyclic compound dibenzo-18-corona-6 with calcium ion.

Example 27

A complex of oxamacrocyclic compound dibenzo-18-corona-6 with a strontium ion of the general formula [Sr (C ₂₀ H ₂₄ O ₆ )] Cl ₂ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent - n-butanol containing water in an amount of 5 wt.%. 172 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 0.859 g of template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 30 ° C with a thermostat, and the relative humidity was 75% with a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C it was hydrothermally treated for 47 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 400 ° C for 5.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 62 wt.%, Had a porous structure with an average pore diameter D _cp. = 12.2 nm and specific surface S _beats. = 127 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.70 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.02 moles of an organic template — a complex of the oxamacrocyclic compound dibenzo-18-corona-6 with strontium ion.

Example 28

A complex of oxamacrocyclic compound dibenzo-18-corona-6 with a barium ion of the general formula [Ba (C ₂₀ H ₂₄ O ₆ )] Cl ₂ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5.5 wt.%. 162 ml of this aqueous-alcoholic 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. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 3 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 30 ° C with a thermostat, and the relative humidity was 75% with a saturated solution of sodium chloride. The mixture was contacted with water vapor at this temperature for 17 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 73 wt.%, Had a porous structure with an average pore diameter D _cp. = 14.3 nm and specific surface area S _beats. = 107 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.75 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.02 moles of an organic template — a complex of the oxamacrocyclic compound dibenzo-18-corona-6 with barium ion.

Example 29

A complex of oxamacrocyclic compound dibenzo-18-corona-6 with a lanthanum ion of the general formula [La (C ₂₀ H ₂₄ O ₆ )] Cl ₃ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 4.5 wt.%. 175 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 4.703 g of a template were dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 3.5 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 17 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 17 ° C with a thermostat, and the relative humidity was 65% with a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 20 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 470 ° C for 5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 81 wt.%, Had a porous structure with an average pore diameter D _cp. = 13.7 nm and specific surface S _beats. = 125 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.79 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide there was 0.1 mole of an organic template — a complex of the oxamacrocyclic compound dibenzo-18-corona-6 with lanthanum ion.

Example 30

A complex of the oxamacrocyclic compound dibenzo-18-corona-6 with a cerium ion of the general formula [Ce (C ₂₀ H ₂₄ O ₆ )] Cl ₃ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 6 wt.%. 185 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 2.356 g of template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 3 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 20 ° C with a thermostat, and the relative humidity was 76% using a saturated solution of sodium chloride. The mixture was contacted with water vapor at this temperature for 17 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 70 wt.%, Had a porous structure with an average pore diameter of D _cp. = 14.8 nm and specific surface S _beats. = 122 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.74 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.05 moles of an organic template — a complex of the oxamacrocyclic compound dibenzo-18-corona-6 with cerium ion.

Example 31

A complex of the oxamacrocyclic compound dibenzo-30-corona-10 with a lithium ion of the general formula [Li (C ₂₈ H ₄₀ O ₁₀ )] Br · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide of the general formula was used as a precursor (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent - n-butanol containing water in an amount of 7 wt.%. 193 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 4.941 g of the template were dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 30 ° C with a thermostat, and the relative humidity was 75% with a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 100 ° C it was hydrothermally treated for 56 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 350 ° C for 5.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 40 wt.%, Had a porous structure with an average pore diameter D _cp. = 10.8 nm and specific surface area S _beats. = 118 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.50 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide there was 0.1 mole of an organic template — a complex of the oxamacrocyclic compound dibenzo-30-corona-10 with lithium ion.

Example 32

A complex of oxamacrocyclic compound dibenzo-30-corona-10 with potassium ion of the general formula [K (C ₂₈ H ₄₀ O ₄ )] J · 2H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide of the general formula was used as a precursor (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-butanol containing 5.7 wt.% Water. 175 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 5.392 g of template were dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 30 ° C using a thermostat, and a relative humidity of 80% was saturated with a saturated solution of ammonium sulfate. The mixture was contacted with water vapor at this temperature for 13 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 180 ° C it was hydrothermally treated for 52 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 52 wt.%, Had a porous structure with an average pore diameter D _cp. = 16 nm and specific surface S _beats. = 122 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.65 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide was 0.1 mole of an organic template — a complex of the oxamacrocyclic compound dibenzo-30-corona-10 with potassium ion.

Example 33

A complex of oxamacrocyclic compound dibenzo-30-corona-10 with a sodium ion of the general formula [Mg (C ₂₈ H ₄₀ O ₁₀ )] Cl · 2H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide of the general formula was used as a precursor (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-butanol containing 5.7 wt.% Water. 168 ml of this aqueous-alcoholic solvent were poured into one glass beaker. 4.606 g of a template were dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber in which the temperature was maintained at about 25 ° C with a thermostat, and a relative humidity of 80% with a saturated solution of ammonium sulfate. The mixture was contacted with water vapor at this temperature for 16 days until the final formation of the mixture of the 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 100 ° C it was hydrothermally treated for 57 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 400 ° C for 6 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 70 wt.%, Had a porous structure with an average pore diameter of D _cp. = 10.6 nm and specific surface area S _beats. = 112 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.71 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide was 0.1 mole of an organic template — a complex of the oxamacrocyclic compound dibenzo-30-corona-10 with sodium ion.

Example 34

A complex of the oxamacrocyclic compound dibenzo-30-corona-10 with a rubidium ion of the general formula [Rb (C ₂₈ H ₄₀ O ₁₀ )] Br · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide of the general formula was used as a precursor (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent - n-butanol containing water in an amount of 6 wt.%. 146 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 1.134 g of a template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 4 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 15 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 15 ° C with a thermostat, and a relative humidity of 69% - with a saturated solution of ammonium nitrate. The mixture was contacted with water vapor at this temperature for 19 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 170 ° C it was hydrothermally treated for 56 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 350 ° C for 6.5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 66 wt.%, Had a porous structure with an average pore diameter of D _cp. = 11.4 nm and specific surface S _beats. = 142 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.70 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.02 moles of an organic template — a complex of the oxamacrocyclic compound dibenzo-30-corona-10 with a rubidium ion.

Example 35

A complex of the oxamacrocyclic compound dibenzo-24-corona-8 with a cesium ion of the general formula [Cs (C ₂₄ H ₃₂ O ₈ )] NO ₃ · 4H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-hexyl alcohol containing water in an amount of 6.5 wt.%. 246 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 1.073 g of the template was dissolved in it. 74 ml of the same solvent were poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 4 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 25 ° C with a thermostat, and the relative humidity was 75% with a saturated solution of sodium chloride. The mixture was contacted with water vapor at this temperature for 15 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 150 ° C it was hydrothermally treated for 58 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 72 wt.%, Had a porous structure with an average pore diameter D _cp. = 12.7 nm and specific surface S _beats. = 90 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.78 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.02 moles of an organic template — a complex of the oxamacrocyclic compound dibenzo-24-corona-8 with cesium ion.

Example 36

A complex of oxamacrocyclic compound dibenzo-30-corona-10 with a magnesium ion of the general formula [Mg (C ₂₈ H ₄₀ O ₁₀ )] SO ₄ · 4H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5.5 wt.%. 176 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 1.092 g of a template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 35 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 35 ° C with a thermostat, and a relative humidity of 80% with a saturated solution of ammonium sulfate. The mixture was contacted with water vapor at this temperature for 12 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C it was hydrothermally treated for 57 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 65 wt.%, Had a porous structure with an average pore diameter D _cp. = 15.7 nm and specific surface area S _beats. = 129 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.67 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.02 moles of an organic template — a complex of the oxamacrocyclic compound dibenzo-30-corona-10 with a magnesium ion.

Example 37

A complex of oxamacrocyclic compound dibenzo-30-corona-10 with a calcium ion of the general formula [Ca (C ₂₈ H ₄₀ O ₁₀ )] Cl ₂ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 7 wt.%. 198 ml of this aqueous-alcoholic solvent were poured into one glass beaker. 5.120 g of template were dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 30 ° C with a thermostat, and the relative humidity was 63% with a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure, together with the mother liquor, was placed in an autoclave, where at a temperature of 175 ° C it was hydrothermally treated for 58 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 52 wt.%, Had a porous structure with an average pore diameter D _cp. = 15.0 nm and specific surface S _beats. = 120 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.61 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide there was 0.1 mole of an organic template — a complex of the oxamacrocyclic compound dibenzo-30-corona-10 with calcium ion.

Example 38

A complex of oxamacrocyclic compound dibenzo-24-corona-8 with a strontium ion of the general formula [Sr (C ₂₄ H ₃₂ O ₈ )] Cl ₂ · 2H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and a titanium tetraethoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is ethanol containing water in an amount of 6 wt.%. 124 ml of this aqueous-alcoholic solvent were poured into one glass beaker. 4.693 g of the template was dissolved in it at room temperature. 32 ml of the same solvent was poured into another glass beaker. At room temperature, 18 g of the precursor was dissolved in it. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 3 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 2 ° C with a thermostat, and the relative humidity was 75% with a saturated solution of sodium chloride. The mixture was contacted with water vapor at this temperature for 17 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 100 ° C it was hydrothermally treated for 56 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 50 wt.%, Had a porous structure with an average pore diameter D _cp. = 12.0 nm and specific surface S _beats. = 77 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.62 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 moles of an organic template — a complex of the oxamacrocyclic compound dibenzo-24-corona-6 with strontium ion.

Example 39

A complex of the oxamacrocyclic compound dibenzo-30-corona-10 with a barium ion of the general formula [Ba (C ₂₈ H ₄₀ O ₁₀ )] Cl ₂ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrapropoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-heptyl alcohol containing water in an amount of 7 wt.%. 270 ml of this aqueous-alcoholic solvent were poured into one glass beaker. 2.915 g of the template were dissolved in it at room temperature. 75 ml of the same solvent was poured into another glass beaker. At room temperature, 21 g of the precursor was dissolved in it. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 30 ° C with a thermostat, and the relative humidity was 75% with a saturated solution of sodium chloride. The mixture was contacted with water vapor at this temperature for 13 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure, together with the mother liquor, was placed in an autoclave, where it was hydrothermally treated for 56 hours at a temperature of 155 ° C. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 54 wt.%, Had a porous structure with an average pore diameter D _cp. = 11.7 nm and specific surface S _beats. = 89 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.59 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.05 moles of an organic template — a complex of the oxamacrocyclic compound dibenzo-30-corona-10 with barium ion.

Example 40

A complex of oxamacrocyclic compound dibenzo-24-corona-8 with a lanthanum ion of the general formula [La (C ₂₄ H ₃₂ O ₈ )] Cl ₃ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 6 wt.%. 184 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 5.349 g of template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 30 ° C with a thermostat, and the relative humidity was 63% with a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure, together with the mother liquor, was placed in an autoclave, where at a temperature of 175 ° C it was hydrothermally treated for 58 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 70 wt.%, Had a porous structure with an average pore diameter of D _cp. = 15.2 nm and specific surface S _beats. = 133 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.78 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide was 0.1 mole of an organic template — a complex of the oxamacrocyclic compound dibenzo-24-corona-6 with lanthanum ion.

Example 41

A complex of the oxamacrocyclic compound dibenzo-24-corona-8 with a cerium ion of the general formula [Ce (C ₂₄ H ₃₂ O ₈ )] Cl ₃ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as the hydroalcoholic solvent - n-butanol containing water in an amount of 5 wt.%. 192 ml of this aqueous-alcoholic solvent were poured into one glass beaker. 5.356 g of template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was kept at about 20 ° C with a thermostat, and the relative humidity was 63% using a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 18 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C it was hydrothermally treated for 57 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 65 wt.%, Had a porous structure with an average pore diameter D _cp. = 16.0 nm and specific surface S _beats. = 123 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.73 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide there was 0.1 mole of an organic template — a complex of the oxamacrocyclic compound dibenzo-24-corona-8 with cerium ion.

Example 42

A complex of the oxamacrocyclic compound dibenzo-24-corona-8 with a cerium ion of the general formula [Ce (C ₂₄ H ₃₂ O ₈ )] Cl ₃ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as the hydroalcoholic solvent - n-butanol containing water in an amount of 5 wt.%. 192 ml of this aqueous-alcoholic solvent were poured into one glass beaker. 5.356 g of template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was kept at about 20 ° C with a thermostat, and the relative humidity was 63% using a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 18 days until the final formation of the spatial structure of the 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the organic template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 61 wt.%, Had a porous structure with an average pore diameter D _cp. = 14.5 nm and specific surface S _beats. = 102 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.63 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.11 moles of an organic template — a complex of the oxamacrocyclic compound dibenzo-24-corona-8 with cerium ion.

Example 43

A complex of the oxamacrocyclic compound dibenzo-24-corona-8 with a cerium ion of the general formula [Ce (C ₂₄ H ₃₂ O ₈ )] Cl ₃ · 3H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, and titanium tetrabutoxide common formula (C ₄ H ₉ O) ₄ Ti, as the hydroalcoholic solvent - n-butanol containing water in an amount of 5 wt.%. 192 ml of this aqueous-alcoholic solvent were poured into one glass beaker. 5.356 g of template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was kept at about 20 ° C with a thermostat, and the relative humidity was 63% using a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 18 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure, together with the mother liquor, was placed in an autoclave, where it was hydrothermally treated for three days at a temperature of 200 ° C. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the crushed dry mixture was poured into a glass beaker. With vigorous stirring, the required amount of ethyl alcohol, preliminarily heated to the boiling point, was added to the glass, and the organic template was removed from the structure by the method described in example 1. After the de-sampling of the structure, the solid phase was separated by filtration from the suspension. It was dried until the solvent was almost completely removed, and then ground.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 36 wt.%, Had a porous structure with an average pore diameter D _cp. = 11.5 nm and specific surface S _beats. = 72 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.53 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide there was 0.1 mole of an organic template — a complex of the oxamacrocyclic compound dibenzo-24-corona-8 with cerium ion.

Example 44

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of oxazazamacrocyclic compound 18-Coronaaz-2-oxa-4 with a lithium ion of the general formula [Li (C ₁₂ H ₂₆ O ₄ N ₂ )] Cl · 3H ₂ O, as a precursor titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-butanol containing 5.5 wt.% water. 184 ml of this water-alcohol solvent was poured into one glass beaker. 5.232 g of template were dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A beaker with the mixture was placed in a chamber where the temperature was maintained at about 25 ° C with a thermostat, and the relative humidity was 62% with a saturated solution of ammonium nitrate. The mixture was contacted with water vapor at this temperature for 16 days until the final formation of the mixture of the 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 200 ° C it was hydrothermally treated for 53 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 76 wt.%, Had a porous structure with an average pore diameter D _cp. = 12.4 nm and specific surface S _beats. = 100 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.73 in the presence of a palladium or platinum catalyst of the dark reaction stage.

0.2 mol of an organic template — a complex of oxazazamacrocyclic compound 18-Coronaaz-2-oxa-4 with lithium ion — was produced per mol of titanium dioxide in the isolated intermediate to obtain mesoporous titanium dioxide.

Example 45

A complex of oxazazamacrocyclic compound 18-Coronaaz-2-oxa-4 with a potassium ion of the general formula [K (C ₁₂ H ₂₆ O ₄ N ₂ )] J · 2H ₂ O was used as an organic template for the synthesis of mesoporous titanium dioxide, titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 5 wt.% water. 194 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 6.779 g of the template were dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 30 ° C with a thermostat, and the relative humidity was 63% with a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 15 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 200 ° C it was hydrothermally treated for 50 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 74 wt.%, Had a porous structure with an average pore diameter D _cp. = 12.7 nm and specific surface S _beats. = 105 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.76 in the presence of a palladium or platinum catalyst of the dark reaction stage.

0.2 mol of an organic template — a complex of oxazazamacrocyclic compound 18-Coronaaz-2-oxa-4 with potassium ion — was produced per mol of titanium dioxide in the isolated intermediate for producing mesoporous titanium dioxide.

Example 46

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of 18-Coronaaz-2-oxa-4 oxazamacrocyclic compound with a sodium ion of the general formula [Na (C ₁₂ H ₂₆ O ₄ N ₂ )] Cl · 3H ₂ O, as a precursor titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 7 wt.% water. 204 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 5.209 g of template were dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 30 ° C using a thermostat, and a relative humidity of 80% was saturated with a saturated solution of ammonium sulfate. The mixture was contacted with water vapor at this temperature for 13 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 200 ° C it was hydrothermally treated for 52 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 78 wt.%, Had a porous structure with an average pore diameter D _cp. = 13.1 nm and specific surface S _beats. = 109 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.71 in the presence of a palladium or platinum catalyst of the dark reaction stage.

0.2 mol of an organic template — a complex of oxazazamacrocyclic compound 18-Coronaase-2-oxa-4 with sodium ion, was produced per mol of titanium dioxide in the isolated intermediate to obtain mesoporous titanium dioxide.

Example 47

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of oxazamacrocyclic compound 18-Coronaase-2-oxa-4 with a rubidium ion of the general formula [Rb (C ₁₂ H ₂₆ O ₄ N ₂ )] Br · 3H ₂ O, as a precursor titanium tetraethoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as an aqueous-alcoholic solvent, is ethanol containing 7 wt.% water. 120 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 3.518 g of template was dissolved in it. In another glass beaker was poured 30 ml of the same solvent. At room temperature, 18 g of the precursor was dissolved in it. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 3.5 hours until a sol was formed from the mixture. The temperature of the mixture during this synthesis step was maintained at about 10 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was kept at about 10 ° C with a thermostat, and the relative humidity was 73% using a saturated solution of ammonium nitrate. The mixture was contacted with water vapor at this temperature for 18 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 100 ° C it was hydrothermally treated for 58 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 50 wt.%, Had a porous structure with an average pore diameter D _cp. = 7.9 nm and specific surface area S _beats. = 76 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.51 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide was 0.1 mole of an organic template — a complex of the oxaazamacrocyclic compound 18-Coronaaz-2-oxa-4 with the rubidium ion.

Example 48

As an organic template for the synthesis of mesoporous titanium dioxide, a complex of oxazamacrocyclic compound 18-Coronaase-2-oxa-4 with a cesium ion of the general formula [Cs (C ₁₂ H ₂₆ O ₄ N ₂ )] NO ₃ · 3H ₂ O was used as a precursor - titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 5 wt.% water. 182 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 3.733 g of template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 3 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 15 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 15 ° C with a thermostat, and the relative humidity was 76% with a saturated solution of sodium chloride.

The mixture was contacted with water vapor at this temperature for 17 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 100 ° C it was hydrothermally treated for 55 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 53 wt.%, Had a porous structure with an average pore diameter D _cp. = 7.8 nm and specific surface area S _beats. = 71 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.68 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide was 0.1 mole of an organic template — a complex of the oxaazamacrocyclic compound 18-Coronaase-2-oxa-4 with cesium ion.

Example 49

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of oxazazamacrocyclic compound 18-Coronaase-2-oxa-4 with a magnesium ion of the general formula [Mg (C ₁₂ H ₂₆ O ₄ N ₂ )] SO ₄ · 3H ₂ O as a precursor - titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-butanol containing water in an amount of 5.5 wt.%. 168 ml of this aqueous-alcoholic solvent were poured into one glass beaker. At room temperature, 3.185 g of template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 25 ° C with a thermostat, and the relative humidity was 65% using a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 15 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C it was hydrothermally treated for 52 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 61 wt.%, Had a porous structure with an average pore diameter D _cp. = 9.6 nm and specific surface S _beats. = 92 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.70 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the selected intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide was 0.1 mole of an organic template — a complex of oxazazamacrocyclic compound 18-Coronaase-2-oxa-4 with a magnesium ion.

Example 50

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of oxazazamacrocyclic compound 18-Coronaase-2-oxa-4 with a calcium ion of the general formula [Ca (C ₁₂ H ₂₆ O ₄ N ₂ )] Cl ₂ · 3H ₂ O as a precursor - titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing water in an amount of 4.5 wt.%. 170 ml of this aqueous-alcoholic solvent were poured into one glass beaker. 3.118 g of template were dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 25 ° C with a thermostat, and the relative humidity was 65% using a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 15 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C it was hydrothermally treated for 53 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 64 wt.%, Had a porous structure with an average pore diameter of D _cp. = 10.2 nm and specific surface S _beats. = 89 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.67 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 moles of an organic template — a complex of the oxaazamacrocyclic compound 18-Coronaase-2-oxa-4 with calcium ion.

Example 51

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of oxazazamacrocyclic compound 18-Coronaase-2-oxa-4 with a calcium ion of the general formula [Ca (C ₁₂ H ₂₆ O ₄ N ₂ )] Cl ₂ · 3H ₂ O as a precursor - titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-butanol containing 4.5 wt.% water. 170 ml of this water-alcohol solvent was poured into a glass beaker. 3.118 g of template were dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 25 ° C with a thermostat, and the relative humidity was 65% using a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 15 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure, together with the mother liquor, was placed in an autoclave, where it was hydrothermally treated for four days at a temperature of 150 ° C. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the crushed dry mixture was poured into a glass beaker. With vigorous stirring, the required amount of ethyl alcohol, preliminarily heated to the boiling point, was added to the glass, and the organic template was removed from the structure by the method described in example 1. After the de-sampling of the structure, the solid phase was separated by filtration from the suspension. It was dried until the solvent was almost completely removed, and then ground.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 34 wt.%, Had a porous structure with an average pore diameter D _cp. = 13.2 nm and specific surface S _beats. = 73 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.57 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 moles of an organic template — a complex of the oxaazamacrocyclic compound 18-Coronaase-2-oxa-4 with calcium ion.

Example 52

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of oxazazamacrocyclic compound 18-Coronaase-2-oxa-4 with a calcium ion of the general formula [Ca (C ₁₂ H ₂₆ O ₄ N ₂ )] Cl ₂ · 3H ₂ O as a precursor - titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing water in an amount of 4.5 wt.%. 170 ml of this aqueous-alcoholic solvent were poured into one glass beaker. 3.118 g of template were dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 25 ° C with a thermostat, and the relative humidity was 65% using a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 15 days until the final formation of the spatial structure of the 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 5 hours until the organic template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 61 wt.%, Had a porous structure with an average pore diameter D _cp. = 11.4 nm and specific surface S _beats. = 81 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.62 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide was 0.11 moles of the organic template-complex of the oxazamacrocyclic compound 18-Coronaaz-2-oxa-4 with calcium ion.

Example 53

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of oxazamacrocyclic compound 18-Coronaase-2-oxa-4 with a calcium ion of the general formula [Ca (C ₁₂ H ₂₆ O ₄ N ₂ )] Cl ₂ · 2H ₂ O as a precursor - titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing water in an amount of 4.5 wt.%. 170 ml of this aqueous-alcoholic solvent were poured into one glass beaker. At room temperature, 3.118 g of the template was dissolved in it, then 0.105 g of lanthanum chloride. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. Under vigorous stirring, a precursor solution was introduced dropwise into the solution of the template and lanthanum salts. After the entire portion of this solution was introduced into the solution of the template and lanthanum salts, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 25 ° C with a thermostat, and the relative humidity was 65% using a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 15 days until the final formation of the spatial structure of the 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the organic template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 60 wt.%, Had a porous structure with an average pore diameter D _cp. = 12.2 nm and specific surface S _beats. = 75 m ² / g. In addition, it additionally contained lanthanum in an amount of about 0.012 g per g of substance. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.59 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide accounted for 0.11 moles of an organic template — a complex of oxazazamacrocyclic compound 18-Coronaaz-2-oxa-4 with calcium ion and about 0.006 moles of lanthanum chloride.

Example 54

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of oxazamacrocyclic compound 18-Coronaase-2-oxa-4 with a strontium ion of the general formula [Sr (C ₁₂ H ₂₆ O ₄ N ₂ )] Cl ₂ · 2H ₂ O as a precursor - titanium tetraisopropoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-propanol containing water in an amount of 6.5 wt.%. 142 ml of this aqueous-alcoholic solvent were poured into one glass beaker. At room temperature, 1.667 g of the template was dissolved in it. 41 ml of the same solvent were poured into another glass beaker. At room temperature, 21 g of the precursor was dissolved in it. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 3 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 20 ° C with a thermostat, and the relative humidity was 76% using a saturated solution of sodium chloride. The mixture was contacted with water vapor at this temperature for 18 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 69 wt.%, Had a porous structure with an average pore diameter D _cp. = 10.9 nm and specific surface S _beats. = 86 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.72 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide accounted for 0.05 moles of an organic template — a complex of the oxaazamacrocyclic compound 18-Coronaase-2-oxa-4 with strontium ion.

Example 55

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of oxazazamacrocyclic compound 18-Coronaase-2-oxa-4 with a barium ion of the general formula [Ba (C ₁₂ H ₂₆ O ₄ N ₂ )] Cl ₂ · 3H ₂ O as a precursor - titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-butanol containing water in an amount of 5.5 wt.%. 177 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 1.914 g of the template were dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 30 ° C with a thermostat, and the relative humidity was 63% with a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature was ensured for 14 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 155 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 72 wt.%, Had a porous structure with an average pore diameter D _cp. = 12.3 nm and specific surface S _beats. = 83 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.63 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide accounted for 0.05 moles of the organic template of the complex of oxazamacrocyclic compound 18-Coronaaz-2-oxa-4 with barium ion.

Example 56

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of oxazazamacrocyclic compound 18-Coronaase-2-oxa-4 with a lanthanum ion of the general formula [La (C ₁₂ H ₂₆ O ₄ N ₂ )] Cl ₃ · 7H ₂ O as a precursor - titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 7 wt.% water. 167 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 0.928 g of template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 20 ° C with a thermostat, and the relative humidity was 81% using a saturated solution of ammonium sulfate. The mixture was contacted with water vapor at this temperature for 18 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C it was hydrothermally treated for 55 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 70 wt.%, Had a porous structure with an average pore diameter of D _cp. = 12.8 nm and specific surface area S _beats. = 97 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.69 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide accounted for 0.02 moles of an organic template — a complex of the oxaazamacrocyclic compound 18-Coronaaz-2-oxa-4 with the lanthanum ion.

Example 57

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of oxazazamacrocyclic compound 18-Coronaase-2-oxa-4 with a cerium ion of the general formula [Ce (C ₁₂ H ₂₆ O ₄ N ₂ )] Cl ₃ · 2H ₂ O as a precursor - titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-butanol containing 4.7 wt.% water. 157 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 0.794 g of template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 20 ° C with a thermostat, and the relative humidity was 76% using a saturated solution of sodium chloride. The mixture was contacted with water vapor at this temperature for 19 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 67 wt.%, Had a porous structure with an average pore diameter D _cp. = 11.9 nm and specific surface S _beats. = 99 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.71 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide accounted for 0.02 moles of an organic template — a complex of the oxaazamacrocyclic compound 18-Coronaaz-2-oxa-4 with cerium ion.

Example 58

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of the oxazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with a lithium ion of the general formula [Li (C ₂₀ H ₂₅ O ₅ N)] Cl · 3H ₂ O as a precursor - titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-butanol containing water in an amount of 3.7 wt.%. 207 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 2.623 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 3 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 20 ° C with a thermostat, and the relative humidity was 65% using a saturated solution of ammonium nitrate. The mixture was contacted with water vapor at this temperature for 18 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 200 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 76 wt.%, Had a porous structure with an average pore diameter D _cp. = 13.5 nm and specific surface S _beats. = 119 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.77 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide there was 0.1 mol of the organic template of the oxazamacrocyclic complex of dibenzo-18-coronaase-1-oxa-5 with lithium ion.

Example 59

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of the oxazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with a potassium ion of the general formula [K (C ₂₀ H ₂₅ O ₅ N)] J · 2H ₂ O as a precursor - titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 7 wt.% water. 211 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 3.398 g of template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 20 ° C with a thermostat, and the relative humidity was 65% using a saturated solution of ammonium nitrate. The mixture was contacted with water vapor at this temperature for 16 days until the final formation of the mixture of the 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 200 ° C it was hydrothermally treated for 52 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 80 wt.%, Had a porous structure with an average pore diameter D _cp. = 13.8 nm and specific surface S _beats. = 112 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.77 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 moles of an organic template — a complex of the oxaazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with potassium ion.

Example 60

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of the oxazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with a sodium ion of the general formula [Na (C ₂₀ H ₂₅ O ₅ N)] Cl · 3H ₂ O as a precursor - titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 5 wt.% water. 191 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 2.611 g of the template were dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 3 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 15 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 15 ° C with a thermostat, and the relative humidity was 81% using a saturated solution of ammonium sulfate. The mixture was contacted with water vapor at this temperature for 21 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 150 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 78 wt.%, Had a porous structure with an average pore diameter D _cp. = 13.0 nm and specific surface S _beats. = 117 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.75 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide was 0.1 mole of an organic template — a complex of the oxazazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with sodium ion.

Example 61

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of the oxazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with the rubidium ion of the general formula [Rb (C ₂₀ H ₂₅ O ₅ N)] Br · 3H ₂ O as a precursor - titanium tetraethoxide of the general formula (C ₄ H ₉ O) ₄ Ti, ethanol containing water in an amount of 4 wt.% as a water-alcohol solvent. 120 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 3.525 g of template was dissolved in it. In another glass beaker was poured 30 ml of the same solvent. At room temperature, 18 g of the precursor was dissolved in it. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 4.5 hours until a sol was formed from the mixture. The temperature of the mixture during this synthesis step was maintained at about 10 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 10 ° C with a thermostat, and 82% relative humidity with a saturated solution of ammonium sulfate. The mixture was contacted with water vapor at this temperature for 20 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 200 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 52 wt.%, Had a porous structure with an average pore diameter D _cp. = 6.9 nm and specific surface S _beats. = 81 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.55 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide was 0.1 mole of an organic template — a complex of the oxazazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with a rubidium ion.

Example 62

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of the oxazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with a cesium ion of the general formula [Cs (C ₂₀ H ₂₅ O ₅ N)] NO ₃ · 3H ₂ O, as the precursor is titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing 4.5 wt.% water. 182 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 3.740 g of template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 5 hours until a sol was formed from the mixture. The temperature of the mixture during this synthesis step was maintained at about 10 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was kept at about 10 ° C with a thermostat, and the relative humidity was 73% using a saturated solution of ammonium nitrate. The mixture was contacted with water vapor at this temperature for 22 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 150 ° C it was hydrothermally treated for 50 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 400 ° C for 6 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 58 wt.%, Had a porous structure with an average pore diameter of D _cp. = 8.3 nm and specific surface area S _beats. = 77 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.67 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 moles of an organic template — a complex of the oxaazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with cesium ion.

Example 63

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of the oxazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with a magnesium ion of the general formula [Mg (C ₂₀ H ₂₅ O ₅ N)] SO ₄ · 3H ₂ O, as the precursor is titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 4 wt.% water. 174 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 3.193 g of template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber in which the temperature was maintained at about 25 ° C with a thermostat, and a relative humidity of 80% with a saturated solution of ammonium sulfate. The mixture was contacted with water vapor at this temperature for 17 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 150 ° C it was hydrothermally treated for 48 hours. After this, 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in the amount of 68 wt.%, Had a porous structure with an average pore diameter D _cp. = 10.3 nm and specific surface area S _beats. = 97 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.78 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.1 moles of an organic template — a complex of the oxaazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with a magnesium ion.

Example 64

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of the oxazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with a calcium ion of the general formula [Ca (C ₂₀ H ₂₅ O ₅ N)] Cl ₂ · 3H ₂ O, as the precursor is titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-butanol containing 7 wt.% water. 170 ml of this water-alcohol solvent was poured into one glass beaker. At room temperature, 3.126 templates were dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 25 ° C with a thermostat, and the relative humidity was 65% using a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 18 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 66 wt.%, Had a porous structure with an average pore diameter of D _cp. = 11.3 nm and specific surface S _beats. = 91 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.70 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide was 0.1 mole of an organic template — a complex of the oxaazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with calcium ion.

Example 65

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of the oxazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with a strontium ion of the general formula [Sr (C ₂₀ H ₂₅ O ₅ N)] Cl ₂ · 2H ₂ O, as the precursor is titanium tetrapropoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-propanol containing 6.5 wt.% water. 143 ml of this water-alcohol solvent was poured into one glass glass. At room temperature, 1,671 templates were dissolved in it. 50 ml of the same solvent was poured into another glass beaker. At room temperature, 21 g of the precursor was dissolved in it. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 3 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 20 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 20 ° C with a thermostat, and the relative humidity was 76% using a saturated solution of sodium chloride. The mixture was contacted with water vapor at this temperature for 20 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 175 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 400 ° C for 5.5 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 63 wt.%, Had a porous structure with an average pore diameter of D _cp. = 11.6 nm and specific surface S _beats. = 89 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.72 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide accounted for 0.05 moles of an organic template — a complex of the oxaazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with strontium ion.

Example 66

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of the oxazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with a barium ion of the general formula [Ba (C ₂₀ H ₂₅ O ₅ N)] Cl ₂ · 3H ₂ O, as the precursor is titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing 6.3 wt.% water. 164 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 1.918 template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 30 ° C with a thermostat, and the relative humidity was 63% with a saturated solution of sodium nitrite. The mixture was contacted with water vapor at this temperature for 16 days until the final formation of the mixture of the 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 125 ° C it was hydrothermally treated for 53 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 71 wt.%, Had a porous structure with an average pore diameter D _cp. = 12.1 nm and specific surface area S _beats. = 92 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.68 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.05 moles of an organic template — a complex of the oxazazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with barium ion.

Example 67

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of the oxazazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with the lanthanum ion of the general formula [La (C ₂₀ H ₂₅ O ₅ N)] Cl ₃ · 7H ₂ O, as the precursor is titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 5 wt.% water. 144 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 0.929 template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2.5 hours until a sol was formed from the mixture. The temperature of the mixture throughout this synthesis step was maintained at about 25 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber, the temperature of which was maintained at about 25 ° C with a thermostat, and the relative humidity was 75% with a saturated solution of sodium chloride. The mixture was contacted with water vapor at this temperature for 18 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 185 ° C 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 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed.

Thus obtained mesoporous titanium dioxide contained anatase crystalline phase in an amount of 76 wt.%, Had a porous structure with an average pore diameter D _cp. = 13.9 nm and specific surface S _beats. = 112 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.73 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, per mole of titanium dioxide accounted for 0.02 moles of an organic template, a complex of the oxazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with lanthanum ion.

Example 68

As an organic template for the synthesis of mesoporous titanium dioxide, we used a complex of oxazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with a cerium ion of the general formula [Ce (C ₂₀ H ₂₅ O ₅ N)] Cl ₃ · 2H ₂ O, as the precursor is titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent is n-butanol containing 4.5 wt.% water. 135 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 0.796 template was dissolved in it at room temperature. 45 ml of the same solvent was poured into another glass beaker. 25 g of the precursor was dissolved in it at room temperature. With vigorous stirring, the precursor solution was introduced dropwise into the template solution. After the entire portion of the precursor solution was introduced into the template solution, the resulting mixture was continued to mix for 2 hours until a sol was formed from the mixture. The temperature of the mixture at this synthesis stage was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. A glass with the mixture was placed in a chamber where the temperature was maintained at about 30 ° C using a thermostat and 85% relative humidity was saturated with a saturated solution of potassium chloride. The mixture was contacted with water vapor at this temperature for 15 days until the final formation of the spatial structure of the mixture of titanium dioxide / organic template.

The formed structure together with the mother liquor was placed in an autoclave, where at a temperature of 150 ° C it was hydrothermally treated for 51 hours. After that, the structure together with the mother liquor was removed from the autoclave. The 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 to obtain mesoporous titanium dioxide. To obtain the required amount of mesoporous titanium dioxide, an appropriate portion of the dry mixture was poured into the crucible. The crucible with the mixture was placed in a muffle furnace, where it was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed.

The mesoporous titanium dioxide thus obtained contained a crystalline anatase phase in an amount of 72 wt.%, Had a porous structure with an average pore diameter D _cp. = 15.7 nm and specific surface area S _beats. = 114 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such mesoporous titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.77 in the presence of a palladium or platinum catalyst of the dark reaction stage.

In the isolated intermediate to obtain mesoporous titanium dioxide, one mole of titanium dioxide contained 0.02 moles of an organic template — a complex of the oxazazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with cerium ion.

The given examples do not exhaust all the possibilities of the practical embodiment of the inventive concept. So, in a more complex form of implementing the inventive concept, which does not contradict the main claims, at the stage of synthesis of mesoporous titanium dioxide from ash formation to the final formation of the spatial structure of the precursor / organic template from the reaction mixture, the temperature of the mixture does not go beyond the specified upper limit and recommended lower the limit can be maintained 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 ambient temperature and its humidity do not change significantly during the time necessary for the synthesis of mesoporous titanium dioxide and the change in these environmental parameters is predictable, the final product, mesoporous titanium dioxide with the above set of properties, can be synthesized according to the above methods without the use of a thermostat and saturated solutions of the corresponding salts.

Industrial applicability

The proposed mesoporous titanium dioxide and intermediate can be easily obtained industrially in accordance with the proposed method using reagents manufactured by the chemical industry. Such mesoporous titanium dioxide can be successfully used in the chemical industry as a sorbent catalyst for the photochemical reactions of molecular hydrogen evolution from water-alcohol mixtures or as a sorbent catalyst for heterogeneous photochemical processes of oxidation of harmful organic compounds in the gas phase to the formation of environmentally friendly products.

Claims (7)

1. A method of producing mesoporous titanium dioxide, including the introduction of a precursor of titanium tetraalkoxide and an organic template into an aqueous organic solvent, exposure of the mixture of reagents to the final formation of a spatial structure from it through successive stages of sol formation, and then gel, separation of the resulting reaction product and its processing to remove the template, characterized in that the process is carried out in a water-alcohol solvent containing not more than 7 wt.% water, as a template in a solvent at least one of the ligands selected from the group of macrocyclic compounds consisting of oxa and oxazamacrocyclic compounds containing at least four oxygen atoms and / or from complexes of these macrocyclic compounds with metal ions selected from the group of alkaline or alkaline earth is introduced , or f-metals, consisting of lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium, until the formation of sol, the mixture of reagents is mixed, maintaining its temperature not higher than 35 ° C, and until Nogo formation of a mixture of the spatial structure of the reactants the mixture was kept at the same temperature in an open vessel under free access to water vapor mixture. 2. The method according to claim 1, characterized in that the template is removed from the obtained reaction product by calcination at a temperature of from 300 to 600 ° C. 3. The method according to claim 1, characterized in that the template is removed from the reaction product by extraction with alcohol. 4. The method according to PP.2 and 3, characterized in that before removing the template, the reaction product is treated hydrothermally at a temperature of from 100 to 200 ° C. 5. The method according to claim 1, characterized in that the lanthanum salt is additionally introduced into the water-alcohol solvent. 6. The intermediate product for the production of mesoporous titanium dioxide containing titanium dioxide and an organic compound, characterized in that it contains as an organic compound at least one of the ligands selected from the group of macrocyclic compounds consisting of oxo and oxazamacrocyclic compounds containing at least four oxygen atoms and / or from complexes of these macrocyclic compounds with metal ions selected from the group of alkaline, or alkaline earth, or f-metals, consisting of lithium, potassium, atria, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium, wherein per mole of titanium dioxide in interm have from 0.001 mole to 0.2 mole of ligand. 7. The intermediate product according to claim 6, characterized in that it further comprises a lanthanum salt in an amount of not more than 0.006 mol per one mol of titanium dioxide.